Inorganic Chemistry in Tables [1st ed.] 3642204864, 9783642204869

Citation preview

Inorganic Chemistry in Tables

Nataliya Turova

Inorganic Chemistry in Tables

Dr. Nataliya Turova Department of Chemistry Lomonosov Moscow State University Moskva Russia [email protected]

ISBN 978-3-642-20486-9 e-ISBN 978-3-642-20487-6 DOI 10.1007/978-3-642-20487-6 Springer Heidelberg Dordrecht London New York Library of Congress Control Number: 2011932247 © Springer-Verlag Berlin Heidelberg 2011 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer. Violations are liable to prosecution under the German Copyright Law. The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Printed on acid-free paper Springer is part of Springer Science+Business Media (www.springer.com)


   



































































   

































































  





























































        



































        





























 



































































   !  !























































" #$%







































































 & ' 







































































( & !  !' !













































 && )      





























"
 *      
































! !



































































 %  ! 





















































( + !





































































,   !!





















































,"       







































, - 





































































,. ) '  



































































" )      









































" )   $  











































", -     /)







































"" &0     /)







































"   !% ! 

















































" & 1    $  

































"( & 1       































"2 3 !



































































 -  ! !'  !











































 3- )      



























"
      














































































































 -     /

































( &0  &0   /







































2 &  









































































4! ! 























































 4& )      































   !5  ! / !















































   !





































































( 1







































































2 1% ! !  !























































. 4 !  !  !



















































." 14       

























. & !  !

























































.. 6 !  !  













































.(  !7  ! !

































( 8  ! !































































(  %





































































(" 8
       





























( 7 !/ !





















































(
''







































































(( & 









































































2 4









































































2 











































































2








































































2" - 7







































































2 9
 -       

































2(   #      



































22    !

































































 #! !





































































   !



































































"  !





































































 ) !



































































( )  !



































































 

































































 3: % 5 %';    '%  /!

















































"  %'/%  











































 0 ) (P O 2 60 H2 (ë , < O O H 2 ëH 2 ); ( vis O 2 ; 
( h nO 4 M ;K

1.64 112 84

2p ;: ;: 3p ;: ;: 4p ;: ;: 5p ;: ;: 6p ;: ;:

H2

0.92 83 19.5

nO

degree of diss. 0.1 N s.,%
n H2O, n ˆ

HI

M

d m.p. b.p. degree of diss. by 1000
H H ì Hal  (gas) " (liq) sol. in H2O

HBr

2s ;: 3s Chlorin Cl0 ;: 4s Bromin Br0 ;: 5s Iodine I0 ;: 6s Astatine At0 ;:

Fluorine F0

OF2 gas, colrl., toxic, with smell of O3 m.p. 224 b.p. 145 dec. 200 DH +24 sol. in H2O 6.5 %

[NR4][HI2]

CaI2 783 Mg I2 633, (dec.) Sn I2 320 SnI4

145, (subl.) (AlI3)2 191 PI3 61 AgI#, yel., 560 CuI#, wh., 605 PbI2#, yel., 412

Cl2

Br2

gas, liq., red yel.-grn. with a sharp smell

I2

At

cr., blk.

met., volat.I+ 3 +I3

sol. in H2O, ( ! O2+ HF)

0.68

3.5

0.03 mass. %

4.94 g/cm3 113.7 183

sol. in RH, R¤, CS2, CCl4 In str. ë Hal2 mol.; CN Hal = 1 (= 8 ë 7)

Hal ë Hal 1.42 (gas)

1.99

2.28

HOCl hypochlorous

Kac.=10 8 angular mol., v. strong Ox

H

(

H

C

t);

Cl2
5.75 H2O Br2
72/3 H2O (8 : 46) (6 : 46) m.p. 9.6 5 with dec. Clathrates in the ice str.

10

9

HOI -iodous ac. 10 5M ì unstab. 10 11 Kbas=10

10

O

2.67

el nm F (i H ) . n F
in s Cl ( x. K o M . an

conc. in saturated 10 3 s. of Hal2 10 2 30% max. conc. 20%, v. strong Ox., distil. in vac. 30

ì 337 302

M

HOBr -bromous

l)

MH

H2CO3 (K1 = 10 7)

MOHal, hypohalites, v. strong Ox.

Hal2 str.

NaOCl, exp. 70 , KOCl, m.p. 2,5 Ca(OCl)2,
3 H2O, (m.p. 86)
1/3 Ca(OH)2
x H2O, "lime chloride" t ( ! O2 + CaCl2)

N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_3, © Springer-Verlag Berlin Heidelberg 2011

MOI, NaOBr
n H2O, known only n=5, 7 in s. KOBr
3 H2O light yel. t ! MBr + MBrO3 (other salts are not known)

4+

3+

Hal2

O3 n, (freo

Br2O3, sld., yel.

 50 )

t

hn(UV) (ëCl2); O3

2

1.9

120

1.8

H2O

80

(HIO3)n iodic ac., cr., colrl., d ˆ 4:63, m.p. 110 with dec., K ˆ 10 1 , in s. n ˆ 2 3,

H 2O

! ClO2+Cl2O7

97

1

1.7

56)

Hal O H Located el. pair

Cl2O7, oil, colrl., m.p. 90, b.p. 87, exp. 120, d ˆ 1:86, (stab. >ClO3, ClO2), DH ˆ ‡275, sol. in ³³l4, m ˆ 0:72, 52) middle Ox.

VII

I2O6 = [IO2][IO4] cr., light yel. dec. >100 + H2O ! ! HIO3 + H5IO6

H I3O8; M I3O8 HClO3 HBrO3 chloric bromic ex. only in s. max. conc. 40% 50% 40 exp. strong ac. v. strong Ox

HClO2, chlorous ac., rapidly dec. in dil. s. (! HCl + HClO3+ClO2) K ˆ 10 2 , v. strong Ox

20

H2O (240 )

H2O (hn-vis.)

t( O2)

exp., ! ClO2 + O2, in liq. and s. in CCl4 ë dimer, in str. ë [ClO2]+[ClO4]ë Cl ì O 1.41 ë 1.47 V

118

[IO]+Xë, 6) X=HSO4, NO3, BF4, "salts of iodyl", yel., paramagn. (p2 ) 6)

ClO3, liq., red, 39, 51) smoky, m.p. 3.5, b.p. 203, DH ˆ ‡156,

45) Br2O5 I2O5 cr., colrl., dec. hn(vis) ! darken, 180 ! I2 + O2 DH ˆ 184

47

7+

ä6+ã

0 1.4

Br2O4 2) ClO2 53) gas, yel.-brn. cr., d=1.64, light.-yel., m.p. ë59, 40 (dec.) liq., red, DH = +104 I2O4= exp., III dimer in ³³l4 & [I O]+[IVO3] cr., yel. str., m=0.78, 130 ! I2 + I2O5 readily sol. in H2O, 6, 37) paramagn. (IO2)n, cr. 1.

5+

115

H2O 1) (P2O5; oleum)

H2O (slow)

H2O (exp.) HClO4 perchloric liq., colrl., d ˆ 1:77, m.p. 101, b.p. 16/18 mm, 3HClO4 > Cl2O7 + + H3O[ClO4]

HN

1 1.90 1.8

O3

55)

HIO4
n H2O

perbromic v. strong Ox, max. conc. 83%, stab. HClO4

100% (exp.), m.p. 50,

K ˆ 38, Ox in conc. s. or when heated, azeotrop ë 72%HClO4; oil, b.p. 111/20,
n H2O, n ˆ 1ë3, 5 52)

I2

98 

HBrO4
2 H2O

1.63 1 1.4

106

112 

56)

periodic ac., cr., colrl. HIO4, " 100 H4I2O9, H7I3O14 " 80 H5IO6, m.p. 122 with dec., K1 ˆ 10 2 ; K2 ˆ 10 8 ; K3 ˆ 10 15 , mol. ì trig. antiprism

H2SO4

38)

Chlorites NaClO2,
3 H2O Ca(ClO2)2
4 H2O Ba(ClO2)2 AgClO2#, Pb(ClO2)2#, yel., not oxidants; t

! MCl+MClO3, exp., angular [:ClO . . 2] anions

H2SO4 (ëBaSO4 #)

MHalO3,

47)

Bromites LiBrO2,
H2O Ba(BrO2)2, t ( O2) wh. powders, t ! MBrn+O2, +H2O!MBrn+ +M(BrO3)n , anion c-tetrah. OH

M

Hal2

(t,

M2IO4 57) MI3O8; 23) paramagn. (s1 )

Chlorates m.p. NaClO3 262 (dec.) KClO3 368, dec. 400 "Berthollet's salt" Ca(ClO3)2,
2 H2O Ba(ClO3)2 414,
H2O poison

l) Ha

M

Hal ì O 1.45 ë 1.50 € OHalO 106

Bromates m.p. NaBrO3 381 KBrO3 343 with dec. AgBrO3 dec. Ba(BrO3)2 260 with dec.,
H2O Ox ë only in melt [ :Hal°3 ] ë c-tetrah. (sp3 ) 1.78 112

t

t ( O2) Iodates NaIO3 (in "saltpetre") KIO3 (str. anal. of MNO3) MIO3
n HIO3 (KHI2O6, NaH2I3O9) AgIO3#, wh. Ba(IO3)2 ! Ba5(IO6)2+ + I2 + O2

1.78 ë 1.82 97 or dist oct.

an. Ox; F2

M2On
m Hal2O7 4)

perchlorates m.p. LiClO4 247 NaClO4 482 (dec.) KClO4 610 (dec.) Ba(ClO4)2 505 AgClO4, dec. 486 strong Ox only in melt

perbromates

43)

periodates

5)

MBrO4, M = Li ë Cs, sol. Li>Cs, stab. Li I2+Br2, dis. 8% (20 ), cr., red, m.p. 42, b.p. 119 (dec.), DH ˆ 10; m ˆ 1:21, I ì Br 2.52; 2 IBr
Dipy, 33)

ë

[ClF2] X , [BrF2] X , [BrCl2]+X ë, [ClBr2]+X ë, [IF2]+X ë, X = AuF4, PF6, BF4, AsF6, SbF6, BiF6, PtF6, Stab.: Sb>As>P, c-tetrah cations. (sp3 )

84

Cl

H [ICl2], K ˆ 10 3 Cs [BrCl2], M [ICl2], M=K (dec. 215), cr., yel., Rb, Cs (m.p. 238, dec. 290) m.p. 205, [²Ö¯], [PCl4], cr., orange dec. 150 .. anions [:HalCl 2] linear (c-trig. bipyr.) .. (sp3 d), I ì Cl 2.55 9)

7, 36)

255 1.19

2 HalF3(liq.) > HalF2+ + HalF4 ´-shaped mol. (c-trig. bipyr.) + E2°n ! EFn + Hal2 + O2 (method for determination of °); + Ir, Os, SiO2 inêam.

)

BrCl (> Br2 + Cl2) dis. 40% (20 ), gas, yel. m.p. 54 b.p. 5 with dec. DHdis. = +15 m ˆ 0:57

[Cl3]+X ë [Brn]+X ë, n = 2, 3, 5; red [In]+X ë, n = 2 ë 5, bl. [I2Cl]+X ë, blue or red [Br2Cl]+X ë, [I3Cl2]+X ë, X = AlCl4, HSO4, SO3F, Sb2F11, SbF6, Sb3F16, IF6 + I3+, I2+ 4 , Br2 , polycations, [I3]+ì angular [I4]2+ì rectangular

IF3 cr., yel. ë dec. 28 ( ! I2 + IF5) 496

BrF3 liq., colrl. 9 127

DH 163 m 0.55 in gas ì (ClF3)2

M[ClF2], M[BrF2], M[IF2], M = K ë Cs, dec. 230, linear anions 64)

Cl ì I 1.58, Br ì I 1.73, 1.70 1.81

8

IF, cr., red ì ì 89 ì

! Br2 + BrF3

F2

SbF 5 +C lF; AsF BrF 5; S 5 ; IF 2O 6F ; 5; 2 P F5 ;

Hal2

Br ì Br 2.4 ë 2.9; I ì I 2.9 ë 3.1 Cs[I(IBr)] is used to purify Cs (salts of K and Rb do not ex.). Stab. of ®HalHal0n increases and sol. in H2O decreases in [Li ë Cs ë R4N] series; CCl4, Et2O, bz. accelerate the dec. ®HalHal0n !®Hal0 +HalHal0 (extr. with Et2O). [I9] ë

20

ClF3 gas, colrl. m.p. 76 b.p. 12

+ H2O ! Hal2 + O2 + HF

KI3
H2O, cr., brn., m.p. 38, dec. 225 CsI3, m.p. 207 KI5
2 C6H6 RbI7
4 C6H6 CsBr5, cr., red RbI9
4 C6H6 Cs2I8, cr., vlt. [Et4N] [I(I2)n], n ˆ 2; 3; 4 4ë [H(theobromine)]+ 4 [I16] , anion ë ë (I3 ì I2 ì I3ë)2 [Hal3] ë, linear (c-trig. bipyr.)

[Me4N]Cl3 RbBr3, dec. 140 CsBr3, m.p. 180

ë

BrF, liq., red 33 20 42 1.29

3+

M[ClF4], M[BrF4], M[IF4], M = K ë Cs, [NO], cr., colrl., squares anions (c-oct., sp3 d 2 ) 3) RbBr2F7

Cl ICl3, cr., yel., m.p. 101 (p), subl., I 2.39 b.p. 64 (dec.) ( ! ICl + Cl2,), Cl DH= 88, mol.: planar dimer

[ICl2]+Xë, cr., red, cation: c-tetrah. [IBr2]+X ë, X = Sb2F11, SbCl6, AlCl4 8, 12) Cl 2

] IN3 bBr 6

I2

+ Cl 5

Sb

HalFn ë v. strong F-agents and Ox., used for the synthesys of comp. with the highest degrees of Ox; hyg., diamagn.; react. decreases in the ClF3>BrF5>IF7>ClF>BrF3>IF5>BrF series. Act. of HalFn decreases with increasing n; at the same n falls in Cl>Br>I series.

NaOH

ClOF3 BrOF3 liq., colrl., liq., colrl., m.p. 42, stab. at 20 53) b.p. 29, dec. 200 35) mol.

IOF3 18) cr., colrl., DH ˆ 552, > IF5+I2O5

IF5

F)

ClO2F3, gas, colrl., m.p. 81, b.p. 105 ! ClO2F + F2, mol. ë trig. bipyr. 2 at. ° ë eq. (ClO2F3)n 23, 24, 35) [NO][OF]

I2O5

c-trig. bipyr.

H l

CsIO4

Hal2

F2



200 [HalF4]+X ë Hal = Cl ë I 19, 20, 42)

colrl., volat., cations ë c-trig. bipyr.



200

PtF6 (20 ); [Kr2F3]+X ; [O2]AuF6

20 (inê.)

M[BrF6] M[IF6], M=KëCs

IOF4(OF), cr., colrl., m.p. 33, mol. ë oct.

IF7 (270)



cr., colrl., anion ë c-sevenapex (sp3 d 3 ) 21)

6

35)

H2O

[R4N][IOF6], anion ë pentag. bipyr. 54)

IF7, gas, colrl., with a musty smack, m.p. 6 (p), dec. 530, DH ˆ 961, mol. pentag. bipyr. (sp3 d 3 ), I ì F 1.86 (equ.), 1.79(ax.), € FIF 72; inê. bz., +MNO3 ! MF+FNO2+ +IF5+O2 16, 26) F

Cl2

al

KI+HCl

KClO3; KIO3

BrF5 liq., colrl. 61 41 400 460 1.51

H[IO2F4], cr., colrl.,  m.p. 36; 130 ! O2, v. strong. ac. (HClO4); +H2O ! HF + H5IO6 M[IO2F4], M = Cs, [Xe2F3] 34)

IOF5, liq., colrl., m.p. 15, mol. ë oct. 50)

bF

K

IF5 31) liq., colrl. 9.4 104 400 883 gas 2.18 liq. 3.67 e ì 8 37.2 2 HalF5(liq.) > [HalF4]+ + [HalF6] in gas ë mol. tetr. pyram. (c-oct. )

HH

ClF5 49) gas, colrl. m.p. 93 b.p. 13 dec. ì DH 238 m ì

(NH

4 )S

M[ClOF4], M[BrOF4], M[IOF4], M = K ë Cs, anions ë c-oct. 16)

CsIO4

BrF5

C

H[ICl4]
4 H2O, cr., orange, K[ICl4], needles, yel., m.p. 116 (dec.), anion ë square 13) (c-oct.),

IO2F3, needles, yel., m.p. 42.5, b.p. 147, v. strong. Ox., in str. ë chain of tetr. bipyr. [IOF3O2/2] 15, 25, 34)

[ClO2F2]+X ë, X = BF4, AsF6, PtF6, cation ë tetrah., stab. >ClO2F3 24) [IO2F2][SbF6], m.p. 102 34,35)

HF (ëMHF2) [ClOF2]+Xë [BrOF2]+Xë, 16) X = BF4, AsF6, NiF6/2, PtF6, cations ì c-tetrah. [:ClF2O]+

22,

5

MHalO4

Cs[ClO2F2] K[BrO2F2], M[IO2F2] 14, 41) cr., colrl., +H2O>MIO3+2HF 14, 40, 41) anions c-trig. bipyr.

F

[ClO2] X , [BrO2] X , [IO2] X X = AsF6, SbF6, Sb2F11, SO3F, PtF6 cation ë angular polymer (c-triangle)

ë 58)

5

+

EF

ë 44)

XeF 2

Cl2O; IF5

+

Br

F5

Br

(H

51)

F

ë 32)

located el. pair

mol. tetrah. KIO3

5

+

F O

IO3F, BrO3F, 22) cr., colrl., cr., colrl., volat., DH ˆ ‡138, dec. 90 act. > ClO3F,

F5

F2

ClO2

H

Halogenylêuorides ClO2F BrO2F IO2F gas, colrl. liq., colrl. cr., colrl. 9 m.p. 115 ì ì b.p. 6 ì polymer in liq. and str. ë mol. chain17, 29, c-tetrah [:Hal°2F] EF

F2

KClO3, HHalO4

39, 60)

ClO3F, 35) "perchlorylêuorid", gas., colrl., m.p. 148, b.p. 47, dec. 400, DH ˆ 21, m ˆ 0:02, chem. passiv.

Sb

BrF5

Hal

7+

5+

[ClF6]+X ë, 27, 28, 59) [BrF6]+X ë, [IF6]+X ë, 48) X = AsF6, SbF6, AuF6, PtF6 cr., yel. cr., wh. + O2 ! [O2]+ + . . . ; + Xe ! XeF+ cations ë oct.

KrF2 (20 )

26)

I2

Cs

NO

3

M[IF8], M=Cs, [NO], [NO2]; 35) +H2O ! O2

9

HALOGEN AND ASTATINE IONS IN AQUEOUS SOLUTIONS 1ë

0

(HF)n, ac. medium strength

:; OH

H+

HCl, strong ac., weak Red.

:; OH

H+

Cl ë

H+

MnO4 ; Cr2O27

H2O Cl2, v. strong Ox.

Cl 2

l HC

H+

:; OH

H+

ClO ë, v. strong Ox., stab. at 20

:; OH

7+

[ :HalO3 ] ë, trig. pyram. (c-tetrah.)

[ HalO4 ] ë, tetrah.

H2O

H+

Br2, strong Ox.

H+ MnOë4

[ClO2]ë, no Ox.

[ClO3] , v. weak Ox. (no react. with I ),

H+

:; OH ë



[BrO] , stab.  0

2

:; OH

H+

an. Ox.

[BrO3] , weak Ox.

20

[ClO4] , at 20 weak Ox.

HBrO4, v. strong Ox., slow react. H+ ë

an. Ox.; XeF2; F2(OH )

HI, strong ac., v. strong Red. +

H

:; OH

ë

I , strong Red.

HAt H+ ë

:; OH

At , coprec. with AgI, TlI

10

O2; Fe(III) ; H2SO 4 H2S S ; 2

NO2 ;

2 SO3

H2O I2, weak Ox.

11

; Fe

;I (HIO3)n, n ˆ 2 K ˆ 10 1 , Ox.

10

+

H

HClO;

Hal2

4

) 6] (OH

[Sn O2

S2O28

3,

Cl2; S2O28 (OH )

(t)

0.1 N HNO3 (100 )

[At(H2O)n]+ Hal

;: OH

[AtHal2] Fe2+

ë

HClO4 (100 , S2O28 )

2

[H4IO6] ë, K2 ˆ 10

8

At , prec. H2S at pH 5 7 H+

:; OH

AtO2ë

;:

Hal OH [AtOHal2] ë 46)

:; OH

H+

:; OH

H+

:; OH

H+

:; OH

15

…pH  7†

[HIO6]4 ë (pH  11) [IO6]5 ë > [H2I2O10]4 ë orthodiperioate oct. ions., strong Ox. (+ Mn2+ ! MnO4 )

3+



K1 ˆ 10

H+

H2O 2ë [IO4], > [H3IO6] , K3 ˆ 10 + H :; OH meta[H2IO6]3 ë

:; OH

[IO3] ë, weak Ox.

At;

:; OH

H5IO6 ,

2+

Cl 2

[H"]; SO2

[BrO4] , stab. < ClO4 , IO4 , weak Ox., react. with SO23 , AsO33

H+

HOI, Kacˆ 10 , Kbas. ˆ 10 , strong Ox., least stab. among HOHal

ed. Zn; cath. (!) R

:; OH

ë

[I(OH)6]+ (pH  0)

HNO3; H2O2; Cl2 ( HCl) SO23

:; OH

ë

HBrO3, strong ac., strong Ox.

:; OH

ë

( HCl)

HClO4, strongest ac., K ˆ 38, at 20 weak Ox. (no react with [H"])

HClO3, strong ac., strong Ox.

ë

HOBr, K ˆ 10 9 , v. strong Ox., unstab.

SO 3 S ; 2

Brë

HClO2, K ˆ 10 2 , v. strong Ox., unstab.

HOCl, K ˆ 10 8 , v. strong Ox.; hn-vis ! [O] + HCl

(OH , 50 )

H2SO4; Cr2O27

:; OH

5+

.. [ :HalO2 ] ë ë angular ions (c-tetrah.)

F2, v. strong Ox.

an. Ox.

HBr, strong ac., Red medium strength

3+

[O])

H 2O(

Fë

1+

[AtO3] ë, coprec. with AgIO3#

IO4 (pH  7, 100 )

[AtO4] ë, coprec. with MIO4# (?) 46)

MANGANESE, TECHNETIUM AND RHENIUM IONS IN AQUEOUS SOLUTIONS 2+

c

H

+

[Mn3O(HCOO)9] 2ë, red, paramagn. [Mn(C2O4)3]3ë, 16) red

:; OH

[MnF6]3 , red ion, v. stab. Fe 2+; H O 2 2; (C H)2; HNO MnO4 ; HO 2 ; O2(H +)

SP = 1013

O2 egia aq. r 3; O N H

OH

+

+

En

OH O 2;

ca

;N

t.

i; P

b;

(

[MnO4]3 ë,bl , tetrah. (d 3 s), paramagn. (d 2 ), ( O2 III ) v. unstab. Mn 2+

Mn

MnO2
x H2O#, brn., + H+ ! Mn2+ + O2

Sn

(H + );

[MnO4] ë, vlt., tetrah. (d 3 s), diamagn., (d 0 ), stab. by pH4 7; v. strong Ox. by pH 11 12

OH ( O2); Red. (deécit, pH >> 7†

Sn2+; [H "]; cat. Red. (pH47)

2ë

[TcO4] ë, colrl., tetrah., weak Ox.

