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CHEMICAL ENGINEERING PROBLEMS IN BIOTECHNOLOGY
CHEMICAL ENGINEERING PROBLEMS IN BIOTECHNOLOGY
Nseabasi Ikput
ARCLER
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www.arclerpress.com
Chemical Engineering Problems in Biotechnology Nseabasi Ikput
Arcler Press 2010 Winston Park Drive, 2nd Floor Oakville, ON L6H 5R7 Canada www.arclerpress.com Tel: 001-289-291-7705 001-905-616-2116 Fax: 001-289-291-7601 Email: [email protected] e-book Edition 2019 ISBN: 978-1-77361-621-6 (e-book) This book contains information obtained from highly regarded resources. Reprinted material sources are indicated and copyright remains with the original owners. Copyright for images and other graphics remains with the original owners as indicated. A Wide variety of references are listed. Reasonable efforts have been made to publish reliable data. Authors or Editors or Publishers are not responsible for the accuracy of the information in the published chapters or consequences of their use. The publisher assumes no responsibility for any damage or grievance to the persons or property arising out of the use of any materials, instructions, methods or thoughts in the book. The authors or editors and the publisher have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission has not been obtained. If any copyright holder has not been acknowledged, please write to us so we may rectify.
Notice: Registered trademark of products or corporate names are used only for explanation and identification without intent of infringement. © 2019 Arcler Press ISBN: 978-1-77361-487-8 (Hardcover) Arcler Press publishes wide variety of books and eBooks. For more information about Arcler Press and its products, visit our website at www.arclerpress.com
ABOUT THE AUTHOR
Nseabasi Ikput, M.Sc., BEng, is a UK-based Chemical Process Engineer whose authenticity, dedication, and aptitude have all earned her the reputation as a seasoned industry leader. Over the course of nearly two decades, she has gained extensive engineering experience. Nseabasi’s affinity for her field began at 14 years of age, when she first visited her father at work. She has had a relentless passion for discovery and lifelong learning ever since.
TABLE OF CONTENTS
List of Figures...............................................................................................xiii
Preface..........................................................................................................xv Chapter 1
Introduction to Chemical Engineering Computing..................................... 1 1.1. Mathematical Formulations of Equations of State................................. 5 1.2. Vapor-Liquid Equilibrium..................................................................... 7 1.3. Chemical Reaction Equilibrium........................................................... 7 1.4. Mass Balances With Recycle Stream.................................................... 7 1.5. Simulation of Mass Transfer Equipment................................................ 8 1.6. Process Simulation............................................................................... 8 1.7. Chemical Reactors............................................................................... 8 1.8. Transport Procession One Dimension.................................................. 8 Practice Questions...................................................................................... 9 References................................................................................................ 10
Chapter 2
Chemical Engineering Fundamentals........................................................ 11 2.1. Clarifying Complex Chemical Processes With Quantum Computers....................................................................... 14 2.2. Mass Production And Networking...................................................... 15 References................................................................................................ 19
Chapter 3
Organic Chemistry: Biological Emphasis.................................................. 21 References................................................................................................ 28
Chapter 4
Fundamentals of Microbiology................................................................. 29 References................................................................................................ 35
Chapter 5
Chemical Engineering Thermodynamics................................................... 37 References................................................................................................ 44
Chapter 6
Structure and Properties of Materials....................................................... 45 References................................................................................................ 52
Chapter 7
Separation Processes................................................................................ 53 References................................................................................................ 61
Chapter 8
Introduction to Biochemistry................................................................... 63 References................................................................................................ 71
Chapter 9
Biochemical Engineering.......................................................................... 73 References................................................................................................ 82
Chapter 10 Electrical Circuits..................................................................................... 83 10.1. Laws of Circuit Analysis and Synthesis............................................. 84 10.2. Kirchhoff’s Current Law (KCL).......................................................... 84 10.3. Kirchhoff’s Voltage Law (KVL)........................................................... 85 10.4. Thevenin’s Theorem......................................................................... 85 10.5. Norton Theorem.............................................................................. 87 10.6. DC Transient.................................................................................... 89 10.7. Static Electric And Magnetic Fields.................................................. 89 10.8. Filters............................................................................................... 90 10.9. Capacitor......................................................................................... 90 10.10. Inductor......................................................................................... 91 References................................................................................................ 93 Chapter 11 Electromechanical Systems...................................................................... 95 References.............................................................................................. 103 Chapter 12 Process Dynamics and Control............................................................... 105 12.1. Sylvester’s Theorem........................................................................ 108 12.2. Integer-Order Continuous Models of Fractional Order Systems...... 113 12.3. Controller Understanding.............................................................. 113 12.4. Analog Understandings.................................................................. 114 References.............................................................................................. 115 Chapter 13 Introduction to Biochemical Methods.................................................... 117 13.1. Standard Interpretation.................................................................. 120
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References.............................................................................................. 125 Chapter 14 Chemical Analysis of Homogeneous Systems......................................... 127 References.............................................................................................. 134 Chapter 15 Methods in Quantitative Chemical Analysis........................................... 135 15.1. Components of a Calibration Program........................................... 137 15.2. Traceability.................................................................................... 137 15.3. Precision Versus Accuracy.............................................................. 138 15.4. Precision Proportion...................................................................... 138 15.5. Regularity of Calibration................................................................ 138 15.6. Recall Solution.............................................................................. 139 15.7. Paperwork...................................................................................... 140 15.8. Recap............................................................................................ 140 References.............................................................................................. 145 Chapter 16 Chemical Engineering Design Principles................................................ 147 16.1. Introduction................................................................................... 148 16.2. Chemical Process Synthesis........................................................... 149 16.3. Principles of The Process Conceptualization.................................. 150 References.............................................................................................. 156 Chapter 17 Material Science and Material Selection................................................ 157 References.............................................................................................. 163 Chapter 18 Chemical Process Engineering................................................................ 165 References.............................................................................................. 171 Chapter 19 Bioprocess Engineering.......................................................................... 173 References.............................................................................................. 179 Chapter 20 Environmental Chemistry and Remediation........................................... 181 20.1. Green Chemistry............................................................................ 182 20.2. Benefits of Chemical Energy.......................................................... 185 20.3. Negative Aspects of Chemical Energy............................................ 187 20.4. Listing of Benefits of Chemical Energy........................................... 188 20.5. Checklist of Downsides of Chemical Energy.................................. 190 20.6. Major Current Environmental Problems......................................... 192 ix
References.............................................................................................. 194 Chapter 21 Chemical Reaction Engineering.............................................................. 195 Chapter 22 Fluid Mechanics and Heat Transfer........................................................ 203 22.1. Phases of Matter............................................................................ 208 References.............................................................................................. 210 Chapter 23 Mathematical Modeling and Numerical Methods.................................. 211 23.1. Mean and Variance........................................................................ 214 23.2. Binomial Probability-Mass Function.............................................. 215 23.3. Normal Distribution....................................................................... 215 References.............................................................................................. 218 Chapter 24 Process Control, Instrumentation, and Safety........................................ 219 24.1. Feedback Control System Characteristics....................................... 223 24.2. Benefits of Advanced Control......................................................... 224 References.............................................................................................. 227 Chapter 25 Chemometrics........................................................................................ 229 25.1. Instrumental Chemical Analysis..................................................... 232 25.2. Optical Methods............................................................................ 232 25.3. Electrochemistry Methods.............................................................. 233 25.4. Chromatography Methods.............................................................. 234 25.5. High Performance Liquid Chromatography (HPLC)........................ 235 25.6. Thin Layer Chromatography........................................................... 235 25.7. Ion Exchange Chromatography...................................................... 235 25.8. Operating Line............................................................................... 235 References.............................................................................................. 237 Chapter 26 Process Modeling and Simulation........................................................... 239 26.1. Process Control.............................................................................. 243 References.............................................................................................. 246 Chapter 27 Polymer Technology............................................................................... 247 27.1. Crystalline Polymers...................................................................... 250
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27.2. Addition Polymerization................................................................ 251 27.3. Bulk Polymerization...................................................................... 251 27.4. Soluble Polymerization.................................................................. 252 27.5. Emulsion Polymerization............................................................... 252 27.6. Suspension Polymerization............................................................ 252 27.7. Regular Double-Strand Polymers................................................... 254 Reference............................................................................................... 256 Index...................................................................................................... 257
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LIST OF FIGURES Figure 9.1. Mass transfer of component A between media B and E with no concentration jump at the interface. Figure 9.2. Mass transfer of part A in between media B as well as E with a focus dive at the user interface. Figure 10.1: Electric Circuit. Figure 10.2. Illustration of Kirchhoffs Circuit Law : Determination of Number of Nodes, Branches, Lopes and Meshes in a Circuit. Figure 11.1. 2 Input AND Gate- AND gate is an electronic circuit that gives a high output (1) only if all its inputs are high. Figure 11.2. OR Gate -The OR gate is an electronic circuit that gives a high output (1) if one or more of its inputs are high. Figure 11.3. XOR Gate-The ‘Exclusive-OR’ gate is a circuit which will give a high output if either, but not both, of its two inputs are high. Figure 11.4 . The NOT Gate -The NOT gate is an electronic circuit that produces an inverted version of the input at its output. It is also known as an inverter. Figure 11.5 . 2 Input NAND Gate - This is a NOT-AND gate which is equal to an AND gate followed by a NOT gate. The outputs of all NAND gates are high if any of the inputs are low. Figure 11.6 . 2 Input NOR Gate- This is a NOT-OR gate which is equal to an OR gate followed by a NOT gate. The outputs of all NOR gates are low if any of the inputs are high. Figure 11.7 . XNOR gate-The ‘Exclusive-NOR’ gate circuit does the opposite to the EOR gate. It will give a low output if either, but not both, of its two inputs are high. Figure 16.1 . Symbols for Drawing Process Flow Diagrams. Bhattacharyya, D., et al (2012) Diagram for Understanding Chemical Processes. Figure 16.2 . Conventions Used for Identifying Process Equipment. Figure 16.3. Temperature and Pressure effect on Conversion for Methanol from Syngas. Figure 20.1. Illustration of the Definition of Green Chemistry. xiii
Figure 21.1. Chemical reaction process. Figure 24.1. Block diagram for feed-forward and feedback control.
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PREFACE
Chemical Engineering Problems in Biotechnology is the engineering activity that is concerned with the exploitation of engineering problems in the wider scope. The goal is to identify different problems in the field of Chemical Engineering Biotechnology which set as a distinct branch of the engineering profession. In the most situation, engineers are normally faced with many questions: What information is needed to solve a problem, what is the best way to obtain it, and the best formulas and methods to solve the problems? The purpose of this book is to identify most problems in areas which chemical engineers experience Chapter 1 introduce the readers to the engineering computing and programming methods using the common engineering computing software programs, program design, analysis and development and computer application in chemical engineering. Chapter 2 aimed at challenging and training the reader to understand complex chemical processes. Chapter 3 addressed the aspects of life sciences covering the principles of organic chemistry, nomenclature of the biological processes and reaction in biological systems. Chapter 4 introduce the readers to the ecological relationship between microorganisms and human disease and response to microbial invasion. Chapter 5 introduced the reader to the principles of thermodynamics and the application of thermodynamics to phase equilibria and reaction equilibria. Chapter 6 introduced the readers to the behavior of materials under various conditions and environments about the atomic and molecular structure and bonding. The chapter cover the effects of microstructure on microscopic properties, microstructure development and materials processing. Chapter 7 will introduce the readers to the fundamentals and modeling techniques of a variety of separation processes in chemical industry. Chapter 8 will cover the chemistry of proteins, carbohydrates, nucleic acids, and lipids. Chapter 9 will cover the biomechanical engineering processes such as fermentation, agitation, and mass transfer about chemical engineering, biochemistry, and microbiology. Chapter 10 will introduce readers to the basic principles of electrical circuits and the basic laws such as Thevenin’s, Kirchhoff’s and Norton’s laws about the analysis of electrical circuits. Chapter 11 will include discussions about the basic principles of electromechanical
systems and include the basic principles of electric machines and motors. Chapter 12 will introduce the readers to the principals of control methods. The chapter will cover topics dealing with modeling for control, linear ordinary differential equations. Chapter 13 will cover the basics of chromatography (paper, thin layer, column, and electrophoresis. Chapter 14 will introduce the readers to ideal mixtures, integral quantities, differential quantities, thermodynamics of open and closed systems. Chapter 15 will cover the basic principles of errors and statistics, calibration methods, general chemistry concepts, activity and ph measurements. Chapter 16 will introduce the readers to the principles of chemical process design with specific focus on synthesis, integration and system level understanding. Chapter 17 will cover the concepts of material balances chemical engineering profession, mathematical methods in biochemical and chemical engineering. Chapter 18 cover topics in the principles of energy conversion, chemical reaction, engineering, process design and biochemical engineering. Chapter 19 introduce the readers to the topics under bioprocess development as an interdisciplinary challenge. Chapter 20 will introduce the readers to the chemistry of air, water and soil with a specific focus on the health effects of human-made chemical products and environmental by-products. Chapter 21 cover the topics such as introduction to chemical reactions, homogeneous and heterogeneous reactions. Chapter 22 covers the advanced principles of heat transfer and fluid mechanics and laboratory processes in fluid mechanics and heat transfer. Chapter 23 will be a continuation of the above chapters that introduced the discussion of ordinary differential calculus and calculations. Chapter 24 The chapter will introduce the readers to the principles of chemical process systems, modern control systems, advanced process control, computational techniques in control engineering. Chapter 25 introduce the reader to instrumental analysis in chemistry, calibration techniques in chemical and biotechnology engineering. Chapter 26 introduced the readers to process and operations modeling, random variables and probability distributions, model design. Chapter 27 will discuss the topics such as nomenclature and fundamental concepts of polymers and polymerization, polymer stereochemistry, crystalline, copolymers and viscoelasticity and polymer processing
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CHAPTER
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INTRODUCTION TO CHEMICAL ENGINEERING COMPUTING The chapter will introduce the readers to the engineering computing and programming methods using the common engineering computing software programs, program design, analysis, and development, and computer application in chemical engineering. The chapter will have practice questions at the end to test the readers understanding and for purposes of practice. With the evolution of computers age, its advancements also nourished the field of engineering and one of them is chemical engineering. The computer technology improvised chemical engineering in applications such as designing and managing different chemical processes, simplifying complex mathematical calculations and construction new drawings that previously used to done manually by the chemical engineers and it took a lot of time which result decreasing the overall output and efficiency of industry. The essential development in the project of Human Genome Project is also one of the major development, not only in chemical engineering but also in genomics and genetic engineering as well. The modern chemical engineering principles are also developing to produce advanced and efficient DNA catalogs in large quantities and helping the mankind. The computers in chemical organizations are nowadays using latest computing techniques in managing different operations in plants and set new circumstances to ensure optimal operation. The chemical engineer utilizes applications to construct new models for design and reactor analysis and using the laboratory data as well as physical parameters such as estimate the performance of reactor in the industry, chemical thermodynamics and
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to solve problems which most frequently appears during the manufacturing process. By the development of different software, chemical engineering has greatly improved by minimizing the concerns in the designing of new plans, detailed analysis, and economics for pilot plants and plant modifications. The chemical engineers can now design the whole manufacturing process with the help of simulation software which can predict the desired output which was previously limited by a certain number of factors. Furthermore, Chemical engineers now develop economic and financial ways of using energy and materials by using much more sophisticated mathematical models with advanced computers. Chemical engineers use software and techniques to reduce the use of raw materials for producing more usable products, which includes petrochemicals, plastics, and medicine which are set on a large-scale manufacturing. Also, they are involved in research and waste management. Chemical engineers use supercomputers to execute plant operations and complex chemical processes. They use Computational Fluid Dynamics to run flow systems and advanced heat transfer problems. Mostly used mathematical software techniques are Matlab, polymath, Wolfram Mathematica to eradicate the problems of complex differential equations for unique solutions. There is much software used these days for the calculation and optimum results than the past. One of the most human-friendly software is CAD (Computer-aided Design). This computing technique assists in the analysis, creation, modification, and optimization of a design. The typical tools, which this software provides, include mass properties of calculations, tolerance analysis, Finite-element modeling and graphical visualization of the current chemical process through various models. Similarly, ‘Flowsheet’ is another computer application for chemical engineering. Flowsheeting is defined as the use of computer aids to perform complex and long calculations of mass and heat balance as well as costing and sizing for the chemical process. Hence, it can be said that Flowsheeting is an essential document in process and design. It also shows the arrangement of the equipment, which are selected to carry out the process, the stream flow-rates and stream connections. It is also known as diagrammatic model of the flow process. This will include instrumentation, piping, and equipment design. One of the most advanced computer application is automation. The days of operating and managing the industries by hand are gone many years ago with the evolution of automation. In every small and large-scale industry, the techniques of automation have been used to eradicate small problem in the finishing of the final product. Automation has
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been growing with a great pace constantly with respect to its sophistication and applicability. It the fundamental step in every organization to increase its efficiency, productivity, effectiveness, and ensures safety. Therefore, all the chemical engineers in operation department, production managers are highly encouraged to use Automation to boost up the overall efficiency. This technique is applied with the help of PLC systems, which are the computerbased controller, and operates on a different set of logic, which is obtained from different boilers and other Instruments and is fed in Controller, which further decreased the operation need to perform a certain process. The integration of fundamental Automation process includes manufacturing in Industry, batch Control and in Automated Systems of Chemical Plants. Similarly, there is other frequently used software in different manufacturing and process industry and one of them is Chemical. It is an integrated animated and simulation-based suite of the process in chemical industries. It is a powerful and flexible chemical process simulation environment, which is programmed in C++ language. There are various advantages of Chemical such as daily chemical process and automated generated flowsheet of the system hence product quality is increased. It helps to design new equipment and processes, to handle increasing fuel and already feedstock costs. It also provides good economic and compares by studying alternative processes, reducing engineering staff (keeps financial situation of industry in the healthy state). It helps in keeping all engineering functions united in the single application software. The applications of Chemical are Distillations and extractions both batch and continuous in tower designing, chemical reactions, in electrolytic processes, Safety analysis, economic analysis in manufacturing, etc. The industries which are using Chemical includes Fertilizer, Pharmaceuticals, Oil exploration and refining, processing of equipment manufacturers, and construction of the plant, Academic university programmers. Another Chemical Engineering computing software is Aspen Plus, which is the original Process Simulation software developed by Aspen Tech in 1990’s. Aspen Plus is a model application used in chemical industries for the process development and design-modeling tool for simulation, monitoring for the polymer, chemical, specialty chemical, metals, and minerals, and coal power industries. Aspen HYSYS, unlike Aspen Plus, is purely used as a process and modeling tool for design, steady-state simulation, performance monitoring, business planning and efficiency, for oil & gas industries and petroleum refining industries. Aspen HYSYS is a model, which is used only in refineries for the process like CIP and distillation. For the simulation and calculation of reactors in industries,
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Batch reactors are the computer simulation-based computer application for the instruments including boilers, process design, etc. Batch Reactor is a simulator designed for chemical reactors, which are running in batch mode. It was built for chemists, technicians, and process engineers who need a robust tool to reduce overall response to environmental, production cost or safety regulations and thus, reducing the time to market of new products. It helps in accelerating the projects from laboratory to pilot and full-scale plants. Similarly, it also helps in reducing the cost through efficiency of operating conditions. Over the years, chemical engineers have adopted the modern use of computing and programming methods in solving technical engineering problems. Therefore, serving much time and money through this medium. Student must have hands-on practical experience in navigating through different problem-solving methods presently used by chemical engineers and have an in-depth knowledge on the right application of these programs to specific engineering problems. Quotes “Computers have revolutionized the way chemical engineers design and analyze processes, whether designing large units to make polyethylene or small microreactors used to detect biological agents” Finlayson, (2006). Despite this revolution, students, and engineers should carefully check through calculations to ensure no errors as computer programs do not work properly when some parameters are given. In this book section, an overview of the fundamental of chemical engineering calculation using computing and programming methods will be discussed. This will be focused on three major approaches namely; The problems that chemical engineers may need to solve; Comparison of the types of computer programs that can be used and illustration of the best for certain application; Description on accurately checking work for errors and corrections. Focus will be made on four computer programs: Excel®, MATLAB®, Aspen Plus®, Comsol Multiphysics®. There are numerous other programs you can access through other researchers, the details may be different but approach will be similar. One of the aims of a chemical engineer is to design a chemical plant and this is likely impossible to achieve without solving equations of state. Equations of state aid in the finding of the specific volume of a gaseous mixture of chemicals at specific pressure and temperature. By calculating and knowing the specific volume and size, the cost of the plant can be determined including the diameter of distillation towers and chemical reactor
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as well as the horsepower of compressors and pumps and the diameter of the pipes. These are vital information to have on hand when designing a plant. Furthermore, in calculating enthalpy and vapor-liquid properties of mixtures, specific volume must first be determined and it’s important to calculate enthalpy when making materials balances to ensure reduction in energy usage to help the environment. Algebraic equations must be solved when attempting an equation of state.
1.1. MATHEMATICAL FORMULATIONS OF EQUATIONS OF STATE The ideal equation of state is a combination of pressure, temperature, and specific volume. or
where
v=
V n
,
where p is the absolute pressure, v is the volume, n is the number of moles, R is the gas constant, and T is the absolute temperature. The unit of R must correspond to the units chosen for the other variables. This equation is correct when pressure is low otherwise numerous chemical processes must have to take place at high pressure. Ammonia gas takes place at pressure of 220 atmospheres. Ideal gas equation of state is not a suitable fit for such high pressures. More so, other equation of state has been developed to address chemical processes at high pressures. The known equation of state for substances in the gas phase is the idealgas equation of state. Therefore, this equation foresees the P-V-T behavior of a gas precisely within some suitably particular region Firstly, ideal gas law was first the Vander Waals equation of state;
where b is the excluded volume; and a is the International force between two molecules. The Redlich–Kwong equation of state is a modification of Van der Waals equation of state ,
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R 2Tc2 c p
T
1
α , b = 0.08664 where a = 0.42748 and r Tc , Tr0.5 In the above equation: Tc is the critical temperature (absolute term); Pc is the critical pressure; Tr is the reduced temperature (absolute temperature divided by critical temperature); and α is the Redlich-Kwong equation of state. The Redlich equation of state was modified further by Soave to give RedlichKwong-Soave equation of state (RK-Soave in Aspen plus) and it is commonly used in process simulators. The parameter α is given by a different formula T =
α=
0.5 α = [1 + m(1 − Tr )] ; 2 m = 0.480 + 1.574 ω – 0.176 ω . 2
The ω parameter is the acentric factor as defined ω = –
(1 + log P ) vp , r
(1+logPvp,r)Tr=0.7, where Pvp,r is the reduced pressure of a saturated vapor, estimated at a reduced temperature of 0.7. Acentric factors for numerous fluid is demonstrated and mentioned by Reid et al. Where acentric factor is unavailable, equation of Edmister can be used to estimate ω, where Tbr is the reduced normal boiling point and Pc is the critical pressure in k Pa. An alternative correlation is given by Lee and Kesler. Tr = 0.7
The Peng Robinson equation has a similar equation compared to RKSoave , , a (T ) = 0.45724
2
R Tc2 α (T ) Pc ,
α 0.5 = 1 + m (1 − Tr0.5 ), m = 0.37464 + 1.54226 ω – 0.269 ω 2 . Excel and MATLAB are used to solve equations aimed at finding specific volumes. Equations are expressed in an algebraic form and either use GoalSeek or solve to solve with excel.
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1.2. VAPOR-LIQUID EQUILIBRIUM A refinery tower normally known as distillation tower is used in separating mixture of chemical into two or more streams, each is relatively a pure stream of one of the chemicals. A physical process that governs such separation is called vapor-liquid equilibrium. Problems in this state can be solved by Excel or MATLAB as it’s all set in algebraic equation.
1.3. CHEMICAL REACTION EQUILIBRIUM Hydrogen is made when water-gas shift reacts with fuel cells. Chemical equilibrium is achieved in reactor when reaction is fast. For instance, hydrogen, and nitrogen reactions form ammonia, which are used to make fertilizer that helps to increase food production for the world. Chemical reaction equilibrium must be known first in order to analyze a process; secondly the reaction rate is determined to decide the volume of the reactor. If chemicals that react are mixed in a vessel. The reaction is represented as A+B ⇒ C+D
If the reaction is reversible
C+D ⇒ A+B
A+B ⇔ C+D Excel, MATLAB and Aspen Plus are used to solve multiple non-linear equation especially when dealing with reactions at equilibrium.
1.4. MASS BALANCES WITH RECYCLE STREAM When designing and running a chemical plant, mass balance is used in deciding which processes are cost-effective. Mass flows of a chemical process including the input flows and output flows, the economic viability of the process by adding up the selling price of the products and subtracting the cost of the raw materials and waste treatment. Mass balance helps to find the energy costs in the process provided the enthalpy of each stream is calculated. Most processes involve a recycle stream and excel is used to solve mass balances with recycle streams. When energy balances affect the mass balances, they are best-solved using process simulator such as Aspen Plus.
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1.5. SIMULATION OF MASS TRANSFER EQUIPMENT There are two key points to remember when modeling mass transfer equipment: (1) thermodynamics is important; and (2) convergence is difficult. Experimental data must be compared with thermodynamic predictions. Aspen Plus is used to solve a variety of distillation problems either with plate-to-plate method (Radfrac) and shortcut method
1.6. PROCESS SIMULATION This is used to determine the size of equipment in a chemical plant; the amount of energy needed, the overall yield, the magnitude of the waste stream. The result of the process simulation depends on thermodynamics & transport processes, the mathematical models are hard to solve without a computer, the use of Aspen plus is used in process simulators.
1.7. CHEMICAL REACTORS Many reactors require a catalyst to speed up the reaction. One of the features that set chemical Engineers apart is being able to handle chemical reactions that require converting of one or more chemicals into other chemicals that are more valuable. Equation for different reactors must be developed plug flow, batch, and CSTR. MATLAB is used to differentiate other equations and reactions and reactor problems in plug flow reactor.
1.8. TRANSPORT PROCESSION ONE DIMENSION Chemical processes involve the transport and transfer of momentum, energy, and mass. Momentum transfer is another word for fluid flow and most chemical processes involve pumps and compressors and perhaps centrifuges and cyclone separators. Energy transfer is used for heat reacting system. Equations governing energy transfer, mass transfer and fluid flow have the same similarities, e.g., heat conduction, steady, and transient, reaction and diffusion in a catalyst pellet, flow in pipes and between flat plates of Newtonian or Non-Newtonian fluids. Femi lab is used to solve waver, stokes equation in many situations, e.g., entry flow into a pipe and transient start-up of pipe flow. Most examples are for laminar flow in two dimensions. One model was turbulent flow into a pipe, the other was for a complicated 3-dimensional geometry.
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Convective diffusion equation in two and three dimensions. Chemical reaction and mass transfer are the core phenomena in defining chemical engineering. Problems of heat conduction and convection, mass diffusion and convection are solved by Femi lab.
PRACTICE QUESTIONS Q. Where batch reactor is used? Q. When AspenTech was developed? Q. What is Chemcad? Q. How automation had change the industrial processes? Q. What is CAD and its applications?
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REFERENCES 1. 2.
3. 4. 5. 6. 7. 8.
9.
Finlayson, B. (2006) (First Edn) An Introduction to Chemical Engineering Computing. 7- 175 Gray, J. R. D. In Equations of State in Engineering Research, Advances in Chemistry Ser. 182, 1977, American Chemical Society: Washington, D.C., p. 253 Hougen, O.; Watson, K. M.; Ragatz, R. A. Chemical Process Principles, Part 11, John Wiley, 1959. Keil, W.; Mackins, W.; YOB, H.; Werther, J. Scientific Computing in Chemical Engineering 1996. Lee, B. I.; Kesler, M. G. AIChEJ, 1975; 21, 510, 1040 Peng, D. Y.; Robinson, D. B. Ind. Eng. Chem. Pundam., 1976; 15, 59. Raman, R. (1985) Chemical Process Computations. Elsevier Applied Science Publishers Robinson, D. B.; Peng, D. Y.; Ng, H. J. In Phase Equilibrium and Fluid Properties in the Chemical Industry, Acs Symp. Ser. 60, American Chemical Society, Washing Dc, 1977; P.200. Schank, Roger (1994). How Students Learn – Educational Software and the Future of Education. Sponsored by Searle Center for Teaching Excellence, April 21, 1994. https://www.journals.elsevier.com/ computers-and-chemical-engineering http://cache.org/computers-inchemical-engineering-education
CHAPTER
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CHEMICAL ENGINEERING FUNDAMENTALS The chapter will aim at challenging and training the reader to understand complex chemical processes. The chapter will include discussions of material balances that involve physical equilibria and chemical reactions, gas behavior, energy balances. The chapter will introduce various laws such as Raoult’s law and the laws of vapor pressure such as Grahams, Charles, Boyles, and combined gas pressure law. After the Industrial revolution, industries were struggling to establish its process units and to cope with this demand, different engineering fields came into existence in which chemical engineering was one of them. At the beginning of 19th century, every organization setup its own Research and Development departments to solve its daily process problems for desired finishing of required product and that resulted in optimal output, thus increase overall efficient of the industry. With the advent of chemistry, two centuries ago, with the realization that everything is matter, helped us to understand various complex chemical processes from very basic chemical processes of nature to chemical reactions take place in different industries. But, no matter how complex it is, it is further simplified by dividing into different elementary processes. Also with the invention of computer, as discussed earlier in the previous chapter, advance control schemes have been developed in which different complex chemical processes which relay on mathematical equations and models are solved. By using different control techniques, the process models are just inserted and the results are obtained within seconds of time. Furthermore,
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different control algorithms are design, to get more efficient results and to reduce the processing time of chemical processes, helps in increasing the overall output of the system. Some algorithms are designed in such a way that they predict the output result of chemical reaction when using unknown compounds and creating simulation of different flow processes of industries. A large number of molecules in a small container of gas does not create any problems, as study of behavior of a gas are much simpler than expected. Only by knowing the few properties of a gas, other properties can be derived from it. The properties are pressure, density, internal energy, temperature, viscosity, diffusivity, and heat conductivity, these properties are interrelated to each other. So, it can be said that only by knowing two parameters, i.e., density and temperature or temperature and pressure, all other parameters can be fixed. For example, if the temperature of Carbon dioxide gas is known, it will have one viscosity, one internal energy and only one pressure. These kinds of calculations are the goal of kinetic theory and statistical mechanics and having predefined complex model equations, the desired results can be easily calculated more efficiently. In discussing the properties of gases, the properties of equilibrium and non-equilibrium systems are different. The equilibrium behaviors of a gas are much sophisticated to observe and analyze, since any change that will occurs on the molecular level must be compensated by the change of any other property to keep the system in its equilibrium state. Since the properties of all the gas are similar, a gas equation known as ideal gas equation is available and all the gases show small deviation from such equation. Mathematically, the equation is written as: PV ∞ RT In this equation, P is the pressure, V is the volume and R is called Gas constant, T is the temperature. Raoult’s Law is also known as Law of vapor pressure from the branch of thermodynamics and it is defined as partial vapor pressure of an ideal solution is equal to the vapor pressure of it individual components multiplied with the mole fraction of given mixture. Similarly, it is also stated as relative lowering of the vapor pressure of a solution having a nonvolatile solute which is equal to the mole fraction of that given solute of the solution. Its mathematical formula is given as: pi = p*ixi
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In the given formula, pi is the partial pressure of the component in the gaseous mixture i and pi* is the vapor pressure of the individual component i and xi is the mole fraction of its element in i in the given solution. Boyle’s law also known as Mariotte’s Law or Boyle-Mariotte’s Law is such a gas law that explains how much pressure of the gas will increase in correspondence with the decrease of volume in a container. In other words, the absolute pressure which is exerted on an ideal gas of given mass is inversely related to the volume if the amount of gas and temperature of a closed container remains unchanged. Mathematically, this law can be written as P ∞ 1/V or PV=K In the above mathematical formula, P is the pressure of the gas and V is the volume and K is Constant. Also, in comparing the matter in two different sets of conditions, the Law can be stated as: P1V1 = P2V2 Graham’s Law of effusion or diffusion is defined as the rate of diffusion/effusion of a gas equals to the inversely proportional to the square root of its mass particles, Mathematically, this law can be written as
Rate1 M2 = , Rate2 M1 In the above mathematical formula, Rate1 and Rate2 are the rate of effusion of first and second gases respectively where M1 and M2 are the molar masses of them. Also, if the molecular mass of one gas is four times higher than the other, it will escape easily through the plugs or from the small holes in the vessel at half rate as compared to the other gas. Charles’ Law is also one of the experimental laws that states that describes the behavior of how a gas will behave when it is heated. In other words, when pressure of the gas is kept constant, the volume and temperature of the gases will increase when it is heated. V ∞ T or V/T=k where V and T are the volume and temperature of the gas and K is the constant.
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Furthermore, when comparing the same gas in two different sets of conditions, it is written as: V2 T2 = = orV1T2 V2T1 V1 T1 The combined Gas Law is basically another gas law that combines further three different gas laws, i.e., Charles’ Law, Boyles’ Law and GayLussac’s Law. It is stated as the product of pressure and volume and the temperature of a container remains constant and mathematically combines the three gas laws and is given as: PV/T = K where P, V & T are the pressure, volume, and temperature of the gas and K is the constant. Similarly, after combining the three laws in two different sets of conditions, it is defined as PV PV 1 1 = 2 2 T1 T2 Chemical engineering problems has met the approval of a genetic algorithm approach in conducting multi-objective optimization problems. A multiple of new operators is used to enhance the computational effort and algorithm performance. To prevent genetic drift, an elitism operator is used to insure the circulation of the best result of each objective function. The algorithm is applied to a batch free-radical styrene polymerization process for maximize the monomer conversion rate and reduce concentration of initiator residue in the product. The algorithm is robust, handling satisfactorily multi-modal and multidimensional problems.
2.1. CLARIFYING COMPLEX CHEMICAL PROCESSES WITH QUANTUM COMPUTERS Over the years, specialist wants a more technological revolution from quantum computers, which allows for problem-solving too complex for classical supercomputers. Area of application include data encryption and decryption, special problems in the field of physics, quantum chemistry and materials research. In other words, concrete questions computers can
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answer are vague from the expert’s point of view. Computers available today calculate the behavior of simple molecules accurately.
2.2. MASS PRODUCTION AND NETWORKING Researchers highlight the fact that quantum computers do not have the ability the ability to handle all tasks, so they work as a supplement to classical computers instead of replacing them. A typical example is associated to the nitrogenize reaction, quantum computers calculates how electrons are distributed within a specific molecular structure. Notwithstanding, classical computers are required to inform quantum computers which structures are important and should be calculated. The three phase catalytic hydrogenation reactors are viable reactors which has complex behavior because of interaction amongst gas, solid, and liquid phases as well with the kinetic, mass, and heat transfer mechanisms. The distribution parameter model is nonlinear, and it is based on mass and energy conservation principles. This consists of balance equations for the gas and liquid phases and the system of partial differential equations are generated. In a possible controller design, detailed nonlinear mathematical models are not suitable; a simple linear mathematical model of the process is preferably determined. Plat data is used to validate these mathematical models. There are a few properties of gases that need attention, pressure, density, temperature, internal energy, viscosity, heat conductivity and diffusivity. Some other properties are by the application of electric and magnetic fields, which has minor interest. It is useful to distinguish the equilibrium properties and the nonequilibrium transport properties. A system in equilibrium has no changes unless some external action is performed on it and its behavior is steady with time with no change, even when the molecules are in ceaseless motion. Major fundamental of chemical engineering consist of thermodynamics; which is the science of energy. One fundamental laws of nature are the conservation of energy principle. This means that energy can neither be created nor destroyed but it can change from one form to another. A study of systems is defined as study of the quantity of matter in a space. Real surfaces that separates a system from its surroundings is called boundary. It can be fixed or movable. Studies shows that systems can be considered open or closed depending whether a fixed mass or fixed volume in space is chosen. The amount of mass in a close system is fixed and cannot cross
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it boundary. In this case, heat energy or work can cross the boundary and the close system volume could not be fixed. When energy is not allowed to cross the boundary of a system, it is considered an isolation system. A system is in equilibrium when there is no change with time and it properties can be measured. Equilibrium consists of different types, which are thermal, mechanical, phase, and chemical equilibrium. A system does not satisfy thermodynamic equilibrium until all the conditions of various types are satisfied. When an entire system has the same temperature that implies that the system is in thermal equilibrium. If there is no change in pressure in a system at any time, the system is said to be in mechanical equilibrium. Most times, system involves two phases, which are; phase and chemical equilibrium. Phase equilibrium is defined when a mass of each phase reaches an equilibrium and not deviate, it is defined as a Phase equilibrium while chemical equilibrium is when there is no chemical reaction in the system. When an equation relates the pressure, temperature, and specific volume of a substance it is called equation of state. This can also be demonstrated by the relationship between properties of a substance at equilibrium state. Equation of states could be simple and complex. The simplest equation of state for substances in the gas phase is the ideal-gas equation of state. It demonstrates the P-V-T behavior of a gas. Often, gas and vapor are commonly used simultaneously. The vapor phase of a substance is called a gas when it is above critical temperature, otherwise called a gas that is not far from a state of condensation. In 1662, Robert Boyles, an Englishman, a pressure of a gases is inversely proportional to their volume. In 1802, J. Charles and J. GayLussac, Frenchmen determined experimentally at low pressure the volume of a gas is proportional to its temperature. That is p=
T R= v
or pv = RT
(2.1)
where the constant of proportionality R is called the gas constant. p is the absolute pressure, T is the absolute temperature and v is the specific volume. where Kelvin scale of the temperature scale is related to the Celsius scale by T(K) = T(°C) + 273.15 The Rankine scale is related to the Fahrenheit scale by T(R) = T(°F) + 459.67 The temperature scales in the two-unit systems are related by
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T(R) = 1.8 T(K) T(°F) = 1.8 T(°C) + 32 The Eq. (2.1) is called the ideal-gas equation of state and a gas that obeys this relation is called an ideal gas. The gas constant value is different for each gas and is determined from R = RU/M (kJ/ kg ⋅ K or kPa ⋅ m3/kg.K)
where Ru is the universal gas constant and M is the molar mass (molecular weight) of a gas. The Ru is the same for all substances and its values is
The molar mass M is the mass of one mole (gram-mole, gmol) of a substance in grams or mass of one kmol (kilogram-mole, kgmol) in kilograms. It is the mass of 1 Ibmol in Ibm. Molar mass of a substance has the same numerical value in both unit systems For instance, a molar mass of oxygen is 32, this simply implies that mass of 1 kmol of nitrogen is 32kg or the mass of 1 Ibmol of nitrogen is 32 Ibm. That is, M = 32 kg/kmol = 32 Ibm/Ibmol. The mass of a system is equal to the product of its molar mass M and a mole number N. m = MN (kg) The value of R and M for several substances are in Table A-1. The idea-gas equation of state can be written in several different forms v = mv → PV = mRT mR = (MN)R = NRu → PV = NRuT
An ideal-gas is an imaginary substance that obeys this relation pv = RT. Experimentally, the ideal-gas relation gives close approximate to the P-v-T behavior of real gases at low densities. The density of a gas decreases at low pressures and high temperatures, and the gas behaves like an ideal gas under these conditions.
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Let’s consider the following example. Example 2–1 Mass of Air in a Room Problem: Determine the mass of the air in a room whose dimensions are 2 m x 3 m x 4 m at 50 kPa and 15°C. Solution: The mass of air in a room is to be determined. Analysis: A sketch of the room is given air at specified conditions can be treated as an ideal gas. From Table A-1, the gas constant of air is R 0.287kPa ⋅ m3/kg.K ((Note the units are (kJ/ kg ⋅ K or kPa ⋅ m3/kg.K)) because the pressure in the problem is given in kPa, and the absolute temperature is T=15°C+273=286K. The volume of the room; V=(2m)(3m)(4m)=24m3 be
The mass of air in the room is determined from the ideal gas relation to
The conversion of energy principle can be defined as the net change in the total energy of the system during a process is equal to the difference in between the total energy entering and the total energy leaving the system during that process. (Total energy entering the system) – (Total energy leaving the system) = (Change in the total energy of the system).
E in − E out = ∆Esystem The equation above is called energy balance and can be applied to any system going through a process. When using this equation to solve engineering problems, adequate understanding of different forms of energy and it transfer forms must be adhered to. When a gas such as ammonia is highly soluble in water, a linear relationship of the Henry’s law which only dilutes gas-liquid solutions does not apply, and the mole fraction of a gas dissolved in the liquid is expressed as a function of the partial pressure of the gas in the gas phase and the temperature. The relations are expressed by Raoult’s law as Pi,gas side = yi,gas side . Ptotal = yi,liquid . Pi,gas(T)
Where Pi,sat (T) is the saturation pressure of the species i at the interface temperature and Ptotal is the total pressure on the gas phase side.
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REFERENCES 1. 2. 3. 4. 5.
Boyles’ Law, Charles’ Law, Roult’s Law from Wikipedia. https://phys.org/news/2017–07-clarifiying-complex-chemicalquantum.html. https://www.britannica.com/science/gas-state-of-matter/Behaviourand-properties. https://www.researchgate.net/publication/305111153_Advanced_ control_of_a_complex_chemical_process. h t t p s : / / w w w. s c i e n c e d i r e c t . c o m / s c i e n c e / a r t i c l e / p i i / S0098135403000553.