[TcCl6 ] , yel. R

ed

HCl

.(

bu

er

PO

12Ð. HC l+I

:; H O 2

[TcOCl4] ë

12 Ð. HCl; I

Tc(OH)4#, dark

3 4 ë

Et

Cl2; S2O28

[MnO4]2 ë, grn., tetrah. (d 3 s), paramagn. (d 1 ) ion, ex. by pH>7; + H2O! MnO2
xH2O+MnO4

MnO2)

HNO3; Ce4+ (pH47); H2O2 (pH>7)

[Tc2Cl8]3ë Cu

+ BiOë3; S2O2ë 8 (Ag ); PbO2; H3PO5

) ( CO 2

2.5+

Tc

[TÔH9]2ë, colrl. ex. by pH>11

2 C 2O 4

Fe2+ (t); H2SO4 ( O2) (pH100

MnO2

[Mn(CO)5]2, cr., gold-yel., m. p. 154 (p), subl. 50/10 2 , sol. in org. solv., 1.79 CO dist. with steam, Mn Mn 2.92 mol. ë cluster, m ˆ 0:98 17) Mn4(CO)16 MnTc(CO)14 OC

C

O OC

H2 O

Na

m. p.

22)

b. p.

DH

930 1640 MnF2, 650 1231 MnCl2, 698 MnBr2, 638 MnI2, MnHal2 ë cr., pink In gas ë linear mol., MnF2 ë rutile MnBr2, MnI2 ë CdI2 str. type

struct.;

CN

H2O (t, t)

15

, sol. in HCl;

MnS, cr., grn., m. p. 1615, DH ˆ 205, NaCl str. type, "manganesian blende" (alabandite). 2)

+

NH

3

"t
H2SO4
4 H2O, red
Cs2SO4
24 H2O, 26) alum, red MnPO4
H2O; MnHP2O7

Manganates (III) 15) Ca3[Mn(OH)6]2 Na5[MnO4]; Na4Mn2O5; MMnO2, red, anions ë tetrah. or oct. Mn ì O 1.86 ë 1.95

22)

H2SO4 (conc.,

O2)

13)

[Mn3O(OAc)7(H2O)6] 6) [Mn3O2(OAc)5(AcOH)1.5] Mn2(C2O4)3
2 H2O

5)

M3[Mn(C2O4)3]
3 H2O red 16)

F2 (250 ); XeF2 600

MnF3, red, DH ˆ 996, in str. ë layers of oct.;
2 H2O; + H2O ! MnO2 + + Mn2++ HF MnCl3, cr., brn., dec. 40, sol in abs. alc., 28)
Dipy, red

MMnF4,
H2O M2MnF5,
H2O M3MnF6, M = K ë Cs, MII/2, red, v. stab., anions ë oct. NaMn3F10 M2[MnCl5], red M3MnCl6 Rb[MnCl4
(H2O)2] 28)

K4[Mn(CN)6]
3 H2O, bl., anion ë oct., (d 2 sp3 , 1 unpair el.), only low-spin compl. Mn(II) 25) M4[Mn(NCS)6] Ba2MnS3, chain of oct.

300 MnS2, blk., "mangankiese" MnSe, MnSe2, MnTe2, FeS2 str. type

O2 H2

Mn2(SO4)3, powd., grn., amorph., dec. 300

KMnF3, M2MnF4, grn., anion ë tetrah. (sp3 ) NaMnCl3; M2MnCl4 Rb3Mn2Cl7; Na2Mn3Cl8 K4MnCl6; MMn4Cl9 4) anions ë oct. Cs3MnBr5; Rb2MnBr4 9)

Mn(CN)2# Mn(NCS)2, cr., yel.,
4 H2O, grn.

#

K2[Mn(C2O4)2]
2 H2O

4 2, 4 4 4

MnS
x H2O#, amorph., êesh-colored, SP = 10 + O2 ! MnO2
n H2O + S (slow.)

MnSO4

KMnO4


nH2O

847 481 377 306

.)

2)

19) MI[Mn(ClO4)3] [NO2][Mn(ClO4)3] [Ph4As]2[Mn(NO3)4] 13) [NO][Mn(NO3)3], yel. NaMnPO4, Cs2Mn(PO3)4; Ba2[Mn(AsO4)2]

250 , vac.

100 MnO(OH) Mn2O3
x H2O#, brn. "manganite", "groutit"

H( con c

(N

Mn2O3, brn., DH ˆ 959, cub. str., oct. [MnO6]



940 ; H2 (230 )

MO

24) Manganates (II) Na4[Mn(OH)6], Na2Mn(OH)4, red M2Mn2O3; BaMnO2 Mn ì O 2.08 ë 2.11

NH4MnPO4
H2O# ! Mn2P2O7, m. p. 1196 MnHPO3
3.6H2O; Mn(H2PO3)2; Cs2Mn(PO3)4

O

MnO2 + Fe2O3

2 SO 4(

C

2 O)

H

C(

. (H

2)

# 1143

O)

O4



in air (OH ) (immed.)

>60

Mn(ClO4)2,
2 H2O,
6 H2O 23) MnSO4, colrl., m. p. 700, dec. 650, 21)
n H2O, n ˆ 7, 6 1 , pink MnSO3
n H2O, n = 1, 3; MnS2O6
6 H2O, Mn(NO3)2,
6 H2O, (m.p. 26), 3 H2O Mn3(PO4)2
n H2O, n = 4, 7; MnHPO4
3 H2O, Mn(H2PO4)2
2 H2O, 12)

O2 (>500 )

II Mn3O4 = MnIII 2 [Mn O4], blk.-brn., m.p. 1705, DH ˆ 1385, "hausmannite"

H2(>1200 )

Mn(OH)2#, wh., stoich. copmos., Kbas. 2 = 10 4 , Kac. 1 = 10 19 , SP = 10 13 , sol. in presence of NH+ 4 ; CdI2 str. type, Mn ì O 2.22, "pyrochroite"



g-, cub. (dist. cl. pack), d ˆ 6:37, a ˆ 3:86

3+(d 4)

Mn4N; Mn2N; Mn3N2; Mn7C3,18) Mn3C, m. p. 1520, MnSi; Mn2P; MnP

12 N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_4, © Springer-Verlag Berlin Heidelberg 2011

M3[Mn(CN)6], brn.,
6 H2O, red oct. anion, paramagn. (d 2 sp3 , 2 unpair el.), isostr. to M3[Fe(CN)6] 10), only low-spin compl. Mn(III) K3[Mn(CN)5(H2O)]
KCN 6)

5 + (d 2)

6 + (d 1)

.) xp (e

530

MnO2 ë x, blk.- grey, D¯ = 519, strong Ox., sol. in ac., b-, "pyrolusite", rutile str. type

t(

O

2

NO

+

Na

NO

Mn(NO3)2

3;

KC

lO

3

+

H2O

Na

2C

M2On(t)

O

3

(m

elt

. in

HMnO4, permanganic ac., cr., vlt., dec. 3;
2 H2O, dec. 20 in s. (Mn2O7 11) in str. ë mol. Mn2O7 and H2O

O2

(slow)

MMnIO6, red, stab., in str. oct. [MnO6] and [IO6], Mn ì O 1.87 M2[Mn(IO3)6], M = K, H 14) (
2 H2O#)

7 + (d 0)

1)

N

a2

SO

3

2)

Manganates (VI) 8) M2MnO4, M = Na (
10 H2O, m. p. 17), MnO2) K (dec. >500), Ba/2#, blk., paramagn., anion ë tetrah. (d 3 s), Mn O 1.66 1.71 +H2O ! MnO2#+MnO4 (slow.) +

N

aO

H

(0  )

> 20%

! MnO2 + O2"

20% oleum

4 + (d 3)

Manganates (VII) Permanganates H2SO4 (conc.) cr., vlt., s. in H2O Li 4 Cs LiMnO4
3 H2O, dec. 190 NaMnO4
H2O, dec. 170 [F]; KrF2; IF5 KMnO4, dec. 250 CsMnO4 #, dec. 320 Ca(MnO4)2
5 H2O Ba(MnO4)2#; AgMnO4#, anion ë tetrah., (d3s), Mn O 1.63, diamagn., stab. by pH 4 7, t; OH ( O2) v. strong Ox. by pH 11 Cl2 (an. Ox.; S2O82 (Ag+) t ! M2MnO4 + M3MnO4 + + MnO2 + O2

"Manganyl" salts [MnO3]HSO4 MnO3F, liq., yel.-grn., m. p. 38, dec. 0, v. strong Ox.; m = 1.5; mol. ë tetrah., Mn O 1.59; Mn F 1.72 MnO3Cl, gas., vlt. 3) exp., b. p. 30

H2SO4(conc.) + MnSO4 F3

Br

[MnCl4], ex. in s. Et2O

rF

Mn

;K F5

SO2 + HSO3Cl

) (E t2 O Cl

KMnF5, red K[MnF5(H2O)], pink K2[MnF6], yel.; M[Mn2F9], M = [O2], XeF, K2MnCl6, red, anions oct.

H

MnF4, cr., bl., volat.; DH = 1080; meff. = 3.87, in str. ë ribbons oct., +H2O ! O2 (exp.)

32)

MnOCl3, liq. yel., dec. 0 3) MnF5
SbF5

30)

Mn

2

MnO2Cl2, liq. 3) brn.

27)

) F 2(p

Sb+

Br

NOCl

K2[Mn(CN)6], yel., meff. = 3.94, dec. hn (vis.) K4[Mn(CN)8], red

7)

13

;

3.5

MRe(PF3)5 H5Re(PR3)3, mol. ë dodecah.

Synthesis of Tc: 92 2 + 42 Mo (1 D , 2n)

16)

)

ReCl5

0 (d )

M3[Tc2Cl8], M = K, NH4, blk., str. anal. of [Re2Cl8]2ë, (1 unpair. el) 22)

Re2(CO)n(PR3)10ën

40)

(p;

t)

Re(NO)2(PR3)I2 M(CO)5Hal [Re(CO)3ClPy2]

[Tc(CO)4]2, cr. brn.

K4[Re(CN)6]
3 H2O, M3[Re(CN)5(H2O)]

n)

92 43 Tc

4.5 m. 2.7h. (Perrier, Segre, 1937) 235 99 99 92 U ! 43 Tc* ! 43 Tc (in nature) g 2
105 y.

aO

Cl

2

ReCl3, cr. vlt., m. p. 257, b. p. 327, sol. in alc., Diox, DH ˆ 264, in str. and gas ë cluster [Re3Cl9], Re=Re 2.48,

K5[Re(CN)6], Re(N2)Cl(CO)4 2) [MI(CO)5] 1,14)

19)

! Re + ReCl5

1,3) 14)

[Re3Cl9(H2O)3]
n H2O
2 CH3COOH ReBr3, cr. red-brn., DH ˆ 163, chains of clusters [Re3Br9] ReI3, blk., in str. ë chains of triangles [(Re3I3)I4I4/2] 38) ReF3(CO)3] [ReCl3(PEt3)]2, mol. cluster 2 crossing tetr. pyr. [ReCl3PRe], Re ì Re 2.22

ReOF2

M3[Re3Hal12], M = Rb, Cs, anion ë [Re3Hal9] + 3Halë (term). M2[Re3Hal11], M = Cs, [R4As], M2[Re3Cl10], anion [Re3Hal9] + nHalë M2[Re2Hal8], Hal = Cl, Br, diamagn. cluster ë 2 tetr. pyr. [ReHal4Re]

450

t

O2 + MBr

ReHal5

H



37)

H2

0 (20

)

K4[ReO2(CN)4], blk., easily Ox.

ReF6 ReCl5

ReF4, cr. yel.-grn., m. p.. 125, b. p.  735, subl. 300 ReCl4, cr. blk.-brn., stab. in atm. N2, sol. in ac., Thf,

t ! ReCl3 + ReCl5; in str. ë chains of pairs of oct. (with common faces), linked by vertices ë [Re2Cl7Cl2/2], Re ì Re 2.73 ReBr4, cr. dark red. ReI4, cr. blk.;

(t)

Renates (IV) Na2ReO3; Ca2ReO4 Ca3ReO5, brn.

TcCl4, cr. red., paramagn., in str. linear chains of oct. with common edge Tc ì Tc 3.62

24)

! Re + ReCl3 + ReO3Cl

Re2O7

N

3.5+ [Re2OCl3(EtCOO)2(PPh3)2] ë 2 [ReO2/2 ClCl1/2P], Re:Re 2.51

500

M2O7; KMO4

19)

M(OH)4 #, brn.-blk., sol. in ac., alk.

Cs2[Re2(HPO4)4 (H3PO4)2], 37) Re= =Re 2.24

ReOCl, + H2O ! H2 + Re(II);

0

[Re(PF3)5]2, cr. colrl., m. p. 182, volat., sol. in org. solv., alk. ! dec. [Tc(PF3)5]2, unstab., {Re[P(OR)3]5}2 21)

92 92 2 43 Tc; 42 Mo (1 D,

H2O H2O ( H2)

[ReCl(CH3COO)2]2, [ReCl2(CH3COO)(H2O)], [ReHal2(CH3COO)]2 24)

60

isostruct. [Mn(CO)5]2, M ì M 3.02 M ì ³ 1.90(ax.) 2.01 2.00(equ.) C ì O 1.20 (ax.), 1.12 (equ.)

)

F2 (500 )

ReCl2
4H2O, bl.
2 HCl
2 H2O, grn. [:ReBr2(PR3)2]2 23) ReI2, blk., diamagn. cluster 23) CO

2O

Re2O3
n H2O#, blk., sol. in HHal (t); + O2 ! HReO4

2.5+ [Tc2(CH3COO)4]Hal, Hal = Cl, Br, Tc=Tc 2.12 13)

Tc2Cl4(PR3)4

[Tc(CO)5]2 [Re(CO)5]2 cr. colrl., poorly. sol. in. org. solv., stab.in air difécult volat., subl. 50/10ë2 m.p. 160 (p) m. p. 177 (p), dec. 250, m ˆ 1:18

H

 0)

HRe3(CO)14 16,20) H3Re3(CO)12, M2[HRe3(CO)12] M2[H3Re3(CO)10] M[H4Re3(CO)10], cluster-triangle M2Re4(CO)16 M2[H2Re4(CO)12]

H

2

(30

N

2

 10 )

Na3Re(CO)4,

20)



0

2.76 4.46 2.76

7

Na[M(CO)5],

(

I 2 (1

H 2) t(

2.73 4.40 2.73

) N2

(30

a c MìM

g

K/H

" H2O

H2

Tc Re met. silver-wh., darken in the air d 11.5 21.0 m. p.  2200 3190 b. p.  4600  5900 s o l . i n H N O 3 , H2SO4 (t), HNO3, aq. regia (H2O2 + NH4OH) +0.37 E0 MO /M +0.47 sld. 4 hex. cl. pack.

K2[MH9], cr. colrl. stab. by pH 4 7 Na2[ReH9], dec. 245 Ba[ReH9], anion trig. prism with centreted faces (d 5 sp3 )

H[Re(CO)5],

6d



>850 ! Re + Re2O7, DH ˆ 446, a-, TiO 2 str. type; b-, rh., chains of oct. with common edge, Re ì Re 2.61 4)

H2

KTcO4 K + En + alc.

KReO4

6p

;:

t

ReO2 26) conc. HHal, HNO3, H2O2

H2 O

6s ;

TcO2 cr. blk., sol. in subl. 1000, DH ˆ 435, monocl., dist. TiO2 str. type

(7

;

(

M4[Re2OCl10], yel.grn., paramagn., [Cl5ReìOìReCl5]4 2 oct. with common vertex, € ReORe 180 K2MF6, M = Tc, Re, grn., anion stab. even at pH > 7 K2MCl6, yel.-grn. K2MBr6, red., K2MI6 25)

550

t

! ReI3 + I2

2.24

;

(NH4)2MCl6; NH4MO4

2)

5d ;

3.4

;:

(N

;

OH

;

NH4MO4

+ 00  H2 ,p )

;

4+ (d 3)

EN

5d

Cl

Re

;

5p

3+ (d 4)

(3

0

;

5s

H

Tc0

4d

2+ (d 5)

0 )

TECHNETIUM, RHENIUM

3.25+ M2[Re4Br15] = Br9]0[ReIVBr6] = M2[ReIII 3

K3[Re(CN)6]
3 H2O, grn. K4[M(CN)7]
H2O, yel., diamagn., anion ë pentag. bipyr. 17)

14 N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_5, © Springer-Verlag Berlin Heidelberg 2011

KBH4

[ReCl4(PR3)3]

Re Hal O

K2[Tc(CN)6], red.

5+ (d 2) Re (t)

Re2O5 (?), cr. bl., dec. 200; + H2O ! ReO2# + HReO4 cat

h. R

ed

6+ (d 1)

[MO2Py4]X
2 H2O X = Cl, ClO4 28)

3

H4Re2O9 = [O3ReëOëReO3(H2O)2], cr. colrl., mol. ë tetrah. and oct. with common vertex, € ReORe 179 strong ac., extr. C5H11OH 31) H2Re2O8
3 Diox, m.p. 110

HTcO4, cr. red, s. fade at dil.

m.p. 48

b.p. 221

260 subl. 150

360

MTcF6 MReF6, cr. colrl., paramagn. PHal3 ( PHal5, 20 )

mol. ë 2 oct., with common edge. ReBr5, cr. bl.-grn.; t ! ReBr3 + Br2; H2O MIV + MO4

:;

[N:ReF2(PR3)2], CN Re 5, [N:ReCl2(PR3)3], oct.

2O

H

TcF6, cr. golden, m. p. 37, b. p. 55 TcCl6, cr. grn.,

ReF6, cr. yel., m. p. 19, b. p. 48, strong Fëagent ReCl6, cr. grn., 20 m. p. 22, stab. only in gas ! TcCl4 + Cl2 v. react. + H2O ! M(OH)4 + HMO4 + HHal; mol. ë oct.

K3[MO2(CN)4], trans-, orange, diamagn. (d 2 !), anion ë oct. (d 2 sp 3 ) 6, 17) M2[ReO(OH)(CN)4], vlt. 7)

N

2H 4+

K

CN

K2[TcO(CN)5]
4 H2O ë yel.

M2[ReF8], pink., anion ë antiprism M[ReF7], cr. yel., unstab.

28)

H2O ( H2)

K2[Re(CN)8], purp.

17)

K3[Re(CN)8]
H2O, brn., diamagn., anion ë dodecah. (d 4 sp3 ) 8) K2[N:Re(ì NC-i)4]
H2O, pink, chains of tetr. pyr. [Re(NC)4N2/2] Cs[Re(NCS)6]

O2

O2

ReS; ReS2 blk., subl. 1000, part of MoS2 "molybdenite"; ReS3 H2 Re2S7, blk., sol. in HNO3, (H2O2 + MOH); M2S7#, pH sediment. Tc2S7>Re2S7; t ! MS2 + S; Re2P, ReP, ReP2, ReP3 TcC, TcC2, ReSi2

O2

Perrhenates 10) Li5[ReO6], anioin ë oct., Ca5Re2O12, M[ReO4], colrl., sol. in H2O < MTcO4 m. p. 555, b. p. 1370 anions ë tetrah. M3ReO5, "mesoperrhenates", orange, anion ë tetr. pyram. m. p. b. p. 18 100 ë 25 M2ReO3F3, 32) anion ë oct. 147 164 M2ReO3Cl3, M = K, Cs, [R4N], 5 132 M[ReO3Cl2], M2[ReO3N] 40 163

Pertechnates M[TcO4], KMO4, m. p. 540, b. p. 1000

11,36)

O2; Bi2O3

ReNCl3, blk., nonvolat, meff = 1.75

H2O

TcOF4, m. p. 134, mol. ë cycle [TcOF3F2/2]3, Tc=O 1.66, t Tc ì F  1:8 ! Re + ReO3Hal + Hal2; TcOCl4, m. p.  35, chains of oct. [ReOF  3F2/2]-cis, > 78 ! Cl2+TcOCl3 Re=O 1.65, in gas ë mol., Re=O 1.66

HClO4; H2SO4

TcO3F, liq. yel. TcO3Cl, liq. colrl. ReO3F, cr. yel. ReO3Cl, liq. colrl. ReO3Br, cr. colrl

MIO2 (t)

t ! MF4 + MF6 ReCl5, cr. brn., 190 ! ReCl3 + Cl2;

K[ReOX4], X = Cl, I, SCN, anion tetr. pyr., O ë at the vertex, Re:O 1.72 M2[ReOCl5], M = NH4, K ë Cs, cr., yel-grn., anion oct., Re=O 2.09, 5) meff = 0.4

M[ReOF5], 29) M = K ë Cs, cr. bl., grn., sol. in Et2O, acet. M2[ReOCl6], M = Rb, Cs; + H2O ! M2[ReIVCl6]+MReO4

m. p. b. p. ReOF4, cr. bl. 27) 108 172 228 ReOCl4, cr. grn.-brn. 30 ReOBr4, cr. bl. dec. >80 + H2O ! Re(OH)4 # + HReO4;

160

M; ReO2

TcF5, m. p. 50 ReF5, cr. yel.-grn.,

N2H4 +HHal + PR3

H2O (‡Q)

O

Rhenates (VI) Li4ReO5, Li6ReO6, M2ReO4, M = Na, K, Ba/2 #, cr. grn.; + H2O ! Re(OH)4 # + MReO4

[SnO2(RCOO)2]2

ReOF3, cr. bk., unvolat. ReOCl3 [ReOCl(RCOO)2]2, [ReOCl3(PPh3)2] ReOX3Dipy, X = Cl (grn., vlt.), Br (grn.), ClO4 (bl.) 15)

Re2O7

HN

BaTcO4,

HNO3

[R4N][ReBr4O(H2O)], (NH4)2[TcOCl5]

TcOCI3, cr. brn., subl. 900 TcOBr3, cr. brn., subl. 400.

CO; M

26, 30) Tc2O7 30) Re2O7 yel., volat., hyg. not Ox. org. subst. (see Mn2O7 !), sol. in Re (200 ) H2O, alc., Et2O, ac., Py  O2 (160 ) m. p. 120, m. p. 301, b. p. 362, dec. 600, b. p. 311,
H ˆ 1234, O2 t dec. 260, baking) (Ox. colrl. > yel. > dark (in 80
H ˆ 1127, "m ReS oly 2 weak paramagn. layers of tetrah. and oct. with combd eni mon vertex. In gas ë mol. ë te" ) 2 tetrah. with common vertex,
3 Py.

ReO3
En = [ReVO2En2] [ReVIIO4]

5.85+, H0.15ReO3#, cr. golden, sol. in HNO3, semiconduct. t ! H2O + ReO3 x 26)

7+ (d 0)



H2O

ReO2F

Rhenates (V) NaReO3, meta-, light yel. M4Re2O7, pyro-, M3ReO4, ortho-, + H2O ! Re(OH)4 # + MReO4

37)

VII

[Re O2] [Re O4], "blue"

TcO3 ReO3 26) cr. red with met. lustre (grn. in thin layers), sol. in conc. alk. m. p. 160,  DH ˆ 602, >400 ! ReO2 + Re2O7; + NaOH ! ReO2 + NaReO4, frame of oct. (t)

MReO4

V

33)

mol. ë tetrah., Re ì O 1.70

ReO3X, X = SO3F, NO3, RCOO TcO2F3, cr. yel., m. p.  200, in str. chains [TcO2F2F2/2] ReO2F3, cr. yel., m. p. 90, b. p. 185 ReO2(SO3F)3, cr. colrl. ReO2(OTeF5)3, mol. ë 12), trig. bipyr.

S2O6F2

13)

ReOF 5 , cr. colrl., m. p. 41, b. p. 73, DH ˆ 1229, 34) mol. ë oct. [ReOF4]+X ë

[R4N][ReO2(OTeF5)4]-cis M[ReO2F4]

12)

M[ReOF6], M = Cs, [NO], 12) cr. grn. M[ReF8], M = K, [NO], [NO2], cr. yel., anion Archimedes antiprism (d 5 sp2 ) 12)

18)

ReF7, cr. yel., m. p. 48, b. p. 72, DH ˆ 1432, mol. ë pentag. bipyr. [ReF6]+X , X = SbF6, Sb2F11

Re

35)

K2[Re(CN)8(OH)]

15

16 N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_6, © Springer-Verlag Berlin Heidelberg 2011

17

3/në

1+

M2Sn, n 4 9, polysulphides, cr., with icreases n colour: yel. ! red. and stab. decreases; sol. in H2O, alc. M3[Cu(S4)n], n ˆ 2, 3 M2[Pt(S5)3] M2[Ag2(S6)2)]

Ionic Covalent +H2O!M(OH)n+H2S Metallike

SiS2; Sb2S3; Bi2S3; P4S5 Al2S3 ZnS; CdS; TiS TiS2 TiS3 Fe1 ë xS CrS0.95 t


n H2O
n
9
5 b.p. 1130 990 ì 514 ì

Stab. in air, sol. in ac., conduct. (MS) or semiconduct. (MS2, MS3) 1.5

t

M2Sn+O2 ! M2SO4 ! M2On+SO2+O2; t

+ C ! M + CS2:

18

SnO, n = 6 ë 10, yel., sol. in CS2, 20

g

Fe[S2], "pyrite"; Mn[S2], "Mangankiese"

Vapour

180 (rapidly) 850

900

1500

S8 > S7 > S6 > S4 > S2 > S orange red yel.