CHAPTER
3
ORGANIC CHEMISTRY: BIOLOGICAL EMPHASIS The chapter will address the aspects of life sciences. The chapter will cover the principles of organic chemistry, nomenclature of the biological processes and reaction in biological systems. The chapter will borrow the principles and knowledge of chemical processes to explain the biological processes. The chapter will introduce the readers to laboratory tasks in performing selected experiments that introduce the students to the fundamental techniques applied in organic chemistry and to familiarize the readers with the properties of organic compounds. The chapter will cover the concept of analytical spectroscopy. The life science is such a branch of science that gives brief concept and understanding of processes and structures of living organisms. There are four principles that make life sciences such as homeostasis, genetics, the cells theory and evolution. This field of science has strong root in the field of chemistry, which has helped the mankind to learn the basics of elementary analysis of different species and different kinds of matters, their atomic numbers, atomic masses and their isotopes. Furthermore, it explained biological processes which possess different chemical reactions and bonds which includes their intermolecular and intramolecular forces, the types of bonds, i.e., ionic, covalent, and metallic bond as well as the concepts of electronegativity. It further illustrates how chemistry of life makes everything possible, also all the living organisms are made up of atoms which follows the rules of chemistry. It helped us to learn the key
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properties of atoms, how they affect the life sciences and their results in biological consequences. The life sciences are essential in improving the standards and qualities of different aspects of our life. Organic chemistry is a sub branch of chemistry which deals with the properties, chemical reactions and structures of all the organic compounds which contains carbon atom. For the study of this field of chemistry includes many parameters such as chemical and physical properties of those compound with their chemical composition and similar methods for their chemical reactivity. The study also includes to examine the compound in its pure form as well as its reactions with nature and its fabrications with other elements of periodic table. The organic chemistry also helps to create such compounds which further utilize in different other field of life such as to create different types of polymers, drugs, petroleum products and focused study of specific compounds both theoretically and laboratory analysis. Moreover, there is diverse range of chemical reactions in organic chemistry including hydrocarbons (the compounds of carbon and hydrogen), the composition of myriad with main atom of carbon, elements including sulphur, oxygen, nitrogen, phosphorus, and the radio elements of the group halogens, In term of periodic table the elements of group 1 and 2 and metalloids. Also, the modern organic chemistry contains its analysis with lanthanides and transition elements (chromium, copper, zinc, palladium, nickel, cobalt, and titanium). There is enormous range of applications of organic compounds and their constituency in many commercial products which includes petrochemicals, pharmaceuticals, and different products made from them such as solvents and lubricants, fuels, and plastics. Hence the study of organic chemistry is one of the essential components of universe as possess fundaments concepts of other fields such as biochemistry, polymer chemistry and many important aspects of material sciences. Biological processes and their reactions are necessary to study living of organisms. It possess many types of complex chemical reactions which required essential elements, persistence, and transformation, i.e., the process of metabolism and homeostasis. These types of processes run by different means such as protein modifications, substrate molecule and interaction with a protein. The examples of biological processes include structural organizations of cells which is basic unit of life, metabolism which is conversion of energy in further cellular components (anabolism) and (catabolism) decomposition of organic matter as human beings require
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energy to maintain internal structural organization of cells. The process of growth is another example of biological process, in which anabolism is at higher rate than catabolism. Another example of this process is response to a stimuli, it can be any form of response, from complex chemical reaction to contraction of cellular organism. To produce new cells also include in this process, to produce new organism with either asexually or sexually with parent organisms. The interaction between different organisms, in this type, one organism has observable effect on another specie. The other biological process are cellular differentiation, fertilization fermentation, germination, hybridization, tropism, etc. The properties of organic compound contain Qualitative and quantitative features in which the properties of qualitative features which are consistency, odor, color, and solubility whereas the properties of quantitative include index of refraction, melting point and boiling point. In term of melting and boiling point, many of the organic compound boil as well as melt in comparison with inorganic compound, they only melts and do not possess the qualities of boiling. These two basic features gives the information regarding the purity and identification of an organic matter. The boiling and melting point also relate with the molecular weight and polarity of the molecules. In the group of organic compounds, it also contains sublime compound, which upon heating, directly evaporate rather than melting and are symmetrical, i.e., para-dichlorobenzene. Over the temperature of 300 degree Celsius, most of the organic compound are instable with a few exceptions. One of the important property of organic compound is solubility, since they are hydrophobic, they are not soluble in aqueous solution, but soluble in organic solvent. There are many exceptions which are soluble in water as well, for example, the compounds containing hydrogen bonding (alcohols, amines, and carboxylic acids). The solubility of organic compounds depend upon the purity of solvent and functional group present in the given solution. There are various solid state properties of organic compounds, from organic polymers to crystalline nature and thermal, electrical, and mechanical properties, for example, electro optical properties, in case of piezoelectricity organic compounds are the main constituents and various electrical conductivity instruments. In the past, they had been also used in material and polymer sciences. Spectroscopy is defined as that field of science which deals with the measurement in radiation intensity with respect to its wavelength. There are many instruments to measure the spectroscopy such as spectral analyzers, spectrophotometers, and spectrometers. Spectroscopy is very essential in
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advance sciences as it is used in analytical chemistry and physics, since every atom and molecule possess special spectra, this technique is used in identification of atoms and molecule with quality of information. Its concept is also explained by Max Planck in black body radiation and Albert Einstein famous theory of photoelectric effect also based in it. Nowadays, most of telescope have spectrograph which is used to physical properties of space objects as well as different chemical compositions of matter. Many techniques and methods are deployed for spectroscopy such as imparting radiation energy, radiated pressure waves, electromagnetic radiations, etc. The solubility of healthy proteins in liquid services of neutral salts has developed one basis for their category as well as characterizations. Therefore, solubility of one course of healthy proteins, the globulins, is boosted by the enhancement of percentages of salt and lowered in extra focused services of electrolytes. Albumins, on the various other hand, are reasonably soluble in water, yet their solubility, additionally, is reduced in completely focused options of salts. The rise in solubility of specific healthy proteins on the enhancement of neutral salts was uncovered. This residential property was ultimately utilized effectively splitting up in between healthy proteins, however, it was not till 1905 that an extensive research of the solubility of globulins in weaken salt options was reported. There have considering that been several various other payments to this detailed chemistry of the healthy proteins. The academic description of the impacts of electrolytes after healthy proteins waited for, of requirement, the advancement of an ample concept of solid electrolytes. Physical Chemistry of Protein X which relied on the “level of dissociation,” and also, as a result, after the variety of fragments existing, ignored the electric communication of ions. Distinctions in the result of various salts, specifically of those of various valence kinds, on healthy protein actions were examined. That explained in the complying with terms the solubility of globulins in salt services. “Remedy of globulin by a neutral salt is because of pressures put in by its cost-free ions. Ions with equivalent valences, whether favorable or unfavorable, are similarly effective, and the performances of ions of various valences are straight symmetrical to the squares of their valences.” This declaration is currently identified as a summary of the concept of the ionic toughness which was later on created. In researching blends of electrolyte options the last located the adhering to empirical connection. “In water down remedies, the task coefficient of a provided solid electrolyte coincides in all options of the exact same ionic stamina.” The ionic stamina does not
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describe distinctions in habits in between salts of the exact same valence kind shown up in extra focused options. The discrepancies from the optimal gas regulations showed by remedies of solid electrolytes have actually been explained in regard to the “task coefficients” of the salts. These formulas have been located to be in close contract with the speculative monitoring for lots of courses of solid electrolytes. Both coming before documents in this collection have handled the solubility of hemoglobin in focused remedies of various electrolytes under differing problems and in potassium phosphate barriers of differing focus as well as pH. In this paper we take into consideration the solubility of the exact same healthy protein in remedies of chlorides and sulfates of extensively differing consent, distribution, particularly in thin down remedies where their solvent result could be examined. Eco-friendly hemoglobin utilized was prepared as for feasible in the salt service where solubility was later figured out. The crystals were positioned in protected containers, the preferred electrolyte remedy included, the mix filled with carbon monoxide gas, and afterwards drunk delicately at 25” in a continuous temperature level bathroom up until stability was gotten to; usually 4 or 5 hrs were needed. The remedies were filteringed system at continuous temperature level and the filtrates examined. The crystals were gone back to their containers and also even more electrolyte option included. Most of the factors on the salt sulfate contour were acquired by duplicated cleaning with a service of a provided focus till continuous solubility was gotten to. The very same treatment was made use of in examining solubility in chlorides, yet the solubility is so high in focused chloride options that it was not feasible to get filtrates of consistent salt web content, however, real balance was gotten to because the factors all rest on a smooth contour. In identifying solubility in the remainder of the electrolytes 2 containers of crystals were made use of as well as the salt focus was initially enhanced from stability to stability and also lastly lowered in the succeeding equilibrations. That the earlier as well as later factors all rest on the very same smooth contour and that the factors in the much more focused services inspect those gotten in the previous collection of experiments show that real balance was gotten to. The quantity of hemoglobin liquefied was established, as previously, by nitrogen evaluations on the filtrates. The sulfate options were examined for salt by heat-coagulating the healthy protein without the enhancement of more salt, cleaning the precipitate salt-free, and very carefully vaporizing, drying out, carefully stirring up, and also evaluating the filtrate. The magnesium sulfate decisions were inspected
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by changing a couple of examples to barium sulfate as well as considering therefore. The ammonium sulfate focus was, nonetheless, established by heat-coagulating the healthy protein in the existence of a minor quantity of phosphate barrier, cleaning the healthy protein salt-free, as well as distilling over the ammonia in the filtrate. The chloride resolutions were made in accordance with the Wilson alteration of the Van Slyke. The pH of all saturated services was figured out with the hydrogen electrode asap after filtering system. The hemoglobin as well as the electrolyte remedies were readjusted as virtually as feasible to pH 6.6 prior to the experiment started, as well as where essential tiny amounts of acid or antacids were contributed to the electrolyte options throughout the experiment. The pH worth as identified lie essentially in between 6.5 as well as 6.8 in the variety of minimal solubility. Task Coefficients of Hemoglobin in Solutions of Chlorides and also Sulfates In a heterogeneous stability where a service is filled with a strong element, at consistent temperature level and also stress, the task of the compound in the strong stage should coincide as that in the fluid stage. This is independent of other elements in the remedy. The enhancement of electrolytes to a saturated remedy of hemoglobin does not alter the task of the hemoglobin although it transforms the solubility, or the focus. The proportion of the solubility of a material at no electrolyte focus, X0, to the solubility in a remedy of offered electrolyte focus, S, is the task coefficient, y, of the compound because service. The solubility of hemoglobin in focused options of multivalent electrolytes could be effectively defined, as was seen in Research studies VIII (ll), by the straight formula for the solubility of nonelectrolytes as well as healthy proteins in focused salt remedies log S = p – K,’/ x (4) where X is once more the solubility as well as P the ionic stamina. p is the obstruct continuous as well as is the theoretical solubility in the lack of salt, called theoretical considering that, naturally, hemoglobin is a globulin whose solubility passes through an optimum with boosting salt consent, supply p is however a hassle-free consistent differing with the temperature level and the amphoteric residential properties of the healthy protein. Ii,’ is a salting out consistent attribute of the healthy protein independent of the temperature level and of the pH when an offered electrolyte is used yet differing with the electrolyte. Evaluate the ion of the constants K,’ as well as 3 pays for an ample characterization of the rainfall of a healthy protein in focused remedies of electrolytes. In examining the solubility of carboxyhemoglobin
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in phosphate barriers of differing ionic toughness and pH. It was located that at the factor of minimal solubility the healthy protein acted as though it were made up not just of the neutral particle, however, of favorably as well as adversely billed particles too. It was additionally located that the pH of minimal solubility differed with the salt concentration. The size of the impact of electrolytes on the acid and standard dissociation constants was such that the percentage of credited uncharged particles at pH 6.6 was about consistent, although a little better in the really weaken options of phosphate. Therefore, although the incline of the solubility contour at pH 6.6 in weaken services was such that the Debye-Hiickel formula did not show up to use, if one taken into consideration the neutral particle alone, it was discovered to act as though A in Formula 1 were 1.5, the worth utilized in defining the phosphate barriers themselves. The variant in the dissociation constants was such that if the solubility had been figured out at pH 6.7 instead of 6.6 the healthy protein would certainly have included an around continuous percentage of credited uncharged fragments. The pH of the saturated services of hemoglobin in sulfates as well as chlorides was not so properly managed as in the phosphate barriers. The factors exist generally on smooth contours, nevertheless, and also the variant in pH is not enough, evidently, to take the healthy protein much from the pH of minimal solubility. A satisfying photo of the variant of task coefficients could be gotten from a research of variant of solubility at roughly pH 6.6.
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REFERENCES 1. 2. 3. 4. 5.
http://books.openedition.org/cdf/3336?lang=en. http://www.freebookcentre.net/chemistry-books-download/BasicPrinciples-of-Organic-Chemistry.html. http://www.massey.ac.nz/massey/research/library/find-information/ subject-guides/life-sciences/life-sciences_home.cfm. h t t p : / / w w w. s c i e n c e d i r e c t . c o m / s c i e n c e / a r t i c l e / p i i / S0301479716305928. https://www.frontiersin.org/research-topics/5464/visualization-andcontrol-of-biological-processes.
CHAPTER
4
FUNDAMENTALS OF MICROBIOLOGY The chapter will introduce the readers to the ecological relationship between microorganisms and human disease and response to microbial invasion. The chapter will further cover the concepts of cell structure and phylogeny of archaea, bacteria, and eukaryotic microorganisms’ growth, metabolism, and ecological roles relating to diseases. The chapter will cover the symbiotic relationship between microorganisms, gene expression, genomics, and genetic exchange. The ecological relationship is defined as it is such a kind of relationship which is present between living organisms of an ecosystem. Microorganism are present everywhere in this ecosystem and they are microscopic and small species. There are different types of microorganisms, some can cause dangerous diseases, since they are small, but they still can cause death as well. Also, not all microorganism is fatal, some of them are just free living in our environment. Therefore, vast knowledge of microorganism in terms of their effect and their usefulness is necessary to defend them. Microorganism are divided into seven types of categories which as follows: archaea, protozoa, fungi, algae, multicellular animal parasites (helminths), bacteria, and viruses. These 7 types of microorganisms, each type has its own cellular composition, the reproduction system and morphology. Other than the harmful effects, some of them has beneficial effect on mankind as well such as in decomposition of organic material, maintaining human health, producing oxygen and source of nutrients for plants. Many microorganisms
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have adverse effects and are called pathogen. They have capabilities not only to affect some specific part of the body but the whole nervous system as well. Some of the harmful disease caused by the microorganism are malaria cholera, rabies, mumps, etc. These microbial effects also caused the growth and living of plants and animals as well. The whole human body is immune to number of different kind of organisms. Some of them can cause infectious diseases whenever the body is exposed to certain conditions and some of the bacteria helps human body in digestion and human play positive role for the human body, the resident bacteria can also cause different diseases whenever human body is exposed to environment for example, in case of injury, the skin protecting from harmful bacteria is removed and in such a way bacteria can overpass the protecting skin and membrane and successfully enters the body, it can further weakened the immune system, thus the overall protection against the disease deceases considerably and can result in harmful effects. Most of the diseases caused to human body are eubacteria by bacteria, whereas archaea do not possess immense effects. A great of diseases are also caused by fungi and virus, but virus is not considered as microorganism but it is still a harmful pathogen. In living organism, a basic structural and biological unit is called Cell. It is the smallest unit of human body and possess the features, i.e., reproduction and is known as building block of life. Its structural composition is in such a way that its cytoplasm is covered by cell membrane which possess molecules such as nucleic acids and proteins. Cells have different functions from carrying specific information and transmitting such information to latest production of cells. The cells are divided into two basic types, eukaryotic and prokaryotic. Eukaryotic is such time of cells which possess nucleus whereas Prokaryotic do not possess nucleus. The Archaea comes in the domain of unicellular organisms and are prokaryotes, as described earlier, they have no nucleus and no other membranes as well. Previously, Archaea were classified in terms of bacteria, but with help of recent research, this concept is outdated, its cells have such specific and unique proteins that separate it from bacteria and eukaryote. The Archaea are classified as phyla and this classification is still difficult in the modern times as up till now, no analysis is valuable on laboratory scale and they have only been detected in terms of their nucleic acids which are present in the environment. Their shape and size are similar to bacteria, but have such similarity to bacteria is not enough, research shows their
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properties are more similar to eukaryotes. The Eukaryotes are discussed further in this chapter later. Bacteria comes in the range of prokaryotic organisms and were among the first living organism on earth. Moreover, almost all forms of bacteria have been identified in laboratories and half of them can be grown as well. The study of bacteria in the branch of microbiology is called Bacteriology. Bacteria possess vast diversity in terms of sizes and shapes, they are about 0.5 micrometers in length and 1/10th of the size of eukaryotic cells. Moreover, bacteria has intracellular structure which is surrounded by cell membrane and this membrane contains the contents of the cell and acts as a wall to the other body. The eukaryote are multicellular and unicellular organisms and possess nucleus. The most important element in eukaryotes which differentiate itself from other cells is that they contains membrane organelles, i.e., the nucleus, which have genetic material known as nuclear membrane. The other components contained by the organelle of eukaryote are the Golgi apparatus and the mitochondria. The eukaryote cells have such a reproduction that they can be reproduce by sexually, i.e., meiosis and asexually mitosis. In mitosis, one cell replicates itself into two further identical cells and in meiosis, haploid daughter cells are produced which is followed by cell division of DNA replication. From many of the characteristics of microorganism, one is cell growth. There are many chemical and physical factors involve in this case. For the chemical requirement of microorganism, they should have water and other parameters such as many minerals and gases such as oxygen. Since carbon is present in all forms of microorganisms, whether they are lipids, proteins, fats, etc. Other elements that influence the growth are Nitrogen that is used by protein, RNA, and DNA. Also phosphorus is important constituent in the growth of nucleic acid and in the production of phospholipids. Moreover, for cellular respiration, oxygen is used by bacteria. Other chemical element are iron, zinc, copper, etc. Now for the physical quantities, certain factors affect the growth of microorganisms, i.e., temperature, as enzymes activity are purely temperature dependent. Furthermore, microorganism are classified into three groups regarding their temperature dependency which are psychrophilic, mesophilic, and thermophilic. Similarly, the genetics information in viruses and bacteria is also present in DNA. For genetically determined traits, replication of genome is important and genome expression involve transfer of message from DNA to
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RNA and further transcription of mRNA into proteins. The determinants of genetics depend in is genotype. The process of mutation causes changes in its genotype that can be resulted from different type of physical or chemical treatments. The exploration of prescription antibiotics in the last century is just one of one of the most considerable accomplishments of contemporary medication. Methane is of rate of interest to researchers and also culture for several factors: It is just one of one of the most essential nonrenewable fuel sources, a considerable greenhouse gas, in addition to a plentiful all-natural hydrocarbon and also substratum for bacteria. Because of its high activation power, it could just be utilized by a couple of specific teams of archaea and also germs. Cardiovascular methane-oxidizing germs have actually been understood for 110 years (1 ), it was just at the turn of the last century that microorganisms doing anaerobic oxidation of methane (AOM) wased initially determined. These microorganisms pair AOM to sulfate decrease and also come from unique clades within the methanogens (phylum Euryarchaeota), bacteria that usually create methane under anoxic problems. Up until a year back, sulfate, a significant component of salt water, was the just recognized electron acceptor for anaerobic oxidation of methane. A selection of various other eco essential oxidized substances— most especially Fe3+, Mn4+, nitrate (NO3 −) as well as nitrite (NO2 −) are thermodynamically much more desirable electron acceptors compared to sulfate. The absence of recognized methanotrophs with the ability of combining AOM to steel oxide decrease specifically stands for a basic void in our understanding of the characteristics of AOM in the atmosphere. Purposeful, guided movement, plainly identified from Brownian activity and also diffusion, is a distinct biosignature that makes no presumptions regarding the chemical make-up of the microorganisms under research. For both movement and also morphology, straight tiny monitoring stays among the very best approaches for identifying prokaryotes, the non-nucleated and also tiniest microorganisms in the world Microorganisms that show up unclear under still pictures, particularly when below settled, are plainly to life under time-lapse imaging, with activity unique in trajectory as well as speed from Brownian activity as well We could make use of the resolution limitation of the microscopic lenses to approximate a ceiling for the diffusivity to make use of in the
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diffusion formula. The observed dimension could be made use of when the bits are big sufficient to acquire settled photos. Solid currents or disturbance could produce uncertainty and also will certainly weaken price quotes of diffusivity, making imaging in a reasonably quiescent atmosphere such as a tiny container crucial. Quickly, living microorganisms step (a) 10s to thousands of times much more quickly compared to Brownian activity as well as (b) meaningfully, towards or far from stimulations. With the exemption of infections, all microorganisms in the world have actually been originally recognized as living by aesthetic monitoring (tiny or macroscopic imaging). If microorganisms in an example are non motile, as an example in a biofilm, imaging information might match chemical information and also supply essential info sustaining the debate of extant life. As simple as imaging could appear, it is testing to carry out precede or from another location in earthbound settings. Various other imaging innovations consisting of interferometry, scanning near-field optical microscopy, as well as electron microscopy methods ought to likewise be created for spaceflight applications’ Theory; The underlying theory of this job is that motile germs are a fundamental attribute of all-natural water environments, also severe ones; not all residents could trust activity to finish their biography, yet some portion of the neighborhood will certainly have progressed the capability to accomplish guided movement by means of swimming. Otherwise swimming at the time of sitting imaging, a regulated change in some facet of the ecological problems (temperature level, oxygen, nutrients) could boost or generate mobility in sufficient microorganisms to allow discovery. Purposeful, guided activity, plainly differentiated from Brownian movement as well as diffusion, is a distinct biosignature that makes no presumptions concerning the chemical structure of the microorganisms under research study. Microorganisms that show up unclear under still photos, particularly when below settled, are plainly to life under time-lapse imaging, with movement distinctive in trajectory as well as speed from Brownian activity. With the exemption of infections, all microorganisms in the world have actually been originally recognized as living by aesthetic monitoring (tiny or macroscopic imaging). If microorganisms in an example are nonmotile, as an example in a biofilm, imaging information might match chemical
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information and supply essential info sustaining the disagreement of extant life. Otherwise swimming at the time of sitting imaging, a regulated change in some element of the ecological problems (temperature level, oxygen, nutrients) could promote or generate mobility in sufficient microorganisms to allow discovery.
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REFERENCES 1. 2. 3. 4.
http://needtoknow.nas.edu/id/infection/microbes-and-humans/ https://courses.lumenlearning.com/boundless-microbiology/chapter/ microbes-and-the-world/ https://cspwproject.wordpress.com/genetic-exchange https://www.ncbi.nlm.nih.gov/books/NBK7908/
CHAPTER
5
CHEMICAL ENGINEERING THERMODYNAMICS The chapter will introduce the reader to the principles of thermodynamics and the application of thermodynamics to phase equilibria and reaction equilibria. The chapter will cover the laws covered in thermodynamics such as Joule’s and Carnot’s laws. The chapter will contain illustrative calculations to guide the readers. The chapter will cover properties of pure materials, the p-h chart, gaseous, liquid mixtures, chemical potentials in gas and condensed phases, solvent-solvent mixtures, liquid-liquid equilibria and molecular basis of thermodynamics. The chemical thermodynamics is defined as the relationship between work and heat as a result of a chemical reaction or as a result of the physical change which is within the limitation of laws of thermodynamics. Therefore, the chemical thermodynamics not only involves the properties of thermodynamics, but also different mathematical equations are applied to study the chemical process and spontaneous reactions resulted with such calculations. The branch of thermodynamics is constituents of four law of thermodynamics with physical parameters, i.e., entropy, energy, and temperature that defines a thermodynamics system at equilibrium. The four laws are defined as: •
Zeroth Law of thermodynamics: for two systems present at thermal equilibrium with the third system, then as a result, they are at thermal equilibrium with each other and this law of thermodynamics helps us to define the study of temperature.
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•
First law of thermodynamics: Whenever energy enters or leave from the system, in terms of heat or work, the internal energy of the system changes accordingly with law of conversation of energy. ∆USYSTEM = Q • Second law of thermodynamics: for a thermodynamics process, all the sum of entropies of systems increases. δQ = T dS • Third law of thermodynamics: when the temperature of a system approaches to absolute zero, in the entropy of the entire system approaches to a constant value. S = kB ln Ω Now, this chapter will further discuss for phase equilibria so first we have to understand the terminology Phase which is defined as it is portion of such systems which depicts chemical and physical characteristics uniformly, in way that it can be separated from the whole system, for example, for a gaseous state, it possess only one phase and for liquid state have two immiscible liquids, have two phases and moreover for solid state, different solid state have different phase characteristics, i.e., ZnO & SiO2 count the number of phases as two. Phase equilibria is defined as such an equilibrium phase which have the lowest energy. Mathematically, it is given as: ∆G=∆H–T∆S Similarly, chemical equilibrium is such a terminology in a chemical reaction in which products and reactants are present in such huge concentration that no further amount can change with time and forward and reverse reaction are taking place at same pace, their reaction rate not equal to zero. By using the idea discussed first law of thermodynamics, we will illustrate Joules’ law, which states that the temperature of a gas shows no variation when a gas expands in a container/chamber without doing any external work and without any heat exchanges as well. Since this law was designed for ideal gases but air also shows the properties of ideal gas over a number of conditions. This law is purely based on taking into account of internal energy of a gas. As gas neither did any external work dw = 0, nor did any heat exchanges (going in or out of chamber) dq = 0, so by using the first law of thermodynamics, it is given as du = 0. To conclude this law, the kinetic energy of the molecules of the gas is at constant energy if the
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temperature of the gas does not change. Hence, the total internal energy of a gas must remain unchanged during these conditions and also potential energy the molecules of the gas must remain constant (when volume of gas expands as well). So, if the temperature is kept constant, the internal energy of a gas remains constant. This chapter will further discuss the Carnot’s’ Law and this law is derived from 2nd law of thermodynamics. The principle of this law provides a limiting function to maximum efficiencies that a heat engine can obtain. The law purely depends upon the difference between the cold and hot reservoirs of temperature. This law states that all heat engines are less efficient than a Carnot engine using the same two reservoirs. Also, Carnot engines operating between two reservoirs of heat are equally efficient irrespective to the working substance utilized. Mathematically, it is given as: Tc ηmax = ηcarnot = 1 – TH
In the above equation, Tc is the temperature for cold reservoir and TH is the temperature for hot reservoir and the efficiency is defined as ratio of work done the engine to the heat drawn out of the hot reservoir. A substance that is composed of fix chemical composition is called pure substance. It can be of a single element, compound or a homogenous mixture. A pure substance can exist in three phases, i.e., solid, liquid or gas. Furthermore, this chapter will discuss various terminologies of thermodynamics. A p-h chart is Pressure and enthalpy chart that shows pressure and enthalpy of various refrigerant at different conditions. In this figure, pressure is at y-axis measured pounds per inch and enthalpy in x-axis measured in BTU/LB. The U-figure shows change the change of state of a liquid. Moreover, three regions are shown in the Figure which are liquid region, vapor region and liquid vapor mixed region. The properties of a gaseous mixture depend upon the properties of its individual components of the mixture. When two or more gases are mixed, the properties of individual molecules are not affected by the presence of other same or different molecule. However, there prediction in the behavior is made by the P-V-T equation and is given as p V = mm Rm T
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WHERE p = absolute pressure of the mixture (N/m2, lb/ft2), V = volume of the mixture (m3, ft3) mm = mass of the mixture (kg, lb), Rm = the individual gas constant for the mixture (J/kg K, ft lb/slugs oR), T = absolute temperature in the mixture (oK, oR). The mass of a gas mixture can be expressed as: mm = m1 + m2 + … + mn
where, m1 + m2 + … + mn = the mass of each gas component in the mixture.
The individual gas constant of a gas mixture can be calculated as: Rm = (R1 m1 + R2 m2 + … + Rn mn)/ (m1 + m2 + … + mn ) The density of a gas mixture can be calculated as:
ρm = (ρ1 v1 + ρ2 v2 + … + ρn vn)/ (v1 + v2 + … + vn )
where ρm = density of the gas mixture (kg/m3, lb/ft3), ρ1.. ρn = density of each of the components (kg/m3, lb/ft3), v1 + v2 + … + vn = volume share of each of the components (m3, ft3), v1 + v2 + … + vn = volume share of each of the components (m3, ft3). The flexible modulus as well as transverse bend stamina of pure, thick alumina samplings were established as a feature of grain dimension (1 to 250 μ) as well as temperature level (30° to 1500°C). The flexible modulus was basically independent of grain dimension over the temperature level variety covered. The transverse bend stamina for penalty—grain—sized alumina was considerably above that for bigger-grain-sized alumina over the whole temperature level array, although, at the greatest temperature levels, the price of decline of stamina with temperature level was best for
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the grained product. Penalty-grained alumina (1 to 2P) showed significant yielding as well as nonlinear tons deflection actions at 1000°C as well as over. At 1500°C, the 1- to 2-μ samplings curved to the limitation of the device without fracturing (around 7% outer-fiber pressure). The result of 16 pure steels on the artificial insemination development of a kind of tooth decays creating Streptococcus mutants was examined under both cardio and anaerobic problems. Cobalt as well as copper were regularly observed to be repressive. With much less uniformity nickel, titanium, iron, and vanadium additionally displayed capacity to hinder development of the microorganism. Bacteriostatic evidently rests after the visibility of a rust procedure. The bacteriostatic representative is of unsure identification as well as might be a deterioration item or a procedure additional to the incident of rust. Focus of steels after 6 days of electrochemical dissolution in the development tool were gauged through electron microprobe evaluation as well as compared to the quantity of restraint which resulted. Limit focus over which development did not take place were determined. As gauged by limit focus, broad irregularity in between steels exists in the capability to prevent the development, with cobalt being especially efficient at little focus. This indicates a level of sensitivity for the microorganism that is various for various steels. The limit focus ranged cardiovascular and also anaerobic problems. Streptococcus mutans showed up a lot more immune to the results of the steels under anaerobic problems even though little distinction. Outright response prices for a very long time the objective of academic chemistry has been to anticipate, from initial concepts, the outright prices of chain reactions, i.e., to determine the Dumber of particles responding each 2nd, understanding the physical homes of the particles as well as the regulations regulating their habits. To do this it is essential to recognize not just the occasions that happen in the response itself however likewise those which preceding it, along with the pressures in charge of security of both catalysts and items. Such in-depth understanding is not necessary to make up the adjustment from the preliminary to the last state of a thermodynamic balance; essential regulations of thermodynamics were effectively exercised with no in-depth understanding of atomic framework.
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It is difficult, nevertheless, for these legislations alone to offer any type of idea to the size of time that will certainly be called for, under specified problems, for balance to be achieved. They explain the measurable connection in between the price of the forward instructions and the price of the backwards instructions of a response when the proportion of these response prices ends up being continuous and consequently amounts to the stability constant. They additionally define the connection in between the balance continuous intro and the family member focus of recalls as well as overtures, the temperature level, as well as the stress. Just recently have the equivalent legislations or price procedures been developed. The triggered facility is an intermediate particle, with a lifetime of the order of 10–13 sec. The price raises regarding 12% each level, unlike the rise in kinetic power of the system which, for gas particles at average temperature levels, totals up to just regarding percent each level, inning accordance with the kinetic concept of gases, Arrhenius thought about that at consistent temperature level the variety of energetic particles Ma should be symmetrical to the variety of non-active particles. To represent the huge result of temperature level on the price of sucrose hydrolysis, Arrhenius considered it essential to present the brand-new theory of a triggered state. This principle, although ultimately customized and made extra accurate, stays in modern-day price concept. When developed, it breaks down with a global regularity ketch, which coincides for all responses. In this expression T is the outright temperature level, h is Planck’s continuous and also k is the Boltzmann continuous, i.e., RIN, the gas consistent with each particle. The possibility that the development of the turned-on facility will certainly bring about response is designated by the transmission coefficient 1 (which is commonly equivalent to 1). Therefore, in any kind of response, the details price consistent is made up based on a quasi-equilibrium in between the regular and the triggered state (assigned by the consistent Kt) as well as the regularity of decay of the triggered complicated times the likelihood that the turned on. Among biological reactions, including complicated physiological processes, the range in temperature over which the rate conforms to the Arrhenius equation is especially limited, the retaliate range depending upon not only the specific process but often also upon the specific chemical environment.
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At relatively low temperatures, familiarly between 35” and 40°C, the rates of biological reactions go through a maximum, or “optimum,” with rise in temperature because of a reversible and an irreversible inactivation of one or more protein catalysts upon which the process depends. The rate of the inactivating reaction itself often conforms to the Arrhenius equation.
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REFERENCES 1. 2.
http://www.engproguides.com/phdiagram.html https://www.engineeringtoolbox.com/gas-mixture-properties-d_586. html
CHAPTER
6
STRUCTURE AND PROPERTIES OF MATERIALS The chapter will introduce the readers to the behavior of materials under various conditions and environments about the atomic and molecular structure and bonding. The chapter will cover the material types such as metals, polymers, ceramics, semiconductors, atomic, and electronic structure, lattice structures, crystal geometry and defects, thermodynamic properties of materials, and electrical and optical properties. Atoms are not only the foundation of chemistry but also the building block of universe. Atom is the basic unit of all the matters. In case of matters, atoms are tightly packed whereas atoms are in case of gaseous matters, atoms are freely moving in container. The advance research of physics and chemistry have sub-atomic particles, i.e., nucleons and quacks. Irrespective to the subatomic particles, an atom is composed of three basic components which are electrons, protons, and neutrons. The electrons are the smallest particles and have negative charge whereas protons possess positive charge and neutrons have no charge on them. Protons and neutrons reside in nucleus. The number of protons in an atom are fixed and addition and removal of an electron create a special atom known as an ion. The combination of two or more atoms connected by chemical bond produces a molecule. There two basic types of molecules, homonuclear and heteronuclear. The homonuclear are those molecules which are made of same elements, for example, oxygen (O2) and the heteronuclear molecules are those which are composed of more than one chemical element, water (H2O) is the example of heteronuclear molecule. Just like atoms, molecules are joined together by two types of bonds, ionic
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bond and covalent bond. An ionic bond is such type of chemical bond which is produced because of electrostatic attraction which is produced when oppositely charged atoms come in contact. Cations are produced when an atom loses one or more electrons and anion are produced when atom gains one or more electrons. This transfer of electrons is known as electrovalence. In simple words, in an ionic bond, transfer of electrons takes place from metal atom to non-metal atom to complete its outer most shell and full valence. A covalent bond is such type of bond which is produced due to sharing of electron pairs between two or more atoms. The sharing pairs of electrons are known as shared pairs or bonding pairs. The attractive forces and balancing force that is established as a result of these sharing pair of electrons is the covalent bonding between the atoms. Another type of bonding that is produced by metallic atoms is metallic bond and it is such type of bonding which is resulted due to electrostatic attraction of conduction of electrons and atoms induced with positive charge. Metallic bonds result in different properties of metals such as their conductivity, ductility, strength, thermal resistivity and, opacity. It is such type of bond that metals exhibit as a pure substance as well, for example, atom of mercury Hg2. In a three group of elements, one is metals and are such type of elements that are positively charged ions (cations) and establish metallic bonding between its atoms. Metals have such an atomic structure that they possess positive ions covered by cluster of delocalized electrons. In periodic table, a diagonal line from boron to polonium gives the information regarding the metals. The structure of metals atoms consists of three types, body-centered cubic (bcc), face-centered cubic (fcc), and hexagonal close-packed (hcp). Metals in general have high electrical conductivity and density with high thermal conductivity. The electrical properties of atom is created due to the fact that they outermost shell electrons are delocalized. Metals also possess great mechanical properties as they are ductile for their ability for plastic deformation. Polymers are those type of molecules which are composed of macromolecules or large molecules and contains many repeated subunits. Polymers range from synthetic polymers (polystyrene) to biopolymer such as proteins. They are composed of repeated units of molecules of lower molecular mass and repeated structure of covalent bond. Ceramics are such inorganic compounds that can be composed metalloids and non-metallic atoms and held together by ionic or covalent bond. The structure of ceramics can be of semi-crystalline structure to pure crystalline or amorphous depending upon the properties of required ceramic.
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It was located that whilst Perspex recouped virtually when the anxiety was eliminated, rubbers and also polythene revealed postponed recuperation, and also copper, as well as lead, revealed irrecoverable circulation. The sensation of postponed healing is gone over regarding the concept of mechanical leisure as well as memory impacts in the product. Exhaustion examinations to failing of small bovine bone samplings were performed at 5 anxiety amplitudes (65–108 MN/m2) as well as 4 temperature level degrees (21–45°C). The resulting connections in between exhaustion life and stress and anxiety amplitude, bone temperature level, and also bone thickness have actually been reported. In today research, the bone samplings were classified right into 4 microstructure teams based upon the degree of second Harversian improvement. A substantial connection (P < 0 · 001) in between thickness as well as mini-framework team was revealed with key bone samplings usually being even more thick compared to second Haversian samplings. Examples of fully grown bovine cortical bone, with a Haversian miniframework, were acquired from the posterior location of the mid-femoral diaphysis. A nano imprint method was made use of to gauge the neighborhood Youthful’s modulus. The circulation of the bone mineral web content was gotten by backscattered electron imaging making use of a scanning electron microscopic lenses. An unique compression gadget utilizing mini extrasensory methods was established to evaluate regional stress. Digital photo connection was executed on the mini-framework imaged by optical microscopy throughout compression examinations. A favorable relationship (P < 0 · 01) in between exhaustion life and also thickness was disclosed within each architectural team. Additionally, an adverse relationship (P < 0 · 001) in between tiredness life as well as the level of Haversian improvement was revealed after ideal changes for thickness distinctions. These informations recommend that Haversian makeover of key bovine bone decreases exhaustion resistance not just by reducing bone thickness, however, additionally by producing a naturally weak framework. The mechanical residential or commercial properties of cortical bone have actually been thoroughly researched at the macro-architectural range. Nevertheless, expertise of the macroscopic mechanical buildings is not adequate to forecast regional sensations, such as damages or bone makeover,
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both which depend on regional mechanical habits. The goal of this research study is to evaluate the mechanical residential or commercial properties of cortical bone at numerous size ranges, with focus on the mini-framework of Haversian systems. A technique of figuring out the stress-strain relationship of products when anxieties are looked for times of the order of 20 split seconds is explained. The device utilized was an adjustment of the Hopkinson stress bar, and detonators were made use of to generate big short-term anxieties. Slim samplings of rubbers, plastics as well as steels were examined, and also the compressions created were as high as 20% with the softer products. They contain vast mechanical properties, i.e., strength of materials (hardness, elasticity, compressive strength and tensile strength). Some ceramics are semiconductors from the periodic table group of II–VI. They are called semi-metals and exhibits conductivity when certain conditions are met. Their conductive properties can be altered with the addition of impurities. They can pass current in one direction and are excellent devices when used for switching, shows sensitivity to light & heat and variable resistance. Since a great number of atoms shows the properties of semiconductors but mostly used in electronics are atoms of silicon, germanium, and compounds of gallium. They are great source of light (the excited electrons emits light instead of heat to get relaxed). This research study showed that the regional Youthful’s modulus and also pressure were heterogeneous at the range of an osteon. For both buildings, the proportion in between the optimum as well as minimum worths was roughly 2. Thus, regional pressures could not be defined just in regards to the bone mineral material, as the Haversian canal and also osteonal microstructure have a significant impact on these buildings. To conclude, the microstructure has to be taken into consideration in assessing the regional stress as well as stress and anxiety areas of cortical bone. Hydrophobicity and also moving actions of water beads were explored on different hydrophobic pillar-like and also groove frameworks prepared on a silicon wafer by dicing and also ultimately layer with fluoroalkylsilane. The leading hydro phobicity setting was altered from Wenzel’s setting to Cassie’s setting at a smaller sized roughness compared to that anticipated from the computation based upon the sinusoidal surface area by Johnson as well as Dettre. The impact of water breach on the microstructure because of
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droplet weight was exposed to be an essential element controlling the watergliding angle externally. In a contrast of the moving actions of water beads over pillar-like and groove frameworks, it was shown that a correct style of the surface area relative to form and also level of the three-phase line is extra efficient compared to the boost of getting in touch with angles simply by lowering the strong-water call location. Ferroelectric crystals are identified by their crooked or polar frameworks. In an electrical area, ions go through crooked variation as well as cause a little modification in crystal measurement, which is symmetrical to the used field. Such electric-field-induced pressure (or piezoelectricity) has actually located considerable applications in actuators as well as sensors. Nevertheless, the result is typically really tiny as well as hence restricts its efficiency. This big electro-strain comes from an uncommon relatively easy to fix domain name changing (most notably the changing of non-180° domain names) where the recovering pressure is supplied by a basic symmetryconforming home of factor problems. This system supplies a basic technique to attain big electro-strain result in a large range of ferroelectric systems and the result could result in unique applications in ultra-large stroke and also nonlinear actuators. The capability to produce normal spatial plans of bits is a crucial technical and also essential element of colloidal scientific research. We revealed that colloidal bits constrained to a few-micrometer-thick layer of a nematic fluid crystal kind two-dimensional crystal frameworks that are bound by topological problems. Standard crystalline frameworks were observed, depending upon the buying of the fluid crystal around the bit. Colloids causing quadrupolar order take shape right into weakly bound two-dimensional purchased framework, where the bit communication is moderated by the sharing of local topological issues. Colloids generating dipolar order are highly bound right into antiferroelectric-like twodimensional crystallites of dipolar colloidal chains. Self-assembly by topological problems can be put on various other systems with comparable proportion. The duty of problems as important entities in semiconductor products is examined. Early tryouts semiconductors were obstructed by the severe level of sensitivity of the digital residential or commercial properties to minute focus of contaminations.
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Semiconductors were considered as a family member of solids with irreproducible homes. Scientific initiatives conquered this trick and also transformed the art of contamination doping right into today’s extremely valuable and also reproducible modern technology that is utilized to regulate exactly electric conductivity, structure, and also minority-carrier lifetimes over large range. Indigenous problems such as openings as well as selfinterstitials regulate fundamental procedures, primary self- and also dopant diffusion. The architectural residential properties of misplacements as well as greater dimensional problems have actually been examined with atomic resolution, however, a complete academic understanding of their digital residential or commercial properties is insufficient. Responses in between flaws within the host latticework’s are progressively much better recognized and also are utilized for gettering and also electric passivation of undesirable contaminations. Metastable issues such as DX facilities as well as the EL2-related arsenic antisite are quickly talked about. The current growth of isotopically managed semiconductors has actually developed brand-new study chances in this area. Carbon nanotubes are forecasted to be metal or semiconducting relying on their size as well as the helicity of the plan of graphitic rings in their walls. Checking tunneling microscopy (STM) provides the prospective to penetrate this forecast, as it could deal with all at once both atomic framework as well as the digital thickness of states. Previous STM researches of multiwalled nanotubes and also single-walled nanotubes (SWNTs) have actually given indicators of varying frameworks as well as diameter-dependent digital residential or commercial properties, yet have actually not disclosed any kind of specific partnership in between framework and also digital residential or commercial properties. Right here we report STM dimensions of the atomic framework as well as digital buildings of SWNTs. We have the ability to solve the hexagonal-ring framework of the wall surfaces, as well as reveal that the digital buildings do undoubtedly rely on size as well as helicity. We discover that the SWNT examples display several frameworks, without anyone varieties controlling. This chapter will further discuss the optical properties of materials which is the interaction of a material with the electromagnetic radiations. The spectrum of these radiation expands in vast variety from γ-rays 10–12 m in wavelength to x-rays and finally ends at radio waves with wavelength of 105. The interaction of light with material leads to different phenomenon.
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The energy carrying packets known are photons are absorbed by the matter and this energy is emitted by the material in terms of light. At any instance of light interaction with a material, the total intensity of the incident light striking a surface is equal to sum of the absorbed, reflected, and transmitted intensities. I0 = IA + IR +IT where the intensity ‘I’ is defined as the number of photons impinging on a surface per unit area per unit time. Microstructures are defined as such structures that are studied at very small scale. These structures are revealed with the help of a microscope with magnification up to 25x. The microstructure helps us to develop different physical properties such as strength, ductility, hardness, toughness, corrosion resistance and wear resistance. To study the microstructural features of a matter, material property and morphological must be considered. One of the most useful techniques to classify morphological features is Image Processing and describes various features such as inclusion morphology, crystal orientations and volume fraction. Nowadays different synthetic microstructures are made with the help of computer-aided simulation and these synthetic microstructures help to given specific features to a material.
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REFERENCES 1. 2. 3. 4. 5.
http://nptel.ac.in/courses/112108150/pdf/Web_Pages/WEBP_M17. pdf https://depts.washington.edu/matseed/mse_resources/Webpage/ Ceramics/ceramics.htm https://www.journals.elsevier.com/journal-of-molecular-structure/ https://www.sciencedirect.com/science/book/9780444827944 https://www2.chemistry.msu.edu/faculty/reusch/virttxtjml/intro3.htm
CHAPTER
7
SEPARATION PROCESSES The chapter will introduce the readers to the fundamentals and modeling techniques of a variety of separation processes in chemical industry. The chapter will cover various computational approaches for binary and multicomponent separations and the factors affecting efficiency, capacity, and energy requirements in separation processes. The chapter will introduce the readers to the fundamentals and modeling techniques of a variety of separation processes in chemical industry. The chapter will cover various computational approaches for binary and multicomponent separations and the factors affecting efficiency, capacity, and energy requirements in separation processes. Chemical engineering consists of industrial processes which raw materials are separated into useful products. Chemical engineers involve in the development designing and engineering of complete process as well as the equipment usage. They must ensure the choice of raw materials are chosen properly, plants are operated efficiently, safely, and economically and ensure that customers are satisfied with their required products. The field of a chemical engineer is difficult to define as it requires varieties and numerous complex processes and these steps are called operations. Each operation share the same approach and also use the same scientific methods., e.g., solid and fluid separations, heat transfer, distillations, size reduction, drying, and evaporation. Unit operations primarily oversees the physical steps of preparing the reactants, which includes separating and purifying the products, recycling unconverted reactants and controlling the
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energy transfer into or out of the chemical reactor. The chemical aspect is called reaction kinetics. Hence, there is specific SI unit system that is used in separation processes. The use of mass, time, length, temperature, and mole are important during the separation process. Fluid behavior plays a significant role in the study of unit operation purposefully for the flow of heat and separation processes depending on mass transfer and diffusion. Distillation is considered the essential in the unit operation overextraction, absorption, and desorption. Binary distillation has one component in a binary mixture with more volatility than the other and its concentration in vapor phase is greater than light phase. Distillation is a separation method where component of a solution are separated, this factor is dependent on the distributing substances between the gas and light phase. New substances are thereby introduced by a method called gas absorption or desorption. Let’s consider a simple analysis of salt and water solution. During heating, water completely vaporizes from the solution while salt remains. This is the case of evaporation. Liquid-liquid extraction is a separation method that involves two immiscible liquid phase. Every chemical product s made by series of three different types of processes which are purification, synthesis, and separation process. One of the mostly used chemical process for separation process of a chemical industry are distillation, adsorption, absorption membrane processes, crystallization stripping, and extraction. This chapter will give brief introduction of separation processes that are applied in chemical industries with terminologies as well. The separation process is defined as a process that is used by number of different industries to exact particular solute or a mixture that can be separately used for a number of the process or to produce a specific mixture. It can also divide the whole mixture into its constituent elements. Mostly, the elements and compounds are in their impure form and different separation processes are applied on them to make their use possible. One of the most commonly used separation process is distillation. This process is mostly used for a mixture that can be vaporized and also for separating certain components from a mixture on the basis of their boiling point. The liquid and solid are heated and vapors are generated from them and then further condensed to produce liquid products. Among all the separation processes, crystallization is oldest and widely used separation process in chemical industries and laboratories. It is still
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very popular then other separation process because it contain vast other function as well such as separation, solidification, in determination of molecular structure, purification, and concentration. Furthermore, a great amount of energy is saved in the crystallization as much lower amount of heat is used to crystallize the production then vaporization of products which makes crystallization on of the effective means of separation process. In this process, the desired solute can be recovered from the solution by cooling, evaporation, heating, or with the addition of non-solvent to a mixture. Similarly, adsorption is a separating technique, in this method, microporous solids (adsorbents) which have more attraction properties for a particular solute (adsorbates) in a solution. This separation process is basically a cyclic process between adsorption and desorption. Moreover, desorption weakens the bonding between adsorbent and the adsorbates. The description can be increased by increasing the temperature of solution, reduction in the pressure, addition of other components that can be adsorbed as well. Membrane is another separation technique which is used in different chemical industries which involves breaking of two bulk phases physically by a third phase known as membrane. The feed separation takes place in two phases, i.e., the retentate and permeate. The membrane control the transportation of material between two phases as well as with the operating condition, specific types of component or species are allowed to pass through the membrane in preference to other. So, the permeate phase contains the required specifies in this separation process and retentate phase contains none of them. In membrane separation process, different techniques are used such as dialysis, ultrafiltration, and microfiltration. Just like Adsorption separation process, absorption, and stripping is another separation process used in industries. In this process, gas phase is soluble phase and transfer of components takes place from gas phase to liquid phase whereas, stripping is the opposite to absorption process in which components are transferred to liquid phase to gas phase. Furthermore, there are two types of absorption process, separation on the basis of reversible chemical reaction, in terms of irreversible reaction and on the base of physical solution. In this absorption process, areas are generated which are in contact with gas phase and liquid phase. In the vast techniques of separation process, extraction is also one of the oldest and widely used technique and in which separation takes place
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between two immiscible liquids. In this extraction, one of the solvent phase takes out the solute of other solvent phase and this separation is followed by raffinate cleanup and solvent recovery. The designing of this separation process is very important as there are number of different purification methods of by raffinate cleanup and solvent phases. So the selection of solvent is very important. With the help of computer technology and computer-aided animations, the separation process of different industries such as chemical and petrochemical are dramatically improved. The reactors and boilers are monitored with the help of computer and different automated mixing and extraction processes. The automated technology not only surpasses the traditional methods of separation but also resulted in the betterment of efficiency with saving the overall energy requirements in the separation process. The separation process is already very much improved and more than one technology is available for a specific mixture. But these separation techniques still needed to be required improvement in terms of usage of energy and raw material, overall efficiency, and cost of the whole process. Similarly, the changing demands and new needs of customers are also changing with time. For example, for the production an industrial gas, oxygen can be produced from air, since oxygen is less expensive than organic compounds but still its methods of production are expensive as they are greatly used in separation process. Furthermore, the demands of purity of different chemical and different gases have greatly increases with the passage of time so the chemical industries need new ways to produce matter in highly pure forms with cheap production methods especially for argon-hydrogen, oxygen, and nitrogen. Also, the demands of specified mixtures are also increased and to produce them a great amount of energy is utilized. However, the chemical industries will also greatly benefit for the methods of removal of acid gases such as CO2, COS, H2S, SO2, etc., which are produced in process streams. One method that can be used to save energy in separation process of distillation is heating cascade which means that heat realized from one boiler can by other boilers. There are many modern methods are being discovered with the help of modem chemistry which will not only eradicate the problems during the separation process but also will improve the purity of final product in terms of their functionality and composition Considering that biomass is the only carbon-based eco-friendly gas, its application comes to be an increasing number of essential for environment
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defense. Amongst the thermochemical conversion modern technologies (i.e., burning, gasification, as well as pyrolysis), burning is the only tested modern technology for warm as well as power manufacturing. Biomass burning systems are offered in the dimension array from a couple of kW as much as greater than 100 MW. The performance for warmth manufacturing is substantially high and also warmth from biomass is financially possible. Business power manufacturing is based upon heavy steam cycles. The particular price and also performance of heavy steam plants is intriguing at huge range applications. For this reason co-combustion of biomass with coal is encouraging, as it integrates high performance with affordable transportation ranges for the biomass. Nonetheless, biomass burning is associated with substantial contaminant development as well as therefore has to be boosted. To create actions for exhaust decrease, the particular gas residential properties have to be taken into consideration. It is revealed that toxin development happens as a result of two factors: (1) Insufficient burning could result in high discharges of unburnt toxins such as Carbon Monoxide, residue, as well as PAH. Although enhancements to decrease these exhausts have actually been accomplished by maximized heating system style consisting of modeling, there is still an appropriate possibility of additional optimization. (2) Contaminants such as NOX and also bits are created as an outcome of gas components such as N, K, Cl, Ca, Na, Mg, P, as well as S. For this reason biomass heaters display fairly high discharges of NOX as well as submicron fragments. Air hosting as well as gas hosting have actually been established as main procedures for NOX decrease that use a possibility of 50% to 80% decrease. Main actions for bit decrease are not yet securely understood. Nonetheless, a brand-new strategy with thoroughly lowered main air exists that could cause brand-new heater styles with lowered bit discharges. In addition, aiding initiatives for maximized plant procedure are should assure reduced exhausts and also high performance under real-world problems. A lot of these plants launched much less compared to 15 years back. The vehicle drivers, procedures, systems, scale-up techniques as well as companion partnerships for this quick intrusion of a brand-new procedure magnified method are discussed in this paper. Business vehicle drivers are (a) affordable (success): variable price, capital investment as well as power demand decrease. In all instances these are lowered by 20% or even more, when compared with the traditional set up of an activator adhered to by purification. (b) Ecological (world):
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reduced exhausts to the atmosphere. In all situations CO2 and also diffusive discharges are lowered as well as (c) social (individuals): renovations on securely, wellness as well as culture effect are gotten by reduced responsive web content, reduced escape level of sensitivity as well as reduced room line of work. These commercial responsive purification systems consist of uniform as well as heterogeneous catalyzed, permanent as well as relatively easy to fix responses, covering big varieties of responses, significantly hydrogenations, hydrodesulfurization, esterification’s as well as etherification. Numerous industrial techniques for loading heterogeneous driver in columns are currently offered. The systems consist of among others: several driver systems, gas and also fluid inner reuse website traffic over these stimulant systems, splitting up, mass circulation, as well as enthalpy exchange. These are incorporated efficiently in a solitary vessel, a particular function of procedure climax. The scale-up techniques used from pilot plants to business range are strength as well as modeling. Modern technology companies CDTECH and also Sulzer Chemtech have actually utilized these scale-up techniques effectively. Obstacles viewed as well as genuine have actually additionally been gotten rid of by these business. Chemical production business have actually likewise created their very own certain responsive purifications by their very own R&D. These businesses, both by themselves and also in consortia, additionally established heuristic procedure synthesis regulations and also professional software program to recognize the good looks as well as technological usefulness of responsive purification. Heuristic regulations and also specialist software program will certainly exist and also sustained by instances. Academic study likewise created style techniques to determine the expediency of responsive purification, to establish the feed areas, to choose packaging kinds, to series columns ideally and generated approaches to create, optimize and also manage the columns with constant state and also vibrant simulation versions.
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The fast industrial range application of responsive purification by cooperation of companions in study, scale-up, layout as well as dependable procedure could likewise be considered as a version for fast execution of various other procedure climax methods in the chemical sector. About 80% of the present world energy demand comes from fossil fuels. Unlike using fossil fuels, using hydrogen as an energy source produces water as the only byproduct. Use of hydrogen as an energy source could help to address issues related to energy security including global climate change and local air pollution. Moreover, hydrogen is abundantly available in the universe and possess the highest energy content per unit of weight compared to any of the known fuels. Consequently, demand for hydrogen energy and production has been growing in the recent years. Membrane separation process is an attractive alternative compared to mature technologies such as pressure swing adsorption and cryogenic distillation. This paper reports different types of membranes used for hydrogen separation from hydrogen-rich mixtures. The study has found that much of the current research has been focused on nonpolymeric materials such as metal, molecular sieving carbon, zeolites, and ceramics. High purity of hydrogen is obtainable through dense metallic membranes and especially palladium and its alloys, which are highly selective to hydrogen. Thin membranes would not only reduce the cost of materials but also increase the hydrogen flux. Metal alloys or composite metal membranes have been used for hydrogen purification. However, metallic membranes are sensitive to some gases such as carbon monoxide and hydrogen sulfide. Therefore, ceramic membranes, inert to poisonous gases, are desirable. Inorganic microporous membranes offer many advantages over thin-film palladium membranes. More importantly, in microporous membranes, the flux is directly proportional to the pressure, whereas in palladium membranes, it is proportional to the square root of the pressure. The paper also discusses the advantages and disadvantages of different hydrogen separation membranes. Also, the paper reports performance of selected membranes in terms of hydrogen selectivity and permeability. In spite of being an energy-intensive process, distillation remains the most important separation method in the chemical process industry. Especially for the separation of mixtures with three or more components, the total energy requirement and the capital cost are very high.
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In this respect, dividing wall columns (DWCs) represent a very promising technology allowing a significant energy requirement reduction. This article reviews current industrial applications of DWCs and related research activities, including column configuration, design, modeling, and control issues. Furthermore, the application of DWCs for azeotropic, extractive, and reactive distillation is highlighted.
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REFERENCES 1. 2.
3.
https://www.nap.edu/read/6388/chapter/4#15. https://www.omicsonline.org/proceedings/design-of-separationprocesses-from-the-empirical-methods-to-the-computeraidedstrategies-50985.html. https://www.researchgate.net/publication/285660093_Factors_ affecting_efficiency_of_separation.
CHAPTER
8
INTRODUCTION TO BIOCHEMISTRY The chapter will cover the chemistry of proteins, carbohydrates, nucleic acids, and lipids. The chapter will introduce the readers to enzyme kinetics, intermediary energetic, biochemical energetic and regulation processes. The chapter will cover the modern methods used in biochemistry. This chapter will discuss biochemistry and various factors and biological terms that can be helpful for further explanation of the various process that will be discussed in this book later. Biochemistry is defined as it is the branch of science that deals with the study of chemistry that is taking place within the body living organisms. This field has influenced the complexity of human life to a great extent by describing various processes that are happening in the human bodies such as controlling the flow of information signals and chemical energy by metabolism. Nowadays, the theories discovered by this field are utilized by different fields from botany to genetic engineering and further research have been used to study the biological molecules and processes that are occurring in living cells with the understanding of different organs and tissues. The primary focus of biochemistry is to deal with the processes at the molecular level and communication of different types of cells with each other. It also contains a vast range of study of various components such as microbiology, forensics, genetics, and medicine and plant science. Proteins are large or macromolecules that live in all types of living organisms. They take part in all types of chemical processes which are
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necessary for life and are valuable because of their applications. They are made up of amino acid that is joined to make long chains and their size of the molecule is much large then the molecule of sugar and salt. Also, similar proteins have similar amino acids and they perform a vast variety of function that is essential including DNA replication, responding to stimuli, catalyzing metabolic reactions and transporting molecules. A protein molecule exists for a fixed time span and then degraded with the recycling process, their lifespan can be from minutes to years depending upon the type of specie. The molecules of proteins are joined together by peptide bond and possess a specific gene code. Moreover, many proteins are enzymes and take part in different types of chemical reaction and metabolism. They play important role in immune responses, cell signaling, cell adhesion, and recycling of cell. The solubility of healthy proteins in liquid remedies of neutral salts has actually developed one basis for their category as well as characterizations. Hence solubility of one course of healthy proteins, the globulins, is boosted by the enhancement of percentages of salt as well as reduced in much more focused services of electrolytes. Albumins, on the other hand, are reasonably soluble in water, however, their solubility, likewise, is lowered inadequately focused options of specific salts. The boost in solubility of particular healthy proteins on the enhancement of neutral salts was uncovered. This building was ultimately utilized essentially splitting up in between healthy proteins, however, it was not up until 1905 that an extensive research study of the solubility of globulins in thin down salt services was reported. There have actually because been several various other payments to this detailed chemistry of the healthy proteins. The academic description of the results of electrolytes after healthy proteins waited for, of need, the growth of an appropriate concept of solid electrolytes. X which relied on the “level of dissociation,” and also, consequently, after the variety of fragments existing, ignored the electric communication of ions. Distinctions in the impact of various salts, specifically of those of various valence kinds, on healthy protein habits, were researched, that defined in the adhering to terms the solubility of globulins in salt services. “Service of globulin by a neutral salt results from pressures put in by its totally free ions. Ions with equivalent valencies, whether favorable or unfavorable, are similarly reliable, as well as the effectiveness of ions of various valencies are straight symmetrical to the squares of their valencies.” This declaration is currently acknowledged as a summary of the concept of the ionic toughness
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which was later on created. In researching blends of electrolyte services the last discovered the adhering to the empirical connection. In water down remedies, the task coefficient of a provided solid electrolyte coincides in all options of the exact same ionic toughness. The ionic stamina does not describe distinctions in actions in between salts of the exact same valence kind materialized in extra focused remedies. The inconsistencies from the perfect gas regulations displayed by options of solid electrolytes have actually been explained in regards to the “task coefficients” of the salts. These formulas have actually been located to be in close contract with the speculative monitoring’s for lots of courses of solid electrolytes. Both coming before documents in this collection have actually managed the solubility of hemoglobin in focused remedies of various electrolytes under differing problems as well as in potassium phosphate barriers of different focus as well as pH. In this chapter, we take into consideration the solubility of the very same healthy protein in options of chlorides and also sulfates of commonly differing consent, supply, specifically in thin down remedies where their solvent result could be checked out. Environment-friendly 49 hemoglobin utilized was prepared regarding feasible in the salt service where solubility was later identified. The crystals were positioned in protected containers, the preferred electrolyte service included, the blend filled with carbon monoxide gas, and after that trembled delicately at 25” in a consistent temperature level bathroom till balance was gotten to; normally 4 or 5 hrs were called for. The services were filteringed system at a continuous temperature level and also the filtrates evaluated. The crystals were gone back to their containers as well as even more electrolyte remedy included. A lot of the factors on the salt sulfate contour were gotten by duplicated cleaning with an option of an offered focus up until consistent solubility was gotten to. The exact same treatment was made use of in researching solubility in chlorides, however, the solubility is so high in focused chloride services that it was not feasible to get filtrates of consistent salt material, yet real balance was gotten to considering that the factors all rest on a smooth contour. In identifying solubility in the remainder of the electrolytes 2 containers of crystals were made use of and also the salt focus was initially boosted from balance to balance as well as lastly lowered in the succeeding equilibrations. That the earlier, as well as later factors all rest on the exact same smooth
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contour and that the factors in the much more focused services inspect those acquired in the previous collection of experiments, show that real balance was gotten to. The quantity of hemoglobin liquified was identified, as previously, by Kjeldahl nitrogen evaluations on the filtrates. The sulfate services were examined for salt by heat-coagulating the healthy protein without the enhancement of more salt, cleaning the precipitate saltfree, and also very carefully vaporizing, drying out, carefully firing up, as well as considering the filtrate. The magnesium sulfate decisions were inspected by changing a couple of examples to barium sulfate and also evaluating thus. The ammonium sulfate focus was, nevertheless, identified by heat-coagulating the healthy protein in the visibility of a mild quantity of phosphate barrier, cleaning the healthy protein salt-free, as well as distilling over the ammonia in the filtrate. Physical Chemistry of Proteins. X The pH of all saturated services was identified with the hydrogen electrode a.s.a.p. after filtering system. The hemoglobin, as well as the electrolyte options, were changed as virtually as feasible to pH 6.6 prior to the experiment started, and also where essential little amounts of acid or antacids were included in the electrolyte remedies throughout the experiment. The pH worths as figured out lie generally in between 6.5 and also 6.8 in the series of minimal solubility. The ionic stamina, regard to Lewis, B., is computed each 1000 g of H2O. Task Coefficients of Hemoglobin in Solutions of Chlorides, as well as Sulfates In a heterogeneous balance where a remedy is filled with a strong part, at consistent temperature level as well as stress, the task of the material in the strong stage, should coincide as that in the fluid stage. This is independent of other elements in the option. The enhancement of electrolytes to a saturated option of hemoglobin does not transform the task of the hemoglobin although it alters the solubility or the focus. The proportion of the solubility of a compound at absolutely no electrolyte focus, X0, to the solubility in an option of offered electrolyte focus, S, is the task coefficient, y, of the material because of service. The solubility of hemoglobin in focused remedies of multivalent electrolytes could be appropriately defined, by the straight formula for the solubility of nonelectrolytes and also healthy proteins in focused salt options log S = p – K,’/x where X is once again the solubility and also P the ionic
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stamina. p is the obstruct continuous and also is the theoretical solubility in the lack of salt, called theoretical because, obviously, hemoglobin is a globulin whose solubility passes through an optimum with raising salt consent, supply. p is nonetheless a hassle-free consistent differing with the temperature level and also the amphoteric residential or commercial properties of the healthy protein. Ii,’ is a salting out consistent feature of the healthy protein independent of the temperature level as well as of the pH when an offered electrolyte is utilized, yet differing with the electrolyte. The evaluate ion of the constants K,’ and also/3 pays for an ample characterization of the rainfall of a healthy protein in focused remedies of electrolytes. In examining the solubility of carboxy hemoglobin in phosphate barriers of differing ionic stamina as well as pH. It was located that at the factor of minimal solubility the healthy protein acted as though it were made up not just of the neutral particle, yet of favorably and also adversely billed particles also. It was additionally discovered that the pH of minimal solubility differed with the salt concentration. The size of the impact of electrolytes on the acid as well as fundamental dissociation constants was such that the percentage of credited uncharged particles at pH 6.6 was around consistent, although somewhat higher in the extremely water down services of phosphate. Hence, although the incline of the solubility contour at pH 6.6 in water down services was such that the Debye-Hiickel formula did not show up to use, if one thought about the neutral particle alone, it was discovered to act as though A in Formula 1 was 1.5, the worth made use of in explaining the phosphate barriers themselves, as well as Z, Z, were 4, the worth made use of explaining solubility in phosphates at 0.” The variant in the dissociation constants was such that if the solubility had actually been identified at pH 6.7 as opposed to 6.6 the healthy protein would certainly have included an around continuous percentage of credited uncharged fragments. The pH of the saturated remedies of hemoglobin in sulfates and also chlorides was not so precisely managed as in the phosphate barriers. The factors exist generally on smooth contours, nevertheless, as well as the variant in pH is not adequate, evidently, to take the healthy protein much from the pH of minimal solubility. An acceptable image of the variant of task coefficients could be acquired from a research study of a variant of solubility at around pH 6.6. The factor to consider of Formulas 1, as well as 4 in connection with the solubility of
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hemoglobin in phosphate barrier options, exposed the applicability of the very first to water down services as well as of the 2nd to focused remedies. Formula 4 has actually been revealed to be relevant to hemoglobin in focused sulfate services. The applicability of Formula 1 to solubility in both chlorides and also sulfates is taken into consideration in the adhering to. The “valence” kind is obviously “obvious” when one is taking care of a difficult healthy protein particle. The solvent activity of a neutral salt after a healthy protein, oxyhemoglobin, has actually been located the same to the solvent activity of a neutral salt after a bi-bivalent or a uni-quadrivalent substance. In conclusion that oxyhemoglobin is bivalent or quadrivalent may be proper, yet would certainly be unjustified at the here and now time. Our experiments allow neither reduction. They make it specific, nonetheless, that oxyhemoglobin acts in this regard as though it were bivalent or quadrilateral, which the activity of neutral salts in liquidizing healthy proteins corresponds their activity in liquidizing various other a little soluble material. The neutral carboxyhemoglobin particle in remedies of phosphate acts as though it had the exact same evident valence kind. Moreover, Carbohydrates is another biological molecule which is mainly composed of carbon, oxygen, and hydrogen atoms, having the ratio of hydrogen-oxygen atom 2:1 and exists as hydrates of the carbon atom. Its empirical formula is given as: Cm(H2O)n
Carbohydrates contain four chemical groups, i.e., disaccharides, oligosaccharides, monosaccharides, and polysaccharides the lower molecular mass carbohydrates are disaccharides and Monosaccharides. Just like proteins, carbohydrates also play an essential role in living organisms. Polysaccharides perform the role of storage of energy, i.e., cellulose. Carbohydrates are present in almost every kind of food. The important sources include cereals sugarcane, fruits, potatoes, bread, milk & table sugar, etc. similarly, the sugar and starch are the essential components of carbohydrates in our diet in which starch is present in abundance in potatoes, rice, and maize. The carbohydrate that is found in live and other tissues of the human body is Glycogen. Moreover, carbohydrate is also present in plant tissue as the cell wall and also maintains our digestive system. The nucleic acid is those important molecules that transfer genetic information from one generation to the other and are classified into two basic
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types, i.e., ribonucleic acid (RNA) and deoxyribonucleic acid (DNA). The nucleic acid is further composed of nucleotide monomers and nucleotide are made with the composition of three elements which is a phosphate Group nitrogenous Base, five-carbon Sugar. Also, the nucleotide is further joined with each other to produce polynucleotide chains. The nucleotide is held together with the help of covalent bond which is present between the sugar and phosphate. Their joining links are known as phosphodiester linkages and these linkages are the backbone of RNA and DNA. Just like proteins, the nucleotide is combined together by dehydration synthesis. In this synthesis, nitrogen atom is joined with the loss of water molecule. Lipids are such type of macromolecules that are soluble in a nonpolar solvent, for example, fats, monoglycerides, waxes, diglycerides, sterols, etc. The functions of lipids include energy storing, signaling with communication and act as structural components of cell membranes. Also, lipids are divided into 8 types of fats. Lipids are also described as Fats and are called triglycerides. The presence of lipids is also discovered in fatty acids. Enzyme kinetics is defined as that branch of chemistry that deals with the chemical reaction which are catalyzed with enzymes and reaction are recorded with all the other resulting factors. The catalytic mechanism can also be explained with the help of enzymes kinetics as well as its role in metabolism. Enzymes belonging to the family of protein and can manipulate other molecules known as enzymes substrates. The data given by enzyme structure can plat important role in describing the kinetic data and some enzymes can also change their shape during a chemical reaction. Unlike the other chemical reaction, the reaction which is catalyzed by enzymes shows the properties of kinetic saturation. Now, this chapter will discuss the biochemical energetics. It is the field of science that deals with the cell biology and biochemistry of energy that is flowing and produce in the living organisms and also contains the study of different cellular process and transfer of energy. The main objective of this subject is to study how different species produce energies and perform the required biological work. In the living organism, the covalent bond is broken and energy is produced which is then used by the living organism in different types of energy and produce ATP (Adenosine triphosphate). The living organisms take energy from different organic and inorganic materials. There are basically two types of chemical reaction that take place in living organisms which are exergonic and endergonic. In exergonic reaction,
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the spontaneous reaction is taken place and energy is released comes under negative energy ΔG released whereas endergonic reaction are those chemical reactions consume energy, and it is considered positive valve of energy ΔG. The total free energy in a chemical reaction can be calculated from the following formula: ΔG = ΔH – TΔS
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REFERENCES 1. 2. 3. 4.
http://www.biochemistry.org/?TabId=456 https://www.khanacademy.org/science/biology/macromolecules/ lipids/a/lipids http://www.biology-pages.info/E/EnzymeKinetics.html https://www.ncbi.nlm.nih.gov/books/NBK21737/
CHAPTER
9
BIOCHEMICAL ENGINEERING The chapter will cover the biomechanical engineering processes such as fermentation, agitation, and mass transfer of chemical engineering, biochemistry, and microbiology. The chapter will introduce the readers to enzyme technology and representations of microbial systems. The chapter will cover the basics of biology, biotechnology, cell constituents, kinetic enzyme analysis, immobilized enzymes, design, review, and stability of bioreactors, kinetics of receptor-ligand binding and bioproduct recovery and bioseparations and manufacture of biochemical products. Fermentation is such a biochemical process that deals will the breaking of glucose molecules and consumption of sugar without the involvement of oxygen. The products resulted from fermentation are gases, yeast, organic acids, alcohol, and mostly occurs in the presence of bacteria. The overall process of fermentation is given the name of zymology. The ATP produced in microorganisms are resulted due the process of fermentation by dividing the organic materials. It is used in the preservation of many food products such as yogurt and pickled cucumbers and in the production of alcoholic drinks, i.e., wine. The human being also contains the process of fermentation in their gastrointestinal including the animal as well. The process of fermentation is still be used and with the help of advance biochemical techniques many discoveries are still being studied. An example of the modern fermentation process is that they have been used by scientist in studying the transferring of genetic information.
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Another important biochemical process that needs to discuss is the agitation which deals with the induced motion of a matter in a specific way usually the movement is in a circular manner in a fixed chamber and helps in the mixing of two or more component which can be in separate phases previously. The process of agitation is used in different analysis such as mixing of immiscible solutions and suspending the solid particles in a solution. It also deals with the transfer of heat that results due to the mixing of different solutes as well as making a gas dispersed in a given liquid. The most commonly used devices used for agitation are propeller, turbines, and impellers. Mass transfer is the movement of molecules of matter from one location to another and this process is used in many separation techniques absorption, precipitation, evaporation, drying, and distillation and membrane filtration. The mass transfer is described as a physical process of separating solutes from a mixture and this field has vast application in the field of biochemistry such as evaporation of water from tissues. The mass transfer occurs due to the difference in the chemical potentials and results in thermodynamics gradients in term of flow of mass from one matter to other. In a chemical process, the species of a matter tends to move from high chemical potential to low chemical potential and maximum mass transfer is achieved when the chemical potential in both of the matter are in equilibrium. The mass transfer basically depends upon a number of factors such as flow pattern of species of matter and diffusive properties of species. The rate of mass transfer can be quantified as the mass transfer coefficient which is a dimensionless quantity. Since the mass transfer is the transport of species in the liquid and gaseous state which is defined in four categories such as exchange of mass between phases, transportation of mass in case of turbulent flow and in laminar flow, diffusion. The chapter will further discuss microbiology and its relation with biochemistry. Microbiology is defined as it is the branch of science which deals with the study of microorganisms such as bacteria, protozoa, viruses, and archaea. The study of microbiology has deep roots in other fields of science such as cell biology, biochemistry, ecology, and physiology. In this field, the microbiologist only relies on the certain number of tools such as an identification that is purely based on DNA. There are numerous research that results in the betterment of mankind in this field. The process of fermentation was discovered, as described earlier, which is utilized with the help of latest trend of microbiology with its combination of modern biochemistry, similarly, bacteria is produced in industrial scale for the production of amino acids
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and most commonly produced amino acid is Corynebacterium glutamicum. Moreover, different variety of biopolymers are also produced which the help of microbiology such as polysaccharides, and polyamide can the advanced biotechnical discoveries are used to tailor some specific properties in these polymers with eradicating the other features. Furthermore, microbiology is used by different animals and human in producing beneficial vitamins, aiding digestion, producing amino acids. The enzyme technology is the latest discoveries of biotechnology and biochemistry in which fundamental techniques of enzymology are applied and they have been used in different application such as feed, agriculture, food, textiles industries, paper, and leather products. Furthermore, this enzyme technology is also utilized in various pharma and chemical industries to increase the overall efficiency and output of the product. This chapter will also describe the brief introduction of bioreactors. It is defined as such an environment that supports biological activation and it is a vessel that carries a different chemical reaction at an optimum rate. The organism that is produced in bioreactors can be submerged in a liquid solution or can be attached or stick with the wall of vessels of a bioreactor. They are designed in such a way that will the help of biochemical engineering optimum environment is created to perfume specific functions and obtain the desire results from the bioreactors. The conditions such as environmental values which includes pH, and dissolved gases, temperature, nutrient concentrations are set to affect the overall production and growth of organisms. There are four types of bioreactors given as photo reactors, personal reactors, up, and down agitation reactor and cloning bioreactors used by NASA. Various mathematical techniques are applied which are an important tool in bioreactors such as in the case of wastewater treatment. With the help of these models, process control strategies are efficiently designed and can predict the future result of bioreactors. Moreover, these bioreactors are mostly used in beverages, food, and pharmaceuticals industries as they mostly deal with the diverse species of microorganisms. There are three main stages of a bioreactor which are defined as upstream and downstream of processing and bioreaction. The whole process helps in converting raw material into the required finish product. The raw material is first converted into a useable form for processing and this is done by the upstream process and it is the initial stage of the bioreactor, then it is transferred to separation process by downstream and further biological process are applied to obtain the finished product.
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Phytochemicals are of wonderful pharmaceutical and farming significance, yet usually, show reduced wealth in nature. Current demos of industrial-scale manufacturing of phytochemicals in yeast have revealed that microbial manufacturing of these high-value chemicals is an encouraging option to sourcing these particles from indigenous plant hosts. Nevertheless, a variety of obstacles continue to be in the more comprehensive application of this method, consisting of the restricted expertise of plant additional metabolic rate as well as the ineffective reconstitution of plant metabolic paths in microbial hosts. In this Evaluation, we go over current methods to accomplish microbial biosynthesis of intricate phytochemicals, consisting of techniques to: (1) rebuild plant biosynthetic paths that have actually not been completely illuminated by mining enzymes from indigenous as well as non-native hosts or by enzyme design; (2) boost plant enzyme task, especially cytochrome P450 task, by enhancing performance, selectivity, expression or electron transfer; and also (3) boost total response effectiveness of multi-enzyme paths by vibrant control, compartmentalization or optimization with the host’s metabolic rate. We additionally highlight staying difficulties and as well as future possibilities of this method. The optimization of synthesized metabolic paths calls for cautious control over the degrees and also the timing of metabolic enzyme expression. Optogenetic devices are suitable for accomplishing such exact control, as light could be used as well as getting rid of promptly without complicated media adjustments. Below we reveal that light-controlled transcription could be utilized to improve the biosynthesis of useful items in crafted Saccharomyces cerevisiae. We present brand-new optogenetic circuits to move cells from a light-induced development stage to a darkness-induced manufacturing stage, which permits us to manage fermentation with only light. Moreover, optogenetic control of synthesized paths makes it possible for a brand-new setting of bioreactor procedure utilizing regular light pulses to tune enzyme expression throughout the manufacturing stage of fermentation to raise returns. Phage—host communications are essential to ecology, advancement, as well as biotechnology. Central to those is infection effectiveness, which continues to be inadequately recognized, specifically in nature. Right here we use genome-wide transcriptomics as well as proteomics to check out infection performance in nature’s very own experiment: two almost
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similar (genetically as well as from a physical standpoint) Bacteroidetes microbial pressures (host18 as well as host38) that are genetically unbending, however, eco crucial, where phage infection effectiveness differs. With each other, these searching’s to expose several infection inadequacies. While this contrasts the solitary systems typically disclosed in lab mutant research studies, it likely much better mirrors the phage—host communication characteristics that take place in nature. Mass transfer is the transportation of a compound (mass) in fluid and also aeriform media. Relying on the problems, the nature, and the pressures in charge of mass transfer, 4 fundamental kinds are differentiated: (1) diffusion in a quiescent tool, (2) mass transfer in laminar circulation, (3) mass transfer in the unstable circulation, as well as (4) mass exchange in between stages. The most basic situation is mass transfer in a tool at remainder where the driving pressure is the distinction of focus in surrounding areas of the tool as well as the system is molecular diffusion. The material moves, because of the analytical personality of particle movement, from a high focus area to a reduced focus one having the tendency to equalization of focus throughout the whole quantity. This mass transfer is explained by a formula called Fick’s legislation which, when related to a binary combination, has the type form.
dC A m = − DAB Ma dy where is the circulation important A, kg/m2s, in the reverse instructions to the focus slope of this compound dCA/dy (kmole/m3m), is the molecular weight of part A (kg/kmole) as well as BIT (m2/s) is the inter diffusion coefficient important A basically B and also is figured out by the physical residential properties of these materials. BIT has been identified experimentally for lots of gas sets and also could likewise be determined to make use of a molecular-kinetic concept. BIT is understood to rely on temperature level and also stress. The diffusion coefficient in gases under typical problems is of the order of 10 − 4 m2/s, while in fluids it must do with 5 orders reduced. Really, along with focus slope, temperature level and also stress slopes which impact mass transfer by means of thermal and also stress diffusion might enter into play. These results are most substantial in gas blends with a commonly differing particle dimension, e.g., He–Cs. Thermal diffusion underlies among the approaches of splitting up of uranium isotope U235. In laminar circulation of aeriform and fluid combinations, computation of mass transfer does absent certain troubles. For example, for a plate in the
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stream of incompressible fluid, the collection of Formulas (2) explaining the speed and focus areas has the kind.
∂u ∂v + = 0, ∂x ∂y
∂u ∂v ∂ 2u u +v = v 2, ∂x ∂y ∂y u
∂C ∂C ∂ 2C +v = D 2, ∂x ∂y ∂y
where x and also y are the longitudinal and also transverse collaborates, u and also v the longitudinal as well as transverse parts of rate, ν as well as D the coefficients of kinematic thickness as well as molecular diffusion, specifically, and also C the neighborhood focus of a material, C = f(x, y). Under the boundary conditions u = v = 0 and C = C1, at y = 0, u =
u0 and C = C0 at x < 0 or y = ∞ the solution to equation system (2) yields. βx 1/3 Sh = = 0.332 Re1/2 x x Sc , D where β is the neighborhood mass transfer coefficient at the range x from the leading side of home plate (β = [ m / M (C – C )], Re = x u /ν is the 1
0
x
0
Reynolds number, as well as of m or (C1 the Schmidt number. Keep in mind that there is a separation from the straight reliance of or (C1 – C0) at high prices of mass transfer. If the complete size of home plate is L, after that the length-averaged mass transfer coefficient is discovered from the formula
Sh = L
βL
1/3 = 0.664 Re1/2 L Sc , D
where ReL = Lu0/ ν. Mass transfer essentially alters in a change to a stormy circulation. Its vortex circulation features bring about a massive transportation of liquid. This transportation generally has prices which are orders of size above molecular ones and advertises a quicker equalization of the focus area as well as, provided a material resource, fast breeding of the material over the circulation random sample. Considering that a strenuous concept of disturbance is doing not have, it is preferable to explain the circulation itself
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and also warm as well as mass transfer in it by a collection of formulas much like (2) for the laminar circulation utilizing balanced speed worth’s and also changing v as well as D by their efficient worth’s satisfying the problems in the unstable circulation, i.e., by the coefficients of “eddy thickness” and also “unstable diffusion.” The molecular diffusion likewise happens in the unstable circulation, e.g., in between as well as inside swirls. Its duty is boosted (about unstable transportation) as the network surface area is come close to and ends up being primary near it. It is typically thought that the molecular DM, as well as stormy DT diffusion coefficients, are additive, i.e., D = DM + DT. Considering that in an industrialized unstable circulation the compound, power, and energy transportation takes place using large swirls, the transportation price is taken into consideration similar and DT, aT, and also νT have to do with an equivalent. (This is a three-way example in between the transportation of the material, power, as well as energy.) This makes it feasible to make use of empirical dimensionless formulas explaining warm transfer for estimation of mass transfer. Mass exchange in between a gas and a bead is frequently come across in design. For a tool at remainder the service could be composed, therefore; β dd = Sc = 2, D where β is the mass transfer coefficient, dd the bead size, and D the diffusion coefficient of the traded compound in the gas. When the decline relocates relative to a tool in the Red ≤ 200 arrays the Frössling-Marshall formula. 1/3 Sh= 2 + 0.6 Re1/2 d Sc
(where Red = dpu/ ν with u and v is the speed of the gas about the decrease and also the gas kinematic thickness, specifically) is rather constant with the experiment. This formula likewise keeps in the situation of dissipation of beads in a gas stream gave the dissipation price is little or modest. The price of mass transfer from the surface area of the fluid movie (e.g., dissipation) moving on the internal surface area of television towards the main gas circulation could be determined to make use of an empirical formula. βd Sh = 0.023Re0.83 Sc 0.44 , = d D
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0.4 where d is the size of television (cf. Nu = 0.023 Re0.8 for heat transfer). d Pr
Another instance of mass transfer is diffusion of some material, such as A from one relocating tool to one more via a user interface (two-film concept). If it is thought that there is no focus get on the limit, i.e., CABi = CAEi (Fig. 9.1a), after that the circulation important A could be stood for in the type.
= m β AB M A (C AB − C ABi ) = β AE M A (C AEi − C AE= ) K A (C AB − C AE ), where βAB, βAE, as well as KA, are the coefficients of mass transfer for compound A in media B and E as well as the general mass transfer coefficient, specifically, as well as CA the focus important A at the factors suggested in Number 1 (Figure 9.1).
Figure 9.1. Mass transfer of component A between media B and E with no concentration jump at the interface.
Hence,
1 1 1 , = + K A β AB β AC i.e., the overall resistance to mass transfer is a number of resistances in each tool.
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In most cases, the focus of the moving material is not the same as the user interface in both particular media. As an example, if B is a fluid stage, as well as E, is gas, as well as a balance on the border follows Henry’s legislation CABi = H CABi (Number 2), after that = m β M (C − C = ) β M (C − C ) AB
A
AB
ABi
AE
A
AEi
AE
C = K A M A (C AB − HC AE = ) K A M A AB − C AE . H where
1 1 H H . = + = K B β AB β AC K E Offered the circulation criteria for both movies, β could be identified making use of, e.g., the above solutions (Figure 9.2).
Figure 9.2. Mass transfer of part A in between media B as well as E with a focus dive at the user interface.
Mass transfer, primarily in the mix with warmth transfer, is extensively utilized in the market, in chemical procedure devices, metallurgy, power design, and so forth. The devices consist of fractionating towers, absorbers, and also extractors, driers, and also cooling down towers, burning chambers, heterogeneous catalysis devices, and also lots of others.
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REFERENCES 1. 2. 3. 4. 5. 6. 7.
http://www.thermopedia.com/content/940/ https://www.britannica.com/science/fermentation h t t p s : / / w w w. k t h . s e / e n / b i o / r e s e a r c h / i n d b i o / e n z y m e technology-1.432723 https://www.nature.com/subjects/microbiology https://www.omicsonline.org/scholarly/enzyme-technology-journalsarticles-ppts-list.php https://www.sciencedirect.com/topics/neuroscience/bioreactors https://www.slideshare.net/WASSAN14CH18/agitation-and-mixing
CHAPTER
10
ELECTRICAL CIRCUITS The chapter will introduce readers to the basic principles of electrical circuits and the basic laws such as Thevenin’s, Kirchhoff’s and Norton’s laws about the analysis of electrical circuits. The chapter will include discussions of DC circuits and analysis, DC transients, and static electrical fields. The chapter will cover the basics of static magnetic fields, inductors, capacitors, and filters. Electric circuits consist of circuit elements and interconnections which are joined in a way to perform a specific task. The function of circuit elements is to ensure the defined relationship between current and voltage at its terminals, for example, the relationship in Ohm’s law V=iR. The terminals are connected through interconnections also called as wires so that circuit elements can interact with each other by sharing of current and voltages. For example, circuit in Figure 10.1 shows the circuit elements bulb, battery, and switch connected through a wire. Here the defined task is the conversion of energy to light a bulb. The purpose of the switch is to break/ close the circuit.
Figure 10.1: Electric Circuit. https://www.electricaltechnology.org/2014/01/ important-terms-related-to-electric-circuits-and-networks.html
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To facilitate the interconnections the wires of a good electrical conductor like copper are used. Ideally, all point of wires are at the same potential, show no resistance to the flow of current. But in actual wires do not have this property. In order to ease our initiation to circuit theory, we shall assume the ideal behavior.
10.1. LAWS OF CIRCUIT ANALYSIS AND SYNTHESIS Circuit analysis the process of calculating the values of current and voltages in a circuit. Whereas the circuit synthesis is the process of designing the circuit in order to get a specific value of current and voltage. Both synthesis and design can be done by knowing element laws such as Ohm’s law and the connection laws also called Kirchhoff’s laws or circuit laws. In order to analyze a complex circuit, we must have an understanding of the terms like Nodes, Branches, Loops, and meshes, Series and parallel connection. Loop is a closed path, the mesh is a loop that contains no other loop. In Figure 10.2, there are 6 nodes, 3 loops, 3 meshes, 7 branches.
Figure 10.2. Illustration of Kirchhoffs Circuit Law: Determination of Number of Nodes, Branches, Lopes and Meshes in a Circuit. https://www.electricaltechnology.org/2014/01/important-terms-related-to-electric-circuits-and-networks. html
Consider current/voltage through a branch associated with a node/loop, respectively.
10.2. KIRCHHOFF’S CURRENT LAW (KCL) At any instant amount of charge/currents entering a node must equal the sum of all currents flowing out of that node.
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∑ iin = ∑ iout
I1+I2+I3=I4+ I5
10.3. KIRCHHOFF’S VOLTAGE LAW (KVL) At any instant, the sum of all voltage drop around the loop is equal to zero. VAB+VBC+VCD+VDA=0
10.4. THEVENIN’S THEOREM This theorem is used to reduce the complex circuit into a simple circuit by calculating the resistance equivalent to all the resistances in the circuit and connecting it in series with a single voltage source and load. Steps to follow Thevenin’s theorem •
•
Remove the load from the original circuit and calculate the voltage across the open terminals where the load used to be that will be called as Thevenin voltage source. Remove all the power sources from the circuit by replacing voltage sources with the simple open circuit and current sources as wire (closed circuit). Then calculate the total resistance at the open terminals that will be called as Thevenin equivalent resistance
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•
Now draw the Thevenin resistance and Thevenin voltage in series and reconnect the load between the open points of the circuit. That will be the Thevenin equivalent circuit. • Now analyze the values of current and voltage across the load resistance. Example According to the above steps consider R2 as load and remove it from the circuit. Now we have B1, R1, R3, B2 in series. Calculate the total voltage and total current of the series circuit. By using ohm’s law.
The total current of the series circuit will be equal to 4.2A by dividing total voltage 21V by total resistance of 5 ohms. Now the voltage across each resistance will be calculated as 16.8V across R1 and 4.2V across R3. By using KVL the voltage across R2 will be 11.2V.
Remove the power sources and calculate the resistance at the open terminal. Now the three resistances are in parallel connection.
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Connect the voltage 11.2V and resistance of 0.8 ohms in series that will give the Thevenin equivalent circuit and reconnect the load resistance in series.
10.5. NORTON THEOREM This theorem is used to reduce the complex circuit into a simple circuit by calculating the resistance equivalent to all the resistances in the circuit and connecting it in parallel with single current source and load. Steps to follow Norton theorem •
•
•
Remove the load from the original circuit and calculate the current across the short wire where the load used to be that will be called as Norton current source. Remove all the power sources from the circuit by replacing voltage sources with the simple open circuit and current sources as a closed circuit. Then calculate the total resistance at the open terminals that will be called as Norton equivalent resistance Now draw the Norton resistance and Norton current in parallel and reconnect the load between the open points of the circuit. That will be the Norton equivalent circuit.
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•
Now analyze the values of current and voltage across the load resistance by following the rules of a parallel circuit. Example According to the above steps consider R2 as load and remove it from the circuit. Now we have B1, R1, R3, B2 in series. Calculate the total voltage and total current of the series circuit. By using ohm’s law
By considering each loop separately calculate the current across R1 and R3 (by ohm’s law). Then apply the KCL and get the value across the short terminals.
Remove the power sources and calculate the resistance at the open terminal. Now the three resistances are in parallel connection.
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Now draw the Norton resistance and Norton equivalent current in parallel and reconnect the load between the open points of the circuit. That will be the Norton equivalent circuit.
10.6. DC TRANSIENT Transient state is the response of the circuit to the energies stored in the storing elements (capacitors/inductors) in the circuit. In RC/ RL circuit if the capacitor/ inductor has some stored energy that can be dissipated across the resistor. The way the energy is dissipated is known as a transient response or natural response.
10.7. STATIC ELECTRIC AND MAGNETIC FIELDS Electric and magnetic fields are basically force generated by nature but can also be generated by the use of electricity. An electric field is a force generated due to the attraction and repulsion of electrical charges due to which the electric current/ electrons flow. It is measured in volts per meter (V/m). The effect caused by the flow of electrons is also a form of force field that is also created by the magnet is known as a magnetic field. It is measured in Tesla (T). If the electric or magnetic field does not vary with time having steady direction, flow rate and strength then it will be called as steady electric/magnetic fields (thus the frequency of 0 Hz). We see many examples of the electric and magnetic field in our daily life. For example, in lightning, the electric field generates due to the imbalance of charges. In frictional processes, the displacement of positive and negative charges produce an electric field. Cathode ray tubes used in TV and computer screen also generate electric field sometimes which become
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visible due to dust particles. In the compass system the geomagnetic field is used which exerts the force from south to north. In biomedical and industrial application intense field strength is used, for example, in MRI (Medical Resonance Imaging) devices.
10.8. FILTERS In electronics, filters are used to specify the range of frequencies passed through the circuit. There are two types of components used in the manufacturing of filters one is active types of components which includes transistors, integrated circuits and other is passive type components which are inductors, capacitors, and resistors. The active type components use external power to make them enable for working. Active components can also use in amplification of signals. These components can be used in a variety of ways by doing proper analysis here is just the very basic idea about their use. In order to design filters we use capacitors, inductors, diodes, and resistors, etc. depending upon the requirement, for example, capacitors are used to block DC and inductors are used to block high-frequency AC signals. Similarly, for switching mode power supply inductors, capacitors, and diode/ MOSFET can be used. As high-frequency signals can pass through capacitors and only low-frequency signals can cross the inductors. So both inductors and capacitors can be used in circuits in the following ways.
10.9. CAPACITOR The capacitor is like a battery which can store electrical energy due to its structure which is two parallel metallic plates separated by an insulating material (called as dielectric). The plates are connected by terminal wires which are used to connect a capacitor in a circuit. According to the working principle of the capacitor, it can only store charges but it can be used in different sort of applications. For example, it can be used in timing devices because it takes a particular time to store charges depend on its capacitance. As the capacitors allow the certain frequency to pass through them so it can also be used in electronic filters for smoothing the signals/voltages in circuits. The capacitors are used in the circuits made for the tuning of radios and televisions. To stop high-frequency signal (noise) on the power line to an IC capacitor can be connected in parallel to the IC. Similarly to stop low-frequency capacitors will be connected in series. For quick ON/OFF
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switching in which rapid current grip from the power line is required. That can create a problem for the power line. In this case, the capacitor is used. Capacitance can be increase or decrease by varying the size of plates or by reducing the space between. Capacitors are of different types depending on its manufacturing and size or capacitance for different applications. For example, Electrolytic Capacitor, Mica Capacitor, Paper Capacitor, Film Capacitor, NonPolarized Capacitor, Ceramic Capacitor. Large capacitors also called as super capacitors can be used as batteries as well. The unit used to measure capacitance is farad denoted by (F). One farad represents the big amount of capacitance so normally we use prefixes as milli, micro, nano along with Farad. Supercapacitors typically store thousands of farad which is a huge amount of charges. According to the application, capacitors are divided into the following types. High Pass Filter (HPF), Low Pass Filter (LPF), Band Pass Filter (BPF), Band Stop Filter (BSF), Notch Filter, Equalization Filter, etc.
10.10. INDUCTOR An inductor is a coil of an insulating wire wound around a core wire also called as AC reactor it is a passive electrical component which can store electrical energy in the magnetic field when the electric charges flow through it. Due to the flow of electric current through a coil, the voltages are induced because of the varying magnetic field. Lenz’s law defines the induction of electromotive force which opposes the change in current that produces it. Hence the inductors resist the change in current through them. Faraday’s law describes the induced voltages in an inductor. Units used to represent inductance are Henry which is basically the ratio of voltages and change in current through an inductor. As the inductors are characterized by inductance which is the number of magnetic field lines produced by the varying current. Inductance is affected by four factors, Number of turns in a coil, Material of the Core, Cross section area of the Coil, Length of the Coil. Power dissipation is another factor that must be considered which mainly depends on inductor core and inductor winding. Inductors are of different types depending on the applications, sizes, and rating. The sizes are according to the frequency of AC being used and power being handled. Types of inductors are available based on applications sizes, ratings, winding, and core used. Their physical sizes vary from tiny sizes to the huge transformer, depending on the power being handled and the frequency
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of AC being used. Inductors are one of the passive electronic elements other than capacitors and resistors that are used in the signal controlling circuits and noise elimination or as filters and for voltage regulation. For example, In order to reduce noise high-frequency signals inductors can be connected in series in an electric circuit with ICs. Few types of inductors are as follows Ferrite Core Inductors, Toroidal Core Inductors, Bobbin based Inductors, Multi Layer Inductors, etc.