(t) n 3) 2O M NH E; iq. ; l ( M a  ); N 20 ( K

Cycles Sn, cr., orange (S6) ì yel. (S20), d=2.02 ë 2.09, m.p. 39 (S7), 50 (S9), 148 (S12), 128 (S18), 124 (S20); S10 dec. *60, str.: nonplanar cycles 33) S + OH

M2SO4 ; H2

(hn-vis)

SO2 + S; chains of Sn cycles

l 2 H2Sn

SOC

20

! S#+SO2+H2SO4 (slow.)

! S2

+

H2S + H2O (many)

24)

M2SnO6, polythionates, cr., colrl., stab. in s., decreases with increasing n; anion: 2 [SO3S] tetrah., linked 24) zigzag (S)n 4 chain

2)

1.4

S2O ("SO"), gas, colrl., stab., < 196 ë cr., orange, DH= 96, m = 1.47, does not react with °2, 27) angular mol. e rg H2O SO 2 discha w o l G H2S2O2, thiosulphorous ac., SO

>20

! H2S + S + + SO2 HSO3Cl

2

H2S

2.1

2 2 2.0  S 105

[S4O6]2

K2S6O6 K2S5O6 K2S4O6 K2S3O6 S2

15

! S + SO2 + SO3; +H2O ! S + H2SnO6+ +H2SO4; 3)

S2O23

2

78

! H2S + H2S3O6 ! ! S#(orange) + H2SO3 + + H2SO4 HO HO

S

O

HO

S

HS

(AsF6)ë2,

[Sn] n = 16, 19, cr., red, cation [(cyclo-S7)2S5]2+ [S8]2+Xë2, X = HS2O7, AlCl4, AsF6, Sb2F11 [S8][HS3O10]2 ("S2O3"), cr., bl., sol. in oleum;

Cl

H2S2O3, thiosulphuric ac., K2 ˆ 10 2 , liq., oily,

2+

S18 mol.

t) C(

;

(1.7 ë 3.3)+

H2SnO6, n ˆ 20 13, 6, 5, 4, 3, polythionic ac., strong, ex. only in s., n and stab. increases with [H2S]:[SO2]

HClO4 ( KClO4;)

Purple, str.: paramagn. mol. S2 (el. anal. of °2)

445 32)

CO from blast gases (Al2O3)

O

80

in

l-, liq., yel., transparent, >159 ë brn., max. visc. at 200 , S8 > S7 > S6 > S4

pi d

O2

co ol

119

0

Li2S Na2S K2S Cu2S; Ag2S;

95 b-, monocl., d ˆ 1:96, m.p. 119, a ˆ 10:90, b ˆ 10:96, c ˆ 11:02, b ˆ 83, str.: mol. S8

Pt

Sulphides M2Sx m.p. 950 1180 840 1130 842 m.p. 1090 548 685(dec.) 288 1120 (Ó) 1900 (Ó) 1475

2.4

2.37

EN 2.5

Amorph. (plastic) l + m yel., over- brn., cooled polymer liq., sol. (chain of Sn), in CS2 insol. in CS2



2.07

S

3d ;

4

ra

[H3S]+[SbF6] ë, dec. 90, c-tetrah. cation 31)

;: ;

1, 10)

2.04

Hydrosulphides, cr., colrl., sol. readily in ¯2°, alc., salt out from Et2O s. LiHS, dec. 50 NaHS, m.p. 350,
n H2O, n = 2, 3 (m.p. 22) KHS, m.p. 455 Ca(HS)2
6 H2O, dec. 15 Ba(HS)2
4 H2O

3p

;:

a-, rhomb., d = 2.07, m.p. 113, a ˆ 10:46, b ˆ 12:86, c ˆ 24:49, str.: crown mol. S8, S ì S 2.06, € SSS 108.

HCl (conc.)

2.02 2 .06

¯

SnCl2

3s

SCl 2

MCln; M2On (t)

HF SbF 5+

MOEt (alc.)

S0

S, cr., yel., d ˆ 2:1, m.p. 119, b.p. 445, readily 11) sol. in CS2, turpentine, sol. in bz., CN S 2

44)

MOH

00  )

ow

2°

H2Sn, n 4 35, polysulphanes, oils, yel., ex. at Ó¯ 5 7, and in Et2O, bz. s., visc. growing with n, m.p. 88 ë 50 (n ˆ 2 5† H2S2 ë str. anal. of H2O2, m ˆ 1:17, S ì S 2.05. K1 ˆ 10 4 , K2 ˆ 10 6

O2 ( 5% SO3); H2SO4; HNO3(t)

(3

sl

H2S, hydrogen sulphide, gas, colrl., toxic, with characteristic odour, m.p. 86, b.p. 60, dec. 300, DH= 20, m = 0.93, e = 6, solv. for org. subst.; SnCl2 2H2S (liq.) > [H3S+] + [HS ], ( HCl) + 33 [H3S ][HS ] = 10 ; angular mol., S ì H 1.33, € HSH 92 (p2 ), sol. in H2O 75% (vol.), weak ac., K1 ˆ 10 7 , K2 ˆ 10 14

2

S

O2 ; H2 SO 2 H2S2O4, ditionous ac., ex. in s., K1 ˆ 0:5, K2 ˆ 10 3 ; ! S; + H2SO3

O O

HCl Thiosulphates Na2S2O3, 100
5 H2O (m.p. 48); 200 ! Na2S5 + Na2SO4 K2S2O3, dec. 430,
n H2O, n ˆ 0:5; 1.67( H2O, 180 ) BaS2O3
H2O# M3[Ag(S2O3)2 ], [SO3S]2 tetrah.

Dithionites Na2S2O4
2 H2O ZnS2O4; CoS2O4, anion [O2S ì SO2]2 : 2 intersecting .. [SO2S] c-tetrah. , [S2O4]2 > 2 SO2 , strong Red.

O CO C aH O 3 N 2S a N ( 3

S2O6F2; AsF5; SO3+H2SO4 2+

;ë O

2

[S8]2+

(immed.)

[S4] X2 , cr., yel., square cation

2

O

H2 (pumice, 600 ); HI (gas); CnH2n+2

3+

2+

O

2ë

I2

SULPHUR

H2SO2, sulphÑxylic ac., O S(OH)2 > HO ì S H CoSO2
3 H2O, NaHSO2
HCHO
2 H2O, m.p. 63, "rongalit", Red.

N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_7, © Springer-Verlag Berlin Heidelberg 2011

)

2

4+

6+

Na2SO3
7 H2O; K2SO3
2 H2O CaSO3
2 H2O#; BaSO3# 600

H2SO4 > [H3O]++ [HSO4] . 2 [H3O]++[SO4]2 , ( MF+SO2:, soft F-agents: +(PNCl2)3! ! (PNF2)3 + MCl + SO2

m.p. b.p. S2O5F2, liq., colrl. 48 51 S2O5Cl2, liq., colrl. 37 Sulphurilhalides, m.p. b.p. SO2F2, gas 137 51 SO2FCl, gas 125 +7 SO2Cl2, liq. 54 69 SO2FBr, liq. 86 40

colrl. dec. 400 ì 300 ì

SO2

8)

Cs+[SOF5] ë, 210

H2SO4

DH m 856 1.11 ì ì 393 1.80 ì ì

SOF4, gas, colrl., m.p. 100, b.p. 49, mol. ë trig. bipyr., 300 !SF6 +SO2 F2 [SOF3]+[AsF6] ë

x .O

an

Hydrosulphates NaHSO4 (m. p. 186);
H2O=Na[H3O][SO4] KHSO4 (m.p. 210, "mercallit"); [H3O] HSO4] = "H2SO4
H2O"; [NO] HSO4], "nitrososulphuric ac."

Halogensulphonic. ac., HSO3Hal, Hal = F, Cl, Br; liq., colrl. (F, Cl); yel. (Br); m.p. 87, b.p. 169 (F); m.p. 80, b.p. 152 (Cl); m.p. 7(dec.) (Br) HSO3F ë strongest ac., stab., F-agent MSO3F, M = Li, K, XeF‡ , [Sb4 ]2‡ Ba(SO3F)2, Cs[M(SO3F)n], 12) II (t) MSO3Cl, unstab.; M (SO3Cl)2 l a H[SbF2(SO3F)4], most strong ac. H

7)

! SF6 + O2 + . . .

SO3

M

M2S2O8, persulphates, M = K, NH4, Ba/2 (
4 H2O),

MHSO5, ; H2O O2+MHSO4, [SO4 ì OH]

39)

SO3F2 = (FO)SO2F

39)

1.46

100

! M2S2O7+O2 [O3S ë O ë O ë SO3]2

MOH

Sulphates Na2SO4, m. p. 884, b. p. 1430;
10 H2O, "Glauber salt" K2SO4, m. p. 1076, b. p. >2000; BaSO4;, m. p. 1580 MgSO4, dec. 1155;
7 H2O, "Epsom salt" ³aSO4;, m. p. 1450;
2 H2O, "plaster stone"; CuSO4, dec. 650;
5 H2O ("vitriol"); [SO4]2 ë regular tetrah. (sp3); S ì O 1.48, not Ox, mol. M2 SO4 (M = K ë Cs) ex. in gas.

38)

Cl

POHal3

MF

34)

25)

! M2S + M2SO4, readily sol. in H2O [:SO3]2 ë c-tetrah., strong Red.

SO2

SO3

H2O



HSO2F > HF (liq.) + SO2(liq.), êuorsulphine ac., m. p. 84

M2S4O14, [O3S ì OSO2 ì O ë]22

S2O5F4, liq., colrl., m.p. 95, b.p. 35 O

O SOF2

F2OS O

SO4F2, yel. g., b.p. 0, dec. 50, [FSO2OOF] SO3

S2O6F2, liq., colrl., m.p. 55, b.p. 67, (FSO2 ì O ì)2, strong F-agent 120

;:

SO3F, brn., dec. 200

2

33

O2

H 2O

eF

Sulphites Li2SO3, dec. 455

O SO3

X

MHSO3, hydrosulphites, M = Na, K, Cs (cr.); Li, Ca/2 (ex. only in s.)

Ditionates M2S2O6
2 H2O, M = Li, Na K2S2O6 MIIS2O6
n H2O, MII = Ca, Sr (n ˆ 4), Ba (n ˆ 2), Mn, all salts sol. in H2O, anion ë [O3S ì SO3]2 ë 2 intersecting 58) tetrah.

2

H2SO5, Caro ac., cr., colrl., hyg., m.p. 7 (dec.), in s. stab.>H2S2O8, K2 ˆ 10 10 , sol. in Et2O, + H2O ! H2SO4 + + H2O2, v. strong. Ox, + bz. ! exp.

2,

M2CO3 (0 )

H2SO4

SO3 O

54

! S# + H2SO4

Pyrosulphates, M2S2O7, M=Na, K, anion ë 2 tetrah. with a common vertex

H2S2O8, persulphuric ac., cr., m.p. 65 (dec.), strong ac., Ox.

1.

150

an. Ox.

H2SO4, ulp c ac., oil, colrl., v. hyg., ("monohydrate"), m.p. 10, b.p. 340 (dec.), 2 H2SO4 (100%)>[H3SO4]+ + [HSO4] > [H3O]++[HS2O7] ; K ˆ 10 5 K ˆ 10 4 43 e = 100 (25 ), solv. M2(SO4)n, strong Ox., 1. 104 in gas ë mol. ë dist. tetrah. (sp 3 ); 119
H2O, n ˆ 1 4, 6, 5 (m.p. 84), 8 ( 110 ); b.p. of azeotrope (98% H2SO4) 337;

H2O ( HHal)

[SO2]eq.=[SO2]gen. [HSO3 ] [SO32ë];

H2S2O6, dithionic. ac., strong, ex. in s., stab. to Ox.

H2O SO3

36)

n

;Z

Hg

t Sulphurous ac. ("H2SO3") + + 2 SO2+H2 O> SO2
n H2O > H +HSO3 > 2 H +SO3 , ‰H‡ Š‰HSO3 Š Mn ˆ 10 2 , K2 ˆ 10 7 ; Red. K1 ˆ O2 ‰SO2 Šeq::

H2S2O7, di(pyro)sulphuric ac., cr., colrl., hyg. m.p. 35

KHF2; CH2Cl2

1 2.17

HHal

9

NO S; Cu 2 + H (t) ; H 2O ( I; NO H 2S )

2O

2

.45

M2S3O10, trisulphates, M = MI, MII/2, [ClO2], [S8]/2, [NO2]

H2SO4

Na2S2O7; Fe2(SO4)3

H

1.4

t

NaHSO3 (dry) M2S2O5, pyrosulphites ("metabisulphites"), M = Na ë Cs, 20 ! SO2 + M2SO3 4) Na2S2O5
H2O > 2 NaHSO3

F

FeS2

23)

SF5Cl S2O2F10, liq., colrl., m.p. 95, b.p. 49, dec. 200, (F5 ì S ì O ë)2

2

O2 ( Fe2O ) 3

O

>400 ( O2)

3 SO4, m.p. 3 (dec.), O3 S2O7, m.p. 0, +H2O ! [O]; subl. 10 ( O2) +Mn2+ ! HMnO4 low O 2 (g rge) h c SO2 dis a an. Ox.; H2O2 (100%)

SO3, cr., wh., silky, m.p. 17 ë 145 (various forms); DH ˆ 395 (gas); 462 (b). In str. ë cyclic trimers or chains of tetrah. [SO4] (sp3). In gas ë SO3 ë triangle, S=O 1.41, € OSO 120 (sp2); strong Ox.

vi s)

O2 (t; Pt, V2O5, Ag3VO4); O3

hn (

SO2, gas, colorl., with a pungent odour, m.p. 75, 37) b.p. 10, dec. 2500, DH = 297, sol. in ¯2° 98% (vol.), e = 13; liq. SO2 sol. N2, MHaln, org. subst., m = 1.63, angular mol. (c-triangle [:SO2], sp2); 3 strong Red., weak Ox: + H (Pd) ! H2S; 1.4
7 2/3 H2O (6 : 46) ë clathrate 120

19

SULPHUR HALIDES

87

a

1.86

76 

7

55 6

3

M [S2N2H]2, M = Ni, Co, Pt, Pd stab. in air, meff. = 1.9 (Co), 0 (Ni) mol. is planar

N H +

112 

1.59

CS 2

1.64

04 1,

0.51+ 0.66+ S7NH, S6(NH)2, m.p. 113 3 isomers: (1, 3), (1, 4) and (1, 5), S ì S 2.05, S ì N 1.67 ë 1.72 19)

122 

1.73

116 

1.43

1.2+ 1.65 S5(NH)3 2 isomers: (1, 3, 5) 2+ and (1, 3, 6) S4(NH)4,

Sn

Cl

2

[S3N2]X, X = Cl, AsF6,15) cation planar

) n;

O (C Cl 2

M

42)

0.66+ M[Cu(S3N)2], in anion ë 5-member ring [CuS3N]

MII[S2N2], MII = Cu, Pb, Fe, Co, Ni, cr., with intensive colour, sol. in org. solv., paramagn. (MII = Fe, Co (2 and 1 unpair. el. 16)

M

Sn(NH)8 ë n, mol. ë 8-members rings ë "crowns" (4 at. in parallel planes, look S8!), cr., colrl., at. H easily substit. 0.5+ M[S4N], cr., purp., stab. in air, anion ë chain of [S2NS2]

HSO3Cl



109

2.66+ S3N2Cl2

2.5+ [S4N3]+X ë, X = Cl (cr., yel., dec. 170), Br, I, NO3, SCN, HSO4, cation planar 7-member cycle 

 134 2 15 111 

2.75+ M+[S4N4] ë, stab. < 25 , anion paramagn.

; ed . R hf th ca + T K

3

.)

4

2.1

0



Pt

102



1.66

S2Cl2

3.02

+

1.67

114 90 99 

2.2

116  87  104

97

1.6

1.52

5 2.1

(liq

M+[SF5] ë, 6) M = Cs, [R4N], anion ë c-oct.

2.67+ M+[S3N3] ë, M = K ë Cs, exp., anion. ë 6-member planar cycle 30)

108 119

II

121

l) 2 HC

2.3+ [S6N4]2+X2ë , X = FeCl4, SO3F, AsF6 36)

4ë NaR ( RH) Na+ 4 [S4N4] LiAl[S4N4] II

2.0



3

[SF3] [BF4] ë [SCl3]+[AlCl4] ë [SBr3]+[SbHal6] ë, yel., cations ë c-tetrah., 5, 22, 45)

1.56

1.5

111

NH

EHaln +

17)

1.58

(0.31 ë 0.4)+ (S7N)2Sn, m.p. 137 (n ˆ 1), 98 (dec.) (n ˆ 2), 97 (n ˆ 3), 16 (n ˆ 5), sol. in CS2, not hydr., mol. 2 cycles connected of chain Sn



1 12

20

190

54

S

2+ [S2N]+[¿¤6] ë, cr., yel., gr. [S ì N ì S] ë linear,

13) 1.5+ S4N2 (earlier "S5N2"), cr., red, m.p. 23 ( 80 light-yel.), distil. in vac., sol. in org. solv., 100 ë exp., m ˆ 1:74, mol. ë "half-chair" 6 1.6

3

41) 0.57+ [S7N]+[HSO3] ë, cr., red

Imides Sn(NH)8 ë n

05 2.

S, S2Cl2

1.54

769

[SN][AsF6]

1.74

( S nCl 2

2

DH

2+

135 

66

1.



105

10

aF +N

Cl 2

n

2.0

1.70

 );

Hal2 + EHal

5

Na ( H2)

0.54+ S11N2, m.p. 150 (dec.), sol. in CS2, (a; b) 14)

m.p. b.p. SF4, gas, 121 37 colrl., toxic 34 ì SCl4, cr., colrl. (dec.) mol. ë c-trig. bipyr.; SF4 + M2On ! MFn ; + H2O ! SO2 + HHal; F

S

(0.25 ë 0.66)+ Sn(CN)2, n ˆ 3 8, cyansulfanes, m.p. 93 (n ˆ 3), 39 (n ˆ 6), str. anal. SnHal2

43)

F 2(

SULPHUR NITRIDES 0.43+ Na+[S7N] ë, cr., grn.

:

[S2I4]2+(AsF6)2ë, Cl2 (liq.) cation ë trig. HF (gas) prism. 35) > 30

M

AgF; Cl2 (deéc.); Br2 (surp.)

1.57

4+

:





[I2]AsF6

Cl2 (FeCl3)

b.p. 39 60 (dec.)

90

[S7I]+AsF6ë , cr., orange, in cation cycle S7 35)

m.p. 98 125

Cl2) (SF2)2, liq., bl. SCl2, liq., red

20 (slow.,

3+

1.72

20 ( S)

m.p. b.p. DH S2F2, gas, colrl. 133 15 227 80 138 58 S2Cl2, liq., colrl. 40 57/0.2 17 S2Br2, liq., red, d ˆ 2:63 dec. 90 ì ì dec. 30 ì ì S2I2, cr., brn. Str. anal. of H2O2, strong. Hal-agents; S2Cl2 solv. of S, I2, MHaln, org. subst; + H2O ! H2S2O3; S2Cl2
n AlCl3

1.43

H2; H2Sn

2+

I2 + (liq AsF 5 .S O 2)

1+

2.2

S1/n+ n¤2, Hal=Cl ë I, n 4 100, halogensulfanes, oils or sld., orange

40)

S2Cl2; HHal NH3 + SCl2

FeII[S4N4], cr., blk., dec. 100, solv. in Py,

# + H2O

Fe(OH)3

O)

(C Fe

S4N4

5

S N, Hal H

5+

6+

S2F10, liq., colrl., v. toxic, m.p. 53, b.p. 29, DH ˆ 2134, inert at 20 , not react. with H2O, alk., strong F-agent (t), mol. 2 tetr. pyram., S ì S 2.2

sF

C

OF

SF4

3+

(

2

Cs

x)

(SF5)2O, liq., colrl., m.p. 155, b.p. 31, mol. ë 2 oct. with common vertex [SF5]+X , X = OF ("SOF6", m.p. 86, 9) b.p. 35); OCl, CF3, SO4/2

F2

Ag

2

Cl

(C

F b.p. 93 ì ì 18)

9 1.5 113 123

47)

F

 Thiasylhalides 7 F 11 NSF, gas, colrl., hygr., m.p. 79, b.p. 5; + H2O ! NH4F + SO2 (immed.), m ˆ 1:90 1.45 NSCl, gas, yel.-grn., v. unstab. (semiproduct in synthesis of S4N4), angular mol. [Co(NSF)06 ][AsF6 ]2 53) NSBr

S2Cl2

l 4C NH ) S (

cyclo-( NH S=NH)3, diimide 3.5+ M[S4N5], cr., yel., exp., N ë in middles of edges of tetrah. [S4], 52)

F

Cl2 + CsCl

1.6 4

1.61

2.59

Cl 4)

153,

NSF3, gas, colrl., b.p. 73, passiv., not t hydrol.; + H2O ! HF + HSO3NH2; m ˆ 1:91, mol. ë tetrah., S:N 1.42

4+

2

3 (C

AgF2

S(NSiMe3)2

Br

NH

6+

56)

);

H2

[S4N5]+X

S F, N

4

S2N3H3, HN=S=N ì S ì NH2, amidoimidonitride, sld., red, in liq. NH3 ë monobasic ac., + Pb2+ ! PbN2S2 + S(NH)2

MN

( 80 )

Ox-state of S calculated on the assumption of formal Ox-states of N 3 and H 1+

H[OSF5], cr., subl. 65 M[OSF5], M = Cs, Xe/6, W/6 46)

(NSF)4, needles, colrl., m.p. mol. ë 8-membered rings m.p. 74 (NSF)3, cr., colrl. 163 (NSCl)3, yel. ì (NSBr)3, red [N3S3F2]+X ë

Cl2

(300 ! 80 vac., AgF2)

MI3 [S2N3], cr., yel., exp. Na[H2S2N3], cr., brn.



l 4)

gF

2.67+ K[S3N3] anion ë plane cycle 29)

H2O

C (C

H

2.59 S4N4#, cyclotetrathiazyl, thiazen, cr., golden, S ( 100 colrl., >100 red), d ˆ 2:2, m.p.  180, subl. 130/0.1, exp. 130 , DH = + 460, 102 sol. in bz., CCl4, m ˆ 0:72; in mol. ë square [N4], over and under ë at 2 at. S, they form dist. tetrah. 115 62 t 1. + H2O ! NH3 + S3O26 + S2O23 ; + HI ! H2S + + NH3 + I2;
m EHaln, E = B, Sn, Sb, S, Se, Ti, Nb, W N

S2Cl2

SF5OOX, X = H, SO2F, COF, CF3, SF4OSF5 20)

)

3.2+ 3.5+ [S5N5]+X ë, [S4N4]2+X2ë thiazile salts; cations ë plane 10- or 8-membered 50) rings

124 ë 139

S2N2, cr., colrl., volat.; sol. in Et2O.; exp. 30 ; 20 S N ! S4N4 + (SN)x, mol. ë square 29)
SbCl5 N S

m 0 1.58 ì

mol. ë oct. (sp3 d 2 ), passiv., not react. with O2, ac., alk.; + HI (gas) ! HF + H2S + I2; 21) SF6
17 H2O, clathrate

3.6+ S5N6, cr., yel., exp., subl. 45/10 2; mol. ë basket 55)

(SN)x, polythiasyl, golden ébres (bl. in thin layers), exp.  240 , subl. vac. 135, insol. in H2O and org. solv., dec. of alk., str.: zigzag chains, S ì N 1.59 Ë 1.63; € SNS 119.9, € NSN 106.2; paramagn., conduct. (delocalization of p-el. along of chain) 28)
n Hal2 (n ˆ 0:04 0:4) ë canal comp. inclusion, conduct.

DH 1226 ì ì

Cl

)

+

dec. 800 ì ì

1

Cl 2

S

b.p. 64 (subl.) 19 116

10

F

Hal2

m.p. 50 (p) 64 ì

1.61



20 2(

H2 (hn-vis)

SF6, gas, colrl. SF5Cl, gas, colrl. SF5Br

2.66+ S3N2O, liq., red, O=S=(N=S)2

Oxonitrides 51) 4+ S4N4O2, mol. ë cycle

3.33+ S3N2O2, cr., yel., m.p. 101, S=(N=S=O)2

SOCl2

54) 5.33+ S3N2O5, cr., colrl., subl., in mol. ë 6-membered cycle O[S(O)2N]2S

Na

N

NH 3

3

3

4+ K[NSO], thionitrite (tiasat), cr., colrl., exp., m.p. 190

3.3+ M[S3N3O], M[S3N3O2], bl.-vlt. M[S4N5O], anions ë cycles M3[ON(SO3)2], nitrosodisulphonate

m.p. ì 110 139 129 111 ì ì 71 80 99

57)

b.p. ì 16 10 2 18 80 25 25 61 13

Sulfanurhalides, [ N=S(OCl)]3 m.p. b.p. m 138 ì (NSOF)3, a- 17 liq., colrl. b- 13 130 ì (NSOCl)3 a- 145 ì cr., colrl. b- 48 ì mol. ë 6-membered cycles (a-"armchair", b-"bath")

S4N4 SO

N:SF2Cl F2NìSF5 F2NìOSF5 F2NìOSO2F F2NìSO2F Cl2NìSF5 ClFNìSF4 HN(F)ìSF5 FN=(SO2F)2 FN=SF4

3.9 1.9 49)

48) Hg[NSOF2]2 Ag4[SO2N2], sulphamide, anion ë [N ì S(O)2 ì N] 4

21

211 84 Po -3 a!...

212 ! 212 84Po a!... 83Bi b;g 0.158 s. 3
10 7

Synthesis: 209 210 210 83 Bi(n, g) 83 Bi b! ... 84 Po, distil. vac

s.

Cl +H

Mg

H2Po output 4 0.1% 36 +35 v. unstab.

Mn+ H+

Tellurides Na2Te,
9 H2O cr. colrl. Al2Te3 Ag2Te, "hessite" Cu2Se, "berzelianite" AuTe2, HgSe, "calaverite" "timanite"

M ( (N t); N H a 3 l iq. )

m. p. 65 49 b. p. 42 2 DH =+84 +100 dec. 280 >0 sol. in H2O 75 50%(vol.) 10 3 K1 ˆ 10 4 K2 ˆ 10 11 10 5 angular mol. E ì ¯ 1.46 1.66 € ¯E¯ 90.6 90.2

Hg(Se,S) "onofrite" PbSe

Polonides M2Po, M = Na ë Cs, CaF2 str. type MPo, M = Be ë Ra, Zn ë Hg, Ni, Pb; NaCl, str. type, blk., volat.

HgTe, "coloradoite" PbTe, "altaite" Bi2Te22S "tetradymite" ®E, M = Ge ë Pb, Zn ë Hg, As, Mn, Bi; E = Se, Te, semiconduct., photoresistive mater., lasers

22

2;

1.8

PoCl4

Po mÇt., silvery-wh., powd., brn., glows in the dark, in str. ë chains, d ˆ 9:4, m. p. 254, ´e ì Te 2.86, b. p. 962, sol. in ¯³l, conc. HNO3, melt. alk., € TeTeTe 102 E0 Po4+/Po = +0.765

( !blk.) or glass, d=4.3; in str. ë tangled chains #CS2 s. orange with grn. tint #5
107 Pa (I2; Na; hv-UV, X-rays)

Pn, red, insol. in CS2, not toxic, inê. 240 , subl. 429, d = 2.2 ë 2.4, mol. ë chains t of diff. lengths P ì P 2.24, € PPP 102

Gas ƒƒƒ! P P2 2000 [P:P], P ì P 1.90, el. anal. to N2 ƒƒƒ! 1000

ain 0, ch

O 2 (2

Ba[H2P2O5]# O O H



00

3

Ba(OH)2 ( PH3"†

") CO

)

Ca

H2SO4

Pa

P2O5

N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_14, © Springer-Verlag Berlin Heidelberg 2011

O

P

2

H

O

PCl3( P); Hg2+

H+(cationite)

CO

SiO

2)

P O

19)

5

[MCl(P4)2(PR3)2]

SiO

ce)

escen

umin PO l ! . t reac

H3PO2 = H[ H2PO2] hypophosphorous ac. cr., colrl., hyg., m. p. 27 K = 10 1, sol. in alc., Et2O

Pn, blk., subl. 453, m. p.  1000 (p), d=2.69, thermodinamically stab., non-react., inê. 400 , str. ë gauffer layers of trig. bypyr., graphite similar semiconduct.

CN P = 3 in all forms

Ca3(PO4)2 C+

38)



P, met., rhombohedral, As str. type P ì P 2.38, d = 3.56

(15 2

H4P2O4=H2[H2P2O4] 23)

! PH3 + H3PO4 v. strong Red. (in conc. s., t)

# 83000
10

2.18

M = Rh, Ir

H2O

50

2.21

m. p. ì 1580 Conduct. (TiP) or semiconduct. ì (CrP), chem. passiv. 1600 (act. increases with decreasing 1200 content P); sol. in Na2O2 melt 1356 ferromagn.

P2I4

[R4N][Ru4(CO)12(m3-PO)



22)

(PO)n

H[OPH(O) ì PH2]

550

BP#, dec. >2000, insol. in ac. and alk., str. diamond type AlP, dec. 2000, str. + H2O ! PH3 InP#, dec. 1070 sphalerite GaP#, m. p. 1467 (ZnS) type AsP#, dec. 750

Semiconduct.

Salt - like +H2O !PH3 Covalent Metal-like

40

12)

Ca+

co

Ca2PI; Ca3PI3

Li3P; Na3P; Na2P5 (m. p. 650) K2P5; Ba[P5]2; Rb4[P6], in str. ë plane cycles [P5] and [P6] K4P3; K5P4 Mg3P2; Ca3P2 +O2 ë inê., Zn3P2; Cd3P2 +H2O ! PH3+... Cu3P#; CuP2#, insol. in HNO3 (t)

Ti3P TiP Cr3P CrP Fe3P Fe2P FeP FeP2

15)

t) I2 (

Phosphides M3Px

}

vac. ( PH3)

00

P4, wh., soft, waxlike, toxic, (yel. admix. Pred. and As), m. p. 44, b. p., 257, sol. in CS2, NH3, SO2, inê. 40 ; d ˆ 1:83. In cube str. (Cu type), mol. P4 ë tetrah., P ì P 2.21, € PPP 60, CN P 3. Strain in tetrah. causes chem. act. 34)

ol

# 100

a

O

Ca3P2

Na2PH; MAl((PH2)4

3

C

MPH2, dihydrophosphides, cr., colrl., inê. 

O Si

2+

[P8] 2+(HSO3F)2ë [P4] 2+(HSO4)2ë, (ex. only in s.) [P8] 2+, bl., [P4] 2+, colrl., 3) diamagn.

C(

M; M2On ; MHaln(gas)

HX

OH

H3PO3

M (liq. NH3)

C



Si +

O H2

H2O

") O

P2O5

C(

H+

(H ")

(PH)n, yel., not react with ac., alc.

P2H4, diphosphine, liq., colrl., m. p. ë 99, b. p 63, str. analog N2H4, inêam. at 20 (admix. PH3), not react. with ac., >0 ! PH3+(PH)n ;
n (H2O) 15)

+ PH+ 4 +H2O . PH3+H2O > H3O +PH2 K=10 29 K=10 29 v. weak donor; [Ni(PH3)4], [CoN2(PR3)3]

Phosphonium salts [PH4]X, cr., colrl. [PH4]ClO4, exp. PH4Hal > PH3+HHal (gas) t. subl. PH4Cl 28 PH4Br 38 PH4I 18 (m. p.), 80 (b. p.), v. strong Red.; +H2O ! PH3+HHal; cation ë tetrah. (sp3 )

Ca3(PO4)2

H2(300 , p); HCl( PCl3); MOH( MH2PO2)

1+

2.1

;

t( H2) PH3, phosphine, gas, colrl., toxic, with odour of rotten ésh, m. p. 134, b. p 88, inê. 150 , DH=+5, v. strong Red., sol. in H2O 20% (vol.), m = 0.58; mol. ë trig. pyr., P ì H 1.42, € HPH 93 (p3);

EN

3d

;

(25 , 35
108 Pa; Hg, 370 )

3ë

3s

P0

M[ H2PO2]n, hypophosphites Na H2PO2
H2O 19) M H2PO2; NH4 H2PO2 Mg( H2PO2)2
6H2O Ba( H2PO2)2
4H2O Ca( H2PO2)2, r;adi;y so;. in H2O, anion ë dist. t;trah., P ì O 1.52

Cu2+

P4O8 P4O9

Na3HP2O6
4 H2O Na2H2P2O6

ë

[P(OH)4] X , phosphoryl salts

H2O (H+, t)

O4

HP 2

(

1.47

[HPO3]2 ë dist. tetrah.

Pred

) 2"

,H

mol. P4O10

O) H2

SiO SiO 2 3, t )

Ca

Polymetaphosphates MIn[PnO3n ë 1(OH)2], n = 20 ë 70, form from s.; well, but slow. sol. in H2O (with fractional oligomerization) ®5[P3O10], triphosphates NaZn2[P3O10]
9.5 H2O (NH4)5[P3O10]
H2O 10)

M6[P4O13] Na6[P4O13]

tetraglass

M7[P5O16], penta-

10)

tetrameta-, "chair" and "bath" 4) Li4[P4O12]
6 H2O Na4[P4O12],
4 H2O

hexameta-, Li6[P6O18]
5 H2O Na6[P6O18]
6 H2O

16)

Di(pyro)phosphates 300 Na2H2P2O7, dec. 220,
6 H2O; Na4P2O7, m. p. 988,
10 H2O; Ag4P2O7#, wh.; K4P2O7
3 H2O, ( ! H2O,); t II II MII 2 P2O7#, M = Mg ë Ba, Zn, ! M3 (PO4)2+P2O5", anion ë 2 tetrah. whith a common vertex, € POP 130 ë 157

H3PO4, orthophosphoric ac., cr., colrl., hyg., non toxic, m. p. 42, K1=10 2, K2=10 7, K3=10 12, sol. in alc., e = 61 (25 ), 2 H3PO4 > [H4PO4]++[H2PO4] , mol. ë dist. tetrah, weak Ox. (>350 ), react. with M, SiO2;
1/2H2O, m. p. 30 (80% s. H3PO4, visc. liq.); commercial preparation  85%

1.52

112 

H4P2O8 K4P2O8

7

43

106

=

t ( H2O)

H3PO5

5)

H3PO6

5)

H2SO4 Ca3(PO4)2

t

H H ClO 2O 4 (7 ; H 00  N , P O3 ; t, C u)

4(

SO2 )

MH[HPO3], hydrophosphites NaH2PO3,
2.5 H2O, m. p. 42, dec. 100 KH2PO3; Zn(H2PO3)2, anion ë dist. tetrah., P ì O 1.51 11)

H2 SO

(O H 2O

H

Pwh.

OH

! M3PO4 + PH3 + P + . . .

(

H4P2O7, di(pyro)phosphoric ac., glass or cr., colrl., m. p. 61, K1=10 2, K2=10 3, K3=10 7, K4=10 10, sol. in H2O, alc., Et2O



2

M2[HPO3], phosphites 31) Na2HPO3
5 H2O, m. p. 53, dec. 120 K2HPO3; MgHPO3
6 H2O Ag2HPO3#, wh.; CaHPO3#; CrHPO3
2 H2O,

35)

trimeta-, "chair", Li3[P3O9]
3 H2O Na3[P3O9]
n H2O,

t

H+

102 

P4O11

32, 37) Cyclometaphosphates [M(PO3)m]n , n = 3 ë 6, 8, 10, 12, in str. ë nonplanar cyclic anions [PO3]nn from tetrah. [PO4], MH2PO4 t ( H2O) P ì O 1.6 ë 1.7 (br.), 1.4 ë 1.5 (term.), € OPO 100 ë 119, € POP 103 ë 139

M

H3PO3 (cr.) ! PH3+H3PO4 ; strong Red., by 20 not react. with HNO3, 11 6  1.54 H2[HPO3] > P(OH)3 10

glasses

MOH

H3PO3=H2[HPO3], phosphorous ac., cr., colrl., hyg., m. p. 74, dec. 200, K1=10 2, K2=10 7, sol. in H2O, alc.; mol. ë dist. tetrah.;

1.39

liq., nonvolat., visc. cool (polymeric mol.)

(HPO3)n, n = 3, 4, 6, "metaphosphoric ac.", glass paste, colrl., hyg., m. p.  40, subl., sol. in H2O, alc; strong. ac., K3=10 2, K4=10 3, only one P-ac. coagulated protein (large charge of the anion), in str. ë disord. arrangment of cyclic mol. (HPO3)4 and others +

M2[H2P2O5], pyrophosphites Na2H2P2O5; ZnH2P2O5 11)

H2O

t

124

H2O (a lack, 0 )

H2O (300 )

16)

liq., volat., êuent (mol. P4O10)

P O H



H2O (slow.)

H4P2O5 = H2[H2P2O5], di(pyro)phosphorous ac. needles, colrl., m. p. 38, dec. 130 PCl3

a-, hex. (rhombohedral) mol. str., d = 2.3, 422 m. p. 422 (Ó), subl. 359 (volat. < P2O3), t DH ˆ 2988 (for P4O10), v. react.

H4P2O6

M6P6O12
n H2O, M = Rb, Cs, Ba/2, 31) hexametaphosphites Mn3H6P4O12
1.5 H2O

21)

P2O5, phosphoric anhydride, wh., v. hyg. (mixture of amorph. and hex.), rapidly react. with H2O; v. strong dehydrating agent. In gas and hex. str. ë P4O10, in mol. tetrah. [P4], on the edges ë 6 br. Ât °; at each at. ² ë 1 term. at. °, P = O 1.40 ë 1.49 and 3 br. P ì O 1.56 ë 1.65

1.5

P2O3, phosphorous oxide (III) cr., wh., m. p. 24, b. p 175, DH ˆ 1640 (for P4O6), sol. in org. solv. 125 In gas, s., one modif. ë  dimers P4O6. 99 In mol. ë 4 c-tetrah. [:PO3], 5 1.6 with sharing vertex form. the "big tetrah." [P4]. In sld. polymers from tetrah. [PO4].

5+

M2On(t)

4+

3+

Monobasic (primary) M[H2PO4]n, sol. in H2O (any M) NaH2PO4, dec. 200; KH2PO4, m. p. 253 (dec.); (NH4)H2PO4, m. p. 190 ³a(H2PO4)2, "duble superphosphate" ³a(H2PO4)2
H2O+CaSO4#, "simple" t ! M(PO3)n+H2O. In str. ë chains of anions whith H-bonds

Mono(ortho)phosphates 35) Dibasic (secondary) M2[HPO4]n , sol. in H2O only if MI Na2HPO4, (dec. 300),
n H2O n=12 (dec. 35), 7 (48), 2 (95); NaNH4HPO4, "phosphoric salt", t ! NaPO3 + NH3 + H2O; CaHPO4,
2 H2O #, "brushite" t SP = 10 6, "precipitate", ! M4P2O7 + H2O

Threebasic (tertiary), M3[PO4]n, sol. in H2O only at M = Na ë Cs, NH4; Na3PO4, m. p. 1340,
n H2O n = 10, 12 Ca3(PO4)2#, m. p. 1670, SP = 10 25; Ca5(PO4)3(F, Cl, OH), "êuor-", "chlor-", "hydroxylapatites"; anion ë regular tetrah. (sp 3 )

41

PHOSPHORUS HALIDES AND OXOHALIDES 2+

3+

5+

P2O3

Cl2 ; Br2 (rap idly)

18

+ PF3 ! (POF)n

( Hg

Hg

H PF2, gas, colrl., m.p. 124, b.p. 65, m = 1.32, mol. ë pyram., ² ì ¯ 1.41, ² ì F 1.58, € FPF 99, € HPF 96; +H2O ! H2+HPOF2+HF+H3PO2

I 2)

2

+

Hal2 H2 (discharge)

m.p. 86

b.p. 6

PF3, gas, colrl. PCl3, liq., colrl. PBr3, liq., colrl. PI3, cr., red

P2F4, gas, colrl., unstab. 28 180 P2Cl4, liq., colrl. 126 dec. P2I4, cr., orange mol. trans ë Hal2² ì ²Hal2, ² ì ² 2.2ë2.3, ² ì Hal 1.59 (F), 2.48 (I), € Hal²Hal 99 (F), 18) 102 (I), € Hal²² 94

HI

(

PH

)

4 I)

)

P

H l 2; Ha

Ha

m 1.03 0.78 0.52 0.34

Hal2 PHal3 ë hyg., toxic, sol. in CS2, CCl4, Et2O, bz.; 25) t ( Hal2) mol. [:PF3] ë c-tetrah. Hal = ³l (100 ); PF2Cl, PF2Br, PFCl2, PFBr2; Br (35 ) + H2O ! HHal + H3PO3; PCl3
n L, L = Br2 (n = 2, 9); NH3 (n = 5); Me3N [Cr(PF3)6]; KRe(PF3)5; [Pt(PF3)4]; [Ni(PCl3)4]

[P2I5]+[AlI4] ë, cation ë [I3P ì PI2]+, P ì P 2.22, P ì I 2.41

24)

HPF4, m.p. 89, b.p. 36, unstab., mol. ë trig. bipyr. 24) [R4N]+[HPF5] ë H F

S2

DH 959 314 175 46

H3PO3

PI3

AlI 3 I2 + (CS 2)

P2O5; H2O m.p. PF5, gas, colrl. toxic PCl5, cr., colourl. PBr5, cr., orange 27) PI5, cr., blk.

94 160, subl. 106 40

b.p. 85 159 (p) dec. ì

KH2PO4 PF2(O)OOCF3

14)

13) PHal5 ë v. hyg., sol. in ³³l4, CS2, bz.; mol. PF5, PCl5 (gas), ë trig. bipyr. (sp3d), in cr. [PCl4]+[PCl6] , [PBr4]+Br ³sCl str. type PF3Cl2, PF4Cl, PF2Cl3 ë gases; PC4F, PF3Br ë liq.; ! PF5 +PHal5 PCl5
n L, L = NH3 (n = 8, 9); N2O4,

24)

[PF4]+[Sb3F16] ë 8, 9) [PCl4]+X ë, X = F, [PCl6], [PF6], [BCl4] + P2Cl9Br = [PCl4]+ 3 [PCl3Br] Br2 [PCl6]2 [PBr4]+Xë, X = F ë Br, [Cl3], [Br3], [PF6], cations ë tetrah. (sp3 ), P ì Hal 1.98 (Cl), 2.15 (Br) 24) [PI4]+[AlI4]ë

®PO3 3 BF

HPF6, oil, colrl.,
6 H2O, m.p. 32, strong ac. M+[PF6] ë, M = Na(
H2O), K ë Cs, Tl, Ag (sol. as MClO4), [O2], [NO], [NO2], [PCl4], [PBr4], [Xe2F11], stab. at pH>7 [ECl4]+[PCl6] ë, E = P, As, anion ë oct. (sp3 d2 )

O2F2; NOCl; N2O4; XeF6

42

DH 1594 433 231 ì

.) ow  (sl ) 20 liq. 2 (SO

2 (C

F r,

B l(

b.p. 101 75 173 dec.

H[PO2F2], liq., colrl., m.p. 90, b.p. 108, d ˆ 1:6, strong ac.; M[PO2F2], anion ë dist. tetrah., € OPO 122, € FPF 97 H[PO2Cl2], liq., colrl., m.p. 28, stab. at 20 ; M[PO2Cl2] 30) M[PO2Br2]

HF

;I

m.p. 151 90 40 + 61

O

Oxohalides 7) m.p. b.p. DH POF3, gas, colrl. 39 (p) 40 1218 ©1 107 602 POCl3 liq., colrl., toxic 56 192 460 POBr3, cr., colrl. POI3, cr., vlt. 50 ì ì POFCl2, POF2Cl ë gases, POCl2Br ë liq. colrl., POHal3, hyg., sol. in org. solv., +H2O ! H3PO4 + HHal; mol. ë dist. tetrah. (sp3), P=O 1.45

F O3

SO

; Cl 2 2

P2O5(t)

HS

HI

) ,t Pt ( 2

NH4F; HF (40%)

H2[PO3F], liq., colrl., d ˆ 1:8, K1  K2  10 5 ; + H2O ! HF + H3PO4 M2[PO3F], M = MI, NH4, Ca/2, cr., not hydr., anion ìtetrah. P ì O 1.51, P ì F 1.59 6)

PO2Cl, oil colrl., +H2O ! H2+HP2OCl2 (POCl2)2O, m.p. 16, b.p. 65

HPOF2, mol. ë dist. tetrah., P ì H 1.39, P ì F 1.54, P ì O 1.44

(PF2)2O, gas, b.p.

P2O5

NITROGENOUS DERIVATIVES OF PHOSPHORUS 3+

5+ 100

H2[PO3(NH2)], cr., colrl., K1 ˆ 10 3 , K2 ˆ 10 8 , ! NH4PO3 + H2 ! (NH4)2HPO4 Ag2[PO3(NH2)]#; 210  450 Na2[PO3(NH2)] ! Na4[(PO3)2NH] ! Na6[(PO3)3N] PCl5

NH3 [HNPNH2], amido-imide NH3

NH3

NH3 (>125  , vac.)

P2S5

3 NH  ) 0 5 (8

H2

N2; 700

PN N

! P4 + N2; insol. in ac., alk.; mol. PN ex. in gas, P ì N 1.49, m=2.75

POCl3

Li



0

70

>

800

Mg2[PN3], anionëchains of tetrah.

N:P=NH, imidonitride, ("phospham"), powd., wh., insol. in ac., alk., b-cristobalite str. type 400 , ÄÂÍ. ( NH3)

P:N, nitride, cr., yel.-brn.;

}

H2O

nitridophosphate

H[PO2(NH2)2], cr., colrl., pentabasic. ac., K1 ˆ 10 5 cyclo-{ ¯n[ì PO2(NH)]}n, n = 3 ë 6, metaphosphimic ac., v. stab., sol. in H2O, NH O O 100 P OH HO P ! NH4PO3 (slow.), HN v. stab. at n = 4 NH P #M (liq. NH3 ) OH M2n[PO2N]n O Mn[-PO2NH]n

N:P(NH2)2, amidonitride, m. p. 162

P4N6, cr., colrl., insol. in ac., alk., iêam.

2

t

H2

N

P2(NH)3, imide

}

NH3 [HNP(NH2)3]

imido-

NH (CH 3 Cl ) 3

[NH 4 ]H2 P O4 (927  )

Li[PN2], cr., colrl., dec. 1000 , v. stab., insol. in ac., alk. 28)

P3N5, nitride, amorph,, wh., dec. 800 , insol. in ac., alk., org. solv., stab. + H2O(180 , p) ! H3PO4 + NH3 >700 ! P + N N:P(N3)2 = "PN7", azidonitride

PO(NH2)3, cr., colrl., slow. hydr., mol. ë dist. tetrah., P ì O 1.51, P ì N 1.66; [PO(NH2)(NH)]4, oxoamidoimide

; t(

H2O

NH3)

(PON)n, oxonitrides, wh., amorph. or cr., insol., involat. 1000 (vac.)