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REFERENCES 1. 2. 3. 4.
https://arslanhelpyoucom.files.wordpress.com/2016/07/sergio-francoelectric-circuits-fundamentals.pdf https://electronics.stackexchange.com/questions/84861/ fundamentally-knowing-when-to-use-capacitors-inductors https://www.allaboutcircuits.com/ https://www.greenfacts.org/en/static-fields/l-2/1-what-are-staticfields.htm
CHAPTER
11
ELECTROMECHANICAL SYSTEMS The chapter will include discussions about the basic principles of electromechanical systems and include the basic principles of electric machines and motors, sensing, and actuation, digital logic gates, analog to digital-digital to analog conversions, and interfacing and communication protocols. In this chapter, various terminologies of electromechanical systems are discussed. One of the essential components of the electromechanical system is electric machine. These are such type of machines uses electromagnetic forces for their operation. They are described as an electromechanical energy converter as in case of the motor, they convert electrical energy into mechanical energy whereas an electric generator converts mechanical energy into electrical energy, also, there is a third category of electric machinery that is term as transfers that also converts energy, i.e., changing of voltage produces alternating current. There are a number of different types of electric machines in which some are rotating machine and some are liner machines, which show liner motion. In an electric machine (rotary or liner), the magnetic field generated by the stator coil produces motion in the rotor coils as a result, electric energy is converted into mechanical energy. A generator is such an electric machine which as described earlier, converts mechanical energy into electrical energy and it forces the electrons to make into the electric circuit, it resembles a water pump, whereas, the motor operates in opposite way. In the case of a transformer, transfer of energy takes place from one coil to another by the principle of induction
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and divides the transformer into three type such as step-up, step-down, and isolation transformer. This chapter will further discuss different technologies such as digital logic gates. A logic gate is the fundamental and building block of digital circuitry and its designs which implement Boolean functions to perform logic operation binary inputs and as a result, a different binary output can be achieved. These logic gates are applied with the help of diodes or electronic limit switches. Furthermore, the digital logic consists of a circuit with a variety of different components such as arithmetic logic units (ALUs), multiplexers, and registers. There are seven basic types of logic gates that are given below: And gate is such a gate which operates on the AND operator and contains two input and one output. The truth table of AND gate is given below with its circuit representation in Figure 11.1
Figure 11.1. 2 Input AND Gate- AND gate is an electronic circuit that gives a high output (1) only if all its inputs are high.
The 2nd gate of the digital logic gate is OR gate and as indicates from its name, it depends upon the OP operator. The truth table of OR gate is given below with its circuit representation in Figure 11.2
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Figure 11.2 OR Gate -The OR gate is an electronic circuit that gives a high output (1) if one or more of its inputs are high.
Another type of logic gate is the XOR gate (exclusive OR) which is true only in a condition when one other both input is true. The truth table of XOR gate is given below with its circuit representation in Figure 11.3.
Figure 11.3. XOR Gate-The ‘Exclusive-OR’ gate is a circuit which will give a high output if either, but not both, of its two inputs are high.
In digital logic, a digital inverter has also existed and which is true only if the input is false. The truth table of NOT gate is given below with its circuit representation in Figure 11.4
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Figure 11.4 The NOT Gate -The NOT gate is an electronic circuit that produces an inverted version of the input at its output. It is also known as an inverter.
The fifth logic gate is the NAND gate, in this gate AND operation is first applied to the inputs and then NOT operation is applied, for a condition to be True by the AND operation, the NOT gate reverts the output and make it False. The truth table of NAND gate is given below with its circuit representation in Figure 11.5.
Figure 11.5: 2 Input NAND Gate - This is a NOT-AND gate which is equal to an AND gate followed by a NOT gate. The outputs of all NAND gates are high if any of the inputs are low.
Furthermore, NOR gate is another such gate of digital logic gates that coverts the output from the OR operation and reverts the result, if the output from the OR gate is false, the NOR gate will make it true. The truth table of NOR gate is given below with its circuit representation in Figure 11.6.
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Figure 11.6: 2 Input NOR Gate- This is a NOT-OR gate which is equal to an OR gate followed by a NOT gate. The outputs of all NOR gates are low if any of the inputs are high.
The last gate is the XNOR gate which is an XOR gate and followed by the NOT operator. It indicates that output is true only if the inputs are the same and vice versa. The truth table of XNOR gate is given below with its circuit representation in Figure 11.7.
Figure 11.7: XNOR gate-The ‘Exclusive-NOR’ gate circuit does the opposite to the EOR gate. It will give a low output if either, but not both, of its two inputs are high.
The combinations from these gates can be utilized in solving complex algorithms and further the logic circuits can be designed accordingly. The analog to digital converters is such devices that convert an analog signal into a digital signal so that it can be processed by a microcontroller or
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a digital computer. It is also known as ADC devices and such devices convert the intensity of a signal into a digital value in a binary form. There are a various form of ADC devices but due to the hardware complexity they are not used and Integrated circuit are mostly used for such type of conversion. The signal processed by the ADC is defined by its bandwidth and the noise ratio present in the analog signal. Further, the bandwidth sampling is done to characterize its performance parameters and different techniques are applied to perform this action. There are many factors the effect the sampling rate of the analog signal such as its resolution, accuracy of signal, jitter, and aliasing, etc. such parameters are very important to obtain the final product in the form of digital signal so that it can be utilized accordingly. However, the resolution of an converter indicates and gives the information that specified discrete valves over the particular range that it can convert the analogue to digital set of data and it determines the magnitude of the error which it further determines the average of the output signal with respect to noise ratio which is required by a perfect analogue to digital converter irrespective the utilization of oversampling. Since the values are stored digitally in the form of binary data to the resolution is defined in bits, for example, an ADC having the resolution of 8 bits indicated that it can encode your required data in analogue form into 1 to 256 different levels and the values are present in unsigned integers from 1 to 255. The quantity Resolution can also be defined in terms of volts which is mathematically given as: Q=EFSR/2M
In the above equation, the quantity Q is equal to the LSB (the minimum change which is required in the output is called Least Significate Bit Voltage), where M is the ADC’s resolution in bits and EFSR is the full-scale voltage range (also called ‘span’). The output error in the conversion of analog to DC can occur and the two mostly known error are Quantization error and non-linearity error, these two errors are measured with Least Significant Bit. Similar to ADC, the digital to analog conversion or DAC is the type of conversion that deals with the converting of the digital signal to analog signal. The most commonly used device is an integrated circuit (IC). To convert a signal into the analog form, the interpolation is done in which the discrete signal is interpolated in a graph and these pulses are reconstructed to produce analog signal again. The Nyquist sampling theorem is very important in this conversion and it states that the DAC can create the analog
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signal only in a condition that the bandwidth of the sample signal should be less than the Nyquist frequency. So when can say that the DAC transform the given finite and precise numbers into required physical quantity and it also can an ability to convert a time defined series data into the respective quantity. This technique of converting the digital signal to analog is used in Pulse width modulator in which a stable current or voltage is passed through a low-pass filter for a particular duration set by the digital code. This technique is also used to control the speed of electric motor digitally. The ADC and DAC have changed the digital and analog technology. The DAC devices bring the voice into a large speaker and your audio voice is transfer to a long range with the help of ADC. These conversions are the latest technology and is the foundation of digital communication and its signal processing. This chapter will further discuss about different communication protocols which are mostly used in the field of telecommunication, this protocol is the set of rules used by the system for the purpose of communications to transfer information by varying the physical quantity. These protocols possess many characteristics such as to recover the errors through different techniques and defines the rules for synchronization of data, syntax, and semantics. These communication systems use defined methods and formats for the transit of information. The required protocols can be utilized with the help of hardware or software and sometimes the combination of both can be used. The information transferred from one system carries specific data to activate a response from a range of responses, which is pre-fixed for a specific protocol. This specific information is independent from how it will be used. Moreover, these protocols are set and defined on particular technical standards. Since there are multiple protocols available for a single system which can describe different aspects as well. For example, the protocols of the Internet are defined by the Internet Engineering Task Force (IETF). There are many techniques to design a protocol but most commonly used is system engineering principles as communication within the system operates in a concurrent manner. One of the important factors for concurrent programming is the synchronization of data for transferring and receiving messages for a communication in the system. The low-level protocols have less complexity for syntax and semantic, hence makes them more human-friendly to operate. For high-level protocols, the complexity increase to a great extent and language interpreters are used, an example of such a protocol is HTML language. The term concurrent programming is just limited to the theoretical extent as in the real world programming
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it contains a great amount of bugs and errors. Therefore, a mathematical technique is implemented for the study of communication and concurrency known as communicating sequential processes (CSP). Another technique for formulating the concurrency is by using finite state machines which are used in Moore and Mealy machines. The Moore and Mealy machines are used as design tools to use in a telecommunication system and digital electronics. However, for designing a complex protocol, it is decomposed in a simpler protocol and such protocols are called protocol family. Similarly for the communication to take place, the respective protocols standard have to be matched and agreed upon. For this purpose, the rules are established with the help of different structural algorithms. The operating system of the protocol software makes itself independent when using portable protocol programming language. In this case, the source code is used as protocol specification tools. However, the need for a protocol can be seen by looking into the protocol designed by IBM named as bi-sync protocol (BSC). It was among the earliest protocol which was only used to connect two nodes and it was not designed to use for the multiple nodes operations and shown a great amount of deficiencies and bugs. Since this absence of a standard protocol give the opportunity for a various organization to establish their own protocol which creates an abundance of complexities and problems which further created non-compatible advance versions of their own protocols. Another purpose of such protocols was to stop users from using devices of other manufacturers. There are also cases when the certain protocols were very famous in the market but they do not possess the standard characteristics. These protocols are named as de facto standards. These de facto are very much popular in niche markets and emerging markets just to monopolize the standards. There are some standard organization s for protocols which are named as International Organization for Standardization (ISO), the International Telecommunication Union (ITU), the Institute of Electrical and Electronics Engineers (IEEE), and the Internet Engineering Task Force (IETF). The organization IETF maintains the protocols used on the Internet. Similarly, the IEEE control the protocols that are implemented in hardware and software for the commercial and electronics. The ITU is the standard organization which maintains the protocol standards used in the telecommunication sector. The NEMA standards are implemented in Marine Electronics and for web technologies, the standards of World Wide Web Consortium (W3C) are implemented. With the help of these organizations, the standards of protocols are maintained and any advancement is also designed by them.
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REFERENCES 1. 2. 3. 4. 5.
http://www.ee.surrey.ac.uk/Projects/CAL/digital-logic/gatesfunc/ http://www.electricaleasy.com/p/electrical-machines.html http://www.electronics-tutorials.ws/logic/logic_1.html https://learn.sparkfun.com/tutorials/analog-to-digital-conversion https://www.allaboutcircuits.com/textbook/digital/chpt-13/digitalanalog-conversion/
CHAPTER
12
PROCESS DYNAMICS AND CONTROL The chapter will introduce the readers to the principals of control methods. The chapter will cover topics dealing with modeling for control, linear ordinary differential equations and Laplace transforms transfer function models, analysis of continuous-time linear systems, SISO control system analysis, synthesis of SISO controllers and SISO controller design. In these days every industrial system is designed to be autonomous. Research and development are totally focusing on designing such control system algorithms which can give a desirable output of dynamical systems in an optimal manner. Synthesis of control algorithms needs the electrical, mechanical, and nanoengineering knowledge of the process in order to focus on fundamental theoretical as well as application problems. Control systems are of two types: process control and system control. Process control is required in the large scale industrial processes, for example, in gas and oil industry, chemical, textile, and food processing industries where temperature, pressure, level, and density is required to measure and maintain. System control involves semi-autonomous devices where expected tasks are required to perform in a specific time and in a repeated manner. The basic principle of any control method is the same as having the following four steps. • •
analysis and measurement of the process conditions; set the controller to do the required task by considering the measured values;
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• get the output result from the actuator through control; and • get the feedback from the output and set the controller accordingly. To follow the basic strategy of control system designing, modeling of the system is the first step to transfer the required results with respect to measured values in the form of logical structure. Mathematical modeling means the conversion of dynamic system conditions in the form of mathematical equations. Each system has a unique mathematical model, for example, a state-space model is useful for optimal control issues and transfer function approach is useful for time-invariant systems and transientresponse analysis. After the mathematical modeling, some computer and analytical tools can be used for control system synthesis. Differential equations are the basic mathematical tools used for modeling. Differentially equations show the rate of change of any physical parameter or quantity with respect to time, in other words, these are the derivative of functions. Ordinary differential equations represent the derivative of one independent variable and it will be called as partial differential equation if it will be the derivative of more than one independent functions. Similarly, linear differential equations are the derivative of a function having degree one (variables for physical quantities have the power of one). Examples of first/ second order linear ordinary differential equations are as below
First-order linear ordinary differential equation:
Second-order linear ordinary differential equation Complex differential equations are converted to the simple algebraic equation in order to make the solution simple. This conversion is done by many methods two of them are Laplace transform and Fourier transform. Laplace transform can be done by four methods. • Laplace transform by using theorems. If f(t) is defined over the interval (0, ∞), the Laplace transform is denoted as f(s) L= ( f ) fˆ= ( s)
∫
∞
0
e − st f (t )dt
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• By using Mathcad (By using this software, we can find Laplace as well as the inverse Laplace transforms.) • By using the Piecewise defined Functions. • By using Delta Function. Every control system has output and an input signal. Transfer function shows the ratio of input to the output of the system. By using block diagram, we can express the whole system in which transfer functions are represented by blocks and arrowed lines represent the flow of the process. The excitation or cause signal also called reference input is operated by transfer function and produces the output called as an effect. Thus, the transfer function is the relation of cause and effect of the system. In different cases, the category of output and input vary in nature, for example, in case of motors electrical energy converts to mechanical energy and in case of generator mechanical energy convert to an electrical output. But for mathematical modeling of a system, all the signals must be in the same form. So we use Laplace conversions and transfer function in Laplace domain. After the mathematical modeling of a system now it’s time to convert these logics into commands in other words to create the communication path between the devices of the system we need different protocols. SISO (single input, single output) is a wireless communications system. Antennas are used in this system on the transmitter side as well as on the receiver side. In this technology electromagnetic field is used as a source of signals but it has a drawback in some cases, for example, in hilly areas, canyons, and due to high building the electromagnetic field gets obstructed and the wavefront get disturbed. Hence scattered and the late arrival of the signal at the receiver side create problems. In order to reduce the effect of this distortions, smart antenna technology can be used which includes SIMO (single input, multiple outputs), MISO (multiple inputs, single output), and MIMO (multiple inputs, multiple outputs). SISO controller can be synthesis according to desired input and output. The key point in the synthesis of any controller is always to keep the poles at predefined locations. So by using different approaches, this can be done. Here is the polynomial approach to doing this task. Let consider a nominal model and make transfer function of the controller and for the model with in the control loop. Let Cs = P(s)/L(s) is the transfer function of controller and Go(s) = Bo(s)/Ao(s) is the transfer function of any model and consider the desired polynomial for the closed loop is
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Now the main objective is to find such solution (values of A and L) so that the polynomial Acl exhibit the desired properties of close loop if provided by values of Ao and Bo (given values). In very general conditions it is quite possible. By considering a general example, let Go(s) = Bo(s)/ Ao(s) is the model of plant with Ao = s^2 +3s +2, Bo(s) = 1. C(s) = P(s)/L(s) where p(s) = P1s + Po and L(s) = l1s + lo, is the controller. Now by comparing close loop characteristic polynomial A0(s)L(s) + B0(s)P(s) = (s^2+3s +2) ( l1s+ lo) +(1)( P1s + P0) with s^3+3s^2+3s+1 and by equating coefficients by making non-singular matrix, the values of P1 = 1, P0 = 1, l1=1, l0= 0 can be find by using the transfer function of controller Cs = (s+1)/s the close loop polynomial assignment is also possible even in linear SISO systems by using Sylvester’s theorem. By considering the following mathematical result lets discuss a general case.
12.1. SYLVESTER’S THEOREM Consider the two polynomials A(s) and B(s) as mentioned above. By making the matric such that determinant of metric is not equal to zero, A(s) and B(s) will be found as co-prime or relative prime which mean having no common factors. Now in order to analyze that how the pole assignment is possible in a closed loop system for SISO controller. Let consider a feedback loop with one DOF. Assume the plant nominal model and controller as same mentioned above {Go(s), C(s)} respectively. If (s) is consider as arbitrary polynomial of degree nc = 2n – 1 then P(s) and L(s) will have degree np = nl= n – 1 such that A0(s)L(s) + B0 (s)P(s) = Acl (s). here the pole assignment is achieved in general case. Additional constraints can also be placed on the obtained solutions. For designing a control system it’s a compulsory requirement that the tracking error of the nominal control loop must be zero in either the input/output disturbance or for reference input that happens because of D.C. components. To achieve this the controller must have one pole at the origin
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and nominal loop must be stable internally. This will give sensitive function zero at zero frequency. In order to get such result to replace L(s) as,
The close loop polynomial equation can be written as Pole assignment technique can also be used for PI and PID controller synthesis. Consider a control of the form
This can be identical to PID controller where
To design a PID controller by pole assignment method, the only requirement is the second order model of the plant. Let there is a plant with nominal model Go = 2/(s+1)(s+2). Now the task is to create a PID controller which return a close loop with dynamics controlled by factors s^2 + 4s + 9. For this purpose solve the pole assignment equations with the given factor as
In result C(s) gives a PID controller with the values of KP5.67, KI = 8 and KD = 0.93 and TD= 0.11:
In solving real-world problems of control systems, the time delay is a very important factor to consider. As the delay in response become donate
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in some cases so to improve the performance it is necessary to reduce this factor. Smith Predictor gives a perfect strategy for the case of a stable open loop plant by building a parallel model which reduces the delay. According to the previous example, the Smith Predictor structure can be made as
Now the controller can be designed with no delay in the loop by the use of Pseudo complementary function between two variables let for r and z can be written as Trz(s). This can be done by considering a standard PID model as
This gives nominal complementary sensitivity between r and Y as According to the procedure mentioned above robustness issues cannot be sorted out, it needs more architecture to involve with this procedure. The mentioned architecture cannot be used for unstable open loop plants some more ideas are required to add with this architecture. For the robust SISO controller synthesis and design for nonlinear systems and such uncertain linear systems which show static nonlinearities can be done in four steps. (1) Identification of methodology to synthesize robust SISO controller for uncertain nonlinear Hammerstein models. (2) Selection of weighting functions H∞ for constraints L∞ by using a systematic approach. (3) Robustness calculation to specify the allowable modeling and inversion error of nonlinearity. (4) Finding such conditions for frequency domain which give output L2 as well as the input related to same output L2.
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Above are the steps for controller synthesis while the whole process is divided into three steps identification, controller synthesis, and system analysis. Identification includes the modeling based on an experimental approach to collect the nonlinear characteristics of the plant. This identification is followed by the dynamics of the uncertain linear plant. The error between the data of the actual system and nonlinear model are combined as unstructured uncertainty. For this uncertainty robust controller design methodologies are required. To explain the procedure mentioned in the above paragraph, consider the example to regulate the mass air flow (MAF) of an engine then apply the design methodology for the synthesis of a robust feedback controller. In this application, if the Hammerstein model of a 4.6L V8 spark ignition engine from an input of electronic throttle to the output of MAF engine is known. The tracking controller H∞ can be designed with steady state error equal to zero while illustrating the nonlinear throttle characteristics and time delay. In order to confirm the performance of a closed loop, for example, maintenance of constraints, and disturbance and noise reduction we should consider the experimental data because it can validate successful the performance. SISO and MIMO are basically techniques or algorithms used in data transmission. SISO is an older technique, MIMO is added recently in order to improve the data transmission rate and to increase the coverage. SISO stands for single input-single output while the MIMO stands for multiple input multiple outputs. Both techniques are based on a number of antennas used at the transmitter and receiver side. As the name suggests in SISO system there is only one antenna on the transmitter side and one on the receiver side while in case of MIMO there are multiple antennas used on both sides. Better bit error rate can be achieved in case of MIMO by using the technique named as Space Time Blocking Code (STBC) which also enhance the coverage. The data rate can be improved by using the technique named Spatial Multiplexing (SM). By the use of beam forming along with SM, both the data rate and coverage in a wireless system can be achieved. SISO is used in radio, satellite, GSM, and CDMA systems while MIMO is used in next generation wireless technologies such as mobile WIMAX -16e, WLAN-11n.11ac,11ad, 3GPP LTE, etc. The QUEST of the enhanced gas economic situation for ground lorries increased in recent times because of the boosted cost of nonrenewable fuel source as well as the problems of ecological effects. Crossbreed electrical
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lorries (HEVs) appear to be one of the most appealing temporary service as well as are under passionate growth by numerous automobile business. An HEV includes an electrical power course to the traditional powertrain, which aids to enhance gas economic situation by engine right-sizing, tons leveling, as well as regenerative stopping. A right-sized engine has far better gas effectiveness as well as smaller sized warm loss. The lowered engine power is made up of an electric device (or equipment). Compared to interior burning engines, electrical equipment’s supply torque faster, specifically at reduced car rate. As a result, releasing efficiency could be enhanced despite decreased total ranked power. Tons leveling could likewise be accomplished by including the electric course, which allows the engine to run extra successfully, independent from the roadway lots. Regenerative stopping enables the electrical device to catch component of the automobile kinetic power and also charge the battery when the lorry is slowing down. Mathematical versions serve for supplying a structure for incorporating information and also getting understandings right into the fixed and also vibrant actions of intricate organic systems such as networks of communicating genetics. We examine the vibrant habits gotten out of design genetics networks including usual biochemical concepts, and also we contrast present approaches for modeling hereditary networks. A typical modeling strategy, based upon merely modeling genetics as ON-OFF buttons, is easily carried out and also permits fast mathematical simulations. Nonetheless, this approach might forecast vibrant remedies that do not represent those seen when systems are designed with a much more in-depth technique making use of normal differential formulas. Previously, most of the genetics network modeling researches have actually concentrated on identifying the kinds of characteristics that could be created by usual biochemical concepts such as responses loopholes or healthy protein oligomerization. For instance, these components could create numerous secure states for genetics item focus, state-dependent feedbacks to stimulations, body clocks as well as various other oscillations, and also optimum stimulation regularities for optimum transcription. In the future, as brand-new speculative methods boost the simplicity of characterization of hereditary networks, qualitative modeling will certainly should be replaced by measurable designs for particular systems. Mass transfer in between stable and also mobile areas issues of synchronized procedures. We establish a “multirate” version that enables
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modeling of the small‐scale variant in prices as well as kinds of mass transfer using a collection of first‐order formulas to stand for each of the mass transfer procedures. The multirate version is included right into the advective‐dispersive formula. Initially, we contrast the multirate design to the basic first‐order as well as diffusion versions of mass transfer. The round, round, and also split diffusion designs are all revealed to be certain situations of the multirate version. Blends of diffusion from various geometries and also first‐order rate‐limited mass transfer could be incorporated as well as stood for specifically with the multirate version. Second, we establish remedies to the multirate formulas under problems of no circulation, rapid circulation, as well as radial circulation to a pumping well. Third, making use of the multirate design, it is feasible to precisely anticipate prices of mass transfer in a mass example of the Borden sand having a combination of various grain dimensions and also diffusion prices. 4th, we check out the impacts on aquifer removal of having a heterogeneous blend of kinds and also prices of mass transfer. Under some conditions, also in a reasonably uniform aquifer such as at Borden, the mass transfer procedure is ideal designed by a combination of diffusion prices.
12.2. INTEGER-ORDER CONTINUOUS MODELS OF FRACTIONAL ORDER SYSTEMS The problem of obtaining a continuous realizable model for a fractional order controller can be viewed as a problem of obtaining a rational approximation of the irrational transfer function, modeling the fractional controller. Among other mathematical methods, two of them are particularly interesting for this purpose, from a control theory point of view: the continued fraction expansion method used for evaluation of functions, and the rational approximation method used in interpolation of functions. On the other hand, the use of frequency identification or curve fitting methods for obtaining rational approximations to the irrational frequency responses, characterizing fractional-order systems are proposed. In this section, the general form of the methods and some especially interesting applications of them are described.
12.3. CONTROLLER UNDERSTANDING Generally, there are two opportunities for recognizing a controller: an equipment awareness based upon using a physical tool, or a software program (or electronic) awareness based upon a program, which will certainly operate
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on a computer system or microprocessor. In electronic devices, equipment awareness indicates making use of digital gadgets or circuits, executing the necessary feature as an admission or resistance feature.
12.4. ANALOG UNDERSTANDINGS For equipment digital awareness, the beginning factor is the admission or insusceptibility feature. For recognizing such features, a minimum of two methods could be utilized: creating a microelectronic particular tool that, for building, has actually the needed admission or insusceptibility or recognizing an approximate reasonable feature by utilizing a limited lumped-element network, in a ladder, tree, plunged, or latticework geography. Because this paper handles logical estimates of the fractional-order drivers, just the last means is gone over listed below.
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REFERENCES 1. 2. 3. 4. 5.
http://csd.newcastle.edu.au/book_slds_download/Ch07t.pdf http://www.sciencedirect.com/science/article/pii/001044859090095T https://pdfs.semanticscholar.org/b525/666eaee3dee0209df03c9ac9b2 9f71c01e64.pdf https://www.electrical4u.com/transfer-function/ https://www.unf.edu/~mzhan/chapter6.pdf
CHAPTER
13
INTRODUCTION TO BIOCHEMICAL METHODS The chapter will cover the basics of chromatography (paper, thin layer, column, and electrophoresis), spectroscopy, and spectrophotometry, centrifugation, ultracentrifugation, and isotopic techniques, viscosity, diffusion, dielectric constant and osmometry, and optical methods. This chapter decried a brief introduction of chromatography and other terminologies which can be useful for the readers in understanding and utilization of different biochemical methods. Just like other techniques as discussed in the previous chapter, chromatography is another separation techniques that is used to separate solute from a solution or mixture. There are two phrases in this technique, one is called mobile phase in which the mixture is dissolved and the other phase is called the stationary phase in which the mobile phases passes and it hold the structure to separate the constituent of the solution. The different speed of the solute particle in the mixture causes them to separate due to their different speed between the stationary phases and mobile. The chromatography can be analytical or preparative technique. In case of analytical chromatography, the relative proportion of different amount of solute is defined in the given mixture whereas, in preparative chromatography, it is method of purification in which solute is separated from the mixture so that further different techniques can be applied by keeping the purity of the solution. There are four type of chromatography on the basis of chromatography bed shape which are column chromatography, planar chromatography, paper chromatography and thin layer chromatography and discussed accordingly. In column chromatography, the stationary bed is fix
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in the tube and the particle of stationary phase fills the tube, since the tube is open from the top, there is unrestricted path for the mobile phase to pass the tube and difference rates of the particle of the mobile phase are calculated. Another separation technique of chromatography is the planar chromatography in which the stationary phase is set on a plane. The plane can be a piece of paper, or a layer of particle in the form of solid. As soon as the mobile phase s passed through it, the different distances are recoded for different particle present in the mobile phase and with the help of Retention factor, the different recorded distances can help in the identification of the particles of the mobile phase, Similarly, in case of paper chromatography, a dot is place on the piece of paper with a solvent which is further sealed. As the solvent t travels, the sample mixture also travels with the solvent, since the paper is made from a polar substance such as cellulose, if the particles of the mobile phase are polar, then they will quick with the paper and in this way the different traveling distance are calculated which indicates the desired particle. One of the widely chromatography used in laboratory is the thin layer chromatography and it is similar to paper chromatography which different biochemical are separated on the basis of their sizes, just like in paper c chromatography, in this technique of chromatography, the adsorbent is composed of cellulose or silica gel and in way, multiple samples can be recorded at the same time and due to this ability of thin layer chromatography, it is mostly used in different drug test and in water purification techniques. It indicates much better result than paper chromatography with better quantitative analysis and separation. Thin layer chromatography is the easiest kind of chromatography to do. An appropriate shut vessel including solvent as well as a layered plate are all that are called for to perform splitting up, qualitative as well as semiquantitative evaluation. With optimization of methods as well as products as well as making use of readily available business tools, extremely reliable splitting up and also precise and also specific credentials could be attained. The approach of paper dividing chromatography in using a little decline of the remedy having the compounds to be divided to a strip of filter paper a brief range type one end. The decline is enabled to completely dry, and also completion of the paper nearby to the area is put on an establishing service, typically a water-containing solvent, to make sure that a solvent circulations past the place by capillary activities as well as on down the size of the paper
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In spectroscopy, it deals with the interaction of light with matter (absorption) and it is radiated in the form of energy and this process is depended on the wavelength of emitted radiations. The study of spectroscopy is further expanded with the interaction of small-scale particles on electrons and ions and with the particles which are the function of energy absorption. This field of science play its vital role in vital discoveries in the field of quantum mechanics as well as quantum thermodynamics and in the general theory of relativity. It has also help the modern physicist to understand electromagnetic forces as well as strong and weak nuclear forces. There are great applications of spectroscopy such as in monitoring systems of optical fiber networks, measurement of different compound and elements in food samples, measurement, and calculation of toxic and harmful compound present in the blood sample, Centrifugation is such an application which involves the separation of solute particle from is its mixture with the help of centrifugal forces. This sedimentation technique is mostly used by laborites and industries to separate two immiscible liquids as well and also helps in the analysis of hydrostatic properties of different macromolecules. In this technique, the particle which are denser move away from the axis of centrifuge and the particle with low density move toward the axis of rotation. The operating principle of this technique is that larger the molecule, higher the density it will possess and more easily they will be separated from the mixture. However, this chapter will further discuss one of the most important centrifugal technique which is known as Ultracentrifuge. This is the optimized centrifugal technique for increasing the rotor speed at extreme rate which is capable of generating an acceleration value of 100 000g. The ultracentrifuge is further divide into two categories known as the analytical ultracentrifuge and preparative ultracentrifuge. These two categories of ultracentrifuge are very useful in many instrumentation techniques in the field of molecular biology, polymer science and biochemistry. Moreover in the analytical ultracentrifuge, the sample is monitored with the help off real time techniques using the optical detection systems ultraviolet light absorption and/or interference optical refractive index sensitive system. By using such advanced system the observer calculates the axis of rotation versus the concentration of the sample and the required data can be monitored accordingly. These modern techniques can be used with the help of advance instrumentations, the results obtained in each experiments can also be stored
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for further analysis, and further mathematical expression can be fed in the given results. There are two very common experiments are applied named as sedimentation velocity and sedimentation equilibrium experiments. The analytical ultra-centrifugal technique can give us many valuable information such as shapes of macromolecules in gross form, various chemical as well as conformation changes in macromolecules and change in the size of macromolecules. Chromatography of healthy proteins on cellulose ion exchangers includes mostly the facility of numerous electrostatic bonds in between charged websites externally of the adsorbent and also websites birthing the other fee externally of the healthy protein particle. The variety of such bonds that could be developed establishes the focus of completing ions needed for the launch of the bound particle. Hence, healthy proteins varying dramatically accountable thickness, or in variety of fees through dimension, might be anticipated to vary in their needs for elution. Cost circulation could likewise be considered a variable. However, it is the overall impact of these variables that establishes the fondness of the healthy protein for the adsorbent, so an easy relationship in between any kind of among them and also the chromatographic habits of the healthy protein concerned is not constantly get. The circumstance is more customized by the opportunity that sometimes nonelectrostatic pressures could play a crucial duty. A very delicate fluorescence response for amino acids making use of o-phthalaldehyde and also 2-mercaptoethanol allows the discovery of amino acids divided on little ion-exchange columns. The benefits are: (1) excellent accuracy at the degree of 0.5 nmole; (2) broadband due to the smaller sized elevation of the column; and also (3) direct partnership in between meter action and also amino acid focus.
13.1. STANDARD INTERPRETATION The International Union of Pure as well as Applied Chemistry (IUPAC) specifies LOD as complies with (1): The restriction of discovery, expressed as the focus, cL, or the amount, qL, is originated from the tiniest step, xL, that could be identified with practical assurance for a provided logical treatment. Applications researchers are continuously in search of alternate methods to discuss a few of the fundamental, however, typically complex, ideas of spectrochemistry.
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Moreover, various other information such as number and subunit of stoichiometry of macromolecules can also be obtained with this centrifugal technique. This form of ultra centrifugal technique has been using to a great extent as different chemical analysis is used with modern computer technique and different software tools are available which makes this technique very useful and manageable. Similarly, Preparative ultracentrifuge is also been used in different chemical experiments as it is available with great variety of rotors which are suitable for experiments and the rotors used in this techniques are designed in such a way that they can hold tubes which contains the samples. This technique is mostly used in biology to find particular kind of fractions such as cellular organelles (mitochondria, microsomes, ribosomes) and viruses. It also been used for different gradient separations by filling the tubes from top till the bottom Moreover, the sucrose gradient is also been used and developed which have been employed for the separation of cellular organelles. However, irrespective to the abundance of advantages of ultracentrifuge systems, there are also disadvantages of this system as well. In high speed of kinetic energy of the rotor, any failure can cause a tremendous loss of eh whole machinery, their rotors are mostly designed with light weight material such as aluminum metal or titanium. The great amount of stress and chemical reactions on the rotors makes them weak with the passage of time and has to be replaced. Therefore, proper usage of the rotors with instrumentation within the give limits is very necessary to maintain the safety level during the experiments. The latest designed in the rotor is of carbon fiber which is 60% lighter and is much more efficient than the other materials of the rotors and also results in fast braking. The viscosity of a fluid is defined as its resistance to its deformation in terms of tensile stress or shear stress and in liquid state, the viscosity is referred as thickness. It is a property of fluid which resists the relative motion between two surfaces. The fluid which possess no viscosity are called ideal fluid and this phenomena is measured at very low temperatures whereas all the fluid have viscosity and are named as viscous fluids. Oxygen and also carbon isotopic evaluations were carried out on carbonate portions of argillaceous sedimentary rocks as well as limey shales by mass spectrometric evaluation of CO2 gas freed by responding examples with HCI at area temperature level. The isotopic proportions were gotten making use of a Micromass 602 mass spectrometer as well as were compared
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to those figured out for examples of the Peedee belemnite sedimentary rock criterion (Craig, 1957). One significant downside of the swirl thickness subgrid‐scale tension designs made use of in large‐eddy simulations is their failure to stand for properly with a solitary global continuous various unstable area in revolving or sheared circulations, near strong wall surfaces, or in transitional programs. In the here and now job a brand-new swirl thickness version exists which reduces much of these downsides. The version is based upon an algebraic identification in between the subgrid‐scale tensions at two various filtered degrees as well as the solved unstable stress and anxieties. The subgrid‐scale tensions gotten making use of the suggested design disappear in laminar circulation as well as at a strong limit, as well as have the right asymptotic actions in the near‐wall area of an unstable limit layer. The outcomes of large‐eddy simulations of transitional as well as stormy network circulation that utilize the recommended version remain in great contract with the straight simulation information. Groundwater recharge suggests various points to various individuals. For instance, to an agronomist, water which relocates below the origin area of plants stands for a loss in return therefore must be reduced. Those that have an interest in water sources, take the contrary sight. A few of the factors for researching all-natural groundwater recharge are: to identify the risk-free return of a groundwater system; to analyze the level of growth of additional salinization adhering to land clearing up; and, for those thinking about storage space of waste products, to recognize locations of really reduced groundwater recharge. Just all-natural recharge, either regional or local will certainly be thought about right here. Neighborhood (or scattered) recharge is specified as that getting to the water level by percolation of rainfall over of evapotranspiration, with the unsaturated area. Local recharge happens adhering to overflow as well as succeeding ponded seepage with low-lying locations, streams or lakes. They are reported in standard symbols about PDB for carbon as well as SMOW (Craig, 1961) for oxygen. Liquid addition resolutions Nondestructive liquid addition evaluations were lugged out on two times as sleek 100- to 200-thick areas making use of a double objective SGE Design III cold home heating phase adjusted with natural as well as steel criteria for temperature levels in between -90° as well as 500°C.
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Homogenization temperature levels of liquid-rich additions were reproducible to -T-0.2°C and those of gas rich incorporations to -T-3°C. Cold factor resolutions were reproducible to -T-0.2°C. Clay Mineralogy as well as iron-rich chlorite (solid and weak basic representations) are the only clay minerals existing in the bulk of examples. Combined layer chlorite-montmorillonite, as well as montmorillonite were determined in nine samplings, every one of which were accumulated near modification facilities. Diffusion is such a movement of molecules from a place of higher concentration of molecules to the place of lower concentration and example of this phenomenon is spreading of smell of a perfume in a room. The rate of diffusion is directly proportion to the concentration of molecules and mathematically it is defined as: j = -D(dc/dx) In the above equation, dc/dx is the rate of diffusion in the x direction and c is the concentration of substance and D is proportionality constant. Dielectric constant is defined as the property of electrical medium which the ratio of capacitance of given material of capacitor to the capacitance of a capacitor at vacuum and mathematically it is given as κ = C/C0
In the above equation, C0 is the capacitance of material at vacuum and C is the capacitance of given material and K is dielectric constant and it is a dimensionless property. This chapter will further discuss one of the most important topic of advance chemistry named as Osmometry. In this branch of chemistry, the number of particles of solute and solvent in the solution are counted. However, it can be affected by the amount of present solvent in the given mixture, so we can say that osmometry is the technique to measure the amount of solute to solvent ratio. However, to use this technique, the osmometers are used to measure the osmolality of the given material. The most common method to perform this technique is the freezing point depression method is the worldwide accepted method in the labs. The observer can used find the osmolality of the sample as the method is very simple and the result can be easily obtained. Its instrumentation in nowadays are used to computer techniques to store the analysis of different samples and different mathematical algorithms can be applied to them as well. In freezing point depression method, the freezing point of the given material is
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depressed with the addition of another material and as a result, the freezing point of material is lowered as compared to the material in its original form. In this way, it measures the freezing point depression of the material for all the sample present in the given sample and its osmolality is measured. There are great amount of advantages of osmometer and osmolality such as clinics nowadays can used this technique to time efficiently diagnose a patient thus the patient necessary time is saved in case of emergencies and its benefits include the development of drugs and media manufacture for proper product stability which insure safety of the patient. The further benefits of osmolality includes their usage in labs and biotechnological researchers use this method for various purpose in different experimentations. Another important terminology needed to be discussed with the osmolality is the osmotic gap, it is the difference of actual and measure osmolality which is calculated from the concentration of all the solutes from Serum, this value indicated the molecular weight present in the Serum. The substance which produce osmotic gap are alcohols, acetone, aspirin, glycols, etc. Furthermore, they are also used in various test result such as in Urine test, the osmolality provides the necessary information of kidney concentrating ability, the free water clearance as well as the hydration status for athletes. The osmolality of stool is very important for the patient suffering from Diarrhea. Another important test is the Serum osmolality which is another important clinical test and used for alcohol toxication in rapid screening, in the differential diagnosis for hypernatremia and hyponatremia.
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REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9.
https://en.wikipedia.org/wiki/Chromatography https://en.wikipedia.org/wiki/Viscosity https://study.com/academy/lesson/what-is-centrifugation-definitionprocess-uses.html https://www.aicompanies.com/education/osmolality/faq/ https://www.britannica.com/science/chromatography/Methods https://www.britannica.com/science/diffusion https://www.britannica.com/science/spectroscopy https://www.khanacademy.org/science/organic-chemistry/ spectroscopy-jay https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3931874/
CHAPTER
14
CHEMICAL ANALYSIS OF HOMOGENEOUS SYSTEMS The chapter will introduce the readers to ideal mixtures, integral quantities, differential quantities, thermodynamics of open and closed systems, fugacity, and activity, Gibbs energy, Wilson equation and regular solutions. The chapter will continue the discussion of chemical engineering thermodynamics introduced above and include specific applications in biotechnology. Ideal mixture is such a mixture whose thermodynamic properties resembles with an ideal gas. As defined in the earlier chapter, the more of the enthalpy is closer to zero, the more is the mixture possess the ideal nature and the mixture also strictly follows Raoult’s law and the activity coefficient is also equal to one. The concepts of the ideal mixtures are the fundamentals of thermodynamics. The properties of an ideal solution are similar than those of ideal gases but with a few differences that the intermolecular forces in a solution are stronger where it can be neglected in the case of gases. So we can say that the average characteristics for gases and liquids are similar to each other. In discussing the ideal solution, an important function as Margules function should be discussed; it is given as a function which is added to the Raoult’s law for the description of a liquid solution to account for deviations from ideality. The amended Raoult’s law description of the vapor pressure above the solution becomes: P1=P*1x1fM,1 P2=P*2x2fM,2
The Margules function has the general form:
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fM,1 = exp(αx22+βx23+γx23+δx24+...)
The function always contains the opposite mole fraction x2 (= 1-x1 for a binary system). The numbers of Margules parameters α, β, γ, δ,.. varies. The larger the deviations from ideality the more parameters are required. However, the Margules function will be later used in this chapter to discuss the mathematical forms of regular solutions. So this function holds a huge rule in the overall result to state a solution ideal or non-ideal. The deviations from this function can make the solutions or the mixtures non-ideal. So we can state that, a single parameter of Margules function can make a solution ideal to non-ideal. But as compared to the ideal solutions where the mixing is always complete with the additive nature of the solution, the non-ideal ones have different case, their volume is not equal the sum of solutes components of the solution as well as their solubility is not constant within the specific range. Dilution is another important and it is among the daily used terms in the chemical labs, it the process of decreasing the amount of solute in the solution and it is mostly done by increasing the amount of solvent in the mixture. So, in simple words, to dilute a given solution we just need to add up more solvent in the solution by keeping the amount of solute fixed. However, the resulting solution is properly mixed to make the overall solution same in all the perspective. For example, if there are 1676 grams of salt (the solute) dissolved in 1 liter of water (the solvent), this solution has a certain salt concentration (molarity). If one adds 1 liter of water to this solution the salt concentration is reduced. The diluted solution still contains 10 grams of salt (0.171 moles of NaCl). Mathematically this relationship can be shown in the equation: C1 x V1 = C2 x V2
where, C1 = initial concentration or molarity, V1 = initial volume, C2 = final concentration or molarity, V2 = final volume.
A thermodynamic system is such a system that follows the properties of thermodynamic such as enthalpy, temperature, internal energy, etc. In a thermodynamics system, an equilibrium state is always considered then in unequilibrium and this type of system is always enclosed with walls so that it can be separated from the walls. A thermodynamics systems is always within the constraints of state variables and they also required a specific type of function called as state function which further define the state variable. Depending upon the functionality of a thermodynamic systems, they are divided into three types named as open system, closed system and isolated
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system. In open systems, energy, and matter are allowed to freely go in and out of the system without any discontinuity, the example of such system is the boiling of water as during the heating of water, stream freely goes out of the system. However, the case of closed system is totally opposite, in closed system the energy and system is restricted within the jurisdiction of the container and are not allowed to go in and out of the system, for example, in case of boiling of water, if the container is cover with lid, the stream is not allowed to go out of the system whereas the heat moves out only. The third type of thermodynamics system is isolated system, it is such type of system in which neither the matter goes in and out of the system nor the heat exchange is possible so we can say that the system is completely sealed, example of such system is insulated gas tank or a thermoflask. Fugacity, in term of thermodynamics of chemistry, it is defined as replacement of mechanical partial pressure of a gas with partial pressure to main the equilibrium of the system. It possess the same chemical potential and pressure as a real gas exerts. The fugacity is determined in various methods and experiments such as Van Der Waal’s gas. The pressure exerted by an ideal gas and fugacity are interrelated and are dimensionless quantity, Mathematically, it is defined as: Φ = f/p The fugacity can be used in terms of chemical equilibrium that the reactants and products can be replaced by fugacities, in case of condensed phase in terms of vapor phase, the chemical potential is equal to the vapor and fugacity is equal to the fugacity of vapors. We can say that the fugacity is the measure of tendency of a gas to escape and the pressure required to make a non-ideal gas to follow the ideal gas equation. Gibbs energy is widely used in the field of thermodynamics and which can be used to calculate the amount of reversible work required in a thermodynamic system at constant pressure and constant temperature. It the amount of work extracted by a thermodynamic closed system and this work can only be taken from a reversible process. So we can say that the transformation of system from initial to final state, the work done on the surroundings by that system is equal to the diseases in the value of Gibbs energy. In other words, Gibbs energy is that amount of energy that released by a chemical process and further it can be used to do work. This free energy is the sum of enthalpy and temperature (in Kelvin) with entropy which is mathematically given as: G = H – TS
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In case of change in enthalpy of system, this equation is given as ∆G = H – T∆S Whereas, this equation in standard state equation becomes ∆G° = ∆H° – T∆S° The standard state condition are the partial pressure should be 0.1 MPa and the molarity of aqueous solution should be 1M. This chapter will further discuss about biotechnology, it is defined as any system that used biological system is called biotechnology. It has huge application is the field of bioengineering, bio genetics biomolecular sciences, etc. in medical biotechnology, it helps in the diagnostic of many diseases in way that the treat of different has been considerably reduced from days to minutes and simple blood samples with different advance technologies can help doctors to give proper information of the comer diseases and can be cure without surgeries. It is also used in the DNA fingerprinting for the identification of individuals. Furthermore, it has also created techniques to deal with diseases associated with the genetics of human body The application of biotechnology are vastly present in the field of agriculture which is known as green biotechnology. With the help of genetically analysis of crops, its DNA is manipulated to produce fine quality of crop and help in various ways such as weed resistance, pest resistance and insect resistance. Biotechnology has also helped farmer and provided them more opportunities and facilities to work with nature, the modern biotechnology have created many medicine for the plants as the defense system is activated when they feel danger from any bacteria or insets. The field of biotechnology has been also used for the discoveries of various antibiotics, different vaccines and creation of artificial hormones. Biotechnology had to modern the field of fermentation as it has boasted the overall efficiency in the making of beverages and alcohol. It had been used to create explosive in World War 1. There are great amount of applications nowadays that are used with the help of chemical engineering thermodynamics in the field of biotechnology. One of the common application of such field the separation of specific protein and different types of viruses from various macromolecules in the bioreactors. For this liquid-liquid extraction is employed and it is discussed in later chapters of this book. Another application of this field with the usage of thermodynamics principles for the drug development of one of the fatal disease known as AIDS. In this application, the technique of Isothermal Titration Calorimetry is utilized through interpretation in various experimental results. Similarly, the separation of protein in bioreactor is also
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an application of this field in which a special salt is added to the reactor. n. To provide guidance for attaining the desired results, we require a pertinent phase diagram, i.e., a plot of temperature vs protein concentration (or its equivalent, protein density) designated by number density F. A common way to express protein density is provided by the protein packing fraction η = π/6 Fσp3 where σp is the protein diameter Furthermore, this chapter will discuss another terminology which is known as regular solutions and it is defined as a solution in which “the entropy of mixing is equal to that of an ideal solution with the same composition, but is non-ideal due to a nonzero enthalpy of mixing. Such a solution is formed by random mixing of components without strong specific interactions and its behavior diverges from that of an ideal solution only moderately.” Hence, the entropy of such mixtures are equal to that of the entropy of ideal solutions this is due to the interaction of specific components. Let us take two components, then mathematically it is given as: ∆S = -nR(x1lnx1 + x2lnx2)
where R is the gas constant, n the total number of moles and xi the mole fraction of each component. Only the enthalpy of mixing is non-zero, unlike for an ideal solution, while the volume of the solution equals the sum of volumes of components. However, the mathematical form of regular solution can also be expressed in the form of Raoult’s law with the help of Margules function having just one parameters α: P1 = x1P1*f1,M P2 = x2P2*f2,M
Using the Margules function, the equation becomes: f1,M = exp(αx22) f2,M = exp(αx12)
Notice that the Margules function for each component contains the mole fraction of the other component. It can also be shown using the GibbsDuhem relation that if the first Margules expression holds, then the other one must have the same shape. A regular solutions internal energy will vary during mixing or during process. On contrary in discussing the case of ideal solutions, regular solutions do possess a non-zero enthalpy of mixing, due to the W term. If the unlike interactions are more unfavorable than the like
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ones, we get competition between an entropy of mixing term that produces a minimum in the Gibbs free energy at x1= 0.5 and the enthalpy term that has a maximum there. At high temperatures the entropy wins and the system is fully miscible, but at lower temperatures the G curve will have two minima and a maximum in between. This results in phase separation. In general there will be a temperature where the three extremes coalesce and the system becomes fully miscible. This point is known as the upper critical solution temperature or the upper consulate temperature. In contrast to ideal solutions, the volumes in the case of regular solutions are no longer strictly additive but must be calculated from partial molar volumes that are a function of x1.