! P2O5 + PN; + NH3 ! P4ON6

26)

(NPX2)n, X = F, Cl, Br, SCN, NH2, R, n>3, phosphonitryle halides, -rhodanides, -amides, -alkyls etc. (phosphazenes) X=Cl, cr., colrl., insol in ac., alc., Cl Cl sol. in Et2O P 1.60 n m. p. b. p . N N Cl Cl 3 114 256  4 123 328 ² 102 ² 5 41 224 Cl N Cl 6 90 262 inaromatic syst. 7 18 ì 1 ì >250 at n = 3 ë planar cycle, n = 4 ë nonplanar ; 250 (polymerization) 12 08

[P(NH2)], amide

[P(NH2)5 V. unstab.

NH3 liq.

V. unstab.

NH3 liq.

PCl3

H2O

amido-

PCl5

N (

H

4C

H

l (t

Cl

)

,p )

transparent mass (linear polymer), "inorg. rubber" ; 350 (oligomerization)

chains ë [Cl4P(NHCl2)nCl] (NPCl2)n
m L, L = SO3 (m = 3); HClO4 (m = 1, 2) (NPF2)3 (NPF2)4 (NPBr2)3 (NPBr2)4

m. p. 28 30 192 202

b. p. 52 120 ë ë

43

PHOSPHORUS IONS IN AQUEOUS SOLUTIONS 4+

5+

HNO3 (30%); HClO4 2O 2

H2O (H+, t)

H

H4P2O6 (hypophosphoric ac.), K1>10 2, K2=10 3, KMnO4 H3PO4, H2O H4P2O7, H2O orthophosphoric ac. K3=10 8, K4=10 10, ‡ ac. 2 ; t) pyrophosphoric (H 2 3 K1=10 , not Ox. weak Red. ( H3AsO3, known in s. only, Kac1=10 9, Kbas=10 14, pH  5 HNO3 (conc.)

570

rh., "valentinite", d = 5.75 m. p. 656, subl. 1570

H2O

(c

Sb2O3
n H2O#, wh., sol. in ac. and alk. SbO(OH) MOH (SbO)nX, oxosalts 19) Sb4O5(OH)ClO4
1.5 H2O [Sb(OH)SO4(H2O)]2 Sb4O4(OH)2(SO4), "klebelsbergite" Sb2O(SO4)2; Sb6O7(SO4)2 [H5O2]+Sb4O2(OH)(SO4)4 [(SbO)2(OH)(NO3)]2, disphenoid [:SbO4], c-tetrah. [:SbO3] and oct., SbO(H2PO4)
H2O

M3En 20) Arsenides Antimonides (stibides) Bismuthides liq. As(OH)SO4 M2Bi4; MBi CsSb; M2Sb; Li3Sb2 As (p), Sb, Bi M3Bi, bl.-vlt. M3As, M = Li ë K M3Sb, M = Li ë K t M3As11 M4Sb7; M2Sb4; LiSb2, As(HSO4)3 SrAs3; Sr3As4; Ba3[As7]2 +H2O !MOH+EH3" gas Mg3Sb2; BaSb3; Ca16Sb11 Ca11Bi10 Ca3As2; CaAs2 t t Mg3As2; Cu3As2 Ca11Sb10; Ba3[Sb7]2; Mg3Bi2 E4 > 2 E2 > 4 E H2SO4 (conc.) H2O (surplus) E = As, Sb ZnSb; CdSb Zn3As2; ZnAs2 H 2S Bi2 > 2 Bi, +HCl ! EH3"+MCl; in str. [E7] clusters, rings, chains 2O M [As8] 2+, [As4] 2+, [Sb4] 4+, ex. in Sb(ClO4)3, 7 el. anal. of N2 AlSb AlAs, m.p. 1740 LnBi s., colrl., diamagn. 210 GaAs; InAs, m.p. 1238, GaSb ! SbO(ClO4) 2) 2+ (bl. due to [S ] impurity) 8 ) Sb 943, sphalerite str. type, InSb 2(SO4)3, needles, colrl., 3+ ë 0 9 SbH3 rapid [Bi5] [AlCl4]3 , m.p. 253 O2 (
H2O LnSb semiconduct.; LnAs; 2+ ë cool. [Bi8] [AlCl4]2 Fusible alloys of Bi (eutonics) Sb(NO3)3; Sb2(HPO3)3 + H2O ! AsH3" + . . . CsSnSb3, ex. in gas [Bi9] 5+Bi+[HfCl6]23 ë, cations ë SbPO4, stab. at 1200 Ba[Zn2As2], layers of Ca14AlSb11 30) Alloy compos., % m.p. [Bin] m+, n=3 (triangle), n=5 SbMO4, M = Ta, Nb, [ZnAs4/4] tetrah. Pb Sn Bi (trig. bipyr.), n=8 (square anti"stibiotantalite", Ag, Zn, Cd, TiAs; ZrAs; NiAs, NiAs Ti4Sb ë 16.5 51.5 - In 32.5 60.5 (Fild's met.) prism) and n=9 (three-cap trig. 1) SbCl3 "columbite" prism), Bi ì Bi 3.1 ë 3.9 Pb, Sn, Fe ë str. type, "red Ni pyrite" TiSb; CoSb; NiSb 25 12.5 12.5 - Cd 71 (Wood's met.) 97 Ni do not ("breithauptite"), FeAs; CoAs ì 50 30 92 40 form VAs;CrAs,MnPstr.type; NiAs str. type. As2S3# , yel., SP=10 29, cr., Sb2S3#, orange, SP=10 30, As4S4, glass or cr., orange, m.p. 320, 6 30-Hg 36 28 48 bismuthides V5As3; FeAs2, "l ollingite" TiSb2; CoSb2; NiSb2, golden, m. p. 310, b. p. 723, cr., grey, m. p. 560, b.p. 565, sol. in M2S ì 14-Hg 29 57 melts under friction 2.49 U3Bi4, PtBi2, FeAsS, "arsenopyrite" NiSbS, "ullmannite" DH ˆ 96, sol. in b. p. 1160, DH ˆ 158, sol. in and NaHCO3; 15 25-Sb ì 60 Type-metal alloy ("mispickel") Cu3Sb, Cu2Sb Au2Bi ë (NH4)2CO3, HNO3; conc. HCl (t); As4S4 ë in str. and gas, 3 2 Cu3As2# intermet. +OH ! [ES O ] ; +S ! [ES3]3 ; +S2n ! anal. of S N (but S L n 3 n 4 4 Bi[Co(CO)4]3 + V 3 a comp. Cu 2+ As(HgCl)3#, brn. S ] [E and E at. exchanged Zintl polyanions N 4 BiIr3(CO)9, "antimonite", rh. their places: As4 ë tetrah., S4 ë square); "orpiment", monocl. # HgCl2 [Na2L4]Bi4 EH3 clusters tetrah. 4) HgCl2 bands of c-tetrah. [:ES3] "realgar"; [Na3L4]Sb7 Hg3As2#, blk. 3 O in gas As4S6 mol., str. anal. +KOH ! As# + KAsO2+ K3AsS3 [Na3Ln]As11, Ag3E
3 AgNO3 = [EAg6] 3+(NO3)3 , cr., yel. AgN (CO)n BiHal3 of P4O6, Bi4S4 100 ! As4S3, AsS2 1) L = En, cryptand 30) NaM hn-Vis.

(ac eto ne)

Ag NO 3

2.33

Salt-like

E CN =3+3

in gas ë mol. E4O6 ! E2O3

9.80 271 2531

sol. in alk. (t) +0.80 +0.72 E0 E3+/E +0.30 sld met. conductivity (increases from As to Bi) a- hex. (rhombohedral), blk. P str. ë like a 4.12 4.50 4.75 a 54.1 57.1 57.2 CN 3 (= 8 ë 5) E ì E 2.78 3.18 3.64 between layers 3.33 3.36 3.53 # subl. in atm. H2" " 270 (As) b-, powd., blk. amorph. or mirror stab. in air d 4.7 ë 5.1 5.3 > 80 ( SbH3) g-, cr., yel., wax-like, d=1.97, dec. 358, sol. in CS2, volat. with H2O vapour, v. react. (oxidised in air), In str. As4 mol., contains tetrah., As ì As 2.44 10% SbH3

221

monocl., "claudetite", d=4.29 m.p. 315, b.p. 465 gauffer layers of c-tetrah. [:EO3/2]

m oleu

Covalent

#

l 3; ; AlC 6F 2 l 3+ S 2O BiC 2O 8+ S K 2 O 3F HS

Metal-like

Sb2O3# cr. cub., colrl. m.p. 278, DH ˆ 665, sol. in H2O DH ˆ 707, sol. in HCl, HNO3, ( 2%), "arsenolite", d = 3.87 alk.; "senarmontite", d = 5.58 mol. E4O6 in site of diamond [str. anal. of P4O6;]

(t) ;K CN

6s

As Sb met. grey, brittle d 5.72 m.p. 817/36
105 PÂ b.p. 615, subl.

5p ;

E2S3

As2O3, glass or

2.2

2; H 2O

;:

4d ;

4

HCl

Bi0

5s

;

SO H2

MIAsH2, M = Li ë K, cr. yel., dec. 0 (Li), 10 (Na), 80 (K) ( ! H2 + MAsI) HAs(HgCl)2#, cr. yel. KSbH2, stab. tetr., in str. 35) frame of tetrah. and oct.

135

BiO(OH) ! Bi(OH)3;, wh., sol. in ac. and conc. alk.

Sb2O5;, cr. yel., frame of oct. with common edges and vertices,

As2O5, glass colrl., hyg., dec. 400,

E2°4=EIIIEVO4, 24) AsO2 SbO2;, colrl.

230

t

Bi2O3, cr. yel., > brn., "bismite", d = 8.2 ë 8.9, m.p. 824 (rh.), 860 (tetr.), b.p. 1890, DH = 577, sol. in ac.;  Bi2O3 meltdissolv.Pt;a-,monocl. 729 ! d-,cube, m.p.824; cool. ! 43) b-, tetr. + g-, cube ì metastab.; for all forms frame of oct.  150

5+

KClO3

Bismuthates (V) 38) NaBiO3;, cr. yel. KBiO3, red-vlt. Ba(BiO 3 ) 2
4 H 2 O, orange AgBiO3 ;, blk. M 3 BiO 4 ; Li 5 BiO 5 , anions oct. Li7BiO6, ionic conduct., [BiO6] oct.

M Bi2O3

O2

+

2

550 HSb(PO4)2
4 H2O M[Sb(PO4)2], 41) M = Li ë Cs

M2[AsO3(OOH)] M2[As2O4(O2)F2]

)

M3[AsO3S]; M3[AsOS3];10) Na3[AsO2S2]
11 H2O M3AsS4, M = Na , NH4, Cu/2 ("luzonite"), colrl., anion tetrah.

Sb2S5 (?)#, orange cr., dec. 170 12)

(t) O2

S2 H+

40)

M3[SbS4], M = Na (
9 H2O, Schlippe salt), K (
4.5 H2O), cr. vlt., anion ë tetrah.

47

ARSENIC, ANTIMONY AND BISMUTH HALIDES AND OXOHALIDES

+

ë

[AsF2] [SbF6] [AsCl2]+[SbCl6] ë

As+AsI3

6 16 33 146

63 130 221 403

858 22) 2.81 MHal 336 1.97 201 ì 67 ì

cath. Red .)

nc

Cl

o (c

H

Sb2S3 Bi al 3;

BiH

aq

.re

gia

m.p.

b.p.

SbF3, cr. colrl. 292 319, subl. 916 73 233 382 SbCl3, cr. colrl. 289 260 97 SbBr3, cr. colrl. 171 401 100 SbI3, cr. red SbHal3 (Hal = F ë Br) isostr. to YF3; SbI3 isostr. to PI3. SbHal3 sol. in ROH, bz., Diox;
n L, L = Dipy, C6H6, C10H8 ë p-compl.

3) M[SbF4]; Na2SbF5; KSb2F7; Li3Sb2F9; NaSb3F10; K[F(:SbF3)4]; K3Sb4F15; Na3Sb5F18; anion ë -trig. bipyr. (disphenoid) or oct. M4Sb4F16, anion [:SbF3F2/2] ring M[SbCl4]; M2[SbCl5]; M3[SbCl6]; Cs4SbCl7; Cs5SbCl8; M3Sb2Cl9; Cs5Sb2Cl11; M7Sb3Cl16 Tl2Sb3Cl11, anion oct., -oct. RbSbBr4;K2Sb2Br9;M3SbBr6,oct.

BiOF; Bi7O9F3; Bi3O4F; Bi13O19F BiOCl; Bi4O5Cl2; Bi3O4Cl; Bi12O17Cl2; Bi24O31Cl10 BiOBr; Bi12O15Br6; Bi3O4Br; Bi12O17Br2; Bi24O31Br10 BiOI; Bi5O7I, str. [Bi10O14]2n+ columns, Bi CN 7, 8 n and 9. Str. of other oxohalides: HalBiOBiHal... 6+ 29) layers (in BiOHal) or [Bi12O15] of c-oct. BiSHal, BiSeHal, Hal = Cl ë I, Bi CN 8 H+

Cl 2 Hg 2

m.p. 163; ! Bi + BiCl3; Bi6Cl7; Bi2[GaHal4]2; Bi24Br28, semiconduct. BiI, m.p. 318 with dec. Bi7I2; Bi9I2 1) Bi10I3, m.p. 295

As

O3

+

F2

2

m.p.

b.p.

DH

BiF3;, cr. grey 727 900 899 BiCl3, cr. wh., 234 447 379 darkening in light BiBr3, cr. yel. 219 461 260 BiI3;, cr. brn., 408 439 109 2 sol. in I , S2O3 , 3 AsO3 presence. In gas [:BiHal3] c-tetrah., in ion str. BiF3 and BiCl3 (YF3 type) Bi CN 8+1, in BiBr3 (a- and b-): dist. oct.; BiI3 isostr. to FeCl3, BiCl3
n L, L = NO, NO2, NOCl

7) MBiF4, struct. [BiF9] grs. K2BiF5; K3BiF6; KBi2F7; KBi3F10 MBiCl4; M2[BiCl5]; M3BiCl6; Cs4BiCl7; Rb3Bi2Cl9; Rb7Bi3Cl16; M2Bi2Cl8, anion 2 c-oct. with common edge M2BiBr5; M3BiBr6; Cs3Bi2Br9 M4[Bi2Br10]
4 H2O; M7[BiBr6][Bi2Br10], anions ë oct. or c-oct. KBiI4; HBiI4
4 H2O; M3[Bi2I9] Rb5I(I3)[BiI6]

SbF4 = 2+ [SbVF6]2 [SbIII 2 F4] Sb11F43 = 5+ F [SbVF6]5 , [SbIII 13] 6 cation chain of 2 completed and 3 [:SbF3] c-tetrah. M2[SbVF6][(SbIIIF2) (SbVF6)2] 8) Sb2F4Cl5 [SbCl4], brn. s.

M2SbCl6, M = Rb, Cs, blk., diamagn.; +H2O ! M3[SbCl6]+ +M[SbCl6] M2SbBr6, blk., diamagn., isostr. to K2PtCl6, [SbIIIHal6] and [SbVHal6]

5+ AsO2Cl, cr. colrl., insol. in org. solvs. AsOF3, g. colrl., m.p. 68, b.p. 26 (AsOF3)n, powd., wh., hyg. AsOCl3, cr. colrl., dec. 25 ! (As2O3Cl4)n 32)

M2AsO3F; MAsO2F2 MAsOF4, M = K ë Cs, anion [As2O2F8]: 9) 2 oct. with common edge [O2] M2[(AsF5)2O], M[AsF5(OH)], anion oct.

AsF5, g. colrl., v. hyg., m.p. 80, b.p. 53 DH ˆ 1066, mol. trig. bipyr. (sp3 d), strong F- acceptor 15) AsCl5, ex. in ³l2 s. at t 4 50

M[AsF6], M = MI, [NF4], [AsCl4], [SCl3], [ClF4], [ClO2], [IO2], [IF6], [XeF], [Xe2F3], anion oct., resist to hydr. M2AsF7 M[AsCl6], M = [PCl4], [Et4N], cr., orange

42) [AsF4]+[PtF6] ë [AsCl4]+X ë, X = PCl6, AlCl4, AsF6, SbF6 [AsBr4]+X ë; [AsI4]+X ë, unstab.

Hal2; E BrF5

(SbOF3)n; SbO2F SbO2Cl; SbOCl3;, yel., hyg., insol. in org. solvs.;+ H2O ! Sb2O5
n H2O;

MSbOF4 M2Sb2OF10,M[SbF5(OH)], Na[SbF4(OH)2], H[SbF6 ë n(SO3F)n], n=0ë3

:HO

16)

2

m.p.

b.p.

(SbF5)n, oil colrl., visc., 8.3 149 ì weakly hyg. 3 102/vac. SbCl5, liq. colrl. SbBr5 (?) ì ì DH SbF5 = 439,dissolv.S,Se,Te;v.strong F - acceptor; SbCl5 ë strong Cl - agent. In liq. (SbF5)n (n ˆ 5 10) chains of [SbF4F2/2] oct., instr. tetramers of cis-[SbF4F2/2] oct., 11) in gas [SbF3F2/2]3 cycles. t SbHal5 ! :SbHal3 + Hal2; equ. ax. + H2O ! SbOHal3 + 2 HHal equ. ax. SbCl5
L, L = NOCl, POCl3, SO2, mol. oct.

M[SbF6]; M[Sb2F11], M = MI, [NF4], [AsCl4], [S16]/2, [SF3], [H2F], [Cl3], [HalF2], [HalF4], [XeF3], [XeF5], [XeOF3], [Xe2F11], anions 17) oct. or 2 oct. with common vertex M[Sb3F16], M = [PF4], [Br2], anion chain of 3 oct., [SbF4F2/2]-trans in the centre M2[SbF7]; H3[SbF8], Sb CN 7 and 8 [BrF4]+[Sb7F36] ë HSbCl6
3 H2O, cr. grn., hyg.; [H14O6][SbCl6]2 M[SbCl6], M = MI, [SCl3], [NO], [ICl2], [PyH] M[(SbCl5)2X], X = F, CN, N3 H[SbBr6]
3 H2O; M[SbBr6], oct. 14,16) Cs[SbI6]

[SbF4]+[SO3F] ë; [SbCl4]+X ë, X = SbF6, SO4/2, Hal 44) Sb(OTeF5)6

E2O3

SbF(NO3)4; SbF3(NO3)2 BrF

Bi

 ); 00  ) (5 350 F2 F3 ( Cl

Bi24Cl28 (& "BiCl") = III III 2ë 2ë [Bi9]5+ 2 [Bi Cl5]4 [Bi2 Cl8] cr. brn., hyg.,

MBi3O4Cl2 LiBi2O3Cl BaBiO2Cl

H2O 31)

300

DH

MHal

( 5 0 )

SbCl n , n43, exp. Sb, graphite-like mass, exp. at friction, d=5.8, in str. ë at. Sb, [SbCl] 2+ , [SbCl2]+, Cl

M[AsF4], M = K ë Cs, [SCl3], c-trig. bipyr., KAs2F7 = K[AsF4][AsF3], 22) [SCl3]+[AsF3Cl] ë KAsCl4

8 ) O3 ( 7 C AsHal3 and SbHal3 hyg., sol. in Et2O, AsCl3 (e = 13) dissolv. S, P; melthed SbHal3 l2 ( 105  readily dissolv. MHaln; AsHal3+ H2O > As(OH)3 + HHal (rate of hydr. ,U H2O V) F 4 Cl>Br>I); SbHal3 + H2O > Sb(OH)nHal3 n + HHal ! SbOHal;; SbCl3 sol. in ¯2° *80%; in str. and gas: [:EHal3] mol. c-tetrah., EI3 ë layered polymers, isostruct. to FeCl3

25) Sb3O2F5; SbOF Sb3O4F SbOCl;; Sb4O5Cl2;; Sb8O11Hal2, Sb4O5Br2;; Hal = Cl ë I Sb5O7I Sb3O4I; c-tetrah., trig. bipyr. and Hal , SbEHal, E = S ë Te, Hal = ³l ë I, semiconduct.

E Hal2

48

m

F3

; H2O

DH

Br

As2I4, cr. dark red, m.p. 136 (dec.),

b.p.

+

AsF3, liq. colrl. AsCl3, liq. colrl. AsBr3, cr. colrl. AsI3, cr. red

"4+"

m.p.

M F

3+

H2

BiF5, needles, colrl., m.p. 151, b.p. 230, v. strong Fagent, in a-UF5 str. ë chains of trans-[BiF4F2/2] oct. 17)

3

MF + F2 (p); [NH4]BF4

K[BiOF4] BaBiO2Cl LiBi2O3Cl MBi3O4Cl2

M[BiF6], M = Li ë Cs, Mg ë Ba/2, [BrF2], [O2], [H3O], [XeF3], NF4 17) + H2O ! O2 + H2O2 + . . .

49

50 N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_16, © Springer-Verlag Berlin Heidelberg 2011

51

NIOBIUM, TANTALUM, PROTACTINIUM

;

:;

6p

6d

6d

5f

7s

; 2

1

:;

1.3 1.1

PaO, élm at the met. surface, NaCl str. type, Pa ì O 2.48

2

or 5f 6d 7s

Nb

231 91 Pa

!...

1.83+ Nb6I11 = [Nb6I8]I3, cr. blk., [Nb6I8]3+ ë oct., [Nb6] cluster, enclos. with a cube of 8 I at.

PaF4

2.33+ 4) M6Hal14 = =[M6Hal10Hal2/2]Hal3, M=Nb,Ta,Hal=Cl ë I, cr. dark brn., stab. in air; t ! M + MHal4 , [M6Hal12]X2
8 H2O, X = Hal (cr., grn.), OH (blk.), stab. in air, diamagn.

2.41

;P

b;

1)

subl.

>300

+H

Cd

(t)

2.67+ 4) Nb3Cl8, blk-grn. Nb3Br8, blk., hydr., subl. 400 NbHal3.13; Nb3I8 TaBr2.83 Ta

MHal5

2

NbF3;, 5) bl.-blk., NbF3.13 Nb2Cl6
n L, L = Me2S, PR3 NbI3,blk.

TaF3;, TaCl3+x, grn., strong. Red ; >440 TaCl5 + Ta6Cl14 TaBr3+x, grey-grn. 4) TaI3 t ( NbI5)

(2.33 ë 2.67)+ Kn[(Nb6Hal12)Hal6], n = 2, 3, 4, Nb ì Nb 2.97 ë 3.02 M[(Ta6Cl12)(H2O)6]Hal4 (Me4N)2[Ta6Cl12(OH)6]
21 H2O [Nb 6Cl12 ]n+ , oct. [Nb6 ] ë cluster is surrounded by cubooct. of 12 Cl at., M ì M 2.85 (Nb), 2.88 (Ta), M ì Cl 2.41 (Nb), 2.44 (Ta) Nb(C5H5)2, ex. in s.

52

2.5+ Nb2F5 = = [Nb6F12]F3, ReO3 str. type Ta2Hal5 ;, Hal = Cl, Br, cr., blk.

Nb

29)

HF

2.7+ [Ta6Cl12(OH)4(H2O)9]
10 H2O

Nb Hal

#t

cr., red, tetr.

M2TaCl5, M = K ë Cs, red

! NbCl3 + NbCl5; + H2O ! bl. s. NbBr4, cr. brn. 502 NbI4, cr. grey 264 In NbHal4 str. chains of dist. oct., diamagn. 27)

MIINbF6, meff=1.15 K3NbF7, m.p. 840, isostr.toK3NbOF6, anion pentag. bipyr. 16) M2NbCl6, M4[Nb(CN)8] 6,22)

Nb

y(

P

3.8

MHal5

TaOCl2, TaOBr2 31) M2TaCl6, PaOHal2, TaOI2, blk. cr., Hal = Cl ë I 30) vlt. graphite-like TaCl4, cr. blk.-grn., hyg., subl. 300,

4)

210


H ˆ 320

707; +NbCl5

! TaCl5 + NbCl4 TaBr4,
H ˆ 52:5 TaI4, cr. blk., m.p. 398, isostr. NbI4 TaCl2I2, chains of [TaI4/2Cl2] oct.

N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_17, © Springer-Verlag Berlin Heidelberg 2011

l 2)

Ha

Py

[MHal4Py2],Hal=Cl ë I,cr. grn. or red (2 forms), paramagn.

> TaCl3 + TaCl5;  5)

Nb

3.1

300

4)

l5

Synthesis of Pa 230 231 90 Th(n, g) 90 Th b!

NbBr2 NbI2, blk.

PaCl5 PaI5

PaO2+n, cr. bl., sol. only in HF, CaF2 str. type
H ˆ 1029

bC

1.18 m., 6.75 h.

!




.)

NbOCl2, NbOI2, cr. blk., dec. 500, chains of oct., diamagn.

ì NbF4, cr. blk., + H2O ! NbO2F; 3.7+ ! NbF5 + Nb2F5; K4[H5O2][Nb3O2(SO4)6(H2O)3]
5 H2O, dist. str. perovskite, [Nb3] cluster ë triangle NbCl4, needles, blk.-vlt., 275 DH = 694;

HC l (80 0 )

Ba ( 1500  )

´Â°2 (?), cr., blk.-brn.

N

234 ! 234Pa* b ! 92 U b ,g 91 ,g

vac

3.3+ NaNb3O5F

85

3.28
10 y.

H2

MC, cr. grey, with met. lustre, subl. >3000, m.p. 3500 (Nb), 3900 (Ta), NaCl str. type, Ox >800 NbH1 ë x, x = 0 ë 0.3; TaH0.9, sld. s. inculcat., dec. >600 , sphalerite str. type, met.-like substs., insol. in aq. regia. Sld. s. of the limit comp. PaH3, cr. blk., cube.

2.

4

238 234 92 U ! 90 Th a

(t,

Ferroniobium, 23 ë 75% Nb and Ta; 10 ë 11.5% Si; 7% Ti; 7% Al; 0.15% P; 400, m.p. 680, b.p. 850, UCl4 str. type, 22)
H ˆ 1045 PaBr4,
H ˆ 863

M H2 Nb12O29 Nb22O54 Nb25O62, stab. phases

(4 ë 5)+ MxNbO3, bronzes, M = Na ë Ba BaxTaO3

O2

5+(d 0)

26) Nb2O5 ë n n0.54 Ta2O5 cr. colrl., diamagn., sol. in conc. HF not Red with M not Red with ¯2 DH ˆ 1903 2055 a-, rh., ´Â CN 7 (pentag. bipyr.)

®2CO3 7)

Pa2O5

1.74

Niobates, tantalates (V) 13) [M6O19]8ë [R4N]8H4Nb12O36
28 H2O [M6] oct. is Na14Nb12O37, sol. in ¯2° (Ó¯5!) surrounded by 74 1. [R4N]6[Nb10O28]
n H2O, [O6], ë oct. with # 830 # 1320 t# isostr. to [V10O28]6 1 at. O at centre and b-monocl., m.p. 1490, b-monocl., m.p. 1872, cube, 2.01 Rb4Ta10O27; K3Nb7O19 12 at. at the oct. and tetrah., oct. and m.p. M8[M6O19]
n H2O, M = K (n = 12 ë 16), middles of edges Nb ì O 1.98 and 1.83 pentag. bipyr. layers, 1800 Li#, Na#, v. strongly hydr., not oligomerised. ´Â ì ° 1.71 ë 2.38 NbO2(ClO4) NbO(ClO4)3 2ë 3ë Rb4M6O17; K7[M5O16]
n H2O, n = 10 ë 32; Cs3Ta5O14; KTa5O13 [NbOF ] [NbOF ] 5 6 Nb2O4(SO4); Nb2O3(SO4)2 CaTa4O11; KM3O8; NaNb3O8
H2O; Ca2Ta2O7 H2O 4) 500 Nb5O11Cl3 Sn(Nb,Ta)2O7, "thoreaulite", (Y,U)(Nb,Ti)2O6, "euxenite" Rb[NbO(SO4)2], layers of Nb3O7Cl, cr., bl. Nb2O5
n H2O# Ta2O5
n H2O# Pa(OH)5#, KMO3 (meta-), perovskite type str., ferroelectrics [O=Nb(SO4)5] oct., Nb=O NbO2Hal, Hal = F ë I wh., gelatinous, sol. in conc. HF and alk. not reacts. (FeII,MnII)[MO3]2, "columbite" (M = Nb), "tantalite" (® = ´Â) 1.73, Nb ì O 1.96 ë 2.26 8 15 10 13 (Cl ë yel., I ë red) Kac 1=10 and Kbas 1=10 10 and 10 with alk., MOH (20) (Na,Ce,Ca,Sr)[(Nb,Ti)O3], "loparite" [Ta : Nb = 1 : (12 ë 20)] M[Nb2(OH)2(PO4)3]
n H2O M2CO3 HNb3O8, isostr. to Nb3O7F HTa3O8 CaNa(MO3)2F, M = Nb ("pyrochlore"), ´Â ("microlite") M3[NbO(C2O4)3]; 9) 100 HNbO3 = [H3O]Nb3O8 HTaO3 17) K3MO4 (ortho-) Cs[NbO(P2O7)] 25) Nb2O(SO4)4 MIIITaO4, MIII = Y ("formanite"), Sb ("stibiotantalite"), NbO(NO3)3 Cs[Nb(ClO4)6] Bi ("bismutotantalite"), Al ("simpsonite"); K5MO5; Li7NbO6 TaO(ClO ) ; TaO(NO ) ; 4 3 3 3 NbO(PO4) = NbPO5, CsTaO(ClO4)4 +HNO3 Niobate and tantalate struct. ë condenced tetrag. pyram., oct., Nb2O5 TaO(PO4) str. units of 2 [NbO6] oct. 14) (ion dodecah. or pentag. bipyr. and [PO4] tetrah. exchange) CaNaNb2O6F, "pyrochlore" HC Cs2Ta(ClO4)7; K5(NbO3)4F; NaNbO2F2 Cl lO Ta(ClO4)5; Ta2(SO4)5; CsTa(ClO4)6 2O 4 M3[NbOF6] 7 Ta(SO3F)5; Ta(TeOF5)5; CsTa(PO4)2; M2[NbOF5]
n H2O, M = K 20) H[MO4]
n H2O, Ta3(PO4)5# Nb(ClO4)5; Nb3(PO4)5 KTa(PO3)2(P2O7) (sol. in H2O is 11 times > cr., yel. (Nb) colrl. than that of K2Ta2O3F6) (Ta), dec. >100; 20, 30) 23) method of separation Nb ë Ta Ta3O7Hal, Hal = F, Cl (t) K2Ta4O9F4 MPa(NO3)6, NbOF3  + H2SO4 ! 350 according to Marignac, TaO2X, X = F ë I, ClO4 K3Ta4O8F7 M = MI, H, NbOCl3, cr. colrl., subl. 335; ! 24) ! M O
2 5 n H2O; anion dist. oct. KTaO2F2 NbCl5 + Nb2O5; chains of coupled colrl., unstab. M[NbOF ], chains of 4 M2Ta2O3F6 PaO(NO3)3
n H2O, H2SO4 (dil.) [NbCl2Cl2/2O2/2] oct. with common TaOF3, DH ˆ 1297 trans-[NbO2/2F4] oct., Nb at. (2 K2TaF7
Ta2O5), n=1ë4 edge V H[PaO (SO )] , amorph., wh., TaOCl K [M (O2)4]
n H2O, 2 4 3 3 displaced from equ. plane Marignac salt NbOBr3, yel., subl., isostr. to NbOCl3, ) ] H[PaO(SO v. hyg., DH ˆ 891, dist. dodecah. 4 2 at 0.23  M2TaOF5; BaTaOF9 NbOI3, ruby-red, 150 ! NbOI2 + I2 327 (at. Nb displaced M2[NbOCl5]; M[NbOCl4], " 400 ! Ta2O5 + TaCl5 PaOCl3, cr., colrl. K3[TaOF6], from equ. plane) anion tetr. pyram. H3[PaO(SO4)3] TaOBr3, cr., yel., PaOBr3, Pa CN 7 (pentag. anion ë single-cap H3[PaO(SeO4)3] CN 7 (pentag. bipyr.) DH ˆ 853 bipyr.), Pa ì Br 2.91 (equ.), oct. (d 5sp) (NH4)3[M(O2)2F4], TaOI3, DH ˆ 723 2.6 (ax.), Pa ì O 2.14 ë 2.27 21) 11) anion ë oct. HF H O 2 Pa2OF8 = (F4Pa)2O, colrl., MNbF6, M = H, m.p. b.p. DH 9) isostr. U2F9, Pa CN 9 K ë Cs, [BrF2], [O2] MTaF6, M = K, Ta2O5 C+C l2 ; [SeF3]+[Nb2F11] ë, anion [O2], [XeF5], [Xe2F11], SOC NbF5, cr. colrl., 80 23 1812 l2 ; A KPaF6, Pa CN 8 10) lCl3 2 oct. with common H (
n H2O) ì ì NbCl4F, yel. 15) m.p. subl. DH K 2PaF7#, insol. in M2[TaF7];, vertex, Nb ì F 1.8 ë 2.0 NbCl5, colrl. cr., 205 254 797 t m.p. b.p. DH 5% HF, in str. chains M = H, K ë Cs M2NbF7;, anion single183 ! yel. PaF5, colrl. ì 500 2190 of [PaF9] gr. M TaF5, colrl. 989 1460 1903 K3[TaF8], m.p. 780, cap trig. prism (d 5sp), NbBr5, red 268 362 556
2H O;, M3PaF8, anion cube 2 314 F ì ì TaCl anion ë antiprism Nb ì F 1.8 4 , bronze 320 ì 426 NbI 5 O 4) M; H2 PaCl5, yel.-grn. 301 160 1143 M4[PaF9], Pa CN 9 TaCl5, colrl. 207 239 858 MTaCl6, M=Na ë Cs, K3NbF8; MNbCl6 dec. MPaCl6, yel. PaBr5, orange 317 ì 863 286 349 598 TaBr5, yel. anion ë oct. Hal M3PaCl8, PaI5, blk. 300 ì 496 543 489 TaI5, blk. K[M(OR)6] 33, 34) N] M = [NO], [R 4 subl. PaCl5 ë chains of pentag. bipyr. 2092

1.9

HF (45%)

CBr

4;

SOC

H 2O 2 t) (ë O 2;

l2 Nb+

I2

N

2O 5

H2SO4 (t; p)

2.09

2.08

5

+

ë

[NbF4] [SbF6] , cr. subl. 40, zigzag chains of [NbF2/2F4] oct. and separate [SbF6] oct. 8)

MHal5, cr., volat., hyg., sol. in Et2O, POCl3, liq. NH3; + H2O ! M2O5
x H2O 19) MF5 ë str. anal. of (MoF5)4; str. of other ®Hal5 ë dimers (2 oct. with common edge), in g. ë (MF5)3 ë planar cycle of oct., MHal5 ë trig. bipyr. (d 3sp) ®Hal5
L, L = NH3, Et2O, POCl3, NOCl, NO

NbO(NCS)3 NbO(NH2)3 [M(NCS)5]2, red-brn.

K[M(NCS)6], dark-bl. (Nb), orange (Ta)

53

VANADIUM, NIOBIUM, TANTALUM AND PROTACTINIUM IONS IN AQUEOUS SOLUTIONS 2+

3+

5+

4+

+

[O=V(H2O)5]2+, "vanadyl" HCl ( Cl2); H ( H2O); pH < 1 cis-[VO2(H2O)n]+, red, v. strong Ox [V(H2O)6]2+, vlt., H2O ( H2) [V(H2O)6]3+, bl.-grn., O2 ion, bl., paramagn. (d 1), dist. H2O2( O2) paramagn. paramagn. (d 2), oct. H+ H2O ( H+) K = 10 7 (d 3, 3 unpair e), (d 2sp 3), v. strong Red [H:]; Sn2+ oct. (V=O 5 V ì OH2), Pt; EtOH; [H:]; C2O24 ; [H:]; cath. Red 2+ most stab. of other Vn+ oct. (d 2sp 3) ion, orange, frame of 10 H6V10O28, strong ac. NH2OH; Sn ; I HClO4 :; H2O strongest Red dist. [VO6] oct. [VO(O2)3]3 ë, 1 ë 3.5 [H2V10O28] 4 ë, K = 10 4 H2O ;: H+ 2+ [V(OH)(H2O)5]2+, brn. 2 + MnO4 ; Cr2O7 ; + [VO(O with common edges, H O V + 2)(H2O)n] , 2 2 OH ;: H [VO(OH)(H2O)4] O2 , V H+ :; H2O O2 (pH>2.5) + 5ë 6 red-brn. v. strong Ox agent [ V H OH 3.5 ë 6 [HV10O28] , K = 10 O] 2+ OH ;: H+ {O[V(H2O)5]2}4+, brn. 4.66+ ; H+ OH ;: H+ O2 2+ V O (OH) ;, 6 ë + VO + O2 3 5 4 VO(OH)2;, yel. 6ë7 [V10O28] H :; OH O2 blk. + OH ;: H V(OH)3;, grn.-brn. V(OH)2;, brn. (conc. solns.) OH ;: H+ V2O5
n H2O;, orange O2 [(VO)2(OH)5] ë (="[V4O9(H2O)5]2 ") pH < 6.8 4) yel. [V3O9(H2O)n]3 ë, tri- (meta-), 6 ë 8.5 (3 ë n) ë , (dil. solns.) cycles (?), colrl. H2O2 [HnVO2(O2)2] yel. OH ;: H2O (t) V CN 5 (tetr. pyram. 2 ë 5) {HOV(O2)2]2O} [V2O6(OH)]3 ë, di- (pyro-), HNO3 ; aq.regia or trig. bipyr.) 8.5 ë 11 colrl. OH ;: H2O, K = 1011 8.5 ë 13.5 H+, K ˆ 108 [V(O2)4]3 ë, [VO3(OH)]2 ë>[VO2(OH)2] ë colrl., diamagn. H2O2 bl.-vlt. OH (d 0) tetrah. >13.5 OH ;: H2O; K=1012 (d 3s) 1) [VO4]3 ë, ortho-

}

:;

}

Nb

HF + HNO3 ( NO

3.66+ [Nb6O3(SO4)12]8 ë, bl., ex. in s.

2.17+ [Nb6Cl12]+, grn., stab. in HCl s., oct. cluster

O2

[H:]; cath.

H2O)

H2O

[NbF6] ë > [NbOF5]2 ë > [NbOF6]3 ë oct. HF (>35%) dist. single-cap oct. ions, colrl. HF

Red (H 2 SO

4)

H+ 12 ë

(pH 5 ë 6) HF + HNO3 ( NO

Ta

[Ta6Cl12]+, grn., oct. cluster

H2O)

2

:; OH

OH [M(O )n](2n ë 5) ë, 8ë >[Nb > [Nb4O12(OH)4]8 ë H2O2 M = 2Nb 6O19] (yel.), H+ H+ 2) Ta (colrl.) (pH 8.8 ë 14) (pH > 14) OH

HF

I2

H2O (t,

:; OH

Ta2O5
n H2O;, wh., Kac = 10

H2)

H+

Ta(OH)3;, grn.

8ë

:; OH

10

, Kbas = 10

F

Pa

54

13

[Ta6O19] , colrl. ion, not reduced F

[PaF6] ë > [PaF7]2 ë > [PaF8]3 ë H+ ( H2)

15

[TaF8]3 ë, antiprism [TaOF6]3 ë, single-cap oct.

TaCl3
n H2O (?), grn. s., v. strong Red OH

:; H O

Nb2O5
n H2O;, wh., Kac = 10 3, Kbas = 10

[Nb12O36]

cath. Red

}

Pa4+, strongest Red., stab. as a compl. 3) with SO24

F 2+

Zn/Hg; Cr

H2O; O2

:; H O

3)

2

[Pa(OH)n(H2O)m](5 ë n)+, hydr. polymer ions, form coll. particles, sorbed on prec. and glass; tendency to complexation F > IO3 > SO24 > Cl

CARBON HALIDES 1+ Acetylenedihalides m. p. b. p. Hal ì C:C ì Hal ì 76 C2F2, gas ³2Cl2, liq., exp. 64 32 C2Br2, liq., 23 76 +O2 ! exp. C2I2, cr., colrl. 82 ì (dec.)

KF

Na2C2

Cl2

H

Ethylenetetrahalides Hal Hal C=C Hal Hal C2F4, gas, colrl., insol. in H2O, org. solv.

11 82 231 322 316 subl. 350 ì (dec.)

600

#

m.p.

b.p.

142

76

Zn

Cl 2

ì 121 subl.

NO

] F6 ) ] [E O 2 [O 2 F 6; (W X) NO

(C2F4)n , "teêon", dec. 450, ì does not react. with Na, org. solv. C2Cl4, liq., colrl. 22 C2I4, cr., yel. 187

(

Ha

¯

l2

l(

(p,

Ethanehexahalides Hal3³ ì ³Hal3 C2F6, gas, colrl. C2Cl6, cr., colrl. ³2Br6, cr., colrl. t)

H2O

H2O (p, t)

HCOOH, strong Red, K ˆ 10 4 H+

OH

[HCOO] ë, weak. Red., ion ë triangle

[ì COOH]2, K1=10 1, K2=10 5, Red. H+

MnO 4

F Br

5

m.p.

b.p.

CF4, gas, colrl.

184

128

CF2Cl2, gas, colrl., "freon-12" CCl4, liq., toxic CBr4, cr., yel. CI4, cr., red.

155

30

23 94 171

77 189 90

CO2" "# H2O (slow., pH58) H2CO3, K1 ˆ 10 7 "# CO23 ë + H2O [HCO3] ë, K2=10 11; pH 8 H+"# OH ë (immed.) [CO3]2 ë, triangle, pH > 8

C ì Hal 1.32 1.74 1.92

(alc.)

OS

DH

C ì Hal

223 ì

{

32 + 20 + 73 (subl.)

1.32 1.34 1.74 1.77 1.94 2.12

CF4 ë nCln, "freons", solv. O3, fats, pitch; not hydr., passiv., not burn., mol. ë tetrah. (sp3), stab. CF4 4 CCl4 4 CBr4 4 CI4

O , the most strong ac. OH

CF3COOH, liq., colrl., m. p. 15, b. p. 72, K ˆ 1, e = 8.5 CF3COOM, toxic ìììììì *) Indicated in parentheses b.p.

4+

HgCl2( Hg2Cl2#); Ag+

F2

SiC

13) Compounds of CF3 [CF3]X, X=I (b. p. 22)*, ClO (+47), FO ( 95), SF5 ( 20), NO2 ( 31), NO ( 87, bl.), NF2 ( 77), PI2, PH2; O/2 ( 61), S/2 ( 22), O2/2 ( 37), N/3 ( 70), gas, colrl., passiv. (except FOCH3). In mol. ë v. stab. gr. CF3, strongest acceptor el.,

HSO3CF3, F3C

m

[Ph4P]+[CBr5] ë, in str. ë chains of tetrah. [CBr4] and Br , C ì Br  1.96, Br ì Br 3.19 23) CF3OOX, X = H, Cl, ë CF2OOCF3; (CF3)2C(OH)(OOH) 16)

OH (slow)

³O", poorly sol. in H2O

101 78 189(p) 186 148 210

CF3I + KOH ! KOI + CHF3 H2EIIIO2CF3, H2EVO3CF3, E = P, As, v. strong ac.

CARBON IONS IN AQUEOUS SOLUTIONS

b.p.

Hyg.; + H2O ! H2CO3+¯Hal (speed F 4 Cl 4 Br), mol. ë triangles (sp2). 30) + M2On ! MOxBrn-2x, (M = V, Mo, U, Re)

C amorph.

Hg(CF3)2

m.p.

COF2, gas, colrl. 114 83 0.95 COCl2, "phosgene", gas, ë 128 + 8 1.17 colrl., toxic COBr2, liq., colrl., ì 65 (dec) ì

³)

b.p.

) ¯2

X2

Pd2+ ( Pd); Ag+; MnO4 (Ag+); Cr2O27 (Hg2+); ClO3 (OsVIII )

(act.

; F2

CnHm

3+

m.p.

a

H

[C6F6]+X ë, X = SbF6, Sb2F11, AsF6 (cr., orange, m.p. 61, dec., sol. in liq. HF, 4) meff = 1.3)

2+

Carbonylhalides

CO2

al 2

Phenylhexahalides m. p. b. p. C6F6,liq.. colrl. C6Cl6, cr., colrl. C6Br6, cr., colrl. C6I6, cr., red-brn.

4+

2/n+

OH

[ COO]22 , ion ë 2 triangles

55

56 N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_18, © Springer-Verlag Berlin Heidelberg 2011

t) M(

57

58

SULPHUR AND SELEN DERIVATIVES OF CARBON 2+

4+

CO

H2[CO2S] ë monothiocarbonic ac. K2[CO2S], H2[COS2] ë dithiocarbonic ac. K2[COS2]. OR S C ë xanthic ac. SH

HC(SO2F)3 Cs[C(SO2F)3] HC(SO3F)3 29)

4

1.3

Xanthogenates OR S C SM KSC(S)OEt, yel., dec. 200, sol. in H2O, alc.

S (arch)

MOR

20

CS, v. unstab., stab. as L (thiocarbonyl gr.) [Rh(CS)Cl(PR3)2]

S

I2, S, P; mol. ë linear, C ì S 1.56; + H2O

11)

S

8

! CO2 + H2S; 150

(45
10 PÂ, 200 ) ! blk. polimer, d ˆ 4:9, soften 70 , ! C + S, e ˆ 4, semiconduct., in str. ë chains, donor p-el.; as L ë CS2 angular. [M(CS2)(PPh3)2]n, M = Pt, Pd; [Rh2Cl2(CO)(C2S4)(R3P)2]2

(t)

C

H2CS3, trithiocarbonic ac., oil, sol. in H2O, m. p. 27, K1 ˆ 10 3 , K2 = 10 8 , mol. ë anal. of H2CO3, m ˆ 2:13;

M2S (canc.)

> 27

! CS2 + H2S (slow.); stab. > H2CO3, in str. ë chains mol., S


H  2:8 9)

3+ K2[O2C ì CS2]

Thiocarbonates, MI2[CS3] 10) M = Na, K (
H2O), NH4, [R4N] (
4 H2O), cr. yel., hyg. (s. red), anion ë triangle S [Me4N]2C2S6
0.5 CS2, anion ë from M2SO3 2 triangles, € 87.1 , M2[Ni(CS3)2], M = [Ph4As], [Ni(NH3)6] 29)

Se

2S

e

CH2Cl2

CCl4

CSe2, liq. yel., m. p. 44, b. p. 125, polimerise at 20 , mol. ë linear (CSe2)x, blk. powd. [Ru(CSe2)(CO)2(PPh3)2] 22)

M2Sn

H2CS4, thiomonocarbonic ac., oil, red, m. p. 36, K1 ˆ 10 4 , K2 ˆ 10 7 , unstab. H+

HCl (alc.)

H

1.5+ K2[C4S4], 29) in anion ë square [C4]

150





100

1.33+ C3S2, lig. red, with pungent odour, m. p. 1, easily polymerise

CS2, carbon disuléde, liq., colrl., toxic, exp. by air, d ˆ 1:2630, m. p. 108, b. p. 46, DH ˆ ‡63, insol. in H2O, solv. of fat, pitech,

CO(NH2)2 (110 , CS2) NH3 + Ca(OH)2 (110 , p)

S

CS(NH2)2, "thiourea", cr. colrl., CSF2, gas colrl., b. p. 63 NH2 m. p. 172, readily sol. in H2O, mol. ë plane CSCl2, "thiophosgen", liq., red, toxic, NH3 MCl2
4 [:SC(NH2)2], M = Pt, Pd, Zn, Ni S C 113 hn-(vis) b.p. 76, ! (CSCl2)3, m. p. 116, 1.72 CS(NH2)(NHNH2), thiosemicarbazide, NH2 + H2O ! CO2 + H2S + HHal
n MCl2, M = Ni, Mn, sol. in H2O SO3; H 2 O PCl5 HSC:N, rhodanic ac., liq., colrl., m. p. 110, > 90 ! polymer, m. p. +5 (dec.), strong ac., K ˆ 0:5 (in dil. s.); stab. > HNCO

COS, oxysulphide, gas colrl., toxic, inêam., m.p. 138, b.p. 48, reality sol. in H2O and org. solv., m ˆ 0:71, mol. linear

(t)

Perthiocarbonates, M2CS4 21) M = Na (dec. 90), K, [Me4N] (dec. 125), [Ph4As],

! H2C2N2S3 + HCN; H+, t

+ H2O ! COS + NH‡ 4 ; in gas ë monomeric mol., m ˆ 1:72; + H2S ! CS2 + NH3

Selenocarbonates K2CSe3, BaCSe3, cr., vlt.