Since cataract development in the eye results from the communication of many various lens healthy proteins, a research study of multicomponent aqueous-protein services works for comprehending the specifications that affect stage splitting up. Liu et al. have thoroughly examined liquid twoprotein remedies to get the stage splitting up temperature levels as a feature of total healthy protein quantity portion as well as healthy protein structure. Go is direct in, as well as it is a procedure of the Gibbs power adjustment of the service when a solitary healthy protein particle is contributed to a pure solvent. The second term adheres to from the widely known CarnahanStarling formula; it stands for the worsening of blending for difficult rounds. The last term offers the mean-field estimate of the liquefied healthy protein fragments. The design displayed in Eq. 4.3 for binary options anticipates the crucial quantity portion as 13%, while the mean speculative quantity portion for the four binary mixes was 20.5%. Number 4.3 reveals the stage splitting up temperature level as a feature of the overall healthy protein quantity portion at various repaired make-ups for the liquid two-protein service having γIIIa as well as γIIIB crystallins existing a molecular-thermodynamic version for an liquid mix having greater than one healthy protein. Liu’s research of such ternary systems has revealed that an indigenous γs Crystallin might play a substantial function in preserving openness of the eye lens. Number 4.4 programs that the important phase-separation. As revealed by Benedek et al., the conjunction contour could be customized by a percentage of an additive that reduces the top essential remedy temperature level listed below body temperature level. By protecting against healthy protein gathering, it is feasible to stop development of cataracts. Enhancement of a medicinal representative that could decrease Tc listed below the body temperature
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level could decrease healthy protein gathering in the eye. In the important area (within 10°C of Tc), the conjunction contours could be fitted by the scaling relationship. To recognize communications in a binary protein-water combination Taratuta et al. provided a molecular thermodynamic perturbation design where the recommendation system is a setting up of tough rounds distributed in the continual liquid stage. The Gibbs complimentary power G for this system is offered by where V is the quantity of the service; Go is the common Gibbs cost-free power; ΩP is the quantity of a healthy protein particle; kB is Boltzmann’s consistent; T is outright temperature level; is the quantity portion of healthy protein; as well as U is a dimensionless criterion that evaluates liquid protein-protein, protein-water, as well as water-water communications. Condensation of healthy proteins leads to eye-lens turbidity that could be evaluated by gauging the strength of light spread by the lens. As revealed by Thurston et al., the strength of light spread (Iscatt) is offered by where Io is the strength of case light; t is the age of an individual; as well as ∆Z is a time continuous gotten from speculative information.
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REFERENCES 1. 2. 3. 4. 5.
6.
7. 8.
http://scienceworld.wolfram.com/chemistry/Fugacity.html http://siddharthdey.com/wp-content/uploads/2015/07/Ind.-Eng.Chem.-Res.-2011-Dey.pdf http://surfguppy.com/thermodynamics/thermodynamic-system-openclosed-isolated-systems/ http://www.chem.tamu.edu/class/fyp/stone/tutorialnotefiles/thermo/ gibbs.htm https://chem.libretexts.org/Core/Physical_and_Theoretical_ Chemistry/Physical_Properties_of_Matter/Solutions_and_Mixtures/ Ideal_Solutions https://chem.libretexts.org/Core/Physical_and_Theoretical_ Chemistry/Thermodynamics/Fundamentals_of_Thermodynamics/A_ System_and_Its_Surroundings https://www.geol.umd.edu/facilities/lmdr/fug.html h t t p s : / / w w w. s l i d e s h a r e . n e t / F y z a h B a s h i r / a p p l i c a t i o n s - o f biotechnology
CHAPTER
15
METHODS IN QUANTITATIVE CHEMICAL ANALYSIS The chapter will cover the basic principles of errors and statistics, calibration methods, general chemistry concepts, activity, and pH measurements, systematic treatment of equilibrium, acid-base basics, buffers, and electrochemistry. This chapter will discuss various quantitative analysis of chemistry and their utilization in various methods of science. So first we will analyze the terminology error and in terms of statics, it is defined as the deviation between the actual values to the true value. But the error in the chemistry can be different from the normal definition of error. It can be simply occurred due to inaccurate in the measurement of certain values of different instruments. By using this concept of error in the chemistry, various different resources of errors can be discussed which are as follows: Most of the errors that are occurred in the chemistry are due to mistakes of the person performing the experiment. There are different types of mistakes that can lead to various error in the experiment but the most common among them are misreading the values from the gauges, making mistakes in the calculation or it can be spilling of chemicals during their transfer from one place to other. The magnitude of degree of error is dependent upon the mistake and at the stage of where it was happened. In chemistry different experiment are result on the basis of estimation of measurement and hence it result in error in the end. For example, in a chemical lab, the person filling the beaker to a certain level of volume had to
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watch until the beaker is full to a marked value and unavoidably if the level of volume crosses the marked level, then such mistake of that person can be resulted in the error of the whole chemical experiment and such errors are named as measurement estimation errors and be resulted in further chemical change in a chemical reaction. Similarly, the lab chemist also consider the limitation of measuring devices as a source of error. Every measuring device possess certain level of inaccuracies, irrespective to its measuring ability. For example, the weight measuring instrument are labeled be the manufacturer with imprecision of 1 to 5%. So measuring with such instrument will always result in some type of error, also other instruments such as flask measuring devices also gives imprecision in range from 1 to 5% and are resulted in inaccurate in the measurements of device. Improper calibration of the measurement devices also results in producing errors in the measurement result of the experiment. Calibration is defined as checking or adjusting an instrument in such a way so that it can give error free results. Instruments with the passage of time, results in improper calibrations, which leads to errors in the output of the result. Such devices have to be checked otherwise they are also resulted in the sources of error in the whole experimental result. A calibration is a procedure made use of to contrast the assessment, determining, as well as examination tools to an identified referral criterion of well-known qualified precision as well as accuracy, keeping in mind the distinction and also readjusting the tool, where feasible, to concur with the requirement. Essential to an organized program of tool calibration and also routine recalibration is the suggestion that the tools are not continuous. Prolonged usage, wear, style, setting, and also time are several of the aspects that break down the tool efficiency and also its precision. A calibration system is made to ensure the confirmation, upkeep, as well as recognition of the tool’s preferred precision and also accuracy and precision. Choice of suitable evaluation, determining, as well as examination tools is an important component of assessment preparation, as well as success depends upon such elements as dimensions to be made and also precision demands. Consisted of are equipment products, such as tools, components, evaluates, and also themes, software program for computer-aided evaluations, and also procedure instrumentation. Likewise consisted of is all screening tools made use of in the growth, manufacture, installment, and also
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maintenance of an item. Discovering an across the country acknowledged resource to execute calibration is very important. The needs for the calibration research laboratories are covered in ISO/ IEC Overview 25 as well as consist of needs such as lawful identification impartiality, properties, tools, and also technological proficiency of workers, treatments, as well as self-assessment.
15.1. COMPONENTS OF A CALIBRATION PROGRAM A calibration program is made to preserve control over all the evaluation and also dimension systems. The aspects of the program consist of: • •
choice and also purchase of devices proper to the demand; recognition of devices (equipment, software program, and also treatments), precision, and also accuracy before very first usage; • ideal ecological problems for calibration, evaluation, screening, and also dimension; • traceability to a referral requirement of well-known precision as well as security; • precision proportion; • regularity of calibration; • handling, protecting, and also storage space; • remember system for regular upkeep, repair services, modifications, and also recalibration; • facility of treatments for regular recalibrations; • documents choice as well as procurement of ideal tools and also recognition of their precision and also accuracy become part of the assessment or high quality preparation choice. The staying components from above are the key elements of a calibration system.
15.2. TRACEABILITY Traceability includes the chain of dimensions as well as precision transfers that are made that attach the country’s criteria of dimensions, as preserved by the National Institute of Specifications and also Screening (NIST) with the dimensions made in research study, production, and also the market. It
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is essential to supply the proof that the chain exists which it is undamaged. It needs to offer proof that at each web link in the chain or transfer from the main recommendation requirements at NIST or various other additional criteria, factor to consider is offered to the dimension mistakes related to that specific transfer. This brings us to the principles of precision, accuracy as well as precision proportion.
15.3. PRECISION VERSUS ACCURACY These are necessary ideas in calibration. Precision is specified as an arrangement in between the gauged worth as well as truth worth. When this contract is within appropriate array, it is called within resistance. The accuracy, on the various other hand, is the nearness of numerous dimensions worths. Hence, a tool could be specific yet not precise.
15.4. PRECISION PROPORTION The precision proportion is the relationship in between the precision of the dimension requirement as well as the precision of the devices or tool being adjusted. In order to designate a mentioned precision to a specific quality of a gauging tool, it is required to have a tool with a “rather far better precision” with which to contrast. The more away you go from the main criterion in regards to the traceability chain, the even worse off you are mosting likely to remain in regards to precision. Depending upon the precision proportion in tool calibration, settlement could need to be offered in the recalibration. These techniques could consist of establishing resistance bands for precision, adjustment elements, analytical approaches, duplicated screening, as well as various other extra innovative methods.
15.5. REGULARITY OF CALIBRATION The following essential idea is the regularity of calibration or period in between recalibrations. A lot of recalibration programs are based upon some feature of time. Periods in between recalibration must be based upon such variables as the tool’s function, security of dimension (over various problems), monitoring of drift (sluggish variant gradually) and also the level of use. The period in between calibrations need to be reduced to guarantee ongoing necessary precision based upon the previous calibration background. It might be feasible to extend the period if historic calibration information
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suggests no destruction of the tool’s precision. A set period recalibration program for all determining tools is the easiest to carry out, yet it cannot acknowledge the distinctions in tool kind as well as application. A minor variant of a taken care of period recalibration program entails establishing recalibration periods based upon the tool kinds or teams. This approach acknowledges the distinctions in sorts of tools yet have no factor to consider for variants in applications or the distinctions in private tools within the team. An extra complex variation of the above approach is to readjust these periods periodically, based upon the evaluation as well as recalibration outcomes. One of the most advanced technique is the one that considers distinctions in between tool kinds, in between tools of the very same kind, as well as in between applications. It begins by developing a preliminary period for a kind or team of tools and afterwards changes the period of each tool separately accordinged to the evaluation of its very own recalibration background. The evaluation is reasonably easy and also includes figuring out whether the tool was “in” or “out” of precision resistances at the time of each recalibration. If the tool is still within calibration, you might boost the calibration period or vice versa, you need to reduce the period if the tool is discovered to be from calibration at the time of recalibration. The underlying presumption to this technique is that tools have an independently one-of-akind capability to stay within resistances for a particular duration, besides any kind of failures. Although it is practically one of the most advanced, budget-friendly, and also vibrant approach, its management intricacies need a high level of assistance from the automated information handling system to preserve the calibration background for each and every tool.
15.6. RECALL SOLUTION Recall systems need to be based upon twin triggers. The key elements contain establishing a stock as well as a listing of tools due for recalibration. In a tiny procedure, an easy by hand checked card documents could suffice for the objective. As the amount as well as selection of tools boosts, a digital spread sheet or a data source comes to be an outright need. The various other component of the recall system contains determining the calibration condition of the tools utilizing sticker labels, shade codes, tags, or various other appropriate methods to reveal identification, day of last calibration, as well as day of the following calibration due. This two-part method to tool recall for recalibration could ensure needed recalibration within defined periods as well as lower the opportunity of proceeded use the tool past its recalibration due day.
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15.7. PAPERWORK Documents offer proof of conformity with the program needs in instance of an interior or an exterior quality control audit. Along with the paperwork of the total program needs, one likewise should develop, file, as well as keep calibration treatments for all the tools covered by the program needs. This likewise consists of documents for the recall procedure and also previous calibration background for each and every tool for regularity of recalibration choices. Paperwork ought to additionally consist of the treatments and also preventative measures for taking care of, conservation, and also security of the tools to guarantee its precision as well as accuracy under differing ecological problems throughout storage space, transport, taking care of and also usage.
15.8. RECAP Proceeded usage, wear, atmosphere, and also time are a few of the aspects that weaken the tool efficiency that causes unfavorable result on the precision and also accuracy. A set up recalibration program is a crucial aspect of a dimension guarantee program. It is planned to establish just how well the determining tool procedures, records, as well as replicates the unpredictability (or enhanced self-confidence degree) in the dimensions. Control of evaluation, determining, as well as examination tools are essential components of the ISO-9000 Top quality Monitoring System criteria as well as qualification demands. There are various calibration are applied to correct the reading and output of the instruments to reduce the errors. Calibration of instruments is such a technique in which results obtained from instruments is compared with the substandard readings of a laboratory which is taken at several times to scale the instrument. The calibration reading and substandard readings are plotted against a graph and uncertainties are removed and if the instrument shows deviation from the standard value, it is again calibrated. For calibration, various methods are used which are named as Quantitation, Precision, Specificity, Accuracy, Range, Limits of Detection and Linearity. In specificity, values of calibrated and uncalibrated instrument are fed into graph with respect to time and adjustments are made accordingly and in case of Linearity, the values are place in a linear graph and deviations are checked in a way that how well it follows the calibration curve. In case of limits of detection and quantitation, the sensitivity of the instruments are
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checked, i.e., the lowest value and quantity that can be correctly taken from the instrument. Then, accuracy is another calibration method in which it is seen that how near is the reading taken from a faulty instrument to a true or standard reading and to check the precision of an instrument, it is check that how much the instrument can reproduce the true value from the different set of experiments. One of the important measurement of a chemical process in different industries such as pharmaceutical, chemical, etc. is the pH, which is defined as measurement of concentration of hydrogen ion concentration. The solutions having low pH value are called acidic solution whereas solution with high pH value are called base solution, in a scale from 0 to 14 in which 0 is the defined as strong acidic solution and 14 is strong base and 7 is neutral (water).
The pH of a solution is measure with the help of a paper known as “litmus paper,” this paper is dipped in the solution and changes color, the color is then matched and corresponding pH value is monitored accordingly. There are three classification a substance known as acid, base, and neutral. Many chemist and scientist have proposed different definitions from them such as chemists Johannes Nicolaus Brønsted and Thomas Martin Lowry proposed that an y substance that donated a proton (H+) ion is acid or this proton acceptor is a base whereas Arrhenius states that anything that forms hydrogen ions in aqueous solution is acid where hydroxide ion forming substance are base. Similarly, Lewis stated that any specie that accepts the electrons are the base where the substance that donate electron pair are termed as base. Lewis discredited the concept of acid-base in term of protons and proposed his definition in electron basis. This pair further establishes covalent bond.
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Buffer are such solutions that resist the change of pH when any of the component of acids or base are added into it and possess the ability to neutralize the solution whenever acid or base are added, thus it maintains the pH level stably. These solutions very important in different processes which require certain maintained level of pH is require. The buffer solution have certain range that how much the addition of acid-base it can bear and how much it amount can withstand. This chapter will discuss one of the most useful and important branch of chemistry known as electrochemistry, it is defined as “the branch of chemistry that studies the relationship between electricity and takes it as quantitative and measurable quantity and identifiable chemical change, with either electricity considered an outcome of a particular chemical change or vice-versa. These reactions involve electric charges moving between electrodes and an electrolyte (or ionic species in a solution). Thus electrochemistry deals with the interaction between electrical energy and chemical change.” Similarly when electric current is supplied to a chemical solution to perform the reaction and to obtain the desired result, such as in the case of electrolysis and when the electric current produce due to the result of spontaneous chemical reaction, these types of reactions are called as electrochemical reactions. Furthermore, a chemical reaction in which electrons are transferred or transmit from one atom to another molecule, such chemical reactions are called Redox reaction or oxidation-reduction chemical reaction. So we can say that this branch of chemistry explains different electrochemical reaction taking place as a result of Redox reactions and are also connection with some kind of electric circuitry as well as an intervening electrolyte. Now, we will discuss about the topic of Redox reactions in this chapter. As described earlier, the reduction and oxidation chemical reaction in electrochemistry change the oxidation state of an atom, ion or molecule that takes it part in the chemical reaction. The oxidation state is basically a hypothetical charge number that indicates which types of bonds an atom will have as well as how many of them it will possess. An atom or a molecule give an electron to other element in order to change its oxidation state and become stable. For example, when atomic sodium reacts with atomic chlorine, sodium donates one electron and attains an oxidation state of +1. Chlorine accepts the electron and its oxidation state is reduced to −1. The sign of the oxidation state (positive/negative) actually corresponds to the value of each ion’s electronic charge. The attraction of the differently charged sodium and chlorine ions is the reason they then form an ionic bond. Hence, the loss of electron from an atom is called oxidation
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whereas the gain of electron in the atom is called as reduction. Both of these terminologies always occur in paired form such as one specie gains electron whereas the other specie losses the electron, these electrons are shared between the atoms on the basis of electronegativity, but the case of oxygen is important to discuss here, For reactions involving oxygen, whenever oxidation of oxygen takes place in the chemical reaction, it is assumed that the oxygen atom or atoms are added to the respective chemical reaction. Similarly, in case of organic compounds, such as butane or ethanol, the loss of hydrogen implies oxidation of the molecule from which it is lost (and the hydrogen is reduced). This follows because the hydrogen donates its electron in covalent bonds with non-metals but it takes the electron along when it is lost. Conversely, loss of oxygen or gain of hydrogen implies reduction. Moreover the electrochemical reactions are balanced as well in the end of reaction to visualize the oxidation and reaction of atoms, to understand this phenomenon, water is the easiest example to understand the working of redox reaction using the ion-electron method where H+, OH− ion, H2O and electrons (to compensate the oxidation changes) are added to cell’s halfreactions (the electrochemical reactions that takes place inside an chemical cell for the generation of necessary current) for oxidation and reduction. In case of acidic medium, H+ ions and water are added to half-reactions to balance the overall reaction. For example, when manganese reacts with sodium bismuthate. Unbalanced reaction: Mn2+(aq) + NaBiO3(s) → Bi3+(aq) + MnO4−(aq) Oxidation: 4 H2O(l) + Mn2+(aq) → MnO4−(aq) + 8 H+(aq) + 5 e− Reduction: 2 e− + 6 H+(aq) + BiO3−(s) → Bi3+(aq) + 3 H2O(l)
Finally, the reaction is balanced by multiplying the number of electrons from the reduction half reaction to oxidation half reaction and vice versa and adding both half reactions, thus solving the equation. 8 H2O(l) + 2 Mn2+(aq) → 2 MnO4−(aq) + 16 H+(aq) + 10 e− 10 e− + 30 H+(aq) + 5 BiO3−(s) → 5 Bi3+(aq) + 15 H2O(l) Reaction balanced:
14 H+(aq) + 2 Mn2+(aq) + 5 NaBiO3(s) → 7 H2O(l) + 2 MnO4−(aq) + 5 Bi3+(aq) + 5 Na+(aq)
Similarly, in case of basic medium, in basic medium OH− ions and water are added to half reactions to balance the overall reaction. For example, on reaction between potassium permanganate and sodium sulfite.
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Unbalanced reaction: + KMnO4 + Na2SO3 H2O → MnO2 + Na2SO4 + KOH Reduction: 3 e− + 2 H2O + MnO4− → MnO2 + 4 OH− Oxidation: 2 OH− + SO32− → SO42− + H2O + 2 e−
The same procedure as followed on acid medium by multiplying electrons to opposite half reactions solve the equation thus balancing the overall reaction. 6 e− + 4 H2O + 2 MnO4− → 2 MnO2 + 8 OH− 6 OH− + 3 SO32− → 3 SO42− + 3 H2O + 6e− Equation balanced:
2 KMnO4 + 3 Na2SO3 + H2O → 2 MnO2 + 3 Na2SO4 + 2 KOH
However, there are neutral medium as well and same procedure is also applied on them. For example, on balancing using electron ion method to complete combustion of propane. Unbalanced reaction: C3H8 + O2 → CO2 + H2O Reduction: 4 H+ + O2 + 4 e− → 2 H2O
Oxidation: 6 H2O + C3H8 → 3 CO2 + 20 e− + 20 H+
As in acid and basic medium, electrons which were used to compensate oxidation changes are multiplied to opposite half reactions, thus solving the equation. 20 H+ + 5 O2 + 20 e− → 10 H2O
6 H2O + C3H8 → 3 CO2 + 20 e− + 20 H+ Equation balanced:
C3H8 + 5 O2 → 3 CO2 + 4 H2O
The electrochemical cell is one of the application of Redox reaction in which an electric current is produced due to the spontaneous reaction. This kind of cell includes the Galvanic cell or Voltaic cell, named after Luigi Galvani and Alessandro Volta.
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REFERENCES 1. 2. 3. 4.
5. 6. 7. 8.
http://www.brighthubengineering.com/hvac/50002-calibration-of-themeasuring-instruments/ http://www.labdepotinc.com/articles/pH-information-2.html https://bitesizebio.com/7642/types-of-statistical-errors-and-whatthey-mean/ https://chem.libretexts.org/Core/Physical_and_Theoretical_ Chemistry/Acids_and_Bases/Acid/Lewis_Concept_of_Acids_and_ Bases https://chem.libretexts.org/Core/Physical_and_Theoretical_ Chemistry/Acids_and_Bases/Acid https://sciencing.com/reasons-error-chemistry-experiment-8641378. html https://www.allaboutcircuits.com/textbook/direct-current/chpt-9/phmeasurement/ https://www.zurich.com.au/content/dam/risk_features/product_ liability/risk_topic_instrument_calibration.pdf
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CHEMICAL ENGINEERING DESIGN PRINCIPLES The chapter will introduce the readers to the principles of chemical process design with specific focus on synthesis, integration, and system level understanding. The chapter will cover the principles of the process conceptualization, process flow diagrams, and estimation of thermodynamic properties, thermodynamic feasibility, industrial chemical kinetics, chain reactions, reactor selections, heuristics, and reactor-separator integration strategies. In chemical engineering, design of a process includes all the steps required to get a desired product. Product design and process design are two different tasks but both may have some similar steps depending upon the product. The very basic approach to design a process is to analyze the problem and search for all the possible solutions then study the details in order to select the best solution with authentic reasons and logics, finally implement the selected method. Generic overview of a process can be shown as;
“Molecular Thermodynamics for Chemical Process Design,” By John M. Prausnitz. Thermodynamic properties are essential for quantitative process design to produce chemical products. Caloric properties are required for heat balances, but these properties are usually available or estimated easily. More
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important – and often much more difficult to estimate – are the chemical potentials of components in mixtures; it is these potentials which determine phase equilibria, as required for separation operations, and chemical equilibria, as required for chemical reactors and for separation operations based on chemical reactions. Molecular thermodynamics is an engineeringoriented science for calculating the desired chemical potentials from a minimum of experimental data. This applied science, based on classical and statistical thermodynamics, yields chemical potentials through models that are based on molecular physics and physical chemistry. Selected examples are cited to illustrate the applicability of molecular thermodynamics: groupcontribution methods for obtaining chemical potentials in highly non ideal mixtures as required for distillation-column and process-safety design; equation of state for precipitation of uniform-sized crystals from supercritical fluids; molecular-or-vital calculations to guide process development for alternatives to environmentally dangerous chlorofluorohydrocarbons; molecular-simulation calculations for separation of gas mixtures with porous adsorbents; equilibria in two-phase aqueous systems for separation of protein mixtures; and, finally, extended polymer-solution thermodynamics to guide synthesis of hydrogels suitable for protein recovery from soybeans and for novel drug-delivery devices.
16.1. INTRODUCTION One generation ago, the goal of chemical engineering was stated easily: to establish efficient and economic methods for producing on a large scale what the chemist or material scientist produces in small quantities. Today, that statement is incomplete. Today’s chemical engineer does not start where the chemist stops. Increasingly, chemists and chemical engineers work together on product conception and development. Twenty-five years ago, chemists and chemical engineers worked in series: first the chemist, then the chemical engineer. Today they must work in parallel. If the idea for a new product is to become a reality, then its early development must soon be linked to a process for its production. That process must be concerned not only with production capacity and product quality but, increasingly, with consideration for safety and for environmental protection. Chemical process design is based on several scientific disciplines, whose relative importance depends on the nature of the product. Only a few of these disciplines are always essential; they are the cornerstones of chemical
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engineering. One of these is chemical thermodynamics. This article presents some applications of chemical thermodynamics for chemical engineering. For process design, the first law of thermodynamics gives energy balances which require primarily caloric properties of materials; these properties are usually available from published experimental data or from semi empirical correlations one generation ago, scientist produced a new product on small scale and chemical engineers were responsible to produce the same product on industrial scale by keeping the factors of economics under consideration. But now they both work together and if there need to implement any new idea they do it after keen analysis which increases the production rate along with enhanced quality. During the production a design engineer face the different situations, for example, selection of suitable inputs and route for known output. Another situation is for known input the desirable output is required to find out, product with known properties needs to manufacture or optimization of the path is required to design. Whatever the situation is, a chemical process engineer needs to consider ‘product manufacturing’ along with all the necessary things like energy conservation, cost effectiveness, recycling, and disposal of waste materials.
16.2. CHEMICAL PROCESS SYNTHESIS Problem definition: which means that to study thoroughly about the required conditions and select the best possible solution. The simplest way to represent a process is its block diagram. Mostly flow diagram do not explain the details of chemical reactions, effect of reactions, etc. so ‘problem definition’ must include the all necessary details. If the product manufacturing is related to already existing techniques then the basics data will be available but for the implementation of new methodology basics data will be collected and analyzed by the process design engineer. It includes the Reconsideration of traditional processes, raw materials and assumptions. Finding out the alternative methods depending on the advanced research and development in order to be the part of competition. Optimization of superstructure by setting the new scales and parameters for the equipment as well as for the process reactions, Changing the whole criteria of performance, Interaction, and mixing all aspects of the process invention.
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16.3. PRINCIPLES OF THE PROCESS CONCEPTUALIZATION Chemical engineers use graphical representation to illustrate the schematic of any process. These technical diagrams include the block flow diagram (BFD), the process flow diagram (PFD), and the piping and instrumentation diagram (P&ID). As chemical processes include variety of reactive chemicals, toxic byproducts their reactions at high temperature and pressure so design flow diagrams must be formulated in appropriate way and chemical engineers must skilled enough to analyze and interpret diagrams equipped by others. Block Flow Diagrams. BFD is the very simple approach to describe a chemical process. The diagram contains different blocks having information about unit operations which are connected together by arrows or input, output streams. One of the types of flow diagram is ‘block flow process diagram’ which represents only one process. Another type is ‘block flow plant diagram’ which shows more than one chemical processes. Process Flow Diagram (PFD). PFD is the next step to BFD it contains the details of chemical process. Every industry has its own format for flow diagrams but give the same information. For example, description of the equipment and flow streams of the process will be identified by specifics numbers. Control strategy and utility streams to the equipment of the whole chemical process will be shown (Figures 16.1 and 16.2).
Figure 16.1: Symbols for Drawing Process Flow Diagrams. Bhattacharyya, D., et al (2012) Diagram for Understanding Chemical Processes. http://www.informit.com/articles/article.aspx?p=1915161&seqNum=2
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Figure 16.2: Conventions Used for Identifying Process Equipment. https:// www.slideserve.com/gisela/the-nature-of-process-design
Piping and Instrumentation Diagram (P&ID) or mechanical flow diagram (MFD), show information required to start the construction of plant which includes all the mechanical aspects of plant. The chemical reactors are used to enhance the performance of low level or less reactive performance of a reactor depends on four factors.
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Reaction Kinetics and Thermodynamics: Some variables like pressure, temperature, concentration effect the performance of a reactor, these are defined by kinetics and equilibrium of reaction. These extensive variables directly affect the rate and productivity of reaction by use of specific reactor. Catalyst are also used booster. Thermodynamics of reactions play an important role to define up to what extend the reactants will be converted in to product without conversion to catalysts. Reactor Parameters: For specific design problem with known kinetic properties, thermodynamics, and heat transfer configuration, the fixed reactor volume or inlet volumetric flow rate must give the desirable product. Production of Desired Product: For the desirable product, quantities of reactants are defined by parameters like conversion, selectivity, and yield. These are the functions of extensive variables (temperature, pressure space time, etc.) Heat Transfer in Reactor: As chemical reactions consume and release energy, the temperature highly effects the rate of chemical reaction. For equilibrium it is required to maintain the overall temperature of the reaction, for example, for exothermic reactions excess energy must be drained from the system and in endothermic process specific heat is required to keep the reaction in process. The overall rate of heat transfer depends on the reacting stream properties, medium of heat transfer, temperature maintaining forces and the configuration of reactor. Rate of chemical reaction is measure by the ‘reaction kinetics’. While designing a new reactor for any alteration in the process, reactor must be in the small volume for fast reactions. When we examine a prevailing reactor of fixed volume, a faster reaction shows the increased conversion. Whereas thermodynamic properties show the limitation to the conversion of reaction. Letri is the rate of reaction
The rate of reaction is an intensive property, depends on state variables such as temperature, concentration, and pressure, the rate of reaction not effect by total mass of material. In case of solid catalyst system, the performance of reactor is controlled by mass transfer resistances. Temperature significantly increase the rate of chemical reaction. Thermodynamics limits the obtainable conversion of chemical reaction. This effect can be observed in the following example
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Production of Methanol from syngas can be shown as CO + 2H2 = CH3OH
For stoichiometric input with no inert present, the equilibrium expression can be represented as
where X represents the equilibrium conversion, P shows the pressure in atmospheres, and T represents the temperature in Kelvin. If we make a plot at four different pressures (15 atm, 30 atm, 50 atm, and 100 atm) between equilibrium conversion and temperature. It will be clear that with an increase in temperature the equilibrium conversion decreases at constant pressure. As methanol formation reaction is exothermic in nature so according to Le Chatelier’s principle with increasing pressure at constant temperature the equilibrium conversion increases (Figure 16.3).
Figure 16.3: Temperature and Pressure effect on Conversion for Methanol from Syngas. https://www.researchgate.net/figure/Equilibria-in-methanol-synthesisApproximate-conditions-are-given-for-i-conventional_fig10_258733433
There are two chemical reactors called the ‘continuous stirred tank reactor’ and ‘plug flow reactor’. The plug flow reactor has a pipe in which reactants combine and the variation of pressure, temperature, and concentration takes place from point to point.
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The performance equation is
In the continuous stirred tank reactor (CSTR), all properties are considered to be uniform within the reactor and it is supposed to be well mixed. The performance equation is
where V shows reactor volume FAo represents the molar flow of limiting reactant A τ is the space time (reactor volume/inlet volumetric flowrate) CAo is the inlet concentration of A, XA represents the conversion of A, rA is the rate of reaction of A Heuristic rules that accelerate the choice and positioning of processing operations after the assembly of flowsheets. These rules are created after experience but should be simulated before implementation. •
•
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•
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In case of raw materials and stream reactions. Select those raw materials and chemical reactions which are favorable in handling and storage. Use the reactants in such quantities so that the first reactant completely consumes the seconds reactant so that it must not remain toxic or reactive further. In case of pure products, before the reaction operation the inert species must be eliminated so that the catalyst can remain safe from the effect of inert. Introduce the purgative streams in the form of liquid or vapors in order to remove impurities which generally produced as a result od by products or during the feed to the reaction. But valuable species must not remove during this process. In order to get high yields of the required products in series/ parallel reactions. Temperature pressure and catalyst must be adjusted during the initial distribution of chemicals. The liquid mixtures must be separated by distillation, stripping, liquid-liquid extraction, crystallization, and/or adsorption. The separation of vapor mixtures can be done by partial condensation, cryogenic distillation, absorption, adsorption, and membrane separation.
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To add or remove heat from the reaction, use the excess reactants, an inert diluent, and cold shots early in the synthesis process. These will affect the distribution of. For less exothermic reactions, external cooler having reactor fluid or cooling coils, as well as intercoolers can be used. For pumping and compression fan can be used to raise the gas pressure from atmospheric pressure to a high as 0.1 atm-g (1.47 psig). Blower or compressor can raise the gas pressure to as high as 2 atm-g (30 psig). To increase the pressure of a stream, pumping of liquid must be preferred than compression of gas, unless refrigeration is needed.
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REFERENCES 1. 2. 3.
http://users.metu.edu.tr/yuludag/che417/11_Heuristics.pdf https://www.d.umn.edu/~rdavis/courses/che3791/Green/notes/ ProcessSynthesis.pdf https://dredgarayalaherrera.files.wordpress.com/2015/08/analysissynthesis-and-design-of-chemical-processes3rd-ed.pdf
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MATERIAL SCIENCE AND MATERIAL SELECTION The chapter will cover the concepts of material balances chemical engineering profession, mathematical methods in biochemical and chemical engineering. The readers will be introduced to fluid mechanics for biochemical and chemical engineers. The chapter will further discuss heat transfer for biochemical and chemical engineers, mass transfer for biochemical and chemical engineers, rheology, and polymer processing, introduction to chemical engineering thermodynamic laboratory, chemical engineering transport laboratory, chemical kinetics and reaction engineering and chemical engineering kinetics and reactor design laboratory. The chapter will introduce the readers to the laboratory practices in chemical and biological processes. In chemical engineering the material balance or mass balance is the basic concept required to design any chemical process. For the implementation of safe and economical chemical processing plant it is compulsory to have knowledge about material balance. In a chemical process it is required to convert raw material into desirable product along which unwanted byproducts also generate which are sometimes hazardous. By using material balancing tool of chemical engineering the entering and leaving materials of the process can be controlled. Following are the types of material balance problems that generally arise in chemical processing: •
in the steady state continuous operations models of flowsheet material balance;
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•
in the non-steady state continuous or batch operations models of flowsheet material balances; • mixing and amalgamation material balances; and • analysis of the process data and its understanding. Problem formulation and its solution are the two strategies used for mass conservation in chemical processes. Formulation means the mathematical description of the process by using the laws of physics and chemistry. Mathematical model generally contain large number of complex equations so the formulation must be done in the way to be simulated easily without error. To deal with chemical process the knowledge of fluid mechanics, heat transfer, and mass transfer strategies must be known. Fluid mechanics deals with the mechanics of fluid and forces acting on fluids when it moves during the process. Chemical engineering is incomplete without fluid mechanics. Because a chemical engineer has to handle the chemicals during the whole process through pumps and piping. For example, in case of pneumatic conveying or condense gases through the pipes the variation of densities, temperature, and pressure must be controlled by using logical modeling techniques. Similarly in batch reactors during the mixing of chemicals agitators design always change the material properties. If we consider some other examples like heating and cooling in reactors, fluid like gas, liquid, or condensing steam involves and in case of separation processes (distillation, crystallization, and precipitates separation) again calculations for fluid involve. As discussed earlier in a chemical process raw material is transformed to useful product. During this process the heat and mass transferred in different modes. There are three modes of heat transfer. Although all occur at the same time but we consider each at a time for the sake of simplicity. First mode of heat transfer is condensation in which heat is transfer from one part of body to another part by using a medium in between that can be the same body as well. Second mode is convection in which heat is transferred from one fluid to another by mixing them together. In case of different densities of two fluids natural convection happens due to the temperature difference but in case of forced convection mechanical means are used to force the fluids to move. Third mode of heat transfer is by radiations in which heat transfer without any physical contact between two bodies but through waves in space.
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If the material has ability to change the phase during operation then provision is required for heat transfer to or from the system in order to give latent heat of the phase changing additionally for other effectible heat changes in the system. Heat can be transfer through any of the mode mentioned above but in case of phase change the heat transfer and mass transfer takes place simultaneously. In order to calculate the mass transfer in a chemical process, transport properties such as some empirical factors and diffusivities relates the rate of mass transfer to the driving forces in numerous different conditions and geometries. In case of confusion for the use of fundamental verses applied coefficients check for the fluid flow whether it is parallel to the interface along which mass has been transferred. Where as in case of diffusion in stagnant medium without transverse velocity gradient, normal diffusivities can be suitable for problem-solving. In both cases calculations must done through proper data instead of focusing on correlations. Units used in diffusivity correlations generally consider the CGS system. For mass transfer correlations used the CGS or English system. In both cases SI units are most commonly used. Fick’s First Law narrates flux of a component to its structure gradient, using diffusivity as constant of proportionality. It can be written in numerous forms, depending on the units and frame of reference. Polymer processing operations are categorized in two ways, “by process” or by the “type of unit building blocks.” By process is significance of the unit processes concept used in the literature of chemical engineering and in this situation, we observe the operations of specific polymers to classify from the types like extrusion, injection molding, blow molding compression molding, and so on. Classification of operations with “unit building blocks” is almost related to the unit operation concept. For example, pressurization and pumping of molten polymers, polymer filtration and heat transfer. In all these cases, the knowledge of transport modes and the rheological behavior is required. Rheology is the study of deformation and flow of liquid form of matters or soft solids under the condition that they show plastic flow due to applied force before approaching to elastic deformation. This field of physics covers the study of matters with complex microstructure, for example, mud, sludge, polymers suspensions, many foods and additives, etc.
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Rheology mostly deals with the behavior of non-Newtonian fluids. Which are defined as the fluids whose viscosity change with temperature and flow velocity or strain rate. For example, the Ketchup and emulsion paints change their viscosity with constant stirring. It is very important to consider the elasticity and viscosity of materials and the level of domination of these properties depend on force/stress applied to the material and to the duration of application of stress. Now the question is how these properties vary with the concept of state of matter (solids and liquids). In both cases these properties must be qualified. In our daily life we differentiate the materials in our home, in the laboratories or in the factories by their response on low stresses. Which is usually noticed by human beings or determine by gravitational field with in very short time spectrum. As the difficulties can and do arise while labeling the materials as solid or liquid so we use rheological apparatus in which we apply different values of stress for the wide range of time spectrum so that we become capable to fine solid like properties in liquids or liquid like properties in solids. It became helpful to distinguish the material state. But in some cases still we need to elaborate further more properties of material before labeling it. Chemical thermodynamics deals with the heat change during chemical reactions along with change in state of products within the laws thermodynamics. Chemical thermodynamics is not only about the measurements of thermodynamic properties in labs but it also deals with the mathematical models and equations related to chemical process which show the spontaneity of processes. For the designing of reactors modeling and chemical reaction engineering are needed. In any real problem first step is to identify the body of matter or reactants which can be called as system. Few microscopic properties define the thermodynamic state of the system. Labs having equipment related to some basics laws and thermodynamic applications, for example, boilers, Joule-Thomson apparatus, refrigeration unit and Boyle`s law apparatus allow students to experience practical implementation of chemical engineering and reaction engineering which includes the calculation of heat transfer, change of state during physical and chemical processes. In contrast with thermodynamics which deal with the direction of chemical processes there is a branch of physical chemistry called as chemical kinetics which deals with the study of rates of chemical reactions. In other words thermodynamics can be called as time’s arrow and chemical kinetics can be called as time’s clock. Kinetics is purely related to physical processes and chemical reactions in any of the fields like biology, geology,
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cosmology, and psychology, etc. kinetics of chemical reaction is important to study because it provide the information about the mechanism of reaction which become helpful to find the effective ways of causing the chemical reactions to occur. As many chemical processes can take place by using more than one method so reaction mechanism give the information about the conditions feasible for any particular method. The detailed study of chemical kinetics concluded that some chemical reactions are elementary and some are composite or complex. Rates of reaction also help to identify whether the reaction will take place by one or more steps and what conditions are required in each elementary process. For the study of reaction kinetics first of all it is important to study about the factors affecting the rate of chemical reaction, for example, concentrations of reactants, temperature, pressure, etc. in some cases rate of reaction depends on the concentration of reactants such reactions are called as second order reaction if there are two reactants A and B involved in it. The reaction rate v can be expressed as v = k[A][B], where k is the rate constant. In another case if the rate of reaction will proportional to the concentration of only reactant A then this reaction will be called as first order reaction so kinetics of reaction not correspond in a simple way to the balanced chemical reaction. Means there can be the possibility that a second order reaction will be second order in one direction while first order in the reverse case. When the rate of chemical reaction changes with temperature then rate equation is expressed as Arrhenius equation represented as k = A exp(–E/RT) where R is the molar gas constant, A and E are quantities that can vary depending on the reaction. According to this equation the plot for algorithm of rate constant and reciprocal of absolute temperature must be a straight line. By solving the slop of straight line and its intercepts the kinetic parameters A and E for this equation can be calculated Arrhenius relationship is helpful for many physical processes but still in some cases complications may occur which fail its application. If the reaction is elementary occurring I one step. In this case, if the quantity A is related to the frequency of collisions between the molecules and the activation energy E is zero then rate constant k will be equal to A which means that on each collision atoms combine with the frequency of collision. But for the reactions in which activation energy is not zero and chemical bond is broken. Here the Arrhenius explains it as, in many reactions rate increases by the increase in temp where the collision is not responsible of the increase in rate of reaction. Arrhenius explains that when two reactants A and B react together they form an activated complex also
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called as intermediate which afterward give the final product of reaction. If the intermediate will be of high energy it will be formed in small amount. According to Boltzmann principle the molecules with energy higher than activation energy is expressed as exp (–E/RT). So only those molecules can react which have energy greater than activation energy while all other collisions will be ineffective and the reactant molecules will separate without reaction. In natural, biological, and chemical processes momentum, heat, and mass transfer plays an important role. For the technical study of these processes laboratory courses such as “Unit Operations Laboratory,” “Process Control Laboratory,” and “Transport Laboratory.” are required. These courses and working in laboratories give students the hand on experience of dealing with chemical processes commonly used in manufacturing plants. For example, in Transport theory viscosity of a given sugar solution is measured in a constant water bath using a Cannon-Fenske viscometer. The kinematic viscosity thus obtained is converted to absolute viscosity. By reviewing Hagen-Poiseuille equation students can understand viscosity and makes it less abstractive concept.