‰N..

C

.. S .. .

Š

Hg(SCN)2# M2[Hg(:SCN)4]; [Pt(:SCN)2(NH3)2], thioM2[Co(:NCS)4], isothiocianate 2+ H2O2 !SO4

S;

K

Sn

2

2+

Sn

2-

;S

O6 4

0.9 N C S 9 1.22 1.56

( H N

C

Rhodanides (iso- and thiocyanates), not toxic m. p. dec. NaNCS 323 ì S S KNCS 177 500 NH4NCS 150 170 Ba N Ca(NCS)2
3 H2O Ba(NCS)2
3 H2O AgSCN #, wh., SP = 10 13 , H2O anion linear N 1.65 ‰:N. 1.17C S:.. Š

135

H

H2 O

H+ OH-

t

cr., yel.; ! M2CS3 + S; + O2 + H2O ! M2S2O3; anion [S=SCS2]2 [Ph4As]2[Ni(CS4)2]

SCSe, liq. yel., m. p. 85, b. p. 84 SCTe, liq., red, m. p. 54, m ˆ 0:17, mol. ë linear

H2CSe3, selenocarbonic ac., K1 ˆ 10 2 , K2 ˆ 10 7 , v. unstab., ex. in s.

>5%

H2 S

O4 )

(N:CëS)2, dithiocyanogen, colrl., m. p. 2, stab. (SCN)2 > I2

# 20



(rapidly)

(SCN)n, parathiocyan, red, polymer (SCN)2
2 HHal;
H2O Br2; Pb(IV)

M; I

MCN

CSe(NH2)2, selenourea, m. p. 200 Se(CN)2; (SeCN)2

Iso- and selenocyanates 158

HNCSe, selenocyanic ac., ex. in gas, K ˆ 5

KNCSe, cr. hyg. ! KCN + Se AgSeCN, SP = 10 16 , anion [N=C=Se] linear M2[Fe( ì NCSe)4], M2[Pt( ì SeCN)4]

59

60 N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_19, © Springer-Verlag Berlin Heidelberg 2011

61

t( H 2)

62 N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_20, © Springer-Verlag Berlin Heidelberg 2011

63

64

65

Zr

4d

;

;

6s

MCl4 (melt)

Zr

O2

M

H

TiCl4

4

l

;A TiO2 + Fe2O3 (ore)

hf )

0 Ti

CsZr6I14

2+

MCl4

66

Zr

MTiF4, M = NaìCs, pink, layers of oct. M3TiF6, vlt., bl., Na5Ti3F14 K3TiCl6; CsTi2Cl7 Cs3Ti2Cl9, eff. = 1.3, K2[TiCl5(H2O)] Cs2[TiCl2(H2O)4]Cl3-trans, cr. with dichroism (colrl.ëvlt.) 3) K3TiBr6; K3Ti2Br9 6) K5[Ti(CN)8]

3)

TiF3, purp. or vlt.,
H=ë1490 

950

! Ti + TiF4 TiCl3, subl. 400,
H=ë719, -, vlt., isostr. FeCl3, -, chains of oct., brn.,
6 H2O, vlt. or grn. TiBr3, blk.,
H=ë548,
6 H2O, vlt. TiI3, needle, blk.,
H=ë339 In str. MHal3 (Hal = Cl ë I) ë mol. ë 2 oct. with common faces; t ! M(II) + M(IV);

[Ti(H2O)6]2+, colrl. (?), paramagn. (d 2 ), oct. (d 2 sp 3 )

DH

ZrCl3 #, blk.ë grn., ë755 in str. ë chains ë727 ZrBr3 #, blk. ZrI2.64 ë 3.4, blk.ëvlt. ë536 ZrHal3 ë v. strong Red + H2O ! H2 (immed.) + TiIV ! Ti2+; + K+ (liq. NH3) ! K

HfCl2.8 ë 2.9, 420 ! HfCl2,
H ˆ 758 HfI3, blk.
H ˆ 473; stab. > ZrI3

[H "] H2O( H2)

H+ aq. regia.; HF + HNO3

Ti2S; Zr2S; Hf2S; TiE; Ti2E3; TiE2; Zr2E3; ZrE2, Hf2E3; HfS2; TiS3; HfE3; ZrE3; E = S ë Te conduct., semiconduct., dielectr., stab. in air, sol. in conc. H2SO4, HNO3 MI2TiS3; BaMS3, M = Ti ë Hf. Zr4N, Zr3N4, MN, v. hard, m. p. 3000, sol. in alk. (t), (HF + KMnO4), el. conduct. MN>M; Li5TiN3; BaZrN2 Zr2ON2; ZrO8N4; Zr7O9.5N3 ZrB12 10) TiH1.5 ë 2.0, ZrH1.3 ë 2.0

4+

3+

Li

14)

HfCl1.92 ë 1.98 17) HfBr2, t ! HfHal + + HfHal4

2) Bronzes NaxTiO2, x = 0.2 ë 0.5, blk., layers of oct. Na1.7Ti6O11; NaTi2O4

M[Ti(SO4)2]
12 H2O, M = Rb, Cs, H (
4 H2O) M[Ti3(SO4)5]
n H2O

H2; t

ZrF2, Zr6Cl15 14) ZrBr2, stab. in air [ZrI2]6; ZrI2.4, clusters, Zr ì Zr 3.20, t ! ZrCl + ZrCl4; t ! Zr + ZrI4;
H ˆ 963 (F), 522 (Cl), 260 (I)

C

(T

3

M2TiCl4 CsTiCl3, blk., chains of oct. Na2Ti3Cl8, in str. cluster 18) [Ti3]6+

O2 conjugate react.: H2O + O2 ! H2O2

30)

17)

0(d 4) [MDipy3], cr. vlt., sol. in bz., mol. ë oct. Ti(C6H6)2 K4Ti(CN)4, eff. = 2.17 K5Zr(CN)5, eff. = 2.69

TiOCl; TiOBr

Ti3O5, bl.,
H ˆ 2456 Ti4O7 2)

MTiO2, titanates (III), M = Li, Na, Mg/2

H

O

3.54

Ferroalloys, hard, visc., corrosion resist. "Ferrotitanium", 15 ë 25 or 40 ë 50% Ti, 3 ë 6% Si, 5 ë 8% Al, 3% Cu,  0:1% C, S, P; in system Fe ë Ti ex. sld. s. subtraction, Ti2Fe, TiFe, TiFe2, and TiFe3 "Ferrozirconium", deoxidant in steels; in system Fe ë Zr ex. sld. s. and Zr2Fe3 (m. p. 1640)

M2[Zr(CO)6], 15) Li2[TiDipy3]

6 Thf

TiF2, dec. 354, CaF2 str. 29) type 2.29+ Ti7Hal16, Hal=ClëI, blk., inêam. in air,
H ˆ 514 (Cl), 389 (Br), 268 (I); sol. in H2O, alc., liq. NH3; in str. ë Ât. Ti(II), Ti(IV), Ti ì Ti 2.95 Ti(AlCl4)2, in str. oct. [TiCl6]

lR

MCl, M = Zr, Hf, powd., blk., graphite-like. str. MMClClM . . . ZrCl,
H ˆ 286 HfCln, n = 0.92 ë 0.99
H ˆ 289 ZrBr,
H ˆ 193 HfBr,
H ˆ 204 ZrI1.0 ë 1.3,
H ˆ 142; t ! M + MCl4

; 1760

b-, cub., a-Fe str. type 3.61

al

;A

; 862

Ti(OH)3 #, vlt., sol. in ac., strong Red, + NO3 ! NH3

Ti2(SO4)3 #, grn., sol. in ac.
M2SO4
24 H2O, M = Rb,Cs, red, alum 3 Ti2(SO4)3
H2SO4
25 H2O,vlt. M

13.1 2230 5197 1.57

1518,

sol. in ac.-Ox; ! TiO + TiO2; - Al2O3 (corondum) str. type

Ti(OH)2 # blk., immed. Ox in air H2SO4 (dil.)

sld.

a = 3.32

(t)

Hf

sol. in HF, HCl, conc. ac. resist., H2SO4 alk.; sol. in (HF + HNO3), aq. regia passiv. HNO3 a-, hex. cl. pack. a = 2.95 3.22 3.20 c = 4.68 5.13 5.08

; 882

Ti6O, Ti3O, Ti2O, Zr3O

MI4 ac. t, v ) (ëI 2

t

TiO1x, powd. golden, m. p. 1750,
H ˆ 519, sol. in dil. ac. ( ! H2 "), NaCl str. type

1.3

met., silver-wh., ductile (brittle in presence of trace O, N, C, H), stab. in air d 4.5 6.5 m. p. 1668 1855 b. p. 3260 4340 E0 Ti2+/Ti = 1:63 E0 M4+/M = 1:43 sld. sld. E0 Ti3+/Ti = 1:21

Ti2O3, powd. vlt., m. p. 1830,
H ˆ

T

1.4

6p

;:

a; ;N Mg h. Red cat

Ti

5p

;:

5d

Hf0

5s

1 i(

0

;

0

70

1.5

20 0

;

EN

4p

0 )

0

4s ;:

00

;

3+(d 1)

)

(1

;



2

3d

Ti0

2 +(d 2)

H

TITANIUM, ZIRCONIUM, HAFNIUM

[H "]

[Ti(H2O)6]3+, vlt., paramagn. (d 1 ), oct. (d 2 sp 3 ) ion

[Ti(OH)n(H2O)6 ë n](4 ë n)+, n44 [Ti(OH) Hal n]2 ë, [(TiO)8(OH)12]4+ O2; H2O(Pt) diamagn.n oct.6 ëions, colrl.

[Zr(H2O)6]3+, orange, oct.

H2 O(

H2 )

16)

[Zr4(OH)8(H2O)16]8+ > [Zr(OH)5(H2O)n]ë > [Zr(OH)6]2 ë SO24

! [Zr18O10(OH)26(SO4)13]0

N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_21, © Springer-Verlag Berlin Heidelberg 2011

16)

CN Zr8

4 + (d 0)

60 (70 0 ) 0 )

(> 2

O

Ca 3 NO

Ti

H

(t)

Ti

850

TiO(OH)2
n H2O#, wh., amorph, n < 1, "b-titanic ac.", sol. in HF, conc. HNO3 (t); Xëray lines of anatase " H2O (t, time) n = 1 ë 2, "a-titanic ac.", freshly precipitated, sol. in ac., conc. alk. 11)

+

(1 HC 00 % lO ) 4 3

SO

2O 5 3

N

O H

F

ì

283 subl. ì

DH

K3HTiF8 = K3[HF2][TiF6] H2TiF6, M2TiF6
H2O#, 1644 [O2][TiF5] H2O K TiCl , yel., K PtCl 2 6 2 6 ì str. type MTiCl5, M = [R4N], [R4As] 803 M[Ti2Cl9], M = [SCl3], 619 [PCl4], ì [R4N][TiBr5], 510 K2TiBr6, red 1,12) M2TiI6, dark-red

! TiF4 + TiCl4 TiCl4, liq. colrl. 23 136 40 231 TiBr4, cr. yel. ì ì TiClnI4-n, n=1, 2, 3 TiI4, cr. brn., 155 377 t > Ti + I2 TiHal4 + H2O ! TiO2
n H2O# (pH 5 1.5); in str. and gas ë mol. TiHal4 ì tetrah. (d 3s), in str. a-TiI4 ë chains of oct.
L, L = POCl3, SCl4;
2 L, L = NOCl, R2O, R2S, RCN

M 20) Zirconates, Hafnates Na2[Hf(OH)6]; K3Hf2O3(OH)5; K2Hf2O4(OH)2; Na2Hf4O9
5 H2O; Li8HfO6 K2MO3; CaMO3; PbMO3, ferroelectrics M6Zr2O7; K4Zr5O12, oct. Cs4ZrO4, anion tetrah., 300 ! Cs2ZrO3 CaTi[Zr3O9], "calcirtite" M4[Zr(Mo12O40)]
n H2O

1000

HfO2, m. p.=2900; d=9.68; DH=ë1130 inregular. str. CN M 7, CaF2, str. type, stab. at 20 with introduction of Y2O3, MIIO 1000

a-MO2
n H2O#, b-MO(OH)2,  wh., sol. in ac. 140 yel., sol. in ac., peptizate, alk.

O7 Cl 2

+

lO 4 HC

ZrCl4

7,23) ZrO(ClO4)2
8 H2O, m. p. 145 M(ClO4)4, volat., m. p. 96 (Zr), 105 (Hf), in mol. CN M 8 M(IO3)4#, insol. in HNO3, anion ë antiprism M(OH)2SO4;
4 H2O M2O3(NO3)2
5 H2O, MO(NO3)2
n H2O, n = 3.5 ë 4.5, in str. ë [M(OH)2(NO3)2(H2O)4] ZrO(OH)(NO3)
n H2O, n = 2, 6 M(NO3)4, in str. [M(OH)2(NO3)2(H2O)4] t subl.
x N2O5; Zr(NO2)4 M(HPO4)2
n H2O#, variable composit, unlike other Mn+ expect Pa (pH  7); s. in H2SO4 + H2O ! Hf(HPO4)2# + ZrIV (in s.) MO(C2O4)
n H2O#, sol. in H2C2O4, HCl Zr(RCOO)4; ZrO(CH3COO)2 ZrSiO4#, "zirkon", Ôontain >1% HfO2

subl. m. p. (p) ZrF4 # 903 912 437 ZrCl4 331 450 ZrBr4 357 ZrI4 431 499

subl. m. p. DH (p) 1911 HfF4# 890 1025 1929 979 HfCl4 317 432 988 761 HfBr4 413 278 837 492 485 HfI4 ì 586 + H2O ! MOHal2 In monocl. str. MF4 ë antiprism [MF8]. In str. ZrF4
H2O ë frame of dodecah., MF4
3 H2O ë [(H2O)3F3Zr]2F2 and chains ë Hf ì F ì Hf . . ., CN M 8. In str. MHal4 (Hal=Cl ë I) ë chains of oct. [MHal2Hal4/2], in gas ë mol. tetrah. 25)

DH

NH4OH; (NH4)2S; M2CO3

an

.O

x.

4,7,33)

Cs2[M(ClO4)6]; Cs[M(ClO4)5]; Cs3[Zr(ClO4)7] "Zr(SO4)2
n H2O", n = 4, 5, 7, contain ions [Zr(SO4)4(H2O)4] 4 , [Zr2(SO4)6(H2O)4] 4 , antiprism [MO8] K2[M2(OH)4(SO4)3(H2O)n] Na6[M2(OH)4(SO4)5]; Na12[M2O(SO4)9(H2O)n] Na6[M(SO4)5(H2O)n] [R4N]2[M(NO3)6]; [NO2][NO][Zr(NO3)4], 32) [(NO2)(NO)3]4+[Zr(NO3)5]4 , CN Zr 9 KZrH(PO4)2; Na2Zr(PO4)2
n H2O Na5Zr(PO4)3, LiHf2(PO4)3 19) H4[MO(C2O4)3]
7 H2O Na4[M(C2O4)4]
3 H2O M2Zr[Si2O5]3, M = Na ("elpidite"), M2Zr[Si3O9], M = K ("vadeite"), Na5Zr2[Si6O18]Cl
2 H2O, "eudialyte"

Zr3F8O2; Zr2F6O, M2O3Cl2
5 H2O#; MOCl2 24)

H

125

ì

2300

O

)

HOOM(OH)3#, gels, brn. (Ti), wh. (Zr, Hf); + I ! I2; stab. Ti H3O++ +B10H13

99 ì ì ì ì ì

180 (n) 129 (iso) ì ì ì ì ì strong ac., K2 = 10 8

H

H

B H

H

H

H

B

B H

H

H H H

alloy MgB2 + Mg

H B

120 18 (dec.) 25 +68 0.56 (bz.) stab. slow. hydr. H B

B H

B H

H

H H

Salt-like Polymer Covalent

278 400 500 280 320 ì

CuBH4 Zn(BH4)2, colrl. Cd(BH4)2, Be(BH4)2 colrl. Al(BH4)3 Sn(BH4)4, yel. Ti(BH4)4, grn. Zr(BH4)4 colrl. Hf(BH4)4 U(BH4)4, grn.

12 85 25

} } }

B

H

H

B

H

B

B H

H H

B

B H

B

B

B

H

B B

B

H

H

H B H H B B H H B H H

H B H B H B B H B H B H H

B

1.7 £9¯15 ennea-15

1.6 £10¯16 deca-16

122 63 25 ( !B10H14) +92 ì inêam. rapid hydr.

82 80 ë 90 25 ì ì stab. ! B4H10+H3BO3 +H2

3 ì 75 ì ì stab.

cr.

H H H H B B H H H B B H H H H

B

H

H

H

B

H B

H

H

H B

B H

B

H B H H B B H B B H H H H

H

2

meta(neo)-(³,C-1.3), m. p. 263, m=2.85,

; 615

3

C

2,2 -Bi(nido)-deca

H

H

H

; 475

B

1.3 £20¯26

0

H H

H

mol. ë two fragments of icosah. with common edge £ ì £

H C

1) BnC2Hn+2, carboranes (isoel. of boranes) £3¯3³2¯2, (Se=22=Se B4H10), m. p. 126, b. p. 4 B10¯10³2¯2, "carborane" B (Se=50=Se [B12H12]2 ), cr. colrl., sol. in org. HC CH solv., insol. in ac., alk. Mol. ë icosah. B10H10 Isomers: ÑrtÑ-, (C, C-1.2), m. p. 320, m = 4.53 1

mol. ë 2 basket [B10H14] with 34) bond £ ì £

4

B2O3

ëH2 0.8 (3508, vac.) B ¯ , icosoboran-16, 20 16 cr., colrl., hyg., m. p. 197, stab. in air, sol. in org. solv., +H2O>H[B20H16(OH)2]; mol. ë 2 [B10H14] with common faces

para (iso)- (³, ³-1.4), m. p. 261, m=0

C

B4C, carbide, blk., v. hard, d ˆ 2:5, m. p. 2450, b. p. > 3500, DH = 71, NaCl str. type, ([B12] = Na+, linear gr.,[C=C=C] = Cl )

: 1200 (

C)

BC3,élm,str.anal.ofgraphite 26) B13C2, B2Si, B4Si

t (urotropine) MOH ( H2 M3BO3)

dec. LiBH4, colrl. NaBH4 KBH4 Mg(BH4)2 Ca(BH4)2 MBH4
n H2O

B

2.0 £6¯12 hexa-12

60

Borohydrides

H

2.2 £5¯11 penta-11

2.5 B4H10 tetram. p. b. p. dec. DH m in air + ¯2°

H

I)

BnHn+4 BnHn+6

20

H

H

H

H

0

H

B

(

121.5

97

H B

I2

B

H

Homolog. series

H (S 3 P to O ck 4 )

H

H

H

H

L

165 92 >25 +35 0 inêam. dec. immed.

m. p. b. p. dec. DH m in air + ¯2°

H

Li [B H; (O N M aH e) 3]

1.25 £16¯20 cr.

H H

B2H6

1.4 £10¯14 deka-14

H

b. p.

dec. 80 ì Me2O 83 38 Me2S ì ì MeCN ì ì SiH3CN CO 137 64 NH3, ? [H3NBH2NH3]+(BH4) ë NMe3, 94 171 "borazan" N2H4 61 (dec.) PH3 ì ì PMe3 103 ì PF3 116 62 P(NH2)3 ì ì AsMe3 74 dec. 120 P(NMe2)3; ì ì Mol. ë tetrah., B ì H 1.19 ë 1.21, € HBH 114, B ì L 1.54 (C), 1.56 (N), 1.84 (P)

1.5 £8¯12 octa-12

H

m. p.

1.67 £6¯10 hexa-10

H

BH3 [:L] L

1.8 B5H9 penta-9

3 B2H6 diborane, gas

H 2 e) C 2 arg h isc (d

B2O3 + H2 (Al + AlCl3); BCl3 + H2 (discharge, in vac.); BF3+ LiH ( LiBF4); alloy (MgB2 + Mg)+H3PO4 (Stock method)

B5H9

nonvolat., +¯2°? H2 :, (Li 4 Na > K), strong Red., NaCl str. type, [BH4] ë tetrah.

unstab. insol. in org. solv., hyg. 91 volat., sol. in 65 (m. p.) 45 (b. p.) Et2°, CnHm, 65 immed. hydr., 25 in mol. ë m- H 29 (m. p.) 128 (b. p.) H H Be B 29 (m. p.) 118 (b. p.) H H 70

[

3ë 2.3ë Na[B2H7], Na[B3H8], anion stab. to [H3B


H- hydr.


BH31

2ë 1.4ë M2[B2H6], M[B5H8], 24) M[B9H14], M[B10H15]

B10H

14

1.33ë M[B6H9], H+ OH ë

1.2ë M[B9H12], unstab. M[B10H13], M2[B10H14], stab. to hydr., mol. H

M[B11H14]

]

M=Li ë Cs, [R4N], [R4P], sol. in Et2O 2

B

H

B

H

H H

H

H

B

(H2O)

B

B

H

B

B

H

basket

H

0.9ë M[B9H9]

1.1ë M[B11H13], stab. at pH  7

H B

H B H

B H

Mn

O4 ;

Cr

2O 2 7

0.8ë M2[B10H10], stab. to ac., alk. +MnO4ë ! [B(OH)4] (H3O)2[B10H10], v. strong ac., anion two-cap antiprism ; M2[B12H12], H2[B12H12]
n H2O, v. strong ac. 24) Na2[B20H18], M3[B20H19] 21)

0.75ë 0.67ë M2[B8H8], M2[B6H6] K4[B20H18]. oct.
2 H2O; +H2O ! B18H22

BBr3

BCl3

BI3

Zn

2.0

;

3+

EN

2p

;:

B2O3 (>1000 )

(15 00  ) B 2O

2s

3+

2+

1+

B2O

(BO)x, powd. wh., Âmorph., subl. 1500, v. react.; +H2O ! B2(OH)4+H3BO3 in gas ë linear mol. °=£ ì £=°

Zn O

B0

B2O 2) B6O B7O B13O2

ëH

2O

(250  , vac .)

5,19) M[B(ClO4)4] M[B(HSO4)4] M[B(SO4)2] K[B(SO3Hal)4] M[B(NO3)4] M[B(CH3COO)4] Na[B2O(CH3COO)5] M=KëCs, [R4N] Anions tetrah.

BX3, cr. colrl., v. hyg. B(ClO4)3, dec. 5; B(HSO4)3 B(OTeF5)3 B(NO3)3, dec. 0; BPO4 m. p. 1600 BAsO4 B(CH3COO)3, m. p. 149 19) B2O(CH3COO)4

I2 )

(

200  )

5

10

1.38

o

0

2 (1

100

1.47

H

1. 38

120

1.7

1

1.70

"

M(t); M2On + C (t)

Br 2)

(t,

38 1.