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REFERENCES 1. 2. 3. 4. 5.
http://faculty.poly.edu/~rlevicky/Handout3.pdf http://www.physicsclassroom.com/class/thermalP/Lesson-1/Methodsof-Heat-Transfer https://www.britannica.com/science/chemical-kinetics https://www.crcpress.com/Mathematical-Methods-in-Chemical-andBiological-Engineering/Dutta/p/book/9781482210385 h t t p s : / / w w w . w i l e y . c o m / e n - a u / Biochemical+Methods-p-9783527302994
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CHEMICAL PROCESS ENGINEERING The chapter will cover topics in the principles of energy conversion, chemical reaction, engineering, process design, biochemical engineering, energy systems engineering, process modeling and control, and instrumentation and measurement in a chemical bioprocess laboratory. This will cover various aspects of different process that are used in chemical engineering, but first, we need to understand the basic principles of energy conversion, which is defined as it is the conversion of energy which is provided by the nature to converted in such a way that I can be used by mankind. The energy conversion had been used since centuries and it contain a wide variety of systems and devices. One of a fundamental law which is been used is known as law of conversion of energy which states that the total amount of energy of a system remains constant and it cannot be created or destroyed but can only be converted from one form to other. This statement is not a description for any process but it is stated regardless of the process and not only applied to the nature as a whole but also to the isolated or closed systems. Hence, if the boundaries of the system are defined in such a way that energy cannot be removed or added to the system then it is converted with the system. The different forms of energy include kinetic, thermal, gravitational, elastic, mass energy, electrical, chemical, and nuclear and radiant energy. Let us take the example of a ball toss in the air, the ball keeps traveling in the air but a point comes when it is stationary in the air and returns back to its initial position. When the ball given energy at its initial point 1 it possess kinetic energy which is given as 1/2mv12, and
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it slowly becomes zero to the highest point 2. As the ball rises in the air, it gains potential energy which is given has mgh1, but at the highest point 2 this potential energy becomes mgh2. By the law of conversation of energy and keeping the friction in the air negligible, then it mathematically it can be written as: EK1 + EP1 = EK2 + EP2
/2mv12 + mgh1 = 0 + mgh2
1
In this ideal example of energy conversion, the kinetic energy of the ball is converted into gravitational potential energy of the ball mg (h2 – h1), as the ball comes back to the ground, the potential energy is converted back into kinetic energy and the total energy of the ball at the point h1 is given as 1 /2mv12 + mgh1 so we can say that work done by the gravitational forces on the ball is zero, hence the system is said to be conservative one. Another important terminology in the chemical engineering is the process design, which is defined as the designing of the process to obtain the desired physical and chemical material after applying various different techniques on them. It is said to be the summit of chemical engineering in a way that it bring all the processes of this engineering all together. With the help of the process design, not only the existing process can be modified but also the new techniques can be establish to obtain the final product in an efficient way, thus reducing the raw material and increasing the output of an industry. The initial stage of a design process can be from conceptual level and ends in the form of construction plans and fabrication of the final product. Process design is closer to the designing of unit operation then the designing of the equipment. Before the discussion about chemicals and their reactions it is important to know about the chemical identity and its behavior when combined to other chemicals. The chemical reaction engineering involves the detailed study about the chemicals their rate of reaction and the CRE also deals with the factors affecting the chemical reaction kinetics, for example, environmental conditions and reactors or catalysts (homogeneous or heterogeneous). Sometimes the catalyst do not involves directly in the reaction but integrates with the process. The identity of chemical depends on type, quantity, and configuration of atoms and the reaction happens when a chemical loose its identity, for example, in decomposition, isomerization, combination, etc. Rate of a reaction is defined as the rate at which the chemicals loose its identity per unit volume per unit time. Let there is a reaction in chemical A
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is decomposed to form chemical B, the rB represents the rate of formation of specie B and –rA represents the rate of deformation of specie A. rB is the function of concentration, temperature, pressure, and type of catalyst and other reaction conditions. Reactor design is one of the most important aspect of CRE whose objective is to get maximum possible product in minimum time by using raw materials and by considering quality, quantity as well as safety of environment. The technologies used in this process can be thermodynamics, kinetics, and Stoichiometry. After having the knowledge of chemical engineering the main tasks that an engineer has to do are design a process, maintain, and operate the chemical processes, fix the prescribed problems and reduced the product cost. The fields in which the knowledge of chemical reaction engineering is required are petroleum refining, pharmaceuticals, petrochemicals, and chemicals manufacturing. This field also has scope in biotechnology, microelectronics, in energy preservation from non-fossil resources. Chemical engineers also work for pollution prevention and sustainable development of environment. Biochemical engineering is also known as bioprocess engineering and it is the branch of chemical engineering which deals with the designing and construction of different process which involves organisms such as molecules, atoms, and equipment such as bioreactors. Its applications are in the water treatment industries, food, pharmaceutical, petrochemical industry and biotechnology. Furthermore, the biochemical engineers have many duties such as converting the discoveries of life sciences into materials and techniques which can contribute to the health of mankind. Similarly, they play a lead role to eradicate diseases from the society by creating and producing vaccines for the diseases such as vaccination of AIDS, swine flu, HIV as well as with the creation of engineered tissues for the replacement of human body. Moreover, the biochemical engineers play vital role in obtaining energy from renewable resources, i.e., biofuels which not only reduces pollution from the environment but also create impact in creating similar resources of energy. The modeling and simulation of chemical processes is the key feature of chemical engineering. In which computer based software are used to design chemical processes, which can predict the dynamic behavior of process. The first step of modeling is to make the process flow diagram, which shows the system components and their connections. The perquisites for chemical process modeling are the knowledge of chemical properties of products used and the physical parameters of apparatus involved. Process simulation helps to implement the maximum range of conditions on products under
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consideration in order to know all the possible behaviors of product. It uses mathematical models for analysis, prediction, and testing irrespective to whether the reaction exists in actual or not. Modeling and simulation is now the part of almost every engineering field. It provides the following solutions, research, and development, decision making, training, and education, operation, process optimization, production planning and process design. Mathematical modeling and simulation is the important part of every research project because it reduces the experimental research. There are other steps also involved, for example, reactor design and catalyst selection and process condition as discussed above. Production planning is another important factor to consider because the profitability always remains the main task to achieve, which is obtained by optimal production and processes. Constant evaluation is required to maintain the profitably in case of change in conditions and products. Dynamic simulation evaluates the parameters, targets, and defined control strategies for the sake of controllability and safe environmental limitations. Initially it is used in the design process and then during the process to analyze optimized operation condition. The purpose of this process is to get the process tailbacks and there solution. Dynamic simulation involves the variable ‘time’ for solving the control problems which is not solved by steady state simulation. Modeling not only help to make the process efficient but also help to train the engineers for real world problems. Training of engineers and operators is very important due to advancement in technologies, different virtual training tools are available which produce the natural situation of the process in virtual environment. Training of existing scenarios and process set-up is has the huge influence on process safety and ability of operators to be able to handle unpredicted conditions. Dynamic model assist chemical engineers to continuously run the unit with defined optimized strategy, making the mathematical model by using the complete knowledge of the process and control algorithms also called Advanced Process Control (APC). This approach is giving engineers and operators the ability to nearly run the unit to approach the predefined economic benefits. Decision-making process is done through so many calculations, models, and simulations this approach is more efficient than the decisions built on assumptions. There is a proper strategy that can be followed to make the decision-making process less frustrating and challenging. In short there is almost no field of chemical engineering that can overlook the significance of the process simulation. It is the unavoidable part of chemical engineering and other engineering as well. Process
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simulation is like a guidebook for chemical engineer instructing them to the best engineering solution. The energy system engineering is such a type of engineering that supplies energy to the system in an efficient way. Therefore, it is such a discipline, which deals with the aspects of engineering as well as with economics. On conceptual level, the energy system engineering involves technologies, regulations with its implementation at practical level, for example, development of such grids which saves the energy and minimizes the losses. So, the energy system engineers oversees a complex energy distribution problems and find ways to improve them efficiently and make their contribution to protect the environment by saving the necessary amount of energy as well. The duties of energy system engineers can be from managing the working of wind turbines to efficient using the hydroelectric power production systems. Also, the development of fuel cells is the result of this field and provides effective means of production of other resources of energy systems as well. The energy sector provides marvelous opportunities for investigation, design of energy resourceful equipment and systems, advanced financing and project management, technology development and fundamental research. Engineers with hand on experience in laboratories and an understanding of energy systems is in demand in energy supply companies, energy consulting and financing companies, energy equipment manufacturers, energy-intensive manufacturing and process industries. The energy process engineering can make students capable to evaluate and improve conventional energy systems and design the sustainable energy systems of the future. There is significant scope for entrepreneurship and new start-up companies in this area. Recent advances in Nanoscience and Nano-technology have already resulted in potential applications for new materials in photovoltaics, hydrogen energy storage, improved batteries, super capacitors, fuel cells and provide several opportunities for technology and system development. For the measurement of different parameters in the laboratory level of a biochemical process, different instrumentation and measuring techniques are applied. The modern biochemical processes are monitored by online sensors technology either mounted externally or installed internally in the process such as sensor probes and more advance level of subsystems are employed to measure the state of biochemical process. These subsystem work in such a way that they can transmit signals that can be useful for calculations and feedback of closed loop systems. The different on-line sensing techniques give the corresponding values of different parameters such as to measure
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pressure of the system sensor such as piezoresistive can be used, it works in such a way that the greater the amount of pressure, greater will be the resistive and corresponding voltage will be lessen then further amplification techniques are applied to transmit the signal accordingly. It can be concluded from the brief description of chemical processes, the design process, modeling, and simulation processes that the chemical process engineering is very vast field the detailed knowledge of its all disciplines is very important as it is responsible for all the variety of materials that we have in our life.
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REFERENCES 1.
http://energyfromthorium.com/2006/05/29/principles-of-energyconversion/ 2. http://mime.oregonstate.edu/what-do-energy-systems-engineers-do 3. http://www.sciencedirect.com/science/book/9780080966595 4. http://www.simulatelive.com/simulate/steady-state/processsimulation-as-the-key-discipline-of-chemical-engineering 5. http://www.ucl.ac.uk/biochemeng/about/what-is 6. https://en.wikipedia.org/wiki/Biochemical_engineering 7. https://en.wikipedia.org/wiki/Conservation_of_energy 8. https://moodle.zhaw.ch/pluginfile.php/353962/mod_resource/ content/0/Wo39/Kurzvortraege/Lit2000Sonnleitner.pdf 9. https://www.britannica.com/technology/energy-conversion 10. https://www.researchgate.net/publication/301193635_Basic_ principles_of_energy_conversion 11. https://www.sciencedirect.com/science/journal/1369703X
CHAPTER
19
BIOPROCESS ENGINEERING The chapter will introduce the readers to the topics under bioprocess development as an interdisciplinary challenge, biochemistry 11 including plasmids and recombinant DNA techniques, applications of chemical engineering principles in biotechnology (energy balances, and maintenance of fermentation temperature, heating, and cooling, and sterilization). The chapter will further cover the applications of chemical engineering principles to biotechnology (role of diffusion in bioprocessing). The chapter will cover applications of chemical engineering principles to biotechnology through discussing the topics such as downstream processing, cell disruption, filtration, centrifugation, liquid-liquid extraction, adsorption and chromatography in biotechnology. The chapter will introduce readers to the regulatory compliance through a discussion of regulations and their guidelines. Bioprocess is such a type of the process that uses cells or their components such as enzymes or bacteria to obtain the desired product. For a bioprocess, the transportation of energy and mass are the fundamentals of different bioprocess from converting energy to transportation of different biological mediums. Cell therapy bioprocessing is an important term that needs to be discussed so it is defined as it is such a discipline that combines the field of cell processing with bioprocessing and this field has been derived from bioprocess engineering. The main goal of a cell therapy bioprocess is too robust and reproduces such manufacturing process that can produce therapeutic cells. For example, such technique is being used in to produce
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biopharmaceutical drugs and to maintain their standards, to minimize the cost of goods in the final production of drugs. Furthermore, this chapter will learn development in biochemistry and with the introduction of two techniques named as Plasmids and recombinant DNA. Plasmids are such small DNA biological molecule that is separated from DNA and possess the tendency to replicate itself. Due to their double stranded structure, they are mostly found in bacteria but they are also sometime present in eukaryotic and archaea organisms. Plasmids also help in survival since they carry genes such as antibiotic resistance. Moreover, different bioinformatics software are used for recording the DNA sequence and their manipulation plans. The examples of such software are Gene ConstructionKit, Genome Compiler, LabGenius, Geneious, and Lasergene. In recombinant DNA technology, DNA molecules from two different species are combine which are further inserted into an organism to produce such a genetic combinations that are beneficial to science in terms of industry, agriculture, and medicine. The main goal of this technology is to characterize and manipulate new genes. Finding a specific gene from a DNA is much more difficult than separating a DNA from the collection of cells. This technology has helped the mankind in separating a gene or any specific sample of DNA, which helped the researcher and scientist in many ways such as taking the nucleotide, to experiments its transcript, its further mutation in efficient way and then again inserting the corrected sequence in the living organisms. For the mixing of different type of fluids, mass transfer also take place and for large scale mixing, bulk fluid motion causes such mixing that is why diffusion is very important in bioprocess. Similarly, due to the turbulence in the fluids, the fluid mixing on bulk scale takes place. Moreover, mixing in the molecular scale is accomplished due to diffusion. The diffusion is also used when catalyst are used in solid forms which diffusion is responsible in removing the product molecules away from the site of reaction as discussed in previous chapters, when the reaction took place with diffusion, the overall reaction rate can be slowed down if the process of diffusion is slowed. The study of Chemical engineering and biotechnology provides the extensive elementary skills in chemistry and other disciplines. This study provides broad vision to the industrial processes that are in use. The higher studies in chemical engineering and biotechnology give access to modern apparatus and professional experience in industries and field,
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which develops the managerial and business skills. The greatest scientific revolutions today in chemical engineering and biotechnology are the introduction of nanotechnology, enables the automatic control of reactions at the molecular level, which presents advanced opportunities for new products. Major challenges ahead are to discover environment friendly renewable energy sources. The study of chemistry along with biotech make the student capable to develop these Many people believe that solar cells will solve future energy problems. But the detailed study of in chemical engineering and biotechnology also delivers a basis for developing and adopting new environmental technology, including membrane technology that can constitute a part of CO2-free gas power plants. Today, major development is made within the field of biotechnology. Such as genetic research, cancer research and development of new medicine. Biotechnology involves all from food, natural gas, use of DNA tests, to the preparing of beer and wine. Along with current research efforts for new knowledge, great challenges will emerge in years to come as we attempt to make practical use of this knowledge. For this we need new biotechnologists with interest and critical sense. Biotechnology is defined as the technology to manipulate any biological system or living system for the improvement of products for various purposes. It is widely employed in different fields of life such as agriculture, medicines, and even in genetics. The ideology of traditional biotechnology has changed a lot and there is a line of division between the traditional and the modern view of biotechnology. This difference was defined by European Federation of Biotechnology (EFB) as follows: ‘The integration of natural science and organisms, cells, parts thereof, and molecular analogs for products and services’. The principle of genetic engineering is to modify the existing organisms by changing the genetic material in them. It mainly includes the recombinant DNA technology. Recombinant DNA technology is a technique which changes the phenotype of an organism (host) when a genetically altered vector is introduced and integrated into the genome of the organism. Inserting the desired gene into the genome of the host is not as easy as it sounds. It involves the selection of the desired gene for administration into the host followed by a selection of the perfect vector with which the gene has to be integrated and recombinant DNA formed. This recombinant DNA then has to be introduced into the host. And at last, it has to be maintained in the host and carried forward to the offspring’s.
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The downstream part of a bioprocess constitutes of improving the purity and quality of the cell mass taken from upstream part of the process. Furthermore, the downstream process is divided into three parts named as cell disruption, purification, and polishing. The steps involve in the downstream process consist of following parts, the step is the separation of biomass which is performed by centrifugation. Another alternative for the separation process is ultra-filtration. The next step is cell disruption, in which product is released from the cellular biomass and concentration of broth is performed by concentrating the medium if the product is extracellular. And the water content is eliminated if the amount of product is lower than the concentrated medium then volume of water is removed to increase the concentration of the product and it can be done by reverse osmosis or vacuum drying. In the final step of down streaming, the product is almost 100% pure. The final product is then mixed with other ingredients which is called excipients. The purified product is then packed and send to the market for the consumer. Another separation technique very often employed in bioprocess is known as liquid-liquid extraction which solvents are extracted on the basis of their solubilities in two different liquids. There is transfer of species from one liquid which is aqueous and to the other liquid which is polar solvent due to their chemical potential. The liquid-liquid extraction is abbreviated as LLE and it is used in the making of various organic compounds such as making of perfumes, production of biodiesel and vegetable oil is also examples of LLE. Since, it is one of the initial solvent extraction techniques, but such techniques are not useful when extracting the solvent from same functional groups. The success of LLE is measured in two terms knowns as decontamination and separation factor where the separation factor is such a factor which determines the ability of a mixture to separate further two solutes, also the contamination factor is the such a factor which determines how much amount of contaminates can be separated from the product. The LLE is used in many commercial applications such as DNA purification, the DNA is extracted to study in many modern bioprocesses and it is also used in food industry for separating the smaller molecules such as nucleic acids and peptides. However, the successful percentage of the LLE is determine by decontamination factors and separation factors, the most efficient way to find the success of LLE is to check the extraction column from the given data set. The data set can then be converted into a curve to determine the steady state partitioning behavior of the solute between the two phases. The y-axis is the concentration of solute in the extract (solvent) phase, and the x-axis is the concentration of the solute in the raffinate phase. From
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here, one can determine steps for optimization of the process. There are huge number of techniques in which the LLE can be perform which are as follows: Batch wise single stage extraction is the most commonly used in chemical and bio labs due to their easiness and abrupt results. The whole process includes the data from DLLME and direct organic extraction. In case of Dispersive Liquid-Liquid micro extraction (DLLME), small samples of water compounds are extracted from organic matter. This process is done by injecting small amounts of an appropriate extraction solvent (C2Cl4) and a disperser solvent (acetone) into the aqueous solution. The resulting solution is then centrifuged to separate the organic and aqueous layers. This process is useful in extraction organic compounds such as an organochloride and organophosphorus pesticides, as well as substituted benzene compounds from water samples. Similarly, direct organic extraction is also part of batch wise single stage extraction, it is done by mixing the organic solute in the organic solvent and can be extracted by separation funnel. This process is valuable in the extraction of proteins and specifically phosphoprotein and phosphopeptide phosphatases, the example of this application is extracting anisole from a mixture of water and 5% acetic acid using ether, then the anisole will enter the organic phase. The two phases would then be separated. The acetic acid can then be scrubbed (removed) from the organic phase by shaking the organic extract with sodium bicarbonate. The acetic acid reacts with the sodium bicarbonate to form sodium acetate, carbon dioxide, and water. Furthermore, LLE also possess multi stage extraction, in this technique, used by mostly industries, it is mostly used for metal, i.e., lanthanides because the separation factors between the lanthanides are so small many extraction stages are needed. In the multistage processes, the aqueous raffinate from one extraction unit is fed to the next unit as the aqueous feed, while the organic phase is moved in the opposite direction. Hence, in this way, even if the separation between two metals in each stage is small, the overall system can have a higher decontamination factor. The last technique of LLE is known as extraction without chemical changes and it is mostly used by noble gases. This is the simplest type of solvent extraction. When a solvent is extracted, two immiscible liquids are shaken together. The more polar solutes dissolve preferentially in the more polar solvent, and the less polar solutes in the less polar solvent. Some solutes that do not at first sight appear to undergo a reaction during the extraction process do not have distribution ratio that is independent of concentration. A classic example is the extraction of carboxylic acids (HA) into nonpolar media such as benzene. Here, it is often the case that the carboxylic acid will
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form a dimer in the organic layer so the distribution ratio will change as a function of the acid concentration (measured in either phase). For this case, the extraction constant k is described by k = [[HAorganic]]2/ [[HAaqueous].
In the making of biological products, cellular disruption is an essential step, which involve in downstream process. The cellular disruption is for the extraction as well as retrieval of the final product so it cannot be considered an isolated process as it effect the properties of cell slurry and further influence the downstream process. There are many types of cellular extraction methods as the biological products can be of variety of forms such as intracellular, periplasmic or extracellular. The basic methods of cellular disruption are composed of two types: mechanical and non-mechanical methods. The mechanical methods are consists of liquid shear and solid shear methods whereas for non-mechanical methods include enzymatic, physical & chemical methods. But before cellular disruption, cells are separated and extracted from culture medium. The mechanical methods are bead mill, ultrasound, and non-mechanical physical methods are thermolysis decompression, etc.
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REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9.
http://biotechisfuture.weebly.com/uploads/1/4/1/6/14160671/unit_ iibpeii.pdf https://byjus.com/biology/biotechnology-principles/ https://chem.libretexts.org/Demonstrations_and_Experiments/Basic_ Lab_Techniques/Liquid-Liquid_Extraction https://en.wikipedia.org/wiki/Bioprocess https://en.wikipedia.org/wiki/Bioprocess https://en.wikipedia.org/wiki/Liquid%E2%80%93liquid_extraction https://en.wikipedia.org/wiki/Recombinant_DNA https://www.britannica.com/science/recombinant-DNA-technology https://www.sciencedirect.com/topics/agricultural-and-biologicalsciences/liquidliquid-extraction
CHAPTER
20
ENVIRONMENTAL CHEMISTRY AND REMEDIATION The chapter will introduce the readers to the chemistry of air, water, and soil with a specific focus on the health effects of human-made chemical products and environmental by-products. The topics covered will include an introduction to environmental problems, sustainability, and green chemistry, stratospheric chemistry and the ozone layer, ozone holes, chemistry of ground-level air pollution, environmental, and health consequences of polluted air. The chapter will include the topics of the greenhouse effect, energy use, fossil fuels, global climate change and the health effects. The topics of biofuels and alternative fuels, the chemistry of natural waters, pollution, and purification of water, pesticides, dioxins, furans toxic heavy metals, and PCBs, and wastes, solids, and sediments will be included. This chapter will give the knowledge the readers about chemical by product and their beneficial and adverse side effects. Everything is made up of chemical substance, the chemical substance can be made from manmade or it can be extracted from the nature which have given prosperity to the mankind but some of the chemical by-product have greatly affected mankind and environment of the earth. As, not all the chemical substance are dangerous but still they can be proof poisonous if they are handled incorrectly. Almost, everything leaves behind chemical waste. Household create garbage where the industrial waste if not properly treated can threaten the life of human as well as animals and sea species. Chemistry is the study of the science of matter and matter is anything that has mass and occupies space. Environmental chemistry and green chemistry are involving the study
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of matter. Wrong matter in wrong places can cause serious pollution and this has a major significant influence upon the earth and its support system. Humans have an attitude of extracting minerals from the earth thereby, causing environmental problems. The challenge mankind faces today in the environment is sustainability, the ability to maintain and enhance condition that will enable humans and other organisms to live on planet earth. This has resulted in survival actions and that of their descendants. The role of chemistry cannot be overemphasized as we eat, are surrounded by and made up of chemicals. All these are true because chemistry is the science of matter. It is all a combination of the air we breathe, the water we drink, the soil that grows our food, vital life substances and processes. In a holistic view, environmental chemistry is the study of origins, transport, reactions, effects, and fates of chemical species in the water, air, earth, and living environment and the activities of humans.
20.1. GREEN CHEMISTRY In the earlier stage of development, the emphasis of environmental chemistry was detection of pollution, sorting it adverse effects, and having pollutants controlled once produced (Figure 20.1).
Figure 20.1. Illustration of the Definition of Green Chemistry.
The practice of green chemistry is in the framework of industrial ecology, as a comprehensive approach to production, distribution, utilization, and termination of goods and services in a manner that maximizes the mutual benefit of utilizing of materials and energy while preventing the production of waste.
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A chemical product can be a single chemical substance or it can be a mixture, i.e., acetone and petrol. Most of the material nowadays are being made with the help of chemical by-product which is replacing the natural product, these new chemical by-product gives the material some extra properties such as artificial cotton can be fire resistant as well. With the passage of time, the production of chemical byproduct has been increased in a huge rate and in their production, different amount of chemical are emitted in the form of gases in the air or hazardous chemical waste in sea and ocean and contain risk to the mankind and the environment. Some chemical substances and their byproduct do not decompose but they accumulate in the body of animals and human beings. The recent research shows almost 300 different chemical substances in the blood samples of human, which can create different side effects to the hormones and can damage the nervous system. The young people and children can be greatly affected by them as their brain is not fully developed and can have lifelong consequences in their later life. The chemical byproduct can be toxic which means that they could cause corrosive injuries in the outer surface of human body. Some of the chemical substance are non-renewable this means that they cannot be reused and has to be extracted or mined, for example, the nuclear power plant need continuous supply of uranium to run its operation and produces radioactive waste which has to be disposed of an proper manner as such kind of waste emits radioactive radiations and lasts for hundreds or thousands of year. The chemical byproduct greatly effects the reproduction system of humans as they effect the production of eggs and sperms. Our motherland earth is currently facing a lot of environment concerns and with the time passing on, they are increasing day-by-day and effect each human and animal species. Since our environment is changing at a great pace so we need to understand the problems that are happening around us. The patterns of weathers are changing, the natural disasters are also increasing and the periods of heating and cooling are effect in consequences. Major environment are global warming, acid rain, air pollution, urban sprawl, waste disposal, ozone layer depletion, water pollution, climate change and the list goes on. The pollution of soil and water can take great time to recover and the major cause of this problem are industries and automobiles. Another major concern to the mankind is clean water which is now a source of earning and political concern. The toxic waste from industries and agriculture is affecting the drinking water for all the species on earth. Climate change is
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another major environmental concern and which is changing rapidly with past couple of years and as a result, it is changing the weather patterns of the world. The increasing amount of industrial waste and carbon content in the water causing is making the marine life in danger due to which some of their species is in very less amount. The acid rains happen due to the presence of specific type of toxins in the atmosphere. The huge amount of Sulphur and nitrogen oxide comes back to earth as a result of rain. Similarly, a protecting layer from the ultraviolent radiations from the sun is known as ozone layer and the depletion of this layer is caused by Chloroflorocarbons (CFC’s). As these poisonous gases reach the upper atmosphere of the earth, the create depletion by reacting with the ozone and the depletion of the layer result in the form of ozone holes. Noise pollution is another form of pollution that is caused due to excessive amount of unpleasant noise. There are many reasons for it such as construction activities, the increased amount of vehicles in traffic and poor urban planning are among the major causes of this problem. Biofuels are nonconventional and alternative fuels available to us. These alternative fuels are not produce from conventional fuels such as petrol or diesel. The main purpose of these fuels is to capture energy that can be utilized in some other time. An example of biofuel is biodiesel that is produced from which is a renewable fuel and manufactured from vegetable oil, grease, and animal fats. The physical properties of biodiesel are similar to conventional fuels and are cleaner burning fuels. The other alternative types of fuels are renewable energy resources. This type of energy sources is not only efficient but also environment friendly. The examples of such resources are solar energy, tidal, and wind energy. Another non-conventional type of fuel is hydrogen. There are many techniques developed that extract the energy of hydrogen from a chemical reaction but only problem with this type of fuel is that there is no storing of hydrogen yet made. Similarly, air engine is another alternative type of fuel which used air engine and utilize compress air as a fuel. The compressed air is much cheaper than all the other alternative fuels and the economy production of such fuel is much more easy and effective in comparison with conventional fuels of our planet. There is need to change our daily life to save the environment and government should also take steps in the awareness of public regarding the environment. Water pollution can be a physical, biological or chemical factor which affects the aquatic life and those who consume water. Chemical energy describes the saved energy inside chemical bonds, as well as it is launched using exothermic responses. When a response takes place in burning procedures, there is possibility that
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the quantity of energy being launched will certainly differ, considering that it would certainly rely on the chemical bond’s nature.
20.2. BENEFITS OF CHEMICAL ENERGY •
•
•
•
It is a abundance source of energy. Mostly all resources of chemical energy, such as petroleum, timber, natural products like wax and coal, could be located all over the world, and human beings are extremely based on these energy resources. When rates of these energy resources change, this is the reason that globally economic situations are being impacted. Among one of the most usual and large chemical energy resources readily available nowadays is petroleum, which is removed from underlying sedimentary layers of our earth’s crust. It is created from the procedure of chemical conversion that takes place in the fossilized remains of dead plants and pets under terrific stress put in by the Planet’s layer. Inning accordance with data, individuals in lots of nations have an extremely high reliance on petroleum that the condition of all worldwide economic climates is impacted straight by its rate variations. It generates high octane gases that offer a considerable quantity of energy. The energy crammed in by high-octane gases that are acquired by improving petroleum is considerably high in contrast to various other energy resources, making it feasible for automobiles, vehicles, and various other lorries achievement broadband. The energy that is launched by chemical energy via combustion-induced bond damage in gas is enormous, as well as it is among the greatest contributing variables to its appeal as a gas resource. It will certainly ignite quickly. As compared with various other resources of energy, chemical energy creates gases that are merely flammable as well as can breaking down immediate energy. Put simply, instantaneous energy could be created because of the simple combustibility of chemical energy. It will certainly ignite effectively. The performance of burning very depends upon the accessibility of oxygen. If a system is developed well, as an example an automobile engine, effective burning could be attained. With chemical energy resources, the effectiveness of burning is certainly high. This is one exceptional
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•
•
reason that the chemical energy, which is launched with petroleum burning, is extremely liked over other source of energy. The burning’s performance hinges on the oxygen’s accessibility, therefore, the system of a car engine holds a massive influence on the effectiveness of traveling when driving and even airborne. It is the simplest and most effective energy resource to shop and also use. Chemical energy is so easily offered and is discovered in virtually whatever we utilize. Also made use of by our bodies, it has been the resource of life for billions of years, as well as the growths in chemical energy modern technology have caused durable rechargeable batteries. It is likewise really hoped that it will certainly be utilized in generating renewable resource sources in the future. To dig further right into this element, it is significant that chemical energy is a kind of prospective power that relates to the architectural setup of atoms or particles. This setup could be the outcome of bonding chemicals within a particle or otherwise. The energy of a chemical material could be changed to various other kinds of energy via chain reaction. When a gas is shed, the chemical energy is transformed to warm, which resembles food digestion of food metabolized in an organic microorganism. Ecofriendly plants could likewise change power from the sunlight to chemical energy with the procedure referred to as photosynthesis. Electric energy could likewise be transformed to chemical energy with electrochemical response procedures. It plays a crucial duty in culture as well as in some way the atmosphere. Chemical energy is useful to culture through energy cells. Batteries function by utilizing numerous chemicals that engage with each various other, developing electric power. The sort of battery that is extensively utilized around the globe is the zinc-copper cell, which utilizes the chemicals zinc as well as copper, where the previous is being assigned the adverse side and the last being marked the silver lining. By linking a cord to both ends, the acid inside the battery is delighted and will certainly damage down several of the zinc. The electrons from this component are after that complimentary to follow the cable to the copper side, where electric circuits are carried out then permitted to move right into the gadget that the battery is powering up. Various other necessary procedures that include chemical power are photosynthesis, food production and, once more, gas burning.
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Chemical energy plays a vital duty in each of our day-to-day lives, and it would certainly be difficult to overlook the benefits we could delight in from it. We will certainly learn how to value its relevance and will certainly discover means to add to its preservation. Currently, we assess its downsides.
20.3. NEGATIVE ASPECTS OF CHEMICAL ENERGY •
•
•
It could be hazardous to the atmosphere. Prior to the resources are exchanged beneficial energy, burning is needed as well as this could create damaging spin-offs which could add to contamination. Considering that chemical energy is stemmed from natural products, there is a high danger that the setting will certainly be significantly impacted by it, especially due to way too much burning that is needed for its manufacturing. We as customers could do our component in managing such results. Federal governments could develop some plans over the appropriate use chemical energy to minimize carbon impacts. Exclusive establishments within this sector could carry out some brand-new innovations to manage such a disadvantage. It includes a high price. The manufacturing of atomic energy, specifically, requires a great deal of loan to establish and spend up nuclear power terminals. It is necessary to bear in mind that it is not constantly feasible by numerous establishing nations to manage such a pricey resource of energy. It could create contaminated waste. The waste generated by activators should be gotten rid of appropriately to a safe and secure location, considering that it is incredibly dangerous as well as could leakage radiations otherwise saved correctly. The radiations released by this type of waste could last to 10s and even centuries. Hazardous wastes consist of radioisotopes with lengthy half-lives, which implies that they remain in the environment in some type or the various other. These responsive radicals could make sand or water polluted, which is called combined waste that could create unsafe chain reaction and could result in unsafe difficulties. To take care of such waste, plants would generally hide it under sand in a procedure called vitrification. An additional
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•
•
threat this approach brings is that the waste could be utilized to earn nuclear tools. This idea alone could make individuals closeby worried of exactly what the compound could influence their lives. It is non-renewable. Many resources of chemical energy could not be restored. Taking the instance of atomic energy again, some plants make use of uranium, which is a limited source and is not discovered in numerous nations. Several countries depend on various other areas for the consistent supply of this gas. It is bad for human health and wellness. Thinking about that chemical energy is extremely flammable, it is anticipated to add to contamination, which triggers different health problems as well as is never ever helpful for human wellness. Worldwide warming has gotten worse in recent times as a result of hefty air pollution in the various components of the globe, as well as with alternate power resources, its impacts could be regulated as well as minimized. Chemical power describes the saved power inside chemical bonds, as well as it is launched through exothermic responses. When a response occurs in burning procedures, there is likelihood that the quantity of power being launched will certainly differ, given that it would certainly depend upon the chemical bond’s nature.
20.4. LISTING OF BENEFITS OF CHEMICAL ENERGY •
It is a mother lode of energy. Mostly all resources of chemical energy, such as petroleum, timber, natural products like wax as well as coal, could be discovered around the globe, as well as people are extremely based on these power resources. When costs of these power resources change, this is the reason that around the world economic climates are being impacted. Among one of the most usual as well as large chemical power resources readily available nowadays is petroleum, which is removed from underlying sedimentary layers of our earth’s crust. It is created from the procedure of chemical conversion that takes place in the fossilized remains of dead plants and also pets under excellent stress put in by the Planet’s layer. Inning accordance with stats, individuals in several nations have a really high dependence
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•
•
•
•
189
on petroleum that the standing of all international economic situations is impacted straight by its cost variations. It generates high octane gases that offer a significant quantity of energy. The power crammed in by high-octane gases that are acquired by improving petroleum is considerably high in contrast to various other energy resources, making it feasible for autos, vehicles as well as various other automobiles achievement broadband. The energy that is launched by chemical energy with combustion-induced bond damage in gas is tremendous, as well as it is among the largest contributing elements to its appeal as a gas resource. It will certainly ignite conveniently. As compared with various other resources of power, chemical energy generates gases that are merely flammable and also can providing immediate energy. Basically, immediate power could be created because of the simple combustibility of chemical energy. It will certainly ignite effectively. The effectiveness of burning very relies on the schedule of oxygen. If a system is developed well, as an example an automobile engine, effective burning could be accomplished. With chemical energy resources, the effectiveness of burning is certainly high. This is one outstanding reason that the chemical power, which is launched with petroleum burning, is extremely liked over other source of power. The burning’s performance hinges on the oxygen’s accessibility, therefore, the system of an automobile engine holds a massive influence on the performance of traveling when driving and even airborne. It is the most convenient as well as most reliable power resource to shop as well as make use of. Chemical energy is so easily offered as well as is discovered in virtually every little thing we make use of. Also utilized by our bodies, it has actually been the resource of life for billions of years, and also the advancements in chemical power innovation have actually caused durable rechargeable batteries. It is likewise wished that it will certainly be made use of in creating renewable resource sources in the future. To dig much deeper right into this element, it is significant that chemical power is a kind of prospective power that relates to the architectural plan of atoms or particles. This setup could be the outcome of bonding chemicals within a particle or otherwise. The
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•
power of a chemical compound could be changed to various other kinds of power with chain reaction. When a gas is melted, the chemical power is transformed to warm, which resembles food digestion of food metabolized in an organic microorganism. Ecofriendly plants could likewise change power from the sunlight to chemical power with the procedure called photosynthesis. Electric energy power could likewise be transformed to chemical power via electrochemical response procedures. It plays an essential function in culture and also in some way the setting. Chemical energy power is extremely handy to culture through power cells. Batteries function using numerous chemicals that engage with each various others is developing electric power. The kind of battery that is extensively made use of worldwide is the zinc-copper cell, which utilizes the chemicals zinc and also copper, where the previous is being assigned the adverse side as well as the last being assigned the silver lining. By attaching a cord to both ends, the acid inside the battery is thrilled and also will certainly damage down several of the zinc. The electrons from this aspect are after that totally free to follow the cable to the copper side, where electric circuits are performed and afterwards enabled to move right into the tool that the battery is powering up. Various other important procedures that include chemical power are photosynthesis, food production as well as, once more, fuel burning. Chemical energy plays a vital duty in each of our dayto-day lives, as well as it would certainly be difficult to disregard the benefits we could appreciate from it. With this in mind, we will certainly discover how to value its relevance and also will certainly locate means to add to its preservation. Currently, we assess its downsides.
20.5. CHECKLIST OF DOWNSIDES OF CHEMICAL ENERGY •
It could be dangerous to the setting. Prior to the resources are exchanged beneficial power, burning is needed as well as this could generate hazardous byproducts which could add to air pollution. Given that chemical power is stemmed from natural products, there is a high danger that the setting will certainly be considerably influenced by it, specifically due to way too much
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•
•
•
•
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burning that is needed for its manufacturing. We as customers could do our component in managing such impacts. Federal governments could develop some plans over the appropriate use chemical power to decrease carbon impacts. Exclusive establishments within this market could carry out some brandnew innovations to take care of such a drawback. It includes a high expense. The manufacturing of atomic energy, particularly, requires a great deal of loan to establish and also spend up nuclear power terminals. It is essential to remember that it is not constantly feasible by lots of establishing nations to pay for such an expensive resource of power. It could generate contaminated waste. The waste generated by activators should be taken care of appropriately to a safe location, because it is incredibly dangerous and also could leakage radiations otherwise saved appropriately. The radiations sent out by this type of waste could last to 10s and even centuries. Hazardous wastes include radioisotopes with lengthy half-lives, which implies that they remain in the ambience in some kind or the various other. These responsive radicals could make sand or water infected, which is referred to as combined waste that could create unsafe chain reaction and also could cause unsafe problems. To take care of such waste, plants would generally hide it under sand in a procedure called vitrification. An additional risk this technique brings is that the waste could be utilized making nuclear tools. This idea alone could make individuals close-by scared of just what the material could affect their lives. It is non-renewable. Many resources of chemical power could not be renewed. Taking the situation of atomic energy again, some plants utilize uranium, which is a limited source as well as is not located in lots of nations. Numerous countries count on various other areas for the continuous supply of this gas. It is bad for human wellness. Taking into consideration that chemical power is extremely flammable, it is anticipated to add to contamination, which creates numerous health problems as well as is never ever helpful for human wellness. Worldwide warming has gotten worse recently as a result of hefty air pollution in the various components of the globe, as well as with different power resources, its impacts could be managed and decreased.
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20.6. MAJOR CURRENT ENVIRONMENTAL PROBLEMS •
•
•
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•
Pollution: Pollution of water, air, and soil require millions of years to recoup. While water pollution is caused by oil spill, acid rain, urban runoff; air pollution is caused by various gases and toxins released by industries and factories and combustion of fossil fuels; soil pollution is majorly caused by industrial waste that deprives soil from essential nutrients. Global Warming: Climate changes like global warming is the result of human practices like emission of Greenhouse gases. Global warming leads to rising temperatures of the oceans and the earth’ surface causing melting of polar ice caps, rise in sea levels and also unnatural patterns of precipitation such as flash floods, excessive snow or desertification. Overpopulation: The population of the planet is reaching unsustainable levels as it faces shortage of resources like fuel, food, and water. Intensive agriculture practiced to produce food damages the environment through use of chemical fertilizer, insecticides, and pesticides. Globally, people are taking efforts to shift to renewable sources of energy like solar, wind, biogas and geothermal energy. The cost of installing the infrastructure and maintaining these sources has plummeted in the recent years. Waste Disposal: The over consumption of resources and creation of plastics are creating a global crisis of waste disposal. Developed countries are notorious for producing an excessive amount of waste or garbage and dumping their waste in the oceans and, less developed countries. Plastic, fast food, packaging, and cheap electronic wastes threaten the well being of humans. It occurs due to rise in global warming which occurs due to increase in temperature of atmosphere by burning of fossil fuels and release of harmful gases by industries. Climate change has various harmful effects but not limited to melting of polar ice, change in seasons, occurrence of new diseases, frequent occurrence of floods and change in overall weather scenario. Loss of Biodiversity: Human activity is leading to the extinction of habitats and species and loss of bio-diversity. Balance of natural processes like pollination is crucial to the survival of the eco-system and human activity threatens the same.
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Deforestation: Our forests are natural sinks of carbon dioxide and produce fresh oxygen as well as helps in regulating temperature and rainfall. At present forests cover 30% of every year but the land tree cover is lost amounting to the country of Panama due to growing population demand for more cloth, food, and shelter. 25% of CO2 produced by humans. The main impact is on shellfish and plankton in the same way as human osteoporosis. Ozone Layer Depletion: The ozone layer is an invisible layer of protection around the planet that protects us from the sun’s harmful rays. Depletion of the crucial Ozone layer of the atmosphere is attributed to pollution caused by Chlorine and Bromide found in Chloro-fluoro carbons (CFC’s). Once these toxic gases reach the upper atmosphere, they cause a hole in the ozone layer, the biggest of which is above the Antarctic.
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REFERENCES 1. 2. 3. 4. 5. 6. 7.
http://biofuel.org.uk/other-alternative-fuels.html https://greengarageblog.org/11-core-advantages-and-disadvantagesof-chemical-energy https://www.afdc.energy.gov/fuels/biodiesel.html https://www.conserve-energy-future.com/15-current-environmentalproblems.php https://www.health.ny.gov/environmental/chemicals/toxic_ substances.htm https://www.kemi.se/en/guidance-for/consumers/chemicals-in-theeveryday-environment Manahan, S. E. Fundamentals of Environmental Chemistry, Third Edition.#
CHAPTER
21
CHEMICAL REACTION ENGINEERING The chapter will cover the topics such as introduction to chemical reactions, homogeneous, and heterogeneous reactions. The chapter will further discuss the basics of kinetics and contacting, the design of batch reactors, basics of plug flow reactor. The chapter will include topics in basics of mixed flow reactors, the design of mixed flow reactors, kinetics of heterogeneous reactions, kinetics of homogeneous reactions, reaction rates of homogeneous and heterogeneous reactions. The chapter will discuss gas phase homogenous reactions, a combination of reactors, recycle reactors for autocatalytic reactions, multiple reactions, non-isothermal reactors, adiabatic reactors, adiabatic plug flow reactors, and multi-parameter model reactors. This chapter will give the readers a detail description of chemical reactions and their types with different types of reactors. So, first we need to understand about a chemical reaction and it is defined as a process in which one or more substances (reactants) react together to form one or more substances (products). The reacting substances can either be atoms or they can be compounds and can possess different chemical and physical properties. A chemical reaction is represented by a chemical equation, which is given as: A+B C+D In the above equation, the A,B are the reactants and C,D are the products and they are separated by an arrow which gives information about the direction as well as reaction type (reversible or irreversible). In chemistry,
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there are two types of mixtures, homogenous and heterogeneous on the basis of what chemical reaction take place. A Homogenous reaction is such a chemical reaction in which the all the reactant as well as the products are in same phase, i.e., the reaction taken place between two solid and two liquid substance can be term as a homogenous reaction. These types of chemical reactions are much simpler as the products are mainly dependent on the product, a common example of this reaction is the reaction between gas and oxygen to produce flame. Similarly, a heterogeneous reaction is such type chemical reaction in which the reactants, products or both are in different chemical phase, the examples of such chemical change are the reactions of metals with acids, the chemical reaction in batteries and the corrosion of metals is also, the example of heterogeneous reaction. These chemical reactions are far more complex than homogenous chemical reaction in which the final product is entirely dependent on the properties of reactants.
A batch reactor are the vessels that are used in different manufacturing and process industries for different type of applications such as solids dissolution, batch distillation, product mixing, chemical reactions, crystallization, polymerization and liquid/liquid extraction. They have different terms names as well, i.e., crystallizer. In basic construction of a batch reactor, it consist of heating and cooling systems and a tank with agitator. The manufacturing material can be range from steel, glass or exotic alloy, stainless steel and glass-lined steel. The liquids and solids are charged in the vessel through the top and gases escape from the holes of vessels which are present in the top. The liquid can be discharge as well in the bottom of the vessel. A batch reactor is designed for certain applications as well but this chapter will give a general design of batch reactor. An agitator is mounted on the top of reactor
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and contains a shaft where blades are mounted, different type of designs of blades can be used and their manufacturing material is according to the application and their usage. Some reactors also possess baffles as well. The reactors taking place in the batch reactor usually need heat of dissipates heat, therefore, to maintain an desired temperature for reactants and products, heat can be added or removed with the help of a cooling jacket or cooling pipes. There are several types of cooling jackets of batch reactors such as single external jacket which covers the vessel of reactor, heat can be added or removed through the nozzles and in this way the temperature can be regulate according to the desired conditions. Another type of jacket is named as half coil jacket in which vessel is welded around with pipes to establish a circular channel. The fluid is passed through the channel in plug fashion. The more the larger the vessel, more will be the coil around the vessel. The temperature of the vessel is controlled with the help of heating and cooling principles. Moreover, a latest cooling and heating jacket for the vessel is named as constant flux cooling jacket. Unlike a single jacket, it is composed of 20 or smaller jackets and temperature is controlled by using certain amount of jackets accordingly. Furthermore, another type of reactor known as plug flow reactor or continuous tubular reactor which describes a chemical reaction in as flow system with continuous geometry. The main aim of this reactor is to estimate and predict the behavior of chemical reactor which possess a tubular design characteristics with the help of factors, i.e., its dimension can be established. In this reactor, it is considered that the plug is flowing through the reactor as number of coherent plugs and contains uniforms composition. In an ideal flow reactor, it is considered that there is no mixing of the reactors along the x-axis but there can be mixing of the plug in the y-axis.
Further modification of plug flow reactors help us to form a new type of reactor named as recycle reactors which are extensively used in autocatalytic reactions. It is used in a situation when we need the output from the reactor and recycle it for a different number of reasons such as, in case of biological
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reactions, the enzymes are introduce in the process with the help of recycle reactors.
In the above figure, the generated steam from the output is again fed into the recycle reactor. The input to the reactor is from point 1 and its output is from point 3. At point 1, the new input is mixed with recycle input whereas the output at point 2 is further split into recycle input and net output. The batch reactors which are operated isothermally are designed in such a way that the overall temperature of the system is zero and when an ideal isothermal reactor is attached with a heat bath, the heat exchange is very slow and reactor adjust the energy so that the change of overall temperature of the reactor is zero. Similarly, in case of batch reactor working in adiabatic conditions, it monitors the reaction rates, energies involve in the process and the reaction orders of exothermic process. Industrial chemical process aims to produce efficiently a desired product from a wide range of materials that undergo several treatment processes successfully. Raw material experiences several physical treatment steps to ensure that they are in a chemical reaction form. Material is pass through the reactor and the products of the reaction undergo further physical treatment which involves separations, purification, etc., to obtain a final desired product. Chemical treatment steps play a major role in a process economically. Reactor design stages undergo different approaches. It is optimum to consider every part of the reactor design to be economical such as low reactor cost and low material treatment cost. Reactor designs mostly uses information, knowledge, and experience from different areas such as thermodynamics, fluid mechanics, heat transfer, chemical kinetic, mass transfer and economics. Chemical reaction engineering is a combination of all these factor for designing a reactor properly.
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Figure 21.1. Chemical reaction process.
Chemical reactions can be classified in many ways and these depend on the breakdown of the number and types of phases involved. A reaction is homogenous when it occurs in only one phase and consists of variables such as temperature, pressure, and composition while a reaction is heterogeneous when it occurs in two phases to proceed at the rate that it does. The problems become complex when it consists of more variables and materials move from one phase to another during reaction and the rate of mass transfer becomes important. The reaction rate expressions is required in algebraic form when material and energy balances are performed for batch, continuous stirred tank reactor (CSTR) and plug flow (PFR). This is normally expressed in terms of the concentrations or partial pressures of the reactants (and sometimes products) and may be empirically determined based upon an understanding of the mechanism of the reaction. Lets’ consider the irreversible reaction, vAA→vBB where are stoichiometric coefficients. The rate of the disappearance of A, is a reaction rate expression that depends on concentration of A, where n is the reaction order (not equal to vA) kc is a rate constant, CA is the concentration of A1. Rate of reaction could also be expressed in terms of partial pressure and this is where the gas-phase reactions are applicable. where kp is a rate constant and PA is the partial pressure of A. For a gas-phase reaction, kp and kc can be related,
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Considering the ideal gas, PAV = NART where V is the volume of the batch reactor, NA is the total number of moles of A in the reactor, R is the gas constant, and T is the reactor temperature in Kelvin PA = NAVRT = CART where CA is the concentration of A —————————-For gas phase reaction The relationship between kp and kc are same for all reactor type Consider a general reversible reaction Example 21 A rocket engine, Figure A1.1, burns a stoichiometric mixture of fuel (liquid hydrogen) in oxidant (liquid oxygen). The combustion chamber is cylindrical, 75 cm long and 60 cm in diameter, and the combustion process produces 108 kg/s of exhaust gases. If combustion is complete. Find the rate of reaction of hydrogen and of oxygen.
Solution: –rH2 = 1VdNH2dt or –rO2 = 1VdNO2dt The volume of reactor and the volume which reaction takes place are the same Thus, V = π4 (0.5)2 (0.65) = 0.1276 m3 Looking at the reaction occurring; (i) Molecular weight 2 g; 16 g; 18 g
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Therefore,
So from Eq. (i)
and the rate of reaction is
Chemical energy is reserved energy in a chemical bond and released by way of exothermic reactions. They produce combustible energy and give out instant energy. In a process called photosynthesis, Green plants can transform energy from the sun to chemical energy. Electrical energy can be converted to chemical energy through electrochemical reaction processes. Chemical-reactor theory has three ideal reactor types: batch reactors, filled with reactants, continuously stirred during the reaction, and then emptied of products after a given reaction period; plug-flow reactors (PFR’s), reactants continuously enter and products continuously exit with no mixing along the flow path; continuous-flow; and stirred-tank reactors (CSTR’s), which reactants continuously enter and products continuously leave a stirred vessel. The progress is in arising models of digestion from reactor theory is that many conceivable modification to ideal models have analogues in diverse industrial reactor configurations that is already tested and modeled. The suitable flow problem in a tubular reactor is ‘plug flow, as well as under such excellent problems, the residence time in the reactor coincides for all components of liquid as well as there is commonly a consistent speed account throughout the span of the reactor. Extra especially, the reactor defined here could offer several of even more exact temperature level control, reduction of heat transfer right into and/or from the reactor, ideal residence times of response elements as well as or optimized blending. The reactor is therefore specifically well fit for responses consisting of thermally delicate parts such as drivers that might or else show decreased lifetimes, or response elements that undesirably break down or respond at temperature levels within the handling requirements of the procedure desirably performed within the reactor.
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The here and now innovation associates with connect plug flow with the ability of adiabatic procedure and appropriate for performing continuous, gas stage, totally free radical reactions to generate chlorinated and/or fluorinated propene as well as greater alkenes. Processes including the exact same are additionally supplied. The suitable flow problem in a tubular reactor is ‘plug flow, and under such perfect condition, the residence time in the reactor coincides for all aspects of fluid and there is generally a consistent velocity account throughout the radius of the reactor. That is, as the plug flow via the reactor, the plug elements are flawlessly blended in the radial instructions, with blending in the axial direction being non-existent. While in technique, optimal plug flow does not happen, preserving sensibly great plug flow via tubular reactor supplies substantial advantages. Obviously, plug flow offers better splitting up in between responded and unreacted product compared to non-plug reactor. Accomplishing the ideal mix of residence time, reliable blending and excellent plug circulation could cause tubular activators that are numerous meters long. Reactor of such size could after that offer added troubles in temperature level control and also warmth transfer features. It would certainly hence be preferable to give a tubular reactor efficient in estimating plug flow, while yet additionally giving optimum, e.g., residence time, warm transfer features, temperature level control as well as blending. Even more especially, the reactor explained here could give several of even more precise temperature level control, reduction of heat transfer right into and/or from the activator, ideal residence times of response parts as well as or enhanced blending. The reactor is hence especially well fit for responses consisting of thermally delicate elements such as stimulants that might or else display lowered lifetimes, or response parts that undesirably break down or respond at temperature levels within the handling requirements of the procedure desirably accomplished within the reactor. In some personifications, the reactor might additionally make up a layout that reduces the manufacturing of by-products at a wanted conversion. Many such layouts are offered, consisting of: (i) a layout that decreases heat transfer to and/or from the reactor; (ii) a layout that maximizes the circulation of the response parts at the limit in between the response elements as well as at the very least a part of a minimum of one reactor tube wall surface; (iii) a style that assists in a decrease of the temperature level of a reactor effluent to a temperature level listed below which considerable development of by-products does not take place, and/or (iv) a layout that enables the manufacturing price of a procedure carried out in the reactor to be readjusted by managing the temperature level of the reactor effluent.
CHAPTER
22
FLUID MECHANICS AND HEAT TRANSFER
The chapter will cover advanced principles of heat transfer and fluid mechanics and laboratory processes in fluid mechanics and heat transfer. The chapter will be a continuation of the previous chapters that introduced the readers to the principles of fluid mechanics and heat transfer. As, illustrated from the name of the chapter, this chapter will give the readers the information regarding the heat and fluid dynamics and their principles and application in various laboratory analysis. Heat is a physical terminology and it is defined as a thermodynamic property which is transfer of energy across a boundary to another system and it is also the amount of work done which can be performed by a thermodynamic system. It is calculated with the help of heat transfer coefficient and it is proportional to the flux of heat and driving force to continue to the flow of heat. The heat flux is a quantitative property and it is represented by vectors showing the path of heat flux flow across a thermodynamic system. The principles for the transfer of heat are advection, conduction or diffusion, convection, and radiation. In advection, transfer of fluid takes place from one medium to other and it is purely dependent upon the momentum and motion of the concern fluid. The fluid transfer takes place in the form of thermal energy as a physical transfer of cold or hot object from one place to another and example of such heat transfer is the thermal hydraulic system and can be mathematically represented as
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Q = vpCp∆T
Similarly, another mode of heat transfer is condition which is resulted due to rapidly moving or vibrating molecules and transfer their energy to the neighboring molecules. Conduction is significant process of heat transfer in solid or between different solid bodies. In case of metals, the steady state conduction is observed which is the amount of heat entering the solid body is equal to the amount of heat leaving it. Similarly, another form of conduction is the transient conduction which is the change of temperature of body result as a function of temperature and mostly analysis of such conduction is very complex and it is calculated with the help of computer. The expansion of fluid due to thermal energy is caused by the Buoyancy forces or by an external process and such type of thermal energy transfer is called convection. Another formed of convection is known as forced convection in which the fluid is forced to flow by a pump or any other mechanical mean. The convection heat transfer is mostly observed in gases and liquids. The natural form of convection so occurred due to the variation of temperature caused by buoyancy forces and it is observed in bulk fluid only. Another form of heat transfer is the process of radiation which is caused by energy transfer by means of photons and they are emitted by any matter as electromagnetic waves. The thermal radiation have the ability to flow in vacuum as in case of space. The thermal radiations are resulted due to the motion molecules in matter. In industries, the heat transfer is very important in many chemical and manufacturing process as heat addition and rejection of heat is an essential step for example, principle of heat transfer are necessary in reactors in petroleum industries. Similarly on laboratory scale various instrument are designed to conduction various experimentation on different natural processes. There are variety of instruments to study heat transfer on laboratory scale such as This chapter will further discuss about fluid mechanics and its principle and it deep analysis. Fluid mechanics is the branch of mechanics which deals with the properties of forces, statistical conditions and motions on fluids at static or dynamic conditions. This field of mechanics briefly elaborates the science of flow round bodies, flow stability fluid statics, surface tension, flow in enclose bodies, etc. Moreover, the fluid mechanics is one of the complex field of science which is mathematically solved with numerical methods and with latest techniques of computer software and one of the most advanced approach is called computational fluid dynamics, in this type
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field, the fluids which are at motion are only discussed. Similarly another method to visualize the fluids flow is known as Particle image velocimetry. There are two main branches of fluid mechanics which are fluid statics and fluid dynamics. In fluid statics, the fluids are analyzed which are at rest and follows the conditions that fluids are at rest and in stable equilibrium. This branch of fluid mechanics gives brief explanation of different natural phenomenon of fluids such as float of oil on water and change of atmospheric pressure with respect to height, the application of hydraulics which is storing and using the statics motion of fluids, some aspect of astrophysics, medicine, geophysics, meteorology, etc. However, the 2nd branch of fluid mechanics, fluid dynamics, deals with those fluid which are at motion and the motion of liquids and gases in motion are most significant in this field. Fluid dynamics are used to study the measurement of flow and to solve many practical problems, the problems of fluid mathematical properties such as velocity, density, temperature, pressure which is utilized as functions of time and space. This branch of fluid dynamics is subdivided into various other branches such as aerodynamics which is the study gas and air in motion and the field of hydrodynamics which is study of liquids in motion. Similarly, the fluid dynamics possess various practical applications such as calculating the correct aerodynamic forces on aero planes, calculating the mass flow rate of fluid in pipelines in different oil and gas field industries, to predict the next season weather patterns which can be useful for the field of agriculture. Moreover, it can be also useful for the discipline of dynamics of crowd and traffic engineering, to study modeling explosions in space. Furthermore, it is used in many biological process as well in different industries such as analysis of continuous flow of blood in the organs of body, to study in the case of batch reactors, the fluid dynamics is used to cooled down the required mixture and in case of calculation of buoyancy forces to measure the densities of different shapes of matter on the liquid. A fluid is a substance that goes through continuous changes when under shear stress and it is bounded by two large parallel plates, of area A, separated by a small distance H. The bottom plate is held fixed. When force F is applied to the upper plate, it moves at a velocity of U, and the fluid continue to deform when force is applied while solid goes through a finite deformation. Force F is proportional to the area of the plate; the shear stress is 𝜏 = A , within y / H is established; and due to a nothe fluid, a linear velocity profile u = U slip condition. The fluid bounding the lower plate has zero velocity U. The
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velocity gradient is called is called shear rate for this flow. Shear rates are usually reported in units of reciprocal seconds. The ratio of shear stress to shear rate is the viscosity, μ μ ꞊ . The SI units of viscosity are kg/ (m ∙ s) or Pa∙ s (pascal second). The cgs unit for viscosity is poise; 1 Pa∙ s equals 10 poise or 1000 centipoise (cP) or 0.672 Ibm/(ft ∙ s); kinematic viscosity is the ratio of viscosity to density. The SI Unit of kinematic viscosity are /s. The cgs stoke is 1c/s. Fluid flow pattern are more complex in rheology as it is a relationship between fluid deformation and stress. Rheology is the study of relationship in fluid flow and it primary goal is to obtain a constitutive equation by which stresses may be computed from deformation rates. Purely viscous fluids are fluid without any solid like elastic behavior which do not undergo any reverse deformation when shear stress is removed. The shear stress depends on the rate of deformation and not on the extent of strain. The fluid which exhibit both viscous and elastic properties are called viscoelastic fluids. Viscous fluids are time – independent and time-dependent fluids. The shear stress depends on instantaneous shear rate while the shear stress for time-dependent fluid depends on the history of the rate of deformation, because of structure or breakdown at the time of deformation. The Newtonian fluid rheogram is a straight line passing through the origin. The slope of the line is the viscosity, and this is independent of the shear rate and sometimes depend only on temperature and perhaps pressure. Shear thinning fluids are those which the slope of the rheogram decreases with increasing shear rate and they have been called pseudo plastic. Polymer melts and solutions/ solid suspension are shear-thinning. Dilatant fluids shows increasing viscosity with increasing shear rate. Time independent fluids are those which structural rearrangements occur during deformation at a slow rate to maintain equilibrium configurations. The kinematic of fluid flow depends on the quantitative description of the fluid deformation and the rate depends on how velocity is being distributed in the fluid. The velocity of the fluid is the vector quantity with three Cartesian components . Compressible and Incompressible flow has the density of the fluid constant or nearly constant. Fluid are compressible when the density varies by more than 5 to 10%. Practically, compressible flows are normally limited to gases, supercritical fluids, and multiphase flows containing gases. Liquid flows are normally treated as incompressible except in the context of hydraulic transients.
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Laminar and turbulent flow are two types of flow. Laminar flow has smooth streamlines and the fluid velocity components vary smoothly with position and with time if the flow is steady while turbulent flow has no smooth streamlines and the velocity shows chaotic fluctuation in time and space. Reynolds number is defined for a Newtonian fluid as Re = LU where L is a characteristic length. Multiphase flows are generally complex, and several features are identified which poses more complication than single-phase flow. Fluid distribution is important for efficient operation of chemical-processing equipment such as contractors, reactors, heat exchangers, burners, mixers, extrusion dies and textile -spinning chimneys. To have optimum distribution, proper consideration must be given to flow behavior in the distributor, flow conditions upstream and downstream of the distributor and the distribution requirements of the equipment. For turbulent flow, the combine effect of friction and inertial pressure recovery is given by;
ρV 4 fL ∆p = − 2k 1 2 3D 2
(discharge manifold)
where ∆p = net pressure drops over the length of the distribution; L = pipe length; D = pipe diameter; F = Fanning friction factor; V i = distribution net velocity. Fluid mixing is a discipline of fluid mechanics and it is used to speed up slow processes of diffusion and conduction to ensure concentration and temperature are in uniform, blend materials, enable chemical reactions, and allow intimate contact of multiple phases. The proper use of heat transfer knowledge in the design of practical heat-transfer equipment is an art. Designers must have knowledge of the difference between an ideal condition for and under the basic knowledge would be obtained and as well as the mechanical expression of their design and its environment. Process heat exchangers design normally adhere the following steps: The condition of the process must be specified (stream compositions, flow rates, temperatures, pressures).
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•
is
Physical properties over the temperature and pressure ranges of interest must be specified. • The choice of heat exchanger to be chosen. • An estimation of the size of the exchanger is made, using heattransfer coefficient appropriate to the fluids, the process and the equipment. • Design is chosen and complete in all detail necessary to carry out the design calculations. • The above chosen design is evaluated as its strength to meet the process specifications with respect to both heat transfer and pressure drop. • Based on the result of Step 6, a new configuration is chosen if necessary and step 6 is repeated. The overall heat-transfer coefficient design equation for heat exchanger
where dA is the element of surface area required to transfer an amount of heat dQ at a point in the exchanger and the overall heat transfer coefficient is U and the overall bulk temperature difference between the two streams is ΔΤ. Fluid dynamic history gases, air, fluids as well as water are both fluids. Continuing the partial differential formulas that define the activity of such fluids, stipulation of the basis for the difference in between these 2 kinds of fluids and after that the recap of the appropriate thermodynamic connections is talked about.
22.1. PHASES OF MATTER The phases of matter might be generally classified right into fluids and solids. Fluids do not stand up to contortion as well as tackle the form of its container owing to their lack of ability to sustain the shear tension in fixed stability. The difference in between fluids as well as solids is not so easy and is according to both the thickness of the moment and the issue range of rate of interest. A fluid is a liquid with the residential or commercial property that transforms to the form of its container and maintains its continuous quantity independent of stress. A gas is a compressible fluid that
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not only modifications to the form of its container however additionally broadens to inhabit the complete container. A fluid is a liquid with the residential property that transforms to the form of its container as well as stays at its consistent quantity independent of stress. The important kind of the form element for an ellipsoid exists and after that made use of to get logical expressions and mathematical worth for the form elements of many isothermal geometries. It is revealed that the dimensionless form element is a weak feature of the geometry offered that the square origin of the overall energetic area is selected as the body size. The form variable results of this phase are made use of in the phase on all- natural convection to design warm transfer from isothermal bodies of approximate form. When steady-state transmission take place within and outside solids in between getting in touch with solids, it is often dealt with by ways and methods of using conduction form as well as thermal conductance specifically. This phase covers the fundamental formulas, meanings, and connections that specify elements and the thermal contact, space, and joint conductance for adhering, harsh surface areas, as well as conforming surface areas. The basic expression is utilized to establish various and basic expressions in many vital coordinate systems such as (1) round, elliptical. and bicylinder collaborates. (2) spheroidal collaborates round, oblate spheroidal and prolate spheroidal. The essential type of the form and element for an ellipsoid is provided and afterwards utilized to acquire logical expressions and mathematical worth’s for the form and variables of numerous isothermal geometries, oblate, and prolate spheroids as well as elliptical machine. It is shown that the dimensionless form and element is a weak feature of the geometry shape form as well as element proportion supplied that the origin of the overall energetic location is chosen as the size. A basic expression is suggested for precise evaluations of form elements of three-dimensional bodies such as cuboids.
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REFERENCES 1. 2. 3. 4.
Anderson, D. A., Tannehill, J. C., & Pletcher, R. H (2012) Computational Fluid Mechanics and Heat Transfer 244-346 http://www.potto.org/fluidMech/intro.php https://energy.gov/energysaver/principles-heating-and-cooling Perry R. H & Green, D.W (1997) (Seven Edn) Perry’s Chemical Engineers Handbook.6.26 -6.36
CHAPTER
23
MATHEMATICAL MODELING AND NUMERICAL METHODS
The chapter will be a continuation of the above chapters that introduced the discussion of ordinary differential calculus and calculations. The chapter will discuss the topics such as numerical methods in computing with real numbers, numerical differentiation, interpolation, and curve fitting using regression analysis. The chapter will discuss the topics in statistics such as theory (binomial, Poisson, and normal distributions), large sample theory (central limit theorem), and elements of statistical inference using confidence intervals and hypothesis testing, t-tests, and f-tests. Numerical numbers are numbers used to simulate mathematical processes which simulate real world situations. Computing is all about insight and the choice of a formula, logarithm does not only influence the computing but understands the results when they are obtained. The progress of the computing, the number of iterations, spacing used by a formula gives light to the problems. The second main idea is a consequence of the first, if the purpose of computing is insight and not numbers. It is necessary to study families and to relate one family to another therefore, avoiding isolated logarithms and formulas. The difference in numerical methods and analysis elaborates the subject more. Numerical methods are methods which meet the need for method to cope with the potential infinite variety of problems that arises while numerical analysis is the study in-depth of a few, selected and topics and is carried out in a formal mathematical avenue that is not lacking
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to the world. The third measure idea is the round off error and the finite nature of the computing machine which only deals with finitely numbers shown. Numerical differentiation is the process of finding the derivatives of functions. Similarly, ordinary differential equation (ODE) is the mathematical representation of any physical quantity which is the function of any independent variable. If more than one independent variable includes then this equation will be called as partial differential equation. There are two types of ordinary differential equations, linear and nonlinear differential equations. linear differential equations have closed-form solutions that can be added and multiplied by coefficients while nonlinear lack additive solutions so these are complex to deal with. These equations can be solved in graphical and numerical methods by using computer applications or by hand. Consider a very basic example of ODE in which x is any quantity which the function of independent variable is ‘time’. x(t) is a constant function, x(t)=C. where C cant not be specify uniquely if we only have equations for the derivatives of x. for the unique solution of x(t), one must provide some additional data in terms of the function x(t) itself. In order to solve differential equations numerical methods are useful specially in the case where symbolic computation cannot solve the equation. For example, in engineering different algorithms are used to compute numeric approximations. There are various mathematical procedures used to solve problems. • Simultaneous Linear/Nonlinear Equations • Integration/Differentiation • Ordinary/ Partial Differential Equations • Curve Fitting (Interpolation, Regression) • Optimization • Fast Fourier Transforms Curve fitting: is the process of making A curve by joining series of data points to develop a mathematical function. This technique is used to find out the values of coefficient used in function or differential equations in which one independent variable has a function with respect to a dependent variable. If we have data measured with any analytic function, we use two approaches to solve this problem ‘Interpolation and Curve fitting.’ We use assumption in case of interpolation takes precise data, we just consider that the data is correct and the information given by the set of points is
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describing the desired function and the curve pass the all the points. In case of curve fitting or Least squares regression data shows a significant extent of scatter we try to get best fit curve to show the general trend of data which means the curve which covers the maximum data points but it is not necessarily happens in every case. In engineering, these techniques have tow applications one is trend analysis which is the prediction of dependent variables by extrapolation or interpolation Second is hypothesis testing, which is a Comparison of mathematical models or existing algorithms with measured data. Probability is one of the topics of mathematics which deals with the calculation of occurrence of event within 0 and 1. Zero means that event is impossible to happen and 1 means the event will happen. In real-life applications probability distribution can be categorized as discrete (Binomial, Poisson) and continuous (Uniform, Normal, Exponential). For x is in between positive and negative infinities. E(x) = u and V(x) = thus the nominal distribution is characterized by u and standard deviation . Binomial random variable is represented with the symbol X, the probability distribution of X is called the binomial distribution. Let f(x) (non-negative) is the density function of variable X. Then, f(x) is the rate which probability gathers in area of x. Notwithstanding, f(x) h ≈ P(x < X ≤ x + h) when h (a positive number) is necessarily small. Then, P(x1 < X ≤ x2) = Z x2 x1 f(x) dx; (4), we must have Z ∞ − ∞ f(x) dx = 1. Continuous distribution is the exponential distribution that has the following probability density function: f(x) = λe − λx (10) for x ≥ 0. Another useful continuous distribution is the exponential distribution, which has the following probability density function: f(x) = λe − λx (10) for x ≥ 0. The exponential distribution is used to model time intervals between “random events.”… X is called a Poisson random variable and the probability distribution of X is called the Poisson distribution. Its probability mass function is: P(X = x) = e − µ µ x x! (2) for x =0, 1, 2,... The value of µ is the parameter of the distribution.
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23.1. MEAN AND VARIANCE It can be shown that E(X) = µ and V (X) = µ. 13. In this situation, the total number of events, in that interval has a binomial distribution with parameters n and µ/ n. That is, P(X = x) = n! Some probability distributions have appeared in real-life applications individually. Basic study properties and distributions are discussed after much studies: binomial; Poisson; uniform; normal; and exponential. The first two are discrete and the last three continuous.
23.1.1. Binomial Distribution Let’s consider in a sequence of coin flips, the number of heads/tails and vote is numbered for two different candidates in an election. In a company, the number of males and female employees are counted. The number of accounts in compliance or not in compliance with an accounting procedure. The number of successful calls in sales and the number of defective products in a production run. The number of days your company’s computer network experiences a problem in a month. These situations involve the application of binomial distribution.
23.1.2. Canonical Framework There are set of assumptions that leads to a binomial distribution if valid. Let X is the total number of successes. X is called a binomial random variable, and the probability distribution of X is called the binomial distribution. The Poisson distribution is another family of distributions that shows in many business situations. It is applicable when random events occur at a certain rate over a time. Let’s consider this example, the number of customers arriving at a bank, accidents in a stretch of highway daily, number of accesses to a web server, number of emergency calls in New York, number of typos in a book, monthly number of employees that has an absence in a large company, monthly demands for a product. These are all situations where the Poisson distribution are applicable. The Poisson distribution rises when set of canonical assumptions are reasonably valid. The number of events that occur in any time interval that is independent of the number of events in other disjoint interval. The distribution of number of events in an interval is the same for all intervals of same size. The function F(x) ≡ P(X ≤ x) = Z x − ∞. f(y) is called the cumulative distribution function of X. F(x) is used to describe a random variable, since f(x) is the derivative of F(x). Different
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probabilities of interest that has a variable X can all be computed via either f(x) or F(x).
23.1.3. Uniform Distribution The uniform distribution is the simplest example of a continuous probability distribution. A random variable X is uniformly distributed if its density function is given by: f(x) = 1 b − a (5) for − ∞ < a ≤ x ≤ b < ∞.
23.2. BINOMIAL PROBABILITY-MASS FUNCTION Consider a random binomial variable let it be X. Then, its probability function is:
for x = 0, 1, 2,…n. The values of n and p are called the parameters of the distribution. In the given formula the shows the probability of n trials that contains x = successes and n – x = failures. The total number of such sequences is equal to
The total number of possible combinations when we randomly select x objects out of n objects). Poisson Probability. Let X is a random Poisson variable. its probability can be calculated as:
The value of µ is the parameter of the distribution for x = 0, 1, 2,...
23.3. NORMAL DISTRIBUTION For the normal distribution of a random variable X with parameters µ and σ, its density function can be define as
In statistical theory the “central limit theorem (CLT)” states that with the finite level of variance for large size sample of population, the mean
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for the all samples from the same population will be equal to mean of the population with condition that all sample must follow normal distribution pattern with variance of population divided by size of each sample. There are limitations in this theorem application the sample size must be equal to or greater than 30 will be acceptable but in case when sample size increases the mean of sample data become closer to the mean of overall population or the means of the sample should be normally distributed. Statistical inference is the inferring of properties of probability distribution by data analysis. This analysis gives properties of a population: this includes testing hypotheses and deriving estimates. The population is consider as set and observed data is subset or sample from the population. This analysis can be compared with descriptive statistics. Which only consider the properties of the observed data and does not assume that the data came from a larger population. A truly informative statistical inference, however, should provide not only a point estimate but should also indicate how confident we can be that the estimate is correct. So, rather than a single value, we often prefer to use a range of values. This is what is known as an interval estimate: an interval of numbers (usually centred around some point estimate) within which the parameter value is believed to fall. Another name for interval estimates is confidence intervals, because they contain the parameter with a certain degree of confidence. A statistical hypothesis, also called confirmatory data analysis, it is a testable hypothesis that can be observe by the model of the process formed by random variables the hypothesis test uses statistical inference method, in which two data sets are compared a data set from sampling and synthetic data from an existing ideal model. The comparison is basically the alternative of null hypothesis in which there is no relationship between two data sets. According to a threshold probability, the comparison can be statistically significant if the relationship between the data sets would show the understanding of the null hypothesis. Hypothesis tests are used to find out the reasons of rejection of the null hypothesis for a pre-defined level of significance. The characterization of null hypothesis and the alternative hypothesis is assisted by recognising conceptual errors and by defining their parametric limits. An alternative method for statistical hypothesis testing is to postulate a set of statistical models, one for each candidate hypothesis, and then use model selection techniques to select the most suitable model. The common selection techniques are based on either Akaike information criterion or Bayes factor. T-test is used for the estimation of population parameter, for example, population mean, and is also used for hypothesis testing for population mean. It is only applicable
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when population standard deviation is not confirmed. In case of known population standard deviation, Z-test will be used. Both are used to estimate population parameters: population mean and proportion. It is also used in hypothesis testing for population mean or population proportion. Unlike Z-statistic or t-statistic, where we deal with mean & proportion, Chi-square or F-test is used for finding out whether there is any variance within the samples. F-test is the ratio of variance of two samples.
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REFERENCES 1. 2. 3. 4. 5.
http://home.agh.edu.pl/~zak/downloads/MN1–2015-Eng.pdf http://makemeanalyst.com/normal-distribution-binomial-distributionPoisson-distribution/ https://library2.lincoln.ac.nz/documents/Normal-Binomial-Poisson. pdf https://www.essie.ufl.edu/~kgurl/Classes/Lect3421/Fall_01/NM5_ curve_f01.pdf https://www.utdallas.edu/~scniu/OPRE-6301/documents/Important_ Probability_Distributions.pdf
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PROCESS CONTROL, INSTRUMENTATION, AND SAFETY The chapter will introduce the readers to the principles of chemical process systems, modern control systems, advanced process control, computational techniques in control engineering, industrial communication systems, system identification, instrumentation in chemical engineering biotechnology and current control systems. Unlike the previous chapter, this chapter will discuss briefly about different control systems that are used widely in industrial sector to overall increasing the efficiency and improving the finishing of the final product. With increasing demands of various chemical and products on large scale, this has resulted in complexity of operations of an industrial unit and plant design which have further resulted to improvised different control techniques, algorithms and methodologies. The improved control system of an manufacturing unit in an industry not only utilize the raw material efficiently but also increases the productivity and decreases the pollution level in the surrounding areas and improve the safety level of the plant. A control system is such a system which possess predefined condition with the help of variable or set of variables to maintain a specific output or conditions. A control system can be further controlled by electricity or it can be mechanically controlled, by a fluid or it can be controlled with combination of different types of means. With the help of a computer system, a control system can be easily controlled and can be monitored as well with
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further adjustment in the output according to the requirements. A control system is the foundation of automation process of industry. There are two types of control systems which are feedback and feed forward systems. The example of feed forward can be of early Loom of early 18th century, whereas the feedback system was incorporated in the industrial sector in 19th century and solved those problems of industrial sector which was not previously possible and its example is shaper machine followed by an cutting tool and in such away the tool can adjust itself according to the shape of product. A control system is composed of two fundamental characteristics which are as follows: •
The motor can vary the output value of control quantity as it draws the power which is coming from a power source rather than an input signal. So, a large amount of power is viable to effect the value of the quantity which has to be controlled and also the loading the entire system has no effect on the input signal or distort its accuracy and range. • The amount of energy that is fed to the input signal to vary the control quantity is determined from a specific function that lies between the desired and actual values of the quantity to be controlled. Similarly, the efficiency and stability of an control system is determined on the basis to which extent it can compensate and bring the system to normal state when an external signal is fed to that control system. If, with the addition of external signal causes the system to overcorrect itself then a condition is automatically performed by the system known as hunting, in this phenomenon, first the system overcorrect itself in one direction and then after modification, it overcorrects itself in opposite direction. As indicates from the discussion that the process of hunting takes time and it is undesirable in an chemical plant to wait for the system to return to its normal state, so another element is attached to the system called Dampers which slows down the response of the entire system which not only avoids unnecessary overcorrection but also stops the excessive overshoots of the control system of industrial process. The examples of damping can be an electrical resistance in the circuit, in mechanical systems brake plays the role of dampers as well as shock absorbers can also perform damping in the system. Furthermore, another method to determine the stability of a system is frequency response method in which various frequencies are fed in
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continuously varying signal to the system and the output taken from the system is compared with the phase value and amplitude of the system. There are many methods to calculate the frequency response of the system through practically and mathematically (they are useful for such systems that are based on ordinary linear differential equation). To design a modern control system, there are many techniques and different algorithms available such as adaptive control is one of them in which the system is designed in such a way that the system modify itself to give best optimal and desired output. The functions which adaptive control possess are identification of a process, updating, and providing the current state of the system, making comparison with the present result and desired result and making such changes in the system to give optimum performance in the output of the system. Similarly, unlike adaptive control technique, another technique known as dynamic optimizing control technique operates in the system in terms of specific conditions to give specific output in results. This method is mostly used in a situation when control system is moves its position from original position to a new position during small amount of time. Moreover, one of the control technique that is widely used in industrial sector is Model Productive Control (MPC) which is still considered among the most advanced control techniques. Due to its ability to deal with the complex problems and input to output to interactions, this control techniques (it was developed in 1970 and later improved with the passage of time) also possess the ability to deal to various variables and executing it in same time with any inference between them. But the limitations associated with MPC have been removed in past couple of year and it is continuously been removed. The advancements are adequately accomplishing the targets of different control techniques and to design MPC, following are the basic characteristic should be possessed by such system: •
• • •
The controller should have the ability of absorb different uncertainties such as disturbance or sudden change of values of input variables. The controller should have the tendency to perform in an tough environment with state variables and their actuation The controller should be designed in such a way that it should deal with non-linear systems and interacting system variables. If the system goes through the phase of power failure or other uncertainties the controller should remain safe and reliable.
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A process is shown has a manipulated input M, a load input L, and a controlled output C, which is flow, pressure, liquid level, temperature, composition, inventory, environmental, or quality variable holds a desired value identified as the set point R. An open-loop system positions the manipulated variable either manually or a programmed basis, without the use of any measurements. This operation is acceptable for well-defined process without disturbances. A closed-loop system uses the measurement of one or more process variable to move the manipulated variable to achieve control. In feedback control loop, the controlled variable is compared to the set of point R, with the difference, deviation, or error e acted upon by the controller to move m in such a way to minimize the error. The action demotes a negative feedback in that an increase in deviation moves m to decrease the deviation. The action of the controller is selected to allow use on process gains of both signs. A Feed-forward Control system uses measurements of disturbance variables to position the manipulated variable in such a way as to minimize any resulting deviation. The disturbance variables could be either measured loads or the set point, the former being more common. The feed-forward gain must be set precisely to offset the deviation of the controlled variable from the set point. Computers controls have been used to replace analog PID controllers, by setting set points of lower level controllers in supervisory control, or by driving valves directly in direct digital control. Single-station digital controllers perform PID control in one or two loops, including computing functions such as mathematical operations, characterization, lags, and dead time, with digital logic and alarms.
Figure 24.1. Block diagram for feed-forward and feedback control.
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24.1. FEEDBACK CONTROL SYSTEM CHARACTERISTICS Using the diagram above as a simple presentation of closed feedback loop, the load enters the process at the same point as the variable that is manipulated due to the most common point of entry. Due to lack of sufficient information, the transfer function that gains in the path of the manipulated variables are the best estimates of those in the load path. The load has to impact in the controlled variable by passing through the lag in the process. On and Off Controller are used for manipulated variables having only two states. The temperature in homes is commonly controlled, electric water heaters and refrigerators, and pressure and liquid level in pump storage systems. On/Off control is satisfactory when slow cycling is acceptable because it leads to cycling in which the load lies in between the state of manipulated variable. Proportional – Plus – Integral (PI) Control: Integral action eliminates the offset described above by moving the controller output at a rate proportion to the deviation from set point. It is most mostly combined with proportional action in a PI controller when available alone in a integral controller.
where tI is the integral time constant in minutes, it is introduced as integral gain or reset rate 1/tI in repeat per minute in most controller. The last term in the equation is the constant of integration, the value the controller output has when integration begins.
24.1.1. Controller Tuning The performance of a controller depends more on its tuning than its designs. Tuning is applied to the end user to fit the controller to the controlled process. There are different approaches to controller tuning due to performance criteria selected, whether it is load or set-point changes are important, or process is lag-or dead time-dominant and the availability of information about the process dynamics. Controller Performance Criteria: The measures of controller performance in an industrial setting are the maximum deviation in the controlled variable that results from a disturbance and its integral.
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24.2. BENEFITS OF ADVANCED CONTROL The efficiency of most processes is determined by steady-state operating conditions. Economic performance is enhanced by the steady-state operating conditions alterations that lead to more efficient process operation. The following hierarchy is used for process control:
Level 0 - Measurement Devices and Actuator Measurement devices and actuator: These devices and methods are used for sampling biological fluid as well as to measure the target constituent within the biological fluid. Obviously, the subject devices have a sampling device that is used for skin surface work which helps to provide access to biological fluid. The devices are best to used in the sampling and concentration measuring of glucose in interstitial fluids which also provides kit that include subject devices used in practicing the subject methods
Level 1 - Functional Control Magnetic resonance imaging is used to investigate the neural correlation of self-regulatory control across development in healthy individuals performing the strop interference task. Performance of task allows the involvements of self-regulatory control to inhibit an atomized response that is in approval of another, less automatic response. The magnitude of fMRI signal change has an increased age in the right inferolateral prefrontal cortex and the right lenticular nucleus. It is inevitably not possible that age related changes in the ability to read or in the ways used to optimize task performance would affect the findings.
Level 2 - Supervisory Control This is a class of important system that is formed otherwise called discreteevent systems. These systems are modeled by automata together with a mechanism to enable and disable a subset of state transitions. The situation is to ensure by appropriate supervision that the closed loop behavior of the system falls within a legal behavior. If a behavior is decayed into an intersection of component restrictions, conditions are determined which is possible to synthesize the appropriate control in a integrated way
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Level 3 - Production Control Project controls have been focused on after the fact detection of variances. The last planning system made an excellent application by firms with direct responsibility for production management;, e.g., specialty contractors. These application poses two research questions thereby (1) what tools provides and improved implementation of the Last Planner system of production control to increase plan reliability above the 70% PPC Level? (2) How/Can Last Planner be successfully applied in order for plans to increase it reliability during design process. This question is investigated in an extensive case study, that has significant contribution to understanding design process from active control perspective
Level 4 - Information Technology This reports on the development of an instrument that is designed to measure the various perceptions that may be adopting an information technology (IT) Innovation within organizations. Consequently, the lack of a theoretical foundation for these research and inadequate measurement of constructs has been programed as major causes of the outcomes. In recent studies, the diffusion of new end-user IT, focused on measuring the potential adopter’s perceptions of the technology. Measuring these perceptions is a downfall in the innovation diffusion literature. The was based formerly on the five characteristic of innovations formed by Roger (1983) form the diffusion literature, with additional two developed within the study. The main object was to verify the convergent and discriminant the validity of the scales in examining how the items were measured into different construct categories. This analyses inter-judge agreement about item placement that identifies both bad items as well as weaknesses in some of the construct’s original definitions. Levels 2, 3 and 4 clearly affect the process economics, as all three levels are directed to optimizing the process in some manner. Most processes are determined by the constraint; which could be product specifications and problems associated with the constraint causes off-specification product. Also, the constraint is equipment limit and any violation of the constraint causes equipment protection mechanism to activate. In advanced control techniques, the single-loop PID controller is acceptable in many process applications but has a poor performance for processes with slow dynamics, time delays, frequent disturbances, or multivariable interactions.
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In feed-forward control, if the process shows a slow dynamic response and disturbance frequently, there is advantage in the application of feed forward control. Feed forward control (FF) control is different from feedback (FB) control in that primary disturbance or Load (L) is measured with a sensor and the manipulated variable (m) is adjusted. In cascade control, the failures of using conventional feedback controller is because there is not disturbance until controlled variables deviates from its set point. Correction by feedback controller is usually slow and delayed or results in long-term deviation from set-point. One way to improve the dynamic response to load changes is by using secondary measurement point and controller. The measurement point is located as it recognizes the upset condition before the primary controlled variable is affected. Furthermore, selective and override control is when there is more controlled variables than manipulated variables and a chosen selector is used to solve the problem from among a number of available measurements. Selectors can be categories by a number of different options such as multiple measurement points, multiple final control elements or multiple controllers. Selectors help in the improvement of control system performance as well as protect equipment from safe operating conditions.
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REFERENCES 1. 2. 3.
http://accelconf.web.cern.ch/AccelConf/ICALEPCS2013/papers/ thppc081.pdf http://web.mit.edu/cheme/news/seminars-16/PaulsonJoel.pdf https://www.britannica.com/technology/control-system
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CHEMOMETRICS The chapter will introduce the reader to instrumental analysis in chemistry, calibration techniques in chemical and biotechnology engineering, analytical techniques such as variance analysis, correlation coefficients and multivariate analysis. The instrumental chemistry is defined as such branch of chemistry in which different analysis and investigations are made on analyte with the help of instruments whereas an analyte is a substance whose chemical properties are being studied. There are various instrumental techniques in chemistry which are further divided into various categories depending upon the type of analyte. Many methods are quantitative as well as qualitative analysis but the major categories are separatory, spectral, and electroanalytical. The first instrumental method is the spectral method in which electromagnetic radiation are applied which is being scattered or absorbed by the analyte. As the type of radiation emitted by the analyte can be different from one another, in which material properties is identified and spectral instrumental analysis possess the largest instrumental techniques of chemistry. One of the mostly used spectral methods is absorptiometry in which electromagnetic radiations are provided by the instrument and are being absorb the analyte and the quantity of radiations absorbed the material is measured, in radiations the photons strikes the molecule and transfer its energy and make them excited (high energy state) and the energy of incident radiation decreases as well. The absorptiometry is further subcategorized into many types and the types mainly depend upon the type of emitted radiations and the wavelength. There types are radio waves absorptiometry (in which
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nuclear magnetic in terms of resonance spectrometry is studied ultravioletvisible absorptiometry), infrared absorptiometry, and X-ray absorptiometry. The instrument and their tendency to measure the radiations from one spectral region t another can be different but their operating principles is the same and they consist of three essential components which are given as a source which produces the electromagnetic radiations, a specially designed cell which contains such properties that it is transparent to radiations but contains the sample that is being studied and a detecting equipment that measures the amount of radiation which is absorb by the sample. Similarly, nuclear magnetic resonance is another form of spectral method of instrument analysis. The absorption by analyte results in various physical process within it and the radio frequency of radiations causes the nucleus of an atom to spin in different state in the presence of an magnetic field, the nuclear magnetic resonance method helps us in this way to study the nuclei of an atom as well as its possible transition between different spin states. Since different kind of atoms possess different spin state which are further separated from each other by their amount of energy possessed by them, in this way this method of spectral analysis of instrumentation identifies different types of atoms in analyte and the observation on the spin states can only be monitored in the presence of a magnetic field. Another spectral methods is microwave absorptiometry is similar to nuclear magnetic resonance but in this methods electron spin resonance is studied and the absorb radiations by the sample falls into microwave spectral region and transition of spin states of electrons occurs as a result. The presence of magnetic field is also required in this method and this application is mostly utilized in the study of different structures and chemical reactions of materials which contains unpaired electrons. The last method of spectral analysis of instrumentation is heat analysis in which heat is added to the analyte and its properties are being monitored its temperature as well. The change in temperature is compared with internal changes of the sample and this result is then utilized in the quantitative and qualitative analysis and mechanism of decomposition for analyte is determined. Infrared spectrophotometry is another technique for the instrumental analysis in which the infrared radiations are absorbed by the analyte and causes the rotation and vibrational changes in the sample. The changes caused by vibrations are different energy level of vibrations within the same molecule. The infrared spectrophotometry is primarily used for organic
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analysis as the vibrational energy levels are mainly dependent on the type of atoms and on the functional groups attached to the molecule. It also contains its application in quantitative analysis as well. Similar to infrared spectrophotometry, the Ultraviolet-visible spectrophotometry absorbed by the analyte and it causes the electrons of atoms in its outermost shell to jump into unoccupied high energy state. The Ultraviolet-visible spectrophotometry principle is mainly used in quantitative analysis of different types of molecules and their atoms. This method is much more useful as the height of peaks of absorption of ultra-visible region in organic and inorganic compounds is much more as compared with other methods of instrumental analysis. In case of gaseous state, if the analyte is constituent of atoms only then this methods is given the name as atomic absorption spectrophotometry. Another method of instrumentation analysis is X-ray absorption which the X-rays are radiated on the analyte and the occupied outermost electrons are excited which are moved into unoccupied shells. Also the energy of X-rays can even sometimes ionizes the analyte as they also have the tendency to remove the electron or electrons from the atom or molecule. The study of X-ray absorption is only limited to the atom rather than the whole molecules as the inner shell electrons are linked with the atoms. This method is used in quantitative analysis by comparing the results of spectra of unknown substance with the spectra of known analyte. The shapes of spectra obtained in the X-ray absorption are different than the other methods of absorptions but the operating principle of all the methods are same. Various statistical techniques are applied on the result that area obtained from the instrumental analysis of various analyte. The analytical chemistry works in such a way that there are always chances of errors. If results from different sources consisted of variability then the sources of error must be identified and further controlled in an efficient way. Variance is used in such cases which is a statistical technique which estimate such factors whom contribute to the significance of results and removes the error from the calculation. The potential of chemometric is huge and it key is understanding how to perform meaningful calculations on data. Most cases, this calculation is too complex to use by hand or calculator, so software is being used inevitable. Data analysis is not knowledge based but a skilled based subject and the key is to understand few basic principles. MATLAB and Excel could be considered useful simultaneously. Excel provides a good and new interface
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and allows examination of data while MATLAB is best for developing Matrix based algorithms. A design metrics is a very important concept. Chemometric are interested in industrial process control and monitoring plus aspect of analytical chemistry and near-infrared spectroscopy. Chemical analysis is based on measurement of different physical and chemical quantity with the aid of measurement equipment. The accuracy of the measurement is paramount with the use of instrument calibration. Laboratory inspections are vital as a result interlaboratory test are conducted. Large amount of homogenous sample is produced and smaller subsample to the participating sub laboratory are sent. Results of the participant analyses are collected and evaluated. The laboratory assessment is performed on the basic of trueness and precision of its results. Interlaboratory tests are carried out as a test of the practicality of a new analytical procedure, to determine the characteristic of the procedures, to identify the characteristic of a referential material.
25.1. INSTRUMENTAL CHEMICAL ANALYSIS The aim of instrumental chemical analysis is the same as those of qualitative and quantitative chemical analysis; difference is that instrumental techniques are used instead. Equipment which has been specially designed to measure specific phenomena are; optical, electrochemistry, and chromatography. Many types of analysis can be carried out in a effective and efficient way. This is also based on the type of machine used by electricity. The following subsections describes below are the analytic chemical instruments.
25.2. OPTICAL METHODS 25.2.1. Molecular Absorption Spectroscopy Molecular structures at chemical processes are important for predicting molecular reactivity and reaction mechanisms. A laser pulse as an internal clock is used to begin fundamental chemical processes, and molecular structural dynamics is characterized by coherent vibrational motions. Current developments in pulsed X-ray facilities makes structural determination of discrete excited states and reaction intermediates that uses laser-initiated time resolved X-ray absorption spectroscopy (LITR-XAS). Moreover,
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femtosecond X-ray sources starts making significant contributions coherent molecular motion. Further applications with high time resolution allows visualization of fundamental chemical events in many systems and promotes our understanding in photochemistry.
25.2.2. Molecular Fluorescence Spectroscopy There are new tools for the study of individual macromolecules under physiological conditions. This is because of advances in single-molecule detection and single- molecule spectroscopy at room temperature by laserinduced fluorescence. The activity of these tools relay conformational states, conformational dynamics, and activity of single biological molecules to physical observables, which are uncovered by ensemble averaging. Time trajectories and distribution can be measured during a reaction without matching all the molecules in the ensemble.
25.2.3. Atomic Absorption Spectroscopy Metal stress in seawater was studied for a long period; poor analytical techniques and unrepresentative sampling have made published data not useful when acknowledging the role of elements in the geochemical and biological cycles of the ocean. A solvent extraction method is devised to recover copper, zinc, cobalt, nickel, and lead from seawater and then it is transferred to solvent suitable for direct analysis by atomic adsorption spectrometry. At these low levels, extreme care should be taken in the development of a suitable method of analysis and working on the samples. Statistical treatment of the data is developed and enables us to use computer program to process the raw data and calculate confidence limits on each analysis.
25.3. ELECTROCHEMISTRY METHODS 25.3.1. Potentiometry This method is used for performing attractive mode force potentiometry with sub millivolt accuracy and a spatial resolution of order 50 nm. The technique allows measurements made in air on specimens that are passivized or oxidized, conducting or semiconducting, with zero sensitivity to oxide thickness or character. Potentiometric stripping analysis is made for highly sensitive measurements of single stranded DNA at carbon paste electrodes.
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Electrochemical (oxidative) pretreatment is used to condition the carbon paste surface prior to the accumulation process.
25.3.2. Electrogravimetry A model of transport of the charge carriers and neutral species in conducting polymers is presented. Considered the diffusion of anions, cations, and solvent in the polymer and the ion and solvent transfer kinetics at the polymer solution interface. The electrochemical impedance and electro gravimetric transfer function are derived and are calculated and plotted under several experimental conditions. These are carried out on polyaniline film coating one of the electrodes of a quartz crystal microbalance.
25.3.3. Coulometry The discharge and charge endpoint capacities as well as the coulombic efficiency of Li/graphite coin cells examined using the high precision charger. Cells were charged and discharged at different c-rates and temperatures observe the trends in the creation of the solid electrolyte interphase (SEI) on the graphite electrode. The experiments show that time and temperature are the dominant contributors to the growth of the SEI. The charge consumed by the SEI is proportional to the electrode surface area and this increased consumption on high surface area electrodes continues during cycling.
25.4. CHROMATOGRAPHY METHODS 25.4.1. Gas Chromatography In gas chromatography applications, the present invention provides a recirculating filtration system that is used with a transportable ion mobility spectrometer. This has a pump and a set of filters and flow sensors that are connected to an ion mobility spectrometry sensor which comprises of gas chromatograph column at its inlet. The filter cleans the portion of the IMS sensor’s outlet flow and circulates back to the IMS sensor as a carrier fluid stream flow by the pump. The amount of flow equals to the amount of flow introduced into the sensor as the sample is exhausted by the filtration system to maintain a constant total flow volume that is through the system when the sample is being analyzed.
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25.5. HIGH PERFORMANCE LIQUID CHROMATOGRAPHY (HPLC) This is a sensitive method used in determining free and total homocysteine in human plasma which consist of free homocysteine that is protein-bound. The thiol compounds in plasma, which are liberated from plasma proteins with tri-n-butylphosphine, and are derived with thiol-specific fluorogenic reagent, ammonium 7-fluorobenzo-2-oxa-1,3-diazole-4-sulphonate. These are separated by reversed-phase high-performance liquid chromatography.
25.6. THIN LAYER CHROMATOGRAPHY A novel planar liquid chromatographic technique that uses a pressurized ultra microchamber (PUM chamber) has been developed. The sorbent layer is covered by a membrane under external pressure, thereby eliminating vapor phase. The pump system admits the solvent. The main advantage of this technique overpressure thin-layer chromatography (TLC) has a shorter time needed for separation than a classic column chromatography. This method appears is suitable for the accurate modeling of column chromatographic method.
25.7. ION EXCHANGE CHROMATOGRAPHY This unit has the basic steps in planning and carrying out ion-exchange chromatography to separate proteins. These describe both batch adsorption and column chromatography in conjunction with either step or linear elution gradients. The support procedures are (1) Pilot experiments that determines initial conditions for batch or column chromatography, (2) Calculates the dynamic capacity of an ion-exchange column, (3) Methods for producing continuous gradients of pH and salt concentration to elute protein from ionexchange columns, (4) regeneration of used ion-exchange media and (5) storage of ion-exchange media.
25.8. OPERATING LINE The response given by the instrument is converted to an analytical result and one of the frequently used methods is that of an operating line. A graph is mapped out experimentally before a specific analysis before real sample are given. The line produced in response to the signal which shows a chemical parameter (concentration, quantity of material) ensures that analysis is
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carried out within a certain interval. The analytical instrument reacts to a stimulus at entry to produce a response which is a measure of some physical size.
Imagine that x is the concentration of the analyte and that y is the response of the instrument with depends on the way it functions, identification of the relation y=f(x) is possible for an analytical procedure. This links the two value and the graphic representation of the equation is called an operating curve. In making effective change, the calibration curve is reduced to a straight line expressed in an equation like where: • •
is the angle coefficient of the x axis and the slope is the y – intercept; the point of interception with the vertical axis Working out the relationship by tracing the operating line which enables the determination of analyte. One or more standards are used taking the y value from the instrument and mapping the points on the graph. These solutions at various concentrations are used to construct the operating line. Standard solutions at operating points are diluted as necessary ensuring that significant mistakes are not made during their preparation.
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REFERENCES 1.
2. 3. 4. 5.
Funk, W., Dammann, V., & Donnevert, G., (1992) Quality Assurance in Analytical Chemistry. Application in Environmental, Food, and Materials Analysis, Biotechnology, and Medical Engineering. 15-32 http://pubs.acs.org/doi/abs/10.1021/ac00237a051 http://pubs.acs.org/doi/abs/10.1021/ ac50016a715?journalCode=ancham http://www.federica.unina.it/agraria/analytical-chemistry/ instrumental-chemical-analysis/ https://www.britannica.com/science/chemical-analysis/Classicalmethods#ref621130
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PROCESS MODELING AND SIMULATION The chapter will introduce the readers to process and operations modeling, random variables and probability distributions, model design, applications of simulation modeling, analyzing simulation output, advanced arena concepts, inventory theory and queuing, resource allocation problems, applications of linear programming, transportation models, network analysis, and decision analysis. As the previous chapter describes instrument analysis of chemistry but this chapter will discuss different aspects of modeling and simulation techniques and their importance in daily life, some other terminology will also be discussed as well. Modeling and simulation of a process is basically a technique or methodology for the representation of a process or systems by using various mathematical equations or physical measurements. Both, modeling and simulation are treated individually and contain equal importance. Modeling is used for conceptualization and to make various assumptions which can be further utilized during the designing of a specific model and its implementation in the real world. The execution of this model comes under the umbrella of ‘simulation’ in which implementation and experimentation of a model takes place, its behaviors with various environmental parameters is noted and different conditions are applied to it. Modeling and simulation is used for developing data for decision-making and other managerial queries by repeating a set of simulations to visualize its actual impact. It can facilitate to design and implement a systematical model without testing the model in real conditions of the world and its result can be obtained. A very common example is during the design of car spoiler
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or its front hood, different computer simulation software can be run to find out the fractional effect of the car and to remodel the design according to the parameters, so useful information can be obtain without actually designing the car which not only reduces the cost but also saves time in remodeling in further adjustments according to the needs of latest design. Similarly, the simulation can be run by different software for chemical experimentation and other human machine interaction designs where simulation helps in data mining for actual models and also possess the ability to represent the whole system. Moreover, different virtual software are available for the purpose of training which was previously dangerous and expensive in real world environment. Modeling and simulations techniques are the foundation stones of every engineering process and system design and contains all the necessary tools to make models to set new industrial environments. It can be used to reduce the cost of the product, increasing the quality and finishing of product and learning can be done much easily. The simulation-based software are widely used in many application. As described earlier in this chapter, the use of simulation s much cheaper and easier than conducting the experiments in the real world, an example can be use of super computer to simulate the detonation of nuclear explosion and its effects can be seen with the help of it. Similarly, such simulation can be used to describe the damages caused by a hurricane or storm. Different simulation are used to solve the operation problems which can be created in the environment during a process, its example is deep sea analysis of a natural process is done with the help of simulators. Similarly, simulation can be resulted much faster in decisionmaking process. They can be helpful during the state of IF-THEN-ELS where they can find and lead to true state of the system more logically then time taking calculations and experimentations. That is why they are said to be the toolbox of engineering and decision support system. They have been used in analysis support program for experimentation and planning. They can directly lead to an optimal solution can save the time of design and engineering team. Inventory theory is also known as material theory and this terminology is frequently used in inventory and production units of a chemical industry. It is utilized in various operation management and research management, which are concerned with the designs to reduce the cost of overall product. It deals in such organizations in which spare part allocation, manufacturing, logistics, supply chains, warehousing of different parts of product takes place. However, with the help of inventory theory, the manufacturing unit of
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an industry knows that how much they need to make the product to meet the demands of their client. These kind of inventory problems can be eradicated by using mathematical equations of optimal control, network optimization, systematic approach of controlling production and dynamic programming. These kinds of pre-defined models are the part of inventory theory. Mathematically, it is stated as xk+1 = xk + uk – wk uk ≥ 0
in the above equation, the store has Xk items at the time of k, it can receives the amount of orders uk and the number of items sold are represented as wk, Xk is allowed to go on back orders which purely depends upon the demand of particular products. The last topic of this chapter is about linear programming, it consists of such mathematical techniques and models which can give best possible result in a given situation and its representation is in the form of linear relationships. It also can be used for optimization in different design processes as a linear function. There are various applications of linear programming in different fields, they can be used to solve complex engineering problems to mathematics, economics, and businesses sciences and their industrial usage are in, telecommunications, transportation, energy, and manufacturing. They are mainly used for optimization in various departments of industry, some problems such as flow problems of multi commodity and networks are one of the major concern of linear programming which utilizes research on algorithms to generate best possible solution for such difficult problem. In terms of economics, their applications include microeconomics and company managerial problems, for example, production, planning, technology, and transportation. With the passage of time, modern management are changing and every company want to obtain maximum profit but minimum expenditures of resources, so in such scenarios, every organization is seeks the help of linear programming to meet their such demands so that they can cope with the requirements of their clients. A number of different algorithms are available to solve the problems according to the type of organization and their actual demand. A model imitates the reality and mathematical model is a form of identification. Process engineering area the models we deal with are fundamentally mathematical in nature
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The characteristic nature of the process models includes mechanistic models also refers to as phenomenological models due to basic derivation from system phenomena example mass, heat and momentum transfer. They contain empirical parts such as rate expressions or heat transfer relations. Empirical models are result of experiment and observation. It does not rely on the knowledge of the basic principles and mechanisms, which are present in the system. Deterministic models are characterized by cause – effect relationships. Stochastic models arise when the description contain elements with natural random variations that is described by probability distributions. This characteristic is associated with phenomena that are not explained in terms of cause and effect but by probabilities. Modeling characteristics and analyses includes models developing in hierarchies where several models for different tasks with varying complexity in terms of their structure and application area. Models exist with relative precision, affecting how and where it can be used. Models cause us to think about our system and force us to consider key issues. It can be difficult or impossible to validate properly. Models are intractable in terms of their numerical solution. The modeling goals explain the intent usage of the model and have major impact on the level of details needed. In process engineering, the important use of models is written below. In dynamic simulation, models develop to represent change in time. It is possible to predict the outputs O given all inputs i, the model structure M and parameters p. While static or steady-state simulation, the process system is at steady state representing an operating point of the system and the simulation problem computes the output values o given inputs i, the model structure M and its parameters p. Most design problems are solved using an optimization technique that finds parameter values that generates the desired outputs.
Many process models are non-linear and when the model consists of one differential equation, solution may not be too difficult. When multiple
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differential equation is involved, difficulty in getting into the dynamic process behavior can occur.
26.1. PROCESS CONTROL The principle of conversation is based on the fundamental physical law that mass, energy, and momentum can neither be formed or destroyed. A system is usually a defined volume, process unit, or plant. The fundamental problems in process control are to consider a dynamic process model together with measured inputs i, and/or outputs o in order as follows. Design an input which the system responds in a prescribed way, giving a regulation or state driving control problem. Finding the structure of the model using input and output data thus giving the system identification problem. Finding the internal state in giving a state estimation problem using a form of least square solution. Find faulty modes and system parameters corresponding to measured input and output data that leads to faulty detection and diagnosis problems. Process modeling is regarded as more art than science and engineering and it is an engineering activity with a growing maturity. One important aspect is the application of conservation principles for conserved extensive quantities. The development of the constitutive relations that provides a set of relations used in completing the model. This is based on the fundamental principle of physics that mass, energy, and momentum are neither created nor destroyed but can change from one form to another. The possibilities of testing application software before operation was much reduced or impossible, in this case, application software was used in testing and adjusting directly within real technology during putting into operation. Practically, this is time consuming and not efficient for the project. Possibility of testing and verifying reaction of control system to all the fault and emergency events occurs. Present day technology has made it easier for developed tools and programs for testing application software for modeling and simulation of technological processes has been produced. Amongst other things, responses to failure and emergency events are evaluated, control algorithms are designed and optimized, sequential logic and user interface are tested. Control systems presently test is done during the development, and putting into the simulations techniques for the following purposes:
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For the effective functioning of the technology, it is important for control system to provide basic control of actuators, functions according to technological conditions, automatic sequence and regulation of number of operation signals (pressure, flow, temperature, force, velocity, voltage, current, etc.) Feedbacks are collected from technological process such as valve position, auxiliary contacts of contactors and values of the process signals. To keep predefined values of the process signals at précised levels, one affects quality of output of manufacturing process, amount of needed resources and financial demands of a given manufacturing process. A given emphasis is placed on optimization of control algorithm and it parameters. Function of the process simulation provides a feedback for a tested program as close to real technology as possible to test sequential logic and control algorithms and to optimize their parameters. Visualization of all the states and signals needs testing, which includes all failure stated, emergency states, and their arranged display at visualization mimics. Simulation during application development allows programmers to test specific units during early phases of the project, which eliminates amount of possible repetitive errors and consequently simplifies overall application testing. This covers simulations of operator panels that verify their appropriate design and functionality. This makes it possible to test real control of technology and possibly modify the design of operator panels with additional requirements before their manufacture. Specialist intervention experts on process technology monitors simulation of behavior of the process technology. This behavior is verified by functional description of technological unit. Experts on process technology receive feedback since they cannot cover all the states of controlled technology in the functional description. By means of simulation together with a PLC programmer, they are defined and solve possible incomplete description of technology unit yet before putting control system into operation. Training operators simulation system provides a complete set of user interface (simulation of operator panels, control boxes) that are used for training operators of controlled technology and technological processes for functional tests of devices. Operators can control the technology before realization and train failures states that cannot testes under real operation. Advanced operators put up their feedback and reveal possible other pitfalls of the technological
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process before live operation. Workers putting system into operation at the destination is appreciable due to the workers with tuning control loops and their optimization and with adjustments of application software. Linear programming (LP, also called linear optimization) method that achieves the best outcome (such as maximum profit or lowest cost) in a mathematical model. This is a special case of mathematical programming and it is widely used in business and economics and used in some engineering problems. Industries using linear programming models include energy, transportation, telecommunication, and manufacturing. This is useful in modeling diverse types of problems in and for planning routing scheduling assignment. If the problem is strong duality theorem, the primal problem has an optimal solution, the dual problem has one also and there is no duality gap. But it is not an optimal solution, it is unbounded. The unboundedness of the primal + weak duality theorem or dual problem must be infeasible. Duality theorems general LP problems contains equalities or unrestricted variables, these can also be handled easily. Equality constraint corresponds to an unrestricted variable and vice-visa. Duality theorems general problems suppose has no sign restriction. Then we could not conclude that 3x1 + 2x2 ≤ 4x1 + 2x2 holds for all feasible solutions (e.g., if x1 = −1; x2 ≥ 0 holds) In general 3x1 ≤ (y1 + 2y2) x1 [∗], thus set y1 + 2y2 to its maximal value 3, [∗] holds for unrestricted x1 Similarly true that a primal “≥” constraint corresponds to an non-positive variable, and vice-versa. An LP in which all variables are required to be integers is called a pure integer programming (IP) problem. For example, max z = 3x1 + 2x2 st x1 + x2 ≤ 6 x1, x2 ≥ 0 x1, x2 integer. An IP in which only some of the variables are required to be integers is called a mixed integer programming problem (MIP), e.g., x1, x2 ≥ 0 and x2 be an integer (x1 is not required to be an integer). A node of the branching tree is “measured” if there is no feasible solution of the corresponding subproblem and the subproblem yields an optimal solution where all variable has integer values. The optimal z-value for the subproblem does not exceed the current. In the case of LP, the goal was to minimize linear function subject to linear constraints. The interesting maximization and minimization problems the objective function may not be a linear function and some of the constraint are not linear constraints.
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REFERENCES 1. 2. 3.
http://www.inf.u-szeged.hu/~london/LinProg.html https://datasciencebowl.com/useful-applications-of-simulationmodeling/ https://www.engineering.com/Blogs/tabid/3207/ArticleID/920/ APPLICATIONS-FOR-SIMULATION-MODELING.aspx
CHAPTER
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POLYMER TECHNOLOGY The chapter will discuss the topics such as nomenclature and fundamental concepts of polymers and polymerization, polymer stereochemistry, crystalline, copolymers, and viscoelasticity and polymer processing. Polymers are chain-like structures, formed by joining so many structural units together by different types of linkages. Along with natural polymers such as starch, cellulose, rubber, etc., artificial polymers are also prevailing on industrial scale. Polymers have vast applications in different fields, for example, polymers are used to improve the aeration of soil to improve the plants growths and health. In medical field polymers are used to make heart valves and blood vessels. All packaging materials and plastic containers are the applications of polymers. Similarly, on industrial scale polymers have vast application like parts of automobiles, windshield of planes, adhesives, matrix for composites, and elastomers are all forms by polymers. The process of chemical combination of monomers to make chain like structures is called polymerization. Minimum 100 monomers molecules must be combine to make a product having different physical properties. For example, as elasticity, the ability to make fibers, tensile strength, etc. These physical properties and the covalent chemical bond make polymers different from other compounds and molecules formed in other process like crystallization in which molecules combine by weak intermolecular forces. Polymerization is categorized in two classes. One is condensation polymerization, in which molecules of simple compounds like water are formed. Second is addition polymerization, in this process by-products do
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not formed and catalysts are generally used which change certain structures and hence the properties of polymers. Linear polymers are formed by viscous molecules like liquids or solids having different crystallinity. They have tendency to dissolved in some liquids, and soften upon heating. Crossed linked polymers are formed when molecules combine in the form of thermosetting resins having network like structures they do not melt upon heating not even dissolve in solvents. Both linear and cross-linked polymers can be made by either addition or condensation polymerization. Polymer and macromolecule are two different things. Macromolecules combine to form a polymer. The end product is usually measured in terms of molar masses (unit g/mol), its distributions of is called as dispersity (Đ) which is the ratio of the mass-average molar mass (Mm) to the numberaverage molar mass (Mn), i.e., Đ = Mm/Mn. Only in idealized representations Polymer nomenclature is considered by ignoring irregularities of structures. There are two ways to name a polymer. Source-based nomenclature is used where monomer are known. Alternatively, more obvious and common is structure-based nomenclature is used where the structure of polymer is confirmed. Traditionally different syntaxes for names are also acceptable. In every case polymer names must have the prefix poly, followed by round brackets having the rest of the name, e.g., poly (4- chlorostyrene). Locants indicate the position of structural features. Enclosing marks are not important for source-based one word name having no locants. But in case of confusion it should be used, e.g., poly(chlorostyrene) is a polymer but if it is written as Poly chlorostyrene might be a multi-substituted, tiny molecule. End-groups are labeled with α- and ω, for example, α-chloro-ω-hydroxy-polystyrene. When a polymer having chain like structures show stereochemical isomerism, its properties its properties become dependent to stereochemical structures. So the study of the stereochemistry of polymers is significant and NMR spectroscopy tool is so helpful for this study. Tacticity is the word used for defining the stereochemical structures of polymers. In polymers of vinyl monomers CH2=CH-X or vinylidene monomers CH2=CXY, the main-chain carbons with substituent group(s) are called as “pseudo-asymmetric” if carbons at the ends, do not have the four different substituents then it will not be truly asymmetric but its relative handedness increase. In isotactic structures all the substituents are positioned on one side of the zigzag plane showing the chain overextended in
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an all-trans conformation. The structure is represented by a “rotated Fischer projection” in which the main-chain skeleton is shown by a horizontal line.
Syndiotactic structures are regular arrangements in which the groups substitute alternatively from side to side which make the configurations with neighboring units opposite
The unit diad or dyad represents the comparative configuration of the successive monomeric units. For a vinyl polymer, two diads meso (m) and racemo (r) are considered with these representations, an arrangement in an isotactic polymer can be written as -mmmmmm- and incase of syndiotactic polymer it can be written as -rrrrrrrr-. In reality, however, purely isotactic or syndiotactic polymers are seldom attainable but the level of symmetry need analysis. Tacticity [1] is the term used for defining such stereochemical features of polymers.
The quantitative data of tacticity is provided by NMR spectroscopy. By extending the notation of m and r, one can define relative configurations of longer monomeric units can also be defined by using the notations of m and r along the chains. Figure below is representing the three possible triads,
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shown by mm, rr, and mr. Which are also named isotactic, syndiotactic, and heterotactic triads, respectively. Similarly, for the tetrad, the following six distinguishable sequences are possible mmm, mmr, rmr, rrr, rrm, mrm, and for the pentad mmmm, mmmr, rmmr, mmrm, mmrr, rmrm, rmrr, mrrm, mrrr, rrrr. Hatada and Kitayama (2004)
27.1. CRYSTALLINE POLYMERS The term crystalline is used to describe the regions in a polymer where the chains are packed in a regular way. Many polymers have combination of crystalline (ordered) regions and amorphous (unordered) regions. Amorphous areas have more tendency for mobility as the chains are more extended. A polymer chain can be part of an amorphous or crystalline area. Spaghetti can be consider as an example for the representation of different areas. If we observe spaghetti through a glass bowl some regions will be grouped together in a regular arrangement, while some regions will be totally mixed up. After a short-term introduction to the different types of polymers now it’s time to study some important processes for thermoplastic materials. These are named as extrusion and injection molding. Single and twin-screw extruders are used for melting and pumping of polymers and for die extrusion for the production of sheets, pipes, tubing, etc. Injection molding is the process of injecting a molten polymer into mold cavities in order to make parts of different sizes. Various problems create during these processes, for example, die swelling, melt fracture (spiraling, bam booing, regular ripple, random fracture). Other processes like calendaring, compression molding, rotational molding, powder injection molding and thixomolding are also used in polymer processing. Polymer processing is the engineering activity that is concerned with operations carried out on polymeric materials to increase their utility. It primarily deals with the conversion of raw polymeric materials into finished products, that does not only shape but compounding chemical reactions that
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leads to macromolecular modifications and morphology stabilization, and value-added structures. Polymer processing analyses specific processing methods such as extrusion, injection molding calendaring. This approach claims that occurrences in polymer in a certain type of machine is not unique. Polymer is a study of materials of comparatively simple recurring units. They mostly occur in nature and are also made of large number of glucose unit which are natural rubber, these are called polyisoprene and polysaccharides, examples are starch and cellulose.
Most times, rubber is difficult to define but is a material that can stretched to double its original length and can retract quickly to it original length and it can easily be formed in it raw state and can retain its size and form when vulcanized. The effect of vulcanization in a rubber is to reduce it plasticity and reducing it elasticity at the same time. Plastic can be divided into two main subgroups thermoplastics and thermoset materials. Thermoplastic are materials that softens when heat is applied and hardened when cooled while thermosets soften once and harden irreversibly by the application of sufficient heat. The different softening point in a plastic are due to relative strength of their intermolecular forces. Further classification on the basic type of chemical reaction are addition or condensation.
27.2. ADDITION POLYMERIZATION They are usually thermoplastics and the resultant polymer is obtained by a combination of many simple basic substances without loss. These substances are called monomers. There are four basic methods of carrying out addition polymerization with it advantages and disadvantages and these are not based on their monomers being polymerized.
27.3. BULK POLYMERIZATION Pure monomers with the additional of catalyst is used this process of polymerization. This mixture is stirred in a large reactant vessel with or without the application of heat. The advantage of this process is the purity of the final product with excellent color and clear polymers such as Polystyrene. This is economically attractive as raw materials cost only contain monomers.
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Manufacturing process is difficult as addition polymerization are exothermic and with large quantities of undiluted reactants causing difficulties as heat separate. This also involves increase in viscosity and stirring becomes difficult and impossible.
27.4. SOLUBLE POLYMERIZATION This is process where monomer and catalyst are dissolved in an inert solvent when the resultant solutions are being stirred and heated. Both heating and stirring problems are lessened in solution polymerization. Economic problems are inevitable due to the use of large quantities of expensive solvents to be recovered and separated. The concentration of resultant polymer is lower than bulk polymerization with inert solvents. Polymer is soluble in solvent and the removal of the last traces is difficult and for this reason, the solution process is often resorted for those application where polymer is required in soluble form.
27.5. EMULSION POLYMERIZATION In this process, the continuous avenue is water and the monomers are separated instead of being dissolved. Thus, the resultant polymer medium is insoluble and therefore precipitation is formed. The catalysts used are soluble in the dispersing medium and emulsifying agents such as sodium, potassium salts of fatty acids are added to stabilize the emulsion. After completion of the reaction, the precipitated product is washed to remove emulsifying agents and some contamination always remains. In this process, there are few heat transfer problems and molecular weight product.
27.6. SUSPENSION POLYMERIZATION The monomers are suspended in the carrier medium together with a monomers soluble catalyst. The mixture concentration is broken into small droplets containing little of the catalyst. A stabilizer such as methyl cellulose is also included in the mixture, so catalyst is separated from each other during the reaction. After the process, the stabilizer is removed by washing and leaving the polymer in the form of beads. The fundamental properties of polymer depend upon the stereochemistry of the polymer chain. Microstructure determines the final properties of semi crystalline polymer products. These products are dimensional accuracy and
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stability. Further determination is done by the thermo-mechanical history done by every single material element during the state of processing. A model for flow- induced nucleation and crystallization is needed as different parameters are used as a driving force. Examples of such parameter are macroscopic strain, the Cauchy stress, the conformation of molecules, phenomenological molecular deformation factor affecting induction time. The disadvantage of this model is the overall degree of crystallinity without adequate final crystalline structure. Another disadvantage is the inability of models to describe processes which causes no flow occurrence during crystallization. Example of this process is push-pull injection moulding. After the mould has been filled, the flow is kept in a backward and forward motion. The mechanical history of the melt is always present in the final state of the solidified material. These crystals combine to give the total degree of crystallinity. One of the challenging problems in polymer physics is the crystallization of flexible polymers from solutions and melts. This is when a highly entangled collection of interpenetrating polymer chains changes into a crystal. This poses difficulty in such a process to complete as a result of topological connectivity of the polymer molecules. Polymer crystallization is negatively affected by large free energy barrier as a result reorganizes polymer confrontation into ordered states. The crystallization process progresses because of nucleation and growth; hence the major theory of polymer crystallization is the generalization of small-molecule crystallization theory of surface nucleation and growth to incorporate chain folding. The purity of a chemical species by the solid from a liquid mixture can be called solution crystallization or crystallization from the melt. A diluent solvent is added to the mixture and the solution is directly or indirectly cooled. The solid phase is maintained and hence formed below its pure – component freezing point temperature. The chemical structure of a block copolymer material is shown in an interesting way by incompatibility effects giving it many specific, new morphologies, original physical and mechanical properties which leads to valuable technological applications. The most typical feature of block copolymer is a strong repulsion between unlike sequences even when the repulsion between unlike monomers is weak. These results in sequences inclining to segregate and as they are chemically bonded, even the complete segregation does not lead to a macroscopic phase separation as a mixture of two homopolymers.
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The application of the linear theory of viscoelasticity is a recent occurrence, the activity is due to the large-scale development and utilization of polymeric materials. A Newtonian viscous fluid responds to an applied state of uniform shear stress by a steady flow process. When material respond in this manner, it exhibits both an instantaneous elasticity and creep characteristics and this is described as a combine features of each. The terms polymer and macromolecule do not have the same meaning. Here a polymer is a substance that has macromolecules and usually have a range of molar masses (Unit g, mol-1), the distributions are specified by dispersity (D). This is defined as the ration of the mass-average molar mass (Mn) to the number average molar-mass (Mn) which is
.
Polymer nomenclature applies to idealized representations; minor structural irregularities are ignored. A polymer can be identified either as a source based nomenclature sometimes called monomer and a more explicit structure- based nomenclature is used when polymer structure is proven. Traditional names are acceptable where there’s no confusion and polymers have names with prefix poly followed by enclosing marks around the rest of the name. These marks are used in the order: {[()]}. Locants shows the position of structural features, e.g., poly(4-chlorostyrene). In the like hood of a source based name of one word with no locants, the enclosing marks are not important but they are used when there’s confusion, e.g., Poly(chlorostyrene) is a polymer where poly chlorostyrene is a small, multi-substituted molecule. End groups are described with α- and ω-, e.g., α-chloro-ω-hydroxy-polystyrene.
27.7. REGULAR DOUBLE-STRAND POLYMERS Double-strand polymers has chains of rings that do not interrupt. In a spiro polymer, adjacent rings has one atom in common with each ring while in a ladder polymer, adjacent rings has two or more atoms in common. In order to identify the preferred CRU, the chain is broken in order for the senior ring to be retained with maximum number of heteroatoms and minimum number of free valences. The preferred CRU is an acyclic subunit which consist of 4 carbon atoms with 4 free valences with additional one at each atom. This enables the lower left atom to have the lowest number. The free valence locants are written before the suffix and they are cited clockwise from the lower left position as: lower-left, upper-left, upper-right, lower-right.
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Crystallization is a first order transition which is liquid to solids as well as water to ice. A less classical transformation is a glass rubber transition in polymers. At the glass transition temperature, Tg the amorphous portion of polymer soften.
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REFERENCE 1. 2. 3.
4. 5. 6. 7.
8.
Christensen, R. M. (1982) (Second Edn.). Theory of Viscoelasticity: An introduction 1-2 http://www.polydynamics.com/Overview_Polymer_Processing.pdf. http://www.rsc.org/globalassets/05-journals-books-databases/ourjournals/polymer-chemistry/brief-guide-to-polymer-nomenclature. pdf. https://www.britannica.com/science/polymerization. Hatada, K., & Kitayama, T (2004) NMR Spectroscopy of Polymers. Stereochemistry of Polymers. 73-85 ISBN: 978-3-642-07293-2. Leibler, L. (1980). Theory of Microphase Separation in Block Copolymers. 13(6), 1602–1617, DOI: 10.1021/ma60078a047. Miles, D. C., & Briston J. H. (1996). Polymer Technology, Third Edition Meijer, H. E. H., Peters, G. W. M., & Zuidema, H. (Eds.). Development and Validation of a Recoverable Strain-Based Model for Flow-Induced Crystallization of Polymers. Material Technology, Dutch Polymer Institute, Eindhoven University of Technology. Reiter, G., & Strobl, G. R. (Eds.). (2007). Progress of Understanding of Polymer Crystallization. Lecture Notes Phys. Doi: 10.1007/ b11903420.
INDEX
A absorption membrane processes 54 adsorbates 55 adsorption 54, 55, 59 Advanced Process Control (APC) 168 aeriform 77 alcohol 73 algae 29 algebraic equation 106 alternating current 95 Amorphous 250 anaerobic oxidation of methane (AOM) 32 analyte 229, 230, 231, 236 analytical ultracentrifuge 119 antibiotics 32 archaea 29, 30, 32, 74 arithmetic logic units (ALUs) 96 Arrhenius equation 42, 43
Aspen Plus 3, 4, 7, 8 atoms 45, 46, 48, 230, 231 autocatalytic reactions 195, 197 automation 220 automobiles 247 B bacteria 29, 30, 31, 32 Bacteriology 31 Bacteroidetes 77 Band Stop Filter (BSF) 91 batch Control 3 batch reactor 196, 198, 200 Bayes factor 216 Binary distillation 54 binomial distribution 213, 214 Binomial random variable 213 biochemical energetics 69 biochemical process 73, 74 biochemistry 63, 69, 71, 73, 74 Biodiversity 192 bioengineering 130
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biological agents 4 Biomass 57 biomass burning 57 biopharmaceutical drugs 174 Bioprocess 173, 179 bioreaction 75 bioreactors 73, 75, 82 bioseparations 73 biotechnology 127, 130, 134 bi-sync protocol (BSC) 102 black body radiation 24 block flow diagram (BFD) 150 Bobbin based Inductors 92 boiling point 23 Boltzmann principle 162 Boolean functions 96 Boyle-Mariotte’s Law 13 Boyle’s law 13 Brownian movement 33 Buoyancy forces 204 C Calibration 136, 140 Cannon-Fenske viscometer 162 capacitor 89, 90 carboxyhemoglobin 26 Carnot engine 39 Carnot’s laws 37 catalysts 248, 252 catalytic hydrogenation reactors 15 Cations 46 Cell 30 Cell therapy 173 cellular composition 29 cellulose 247, 251, 252 central limit theorem (CLT) 215 Centrifugation 119 Ceramics 46, 52 Charles’ Law 13, 14, 19
chemical engineering 147, 148, 149 Chemical equilibrium 7 chemical kinetics 157, 160 chemical plant 4, 7, 8 Chemical process design 148 chemical process simulation 3 Chemical reaction equilibrium 7 chemical reactions 195, 196 chemical reactor 54 chemical thermodynamics 1, 37, 149 Chemometric 232 Chi-square 217 Chloroflorocarbons 184 chromatography 117, 118, 125 circuit elements 83 circuit synthesis 84 closed-loop system 222 Colloids 49 column chromatography 117 communicating sequential processes (CSP) 102 composites 247 Computational Fluid Dynamics 2 computers age 1 conceptualization 239 Conduction 204 conductivity 46, 48, 50 contamination 187, 188, 191 continuous stirred tank reactor (CSTR) 154, 199 controller 221, 222, 223, 225, 226 control system 219, 220, 221, 226 convection 203, 204, 209 corrosion 196 corrosion resistance 51 Corynebacterium glutamicum 75 Coulometry 234 covalent bond 69
Index
Crossbreed electrical lorries 112 crystalline structure 253 crystallinity 248, 253 crystallization 54, 196 crystallization stripping 54 crystallizer 196 crystals 65 current 83, 84, 85, 86, 87, 88, 89, 91 Curve fitting 212 D Dampers 220 Delta Function 107 deoxyribonucleic acid (DNA) 69 desorption 54, 55 detonators 48 diffusion 8, 9, 32, 33, 173, 174 diffusivity 12, 15 digital inverter 97 digital logic gates 95, 96, 98 Dilution 128 discrete-event systems 224 Dispersive Liquid-Liquid micro extraction (DLLME) 177 distillation 54, 56, 59, 60 Distillation 54 dividing wall columns (DWCs) 60 DNA fingerprinting 130 ductility 46, 51 dynamic programming 241 Dynamic simulation 168 E Eco-friendly hemoglobin 25 ecological relationship 29 elastic deformation 159 elasticity 160 elastomers 247
259
electrical energy 90, 91 Electric circuits 83 electric communication of ions 24 electric field 89 electric generator 95 electric motor 101 electrode 26 electrolysis 142 electrolytes 64, 65, 66, 67 electromagnetic forces 95 electromagnetic radiation 229 electromechanical systems 95 electromotive force 91 electronegativity 21 electronics 90, 93 electrons 45, 46, 48, 230, 231 energy 2, 5, 7, 8 energy absorption 119 energy transfer 8 enthalpy 127, 128, 129, 130, 131 entropy 129, 131, 132 environmental chemistry 182 Enzymes 69 enzymes substrates 69 Equalization Filter 91 Equation of states 16 equilibrium 12, 15, 16 equivalent valencies 64 eukaryote cells 31 European Federation of Biotechnology (EFB) 175 F Faraday’s law 91 feedback control loop 222 Feed forward control (FF) 226 feed-forward gain 222 Fermentation 73 Ferrite Core Inductors 92
260
Chemical Engineering Problems in Biotechnology
Ferroelectric crystals 49 fertilization fermentation 23 filteringed system 25 filtering system 26 filters 83, 90, 92 First law of thermodynamics 38 Flowsheeting 2 flowsheet material balance 157 fluid flow 8 fluid mechanics 203, 204, 205, 207 Fluid mechanics 158 Frössling-Marshall formula 79 F-test 217 fugacity 127, 129 fungi 29, 30 G Galvanic cell 144 gas absorption 54 gas chromatography 234 gas constant 5 Gay-Lussac’s Law 14 genome 31 genome-wide transcriptomics 76 genotype 32 germination 23 Gibbs-Duhem relation 131 Gibbs free energy 132 Global warming 192 globulins 64 Golgi apparatus 31 Graham’s Law 13 H habitats 192 halogens 22 Haversian systems 48 Heat 203, 210 heat conduction 8, 9
heat conductivity 12, 15 heat exchangers 207 heat flux 203 heat transfer 53 heat transfer coefficient 203, 208 hemoglobin 25, 26, 27, 65, 66, 67, 68 heterogeneous catalysis devices 81 heterogeneous reaction 196 High Pass Filter (HPF) 91 homocysteine 235 homogenous chemical reaction 196 homopolymers 253 Hopkinson stress bar 48 Human Genome Project 1 hybridization 23 hydraulics 205 hydrocarbons 22 hydrodynamics 205 hydro phobicity 48 I ideal gas 12, 13, 17, 18 Ideal gas equation 5 ideal-gas equation of state 16, 17 Image Processing 51 immune system 30 Inductance 91 inductor 89, 91 industrial ecology 182 industrial system 105 information technology (IT) 225 infrared spectrophotometry 230, 231 Institute of Electrical and Electronics Engineers (IEEE) 102 instrumental chemistry 229 instrumentation 230, 231 integer programming (IP) 245
Index
intermolecular forces 247, 251 International Organization for Standardization (ISO) 102 International Telecommunication Union (ITU) 102 International Union of Pure as well as Applied Chemistry (IUPAC) 120 Internet Engineering Task Force (IETF) 101, 102 interval estimate 216 intramolecular forces 21 inventory 222 inventory theory 239, 240 Ions 64 isolation system 16 isomerization 166 Isothermal Titration Calorimetry 130 K kinematic viscosity 162 kinetic energy 165, 166 kinetic theory 12 Kirchhoff’s laws 84 Kirchhoff’s Voltage Law (KVL) 85 L Laminar flow 207 Laplace transform 106 laser-initiated time resolved Xray absorption spectroscopy (LITR-XAS) 232 Le Chatelier’s principle 153 Lenz’s law 91 level of dissociation 64 Limits of Detection 140 linear ordinary differential equations 105, 106
261
Linear polymers 248 Locants 248, 254 logic circuits 99 logic gate 96, 97, 98 Loops 84 Low Pass Filter (LPF) 91 M macromolecule 248, 254 magnetic fields 83, 89 Manufacturing process 252 manufacturing unit 219 Margules function 127, 128, 131 Mariotte’s Law 13 mass 2, 7, 8, 9 mass transfer 73, 74, 77, 78, 79, 80 mass transfer coefficient 74, 78, 79, 80 Matlab 2 matters 45 mechanical energy 95 mechanical equilibrium 16 mechanical flow diagram (MFD) 151 melting point 23 meshes 84 metabolism 63, 64, 69 metals 196 meteorology 205 Microorganism 29 microporous membranes 59 microporous solids 55 microreactors 4 mitochondria 31 mixed integer programming problem (MIP) 245 Modeling 239, 240, 242 Model Productive Control (MPC) 221
262
Chemical Engineering Problems in Biotechnology
molar mass 17, 248, 254 Molecular structures 232 momentum 8 Momentum transfer 8 monomers 247, 248, 251, 252, 253 montmorillonite 123 morphology 29, 32 multicellular animal parasites 29 Multi Layer Inductors 92 multiplexers 96 N National Institute of Specifications and also Screening (NIST) 137 network optimization 241 neutrons 45 Newtonian fluid 206, 207 Nodes 84 non-equilibrium systems 12 non-Newtonian fluids 160 Norton theorem 87 Notch Filter 91 nucleons 45 nucleotide 174 Numerical differentiation 212 Numerical numbers 211 Nyquist frequency 101 O Ohm’s law 83, 84 opacity 46 optogenetic control 76 Optogenetic devices 76 ordinary differential equation (ODE) 212 organic acids 73 organic material 29 ozone layer 181, 183, 184, 193
P paper chromatography 117, 118 Particle image velocimetry 205 pellet 8 petroleum 185, 186, 188, 189 phase equilibria 37, 38 Phase equilibrium 16 phosphorus 31 photoelectric effect 24 photovoltaics 169 piezoelectricity organic compounds 23 piezoresistive 170 piping and instrumentation diagram (P&ID) 150 planar chromatography 117, 118 plasticity 251 plug-flow reactors (PFR’s) 201 Pollution 192 polyamide 75 polyisoprene 251 polymath 2 Polymer crystallization 253 polymerization 247, 248, 251, 252, 256 Polymers 46, 247, 256 polysaccharides 75, 251 Polystyrene 251 potentiometry 233 Precision 138, 140 precision proportion 137, 138 preparative ultracentrifuge 119 pressure 11, 12, 13, 14, 15, 16, 18 Probability 213, 215, 218 probability distribution 213, 214, 215, 216 Process control 105 process flow diagram (PFD) 150 productivity 219
Index
protein oligomerization 112 Proteins 63, 66 protons 45 protozoa 29 purification 54, 55, 56, 57, 58, 59 Q quacks 45 Quantitation 140 quantitative analysis 135, 231 quantum computers 14, 15 R radiant energy 165 radiated pressure waves 24 radiation 203, 204 radiation energy 24 radio elements 22 radio waves absorptiometry 229 Raoult’s law 11, 18, 127, 131 Rate of a reaction 166 reactants 160, 161, 195, 196, 197, 199, 201 reaction equilibria 37 reaction kinetics 54, 152 reactors 204, 205, 207 recombinant DNA technology 174, 175 recycle reactors 195, 197 Redox reaction 142, 144 registers 96 reproduction system 29 Reynolds number 207 rheogram 206 ribonucleic acid (RNA) 69 rotated Fischer projection 249 S Second law of thermodynamics 38
263
separation 53, 54, 55, 56, 59, 61 separation processes 53, 54 shear stress 205 simulation 239, 240, 242, 243, 244, 246 single-walled nanotubes (SWNTs) 50 solid electrolyte interphase (SEI) 234 solidification 55 solubility 64, 65, 66, 67, 68 solvents 248, 252 Source-based nomenclature 248 Space Time Blocking Code (STBC) 111 Spatial Multiplexing (SM) 111 Specificity 140 spectrochemistry 120 spectrograph 24 spectroscopy 117, 119, 125 starch 247, 251 statistical mechanics 12 stereochemical isomerism 248 stereochemistry 247, 248, 252 Stochastic models 242 stoichiometric coefficients 199 structure-based nomenclature 248 Sylvester’s theorem 108 syndiotactic polymer 249 T tacticity 249 Task Coefficients 66 telecommunication 245 telescope 24 temperature 12, 13, 14, 15, 16, 18 Thermal diffusion 77 thermal resistivity 46 thermodynamic property 203
264
Chemical Engineering Problems in Biotechnology
thermodynamics 12, 15, 198 thermodynamics gradients 74 thermodynamic system 128, 129 thermoflask 129 thermolysis decompression 178 Thevenin’s theorem 85 thin-layer chromatography (TLC) 235 Third law of thermodynamics 38 Toroidal Core Inductors 92 Traceability 137 transcription 32 transformer 95 Transient state 89 transportation 239, 241, 245 tropism 23 U Ultraviolet-visible spectrophotometry 231 universal gas constant 17
V Vander Waals equation 5 velocity gradient 206 vibrational energy 231 viruses 74 viscosity 12, 15, 160, 162 vitrification 187, 191 voltages 83, 84, 90, 91 W waste disposal 183, 192 wavefront 107 wavelength 119 Wolfram Mathematica 2 World Wide Web Consortium (W3C) 102 X X-ray absorptiometry 230 X-ray absorption 231, 232 Z Zeroth Law of thermodynamics 37 zymology 73