H H B3O3H3, "boroksin", B2(OH)4, hipoboric ac., H2B2O3, + mol.: plane cycle; cr. colrl., sol. in ¯2°, 3 mol. ë plane O O  t alk., strong Red.; B2 H2 ! cycle, m ˆ 0:95 113 B2H6 + B2O3; 4 + +O2+OH ! [B(OH)4] ; SO  +HCl ! H2+BOCl 2 120  M £, powd. Âmorph., colrl. (brn. ë ture) H 1.36 +H2O 90 ! H2+H3BO3 1.1 H H or cr. blk., m. p.  2075, b. p.  3700, 9 H3BO3 hard  diamond, sol. in HNO3, KF BF2(OH), mol. ë triangle F2 (20 ); Cl2 (400 ); Br2 (700 ); I2 (900 ) H2SO4, insol. in alk.; monocr. ë semi4) " B 2O3(t) conduct.; a-, tetr., d=2.37, Â=8.73, m. p. b. p. DH c ˆ 5:03, in str. ë icosah. [B12], K[BF(OH)3] B3O3X3, boroxols, BF3, gas colrl. 127 100 1138 B ì B 1.60 ë 1.80, H[BF2(OH)2], K[BF2(OH)2] m. p. DH stab. decreases in the series: 107 13 404 BCl3, gas colrl. CN B 5 (=8 ë 3); B2F4, gas colrl. 56 ì R>NR2>OR>Hal>H H2O( HF) (BO) x 46 90 243 > H O BBr3, liq. colrl. b-, rhombohedral, 93 491 B2Cl4, liq. colrl. 2 H[BF3(OH)] = "BF3
H2O", Hg , cr. colrl. 50 210 38 BI d=2.46, a = 10.92, 3 +1 ì B2Br4, liq. colrl. >20 cr. colrl., m. p. 10, strong ac. (dec) c ˆ 23:81, cub. cl. (£Hal)n, Hal = F (wh.), B2I4, cr. yel. ì ì 2 [H3O]+[BF3(OH)] ="BF3
2 H2O", (sp ); In cr. and gas ë triangles £Cl pack. [B12], B ì B 1.71; 3 Cl (yel.), Br (red), discharge + H2O ! BHal3 + B2H6; 36) m. p. 6, b. p. 60/133 PÂ, Ânion BF3 + H2O > HBF4 + H3BO3; vitriform £ B12 I (blk.), n = 4, 7, 8 ë 11 +NH3 ! NH4Cl+B2(NH)2; tetrah. ( Hal ) + H O ! H BO + HHal (Hal = BHal 2 3 2 3 3 B4Cl4, cr., yel., volat., +[R4N]Cl ! [R4N]2[B2Cl6]; Cl I); BHal3 ë v. strong Lewise ac. m. p. 95, dec. 200, 0 (slow.) ! (BHal)n+BHal3. M[BF3(OH)] 7) [BHal3(:L)], L = NR3, PR3, AsR3, HF H2O inêam. in air., Hal In str. ë mol. £ 2 4 3 Ba[BF O] [R4N]2B9Hal9, 3 Khydr.=10 R2O, R2S, R2CO, mol. ë tetrah. Hal = Cl, I Hal Hal [BF3(NH3)], m. p. 162(Ó), (4 el. pairs at. £ HBF , ex. only in s., strong ac., toxic 4 M2[B10Cl10], 125 dispensed between £ £ ! BN + NH4BF4, M[BF4], M = Na (m. p. 384, "ferruM = Na ì Cs, 37) 1.72 6 £ ì £ bonds). +H2O ! [NH4]++[BF3OH] cite"), K (m. p. 570), NH4 (subl. 350), dec. >100 Hal Hal B8Cl8, cr., red., mol. ë readily sol. in H2O; Cs# ("avogadrite"), [R4N];, H F Cs2B12Cl12, sol. antiprism [B8] Mol: 2 cross tetrah. 1.60 [NO], [NO2], [ClF2] (m. p. 30), [ClO2], in unpolar. B8Br8, brn., subl. N B [BCl3(NH3)] 33) [NF4] (dec. 240; +H2O ! O2), solv., colour, MI3BO3 + M2On B9Cl9; B9Br9, mol. three-cap. trig. prism [XeF5], [O2] (stab. Ti 1000 ), ac. resist. (TaB2 insolv. in aq. regia), £ ì ® bond ë met. (conduct. ZrB2 about "borazon", cr. yel.-blk., m. p. >3200 Hal=FëBr 3 B24N36, str. 1 10 time > Zr), (p), v. hard, cube, diamond str. type, H O 2 M[BH (OH)], anal. of 3 M[H2B(OH)2] H2O 6) "Ferroboron" (1.2% B, 3 ë 5% Al, 3 ë 4% Si, 0.1% C, 0.02% S, &80% Fe) ë desoxidant. dec. 2000, B ì N 1.57 (sp3) hypoborates ( H2) Na[H2BF2] fullerene 35) M[HB(OH)3]

. th ca

ed

R

.

®

°

¯

#

71

72 N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_24, © Springer-Verlag Berlin Heidelberg 2011

Br Al

73

74 N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_25, © Springer-Verlag Berlin Heidelberg 2011

75

BERILLIUM, ALUMINIUM, GALLIUM, INDIUM AND THALLIUM IONS IN AQUEOUS SOLUTIONS Fë

[Ga(H2O)6]3+ (2 ë n)+

[BeFn(H2O)4 ë n] , n = 1 ë 4, Kdis. = 10 5 (n = 1)

HF

:; H O 2

:;H O (

:]) ( [H H 2O

2

H+

Ga ;

[Be(H2O)4]2+, tetrah. (sp3 ), extract di-(2-ethilhexil)-phosphoric ac. (unlike Al)

H+

Be Hg

Fë

H+

[Ga(H2O)6 ë n(OH)n](3 ë n)+>[Ga13O4(OH)24(H2O)12]7+ n=1, 2 4) stab. 5 Al-anal.

cath. Red; [H:]

OH

OH

OH (NH4OH) (pH 5 5.7)

;: H

+

H )

H2O

:; OH

[Ga2O(OH)6]

(pH>2) 2ë

+

Be(OH)2
n H2O; Kbas. = 10 15 10 Kac. = 10 25 OH (pH>10)

;: H

Ga(OH)3;, wh., ¬ac. = ¬bas., K2 ˆ 10 11 , K3 ˆ 10 12

+

[Be(OH)n (H2O)4 ë n](2 ë n)+ > [Be2(OH)(H2O)n]3+ 1) pH < 7, sol. BeO [Be3(OH)3(H2O)6]3+, [Be6(OH)8]4+

Be/Hg

:;

22

;: H O 2

HCO ë 3 H2 O ( t)

[Be(CO3)2]2 ë

:;

[Be4O(CO3)6]6 ë (?) unstab.

[Be(OH)4]2 ë, tetrah.

In ;

cath. Red.; [H:]

HClO4

:; H O (K 2

[In(H2O)5(OH)] H+

> [Ga(OH)4] ë > [Ga(OH)4(H2O)2] ë, oct. ion, stab. > [Al(OH)4(H2O)2] Cl

[In(H2O)6]3+

+

H

[GaFn (H2O)6 ë n](3 ë n)+ n = 1ë6

H2O OH (Khyd. = 10 3)

hyd.=10

2+

5)

[InCln(H2O)6 ë n](3 ë n)+, n = 1 ë 4 4

)

> [In2(OH)2]4+ > [In4(OH)6]6+

:; OH

(pH 5 3.5)

:; OH

(pH 5 13)

In(OH)3; 3ë

H2O

20

[AlF6] , oct. ion, ¬stab. = 10

;: F

ë

[In(OH)4)] , > [In(OH)6]3 ë Kstab. = 1035

4,6)

[Al(H2O)6]3+

:; H O (K ˆ 10

H+

Al/Hg

)

; NH OH [t, pH 5 4.5] 4

: OH

8

+

H

;: H O

H2O

sis

OH

n

2+

Cl

[TlCl3] ë

, oct.

2

:

H2O Cl

2)

:; Hal

3)

[TlHal3(H2O)3] > [TlHal3(H2O)2] mol. ë oct. and trig. bipyr. H2O

:; Hal

HCl

[TlHal4] ë>[H2TlCl5]

76

)

trans-[TlHal2(H2O)4]+, Hal = Cl, Br, oct., v. stab.

: [Tl(H O) ] ; 2

1

2+

: OH

[TlOH]+

ly

[TlHal3]2 ë

2

hyd.=10

:; H O (pH51)

HCl

io

[Al2O(OH)6] > [Al(OH)4] > [Al(OH)4(H2O)2] tetrah. ions (sp3 ) oct. (sp3 d2 )

ë

O H2

ë

2

Tl2O3
n H2O; brn., v. strong Ox

2

d ra

Hal ë

:; H O (K

[Tl(H2O)5(OH)]

;I SO 2

[TlHal2] , angular ion (p )

(pH > 9.7) 2ë

;: H O

2 3 S 2O

H2O2 (OH )

2

ë

+

:; OH

Hal ë

Cl 2

CO2

Tl ;

(t)

Al(OH)3
n H2O; Kbas. = 10 33 ; Kac. = 10

; Br 2

[Tl(H2O)n]+, toxic

AlO(OH);, "boemite"

H+

4

Cl O H

[(H2O)4Al(m-OH)2Al(H2O)4]4+

icosah., in center ë tetrah. (r ˆ 12:6 A), ("Keggin str.", see "Mo, W")

3;

] [H:

;:

H+

O

H2O

[Tl(H2O)6]3+, oct. (?)

cath. Red.; [H:]

OH

[Al(H2O)5(OH)]2+ oct. >[(AlO4)Al12(OH)24(H2O)]7+

N

H 2O

[H:]

5

H

Hg

H

CO32

Al

+

2

77 N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_26, © Springer-Verlag Berlin Heidelberg 2011

78 N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_27, © Springer-Verlag Berlin Heidelberg 2011

79

MAGNESIUM, ALKALI-EARTH METALS, RADIUM 3s

0

4s

Calcium

Ca0

;:

Strontium

Sr0

;:

Barium

Ba0

;:

Radium

Ra0

;:

5s 6s 7s

MgO+CaO from "dolomit" Si (1 20 0 )

3p

3d

4p

4d

EN

20

C

(>



00

)

5p

5d

6p

6d

7p

7d

MgO

1.0 0.9 0.9

MO Al [1200 Š

Ca

met., lustrous wh. on the surface of the énest élm MgO diamagn. d 1.74 m. p. 651 b. p. 1107 2.34 E0 M2+/M Sld. sol. in dil. ac. (except HF) +NH4X (?H2+NH3); +RHal(?RMgHal)

MgO

1.0

Alkaline earth metals

Mg

t

1.2

;:

O Ca 2 (t, M g ë Ba Ñran ë wh g.; . êa ëy S el.s grn r, Ra h); . êa ë re me d.;

Magnesium Mg

Sr

Ba

Ra soft

wh. light yel. oxidized in air. Ra 4 Mg

wh.

wh. glows in the dark paramagn.

1.54 2.69 3.6 &6 851 1000 10) 727 969 1482 1860 1536 1390 2.84 2.89 2.90 2.92 react. with ¯2°, alk., sol. in liq. NH3 (600 640 632 DH = 623 652 NaCl str. type, in gas ë mol. MO; MgO ë inert after calcination;
8 H2O
8 H2O;
8 H2O; Ba1+xO, red dec. &100 n = 0.5, 2 n=1, 2 n = 1, 2
n H2O2 H 2O 2 t H2O ( MgO) ë O2 O2 (p, t) H 2O Mg(OH)2; Ca(OH)2; Sr(OH)2; Ba(OH)2 "brucite" "portlandite" [Ra(OH)2] ì 450 408 (dec.) m. p. ì M[O2]2 and M[O3]2 see tab. "Oxygen" 3,11) 580 710 (?) ì dec. 350 11 5 4 10 10 sol. in ¯2° S² 10 in str. CN=7 CdI2 str. type CaF2 str.; Ca-at. at the sites of face-centered cube, F ë centers n = 8, 1 n = 8, 1ë3
n H2O of 8 small cubes; 3 2 1 1 10 10 10 Kbas.2 10 CN Ca 8 (cube), F 4 (tetrah.) in str. M(OH)2
n H2O Na2[Mg(OH)4] 4) CN M=8 (antiprism) Ca(OH)Hal
0.5 H2O; CaCl2
3 Ca(OH)2
12 H2O

Mg(OH)Hal m. p.

b. p.

DH 9

NaMgF3, 8) "neighborit" K2MgF4 M4Mg3F10, MMgCl3, M2[MgCl4], Na6MgCl8 9)

Sr(OH)Cl
4 H2O

228 a! 88 Ra


; 235 92 U

RaO

; 6058

Mg light alloys: [Mg+Al (410%) +Zn (44%) + Mn (41.7%)] ë "electron"; [5 ë 30% Mg+Al] ë "magnaly", hardness >Al

238 92 U

BaO

; 2508

g-, cub. (a-Fe str.type) 5.02 5.15 a=4.84

Formation of Ra in nuclear decay;

SrO

cr. colrl., hyg.

MgF2#, "sallaite", 1396 2260 1121 S² = 10 , TiO2 str. type sol. in HNO3 MgCl2 714 1418 644
6 H2O "chloromagnesite", "bischoéte" CdCl2 str. type MgBr2, 710 1430 519
6 H2O CdI2 str. type 633 1014 360
8 H2O MgI2, [Mg(H2O)6][CaCl6] (dec.) CdI2 str. type "tahihydrat" 23) MgHal2
n L, L = NR3, R2O, R2C=O; n = 2, 6

Hex. cl. pack. (Mg str. type), CN 12, at.ë in sites of cell and in centers of 3 from 6 trig. prism; b4.31 a=3.20 3.98 c=5.20 6.52 7.05

232 90 Th

CaO

MCO3

!

6.7 y.

a!




228 224 90 Th a;! g 88 Ra

227 90 Th

223 a,! g 88 Ra

!

3.64 d.;

!


11.3 d. a

(series UëRa and Ac) Isolation of 226Ra from U- ore (&10 5%): 1) coprecipit. with BaSO4;; 2) dissolution in complexone; 3) chromatographic

21)

CaF2#, "êuorite" CaCl2, dist., TiO2 str. type CaBr2, dist., TiO2 str.type CaI2, CdI2 str. type

m. p.

b. p.

1419

&2500

DH 1222

S² = 10

782

&2000

799

760

1830

685

784

1760

536


n H2O n= 1, 2, 6
n H2O n= 3, 6
6 H2O

11

Ba(OH)Cl
2 H2O20)

m. p.

b. p.

DH

SrF2#, 1473 CaF2 str. type 873 SrCl2 CaF2 str. type 643 SrBr2, dist. PbCl2 str., CN 7 12) 515 SrI2, PbCl2 str. type

2460

1222

S²=10

2030

799


n H2O n= 1, 2, 6
n H2O n= 1, 2, 6

ì

685

ì

536


n H2O n= 2, 6

9

m. p.

b. p.

DH

BaF2#, 1353 CaF2 str. type 962 BaCl2 PbCl2 str. type 853 BaBr2, PbCl2 str.type 740 BaI2, PbCl2 str. type

2260

1196

S²=10

1830

858


n H2O n= 1, 2
n H2O n= 1, 2
n H2O n= 2, 6

ì

757

ì

607

6

RaF2#, RaCl2 RaBr2* RaI2 * rapidly yel.

In gas ëlinear mol. MgHal2, CaHal2 (Cl ë I), SrHal2 (Br, I), angular ë CaF2, SrHal2 (F, Cl) and BaCl2

80 N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_28, © Springer-Verlag Berlin Heidelberg 2011

21)

5)

m. p. ì

ì

& 900 728 900 ì


2 H2O
n H2O n= 2, 6 ì

Mg(ClO4)2, "anhydrone", m. p. 246, dec. 382., readily sol. in alc.,
6 H2O, m. p. 147; MI[Mg(ClO4)3] 15) M(ClO4)2, M = Ca, Sr (
H2O), Ba (dec. 505),
n H2O, desiccators M(ClO3)2, dec. 120 (Sr),m. p. 414 (Ba);
n H2O, n = 6 (Mg), 2 (Ca), 8 (Sr), 1 (Ba), readily sol. in H2O Ca(ClO)2;
3 H2O;
1/3 Ca(OH)2
x H2O, "lime chloride" Ba(ClO2)2, dec. 235 M(BrO3)2
n H2O, n = 6 (Mg), 1 (Ca, Sr sol.; Ba;), dec. >200 Mg(IO3)2,
n H2O, n = 4, 1, dec. 210, readily sol. in H2O; M(IO3)2;, SP = 10 6 (Ca), 10 13 (Sr), 10 9 (Ba), 10ë14 (Ra) Ba5(IO6)2; M2I2O9
nH2O;, M = Ca (n = 8); Ba (n = 3) 14)

M(HCO3)2, sol. in H2O (M = Mg, Ca, ë cause "temporary hardness" H2O) t

2

MgCO3;, "magnesite", dec. 350;
n H2O, n = 2 , 3, 5
MI2CO3, MI = K, NH4, Ca/2 ("dolomite") CaCO3;, "calcite", m. p. 1340 (r), "aragonite", dec. 825, S² = 10 9;
n H2O;, n = 6, 3, 1, 0.65 SrCO3;, "strontianite", dec. 1350, m . p. 1497 (r), SP=10 9 BaCO3;, "witherite", dec. 1450, m. p. 1740 (r), SP=10 9 RaCO3; "Magnesite" and "dolomite" are isostr. to "calcite", "strontianite", "witherite" and RaCO3 ë to "aragonite"

200

MgSO4, m. p. 1185 (dec.) ("arcanite"),
n H2O, n = 1, 2, 4 ë 7 ("epsomite", "bitter salt"); 24)
K2SO4
n H2O, n=6 ("scheonite"), 4 ("leonite") 163

;: CO

100

CaSO4;, m.p. 1450, "anhidrite" .
0.5 H2O .
2 H2O; "gyps",

p, 300

DH = 71, TiO2 str. type; ! b-, g- dec. 390 ; in str. ë CN Mg 6 and 8 2) MH2, M=CaëBa, d>d M, dec. &600, stab. Ca>Sr>Ba, insol. in liq. NH3; PbCl2 str. type (CN 9); DH= 188 (Ca); 176 (Sr); 170 (Ba); d=1.90 (Ca); 3.27 (Sr); 4.21 (Ba) + H2O ! H2 (exp. react.); + E2On ! E + MO + H2 (E = Al, Ti, Nb, W); +BCl3 ! B2H6 + MCl2; MH2 + H2 > MHn, n44, M = Sr, Ba

t

! M(NO2)2 + O2 ! NO2 + MO;
n H2O, n = 3, 4 (Ca, Sr), 2 (Ba), 1 (Ca ë Ba) dec.  100 M(NO2)2, dec. 240 (Sr), 217 (Ba); Ra
n H2O, n = 4 (Ca), 1 (Ca Ba, ); K2Na(NO)2)4 5) MN2O2
n H2O;, n = 5(Sr), 4(Ba)

; 400 (

[M(OR)2], aloxides, cr., v. hyg., insol. in ROH, liq. NH3, Mg(OH)2 str. type Mg(OMe)2
3.5 MeOH; Ba(OR)2
n ROH, n=1,4, R=Me, Et, sol. in ROH, liq. NH3 6) 13) Mg(C5H5)2. isostr. Fe(C5H5)2

t, C(

CaSO4

CO

)

2

12)

18) MI2[Mg(NH2)4] KMII(NH2)3, (MII=Ca, Sr)

;:

;: t

; 500 (vac.

BaN2, M3N4, blk.-brn. + H+ > N2 + NH3 + M(OH)2 M(N3)2, azides powd., gray or red M2NHal

ric ct ele e) (in stov

M3(AsO4)2
n H2O, n = 8 (Mg, "hernesite"); 3 (Ca); 0 (Ba;, amorph., m .p. 1605) M(NH4)AsO4
6 H2O;, M = Mg, Ca MHAsO4
n H2O, n = 7 (Mg, "rosslerite"); 1; (Sr, Ba) M(AsO3)2;, n = 4 (Sr), 0 (Ba, dec. 500) 7) M2As2O7, M=Sr, Ba (dec. 800)

CaC2 str.

2

t H2 ( MH2) M3N2, "nitrides", M = Mg (dec. 1500, DH=ë477), Ca (m. p. 1195, DH= 439), Sr (>1000, 389), Ba (1000, 364),cr. colrl., + H2O ! M(OH)n + NH3:; + CO ! MO + N2 + C (M = Ca, Sr);

C

M3(PO4)2;, amorph., m. p. 1357 (Mg), 1670 (Ca), 1727 (Ba);
n H2O (Mg, n = 22, 8, 4; Ca, n = 4, 5); S² = 10 24 (Mg), 10 26 (Ca), 10 28 (Sr), 10 23 (Ba); M(NH4)PO4,
n H2O, n = 6 (Mg), 7 (Ca); Ca5[PO4]3(F, Cl, OH), "apatite"; Ca8H2(PO4)6
5 H2O MHPO4
n H2O;, n = 3, 7(Mg, ); 2 (Ca, S² = 10 6); 0 (Sr, 10 6; Ba, 10 7); M(H2PO4)2,
n H2O, n = 6, 2 (Mg), 1 (Ca, Ba), 0 (Ca, Ba) M2P2O7;, m. p. 1383 (Mg), 1230 (Ca),
n H2O, n = 6, 3 (Mg), 5 (Ca)

NH3)

MNH, imides, cr., yel.

M(CN)2, M = Mg, Ca, Ba , Sr (
4 H2O), linear mol., in str. ë polymer chains with bonds M ì C, M ì N CaCN2, cyanamide, subl. 1200 ; +H2O ! NH3: M(NCS)2,
n H2O, cr. hyg., readilty sol. in H2O, alc., in str.-oct. [MgN2(H2O)4], Mg ì N 2.10, Mg ì O 2.09 22)

Ba(C:CH)2
4 NH3, M[C2], carbides (acetylides), M = Ca (m. p. 2300, DH=ë58), Sr, Ba (1780, 50); dec.  2000, CaC2 str. type, tetr., dist. NaCl str. ([C2]2 = Cl ); +H2O ! M(OH)2 + C2H2: (BaC2 ë inêam.); + N2 ! MCN2  MgC2 600 ! Mg2[C=C=C]; DH=+88; + H2O ! CH3C:CH + CH2=C=CH2

KMgH3 17) K2MgH4 Li[MH3], M = Ca ë Ba Cs2CaH4, K2NiF4 str. type

H

M(NH2)2 "amides", M = Mg (inê.), Ba (m. p . 290), wh., insol. in liq. NH3; in str. ë tetrah. [MgN4/2]

N2

Mg(NO3)2, dec. >300,
N2O4;
n H2O, n = 6 .2 M(NO3)2, m. p. 561(dec.) (Ca), 570 (Sr), 592 (Ba),

MH

R2Mg

M

N2 t

175 ; LiAlH4

N2 (t)

H2O

S² = 10 5, K = 10 3;
M2SO4, M = H, K, NH4, Na. MSO4;, M = Sr (m. p. 1500 (p), dec. 1580, SP = 10 7), Ba (m. p. 1580, dec.), SP = 10 10, "baryta"; Ra, SP = 10 12, sol. in EDTA 16) MSO3
n H2O;, n = 6 (Mg), 2, 4 (Ca), 0 (Sr, Ba) MS2O3
n H2O, n = 6 and 3 (Mg, Ca); 5, 1 (Sr,), 1, 2 (Ba;) MS2O6
n H2O, n = 4 (Ca, Sr), 2 (Ba), readily sol. in H2O MSeO4
n H2O, n = 6 (Mg, readily sol. in H2O), 2 (Ca, sol.), 0 (Sr;, SP=10ë5; Ba;; Ra;) MCrO4
n H2O, yel., n = 7 (Mg, readily sol.), 2 (Ca, sol.), 0 (Sr;, SP=10ë5; Ba;; Ra;, SP=10ë10), MCr2O7
n H2O, n = 3 (Sr), 2 (Ba), red, readily sol. in H2O

M(CH3COO)2, M=Mg(m. p. 323, dec.), 450 (Ba),
n H2O, n = 4 (Mg), 1, 2 (Ca), 0.5 (Sr), 3 and 1 (Ba) M(HCOO)2,
2 H2O , M = Mg ì Sr, Kdis.=10ë3 MC2O4
n H2O;, n = 2 (Mg), 3, 2 , 1 (Ca), 1 (Sr), 0 (Ba); SP = 10 4 (Mg), 10 9 (Ca), 6
10 8 (Sr), 10 7 (Ba)

Hydrides (MgH2)n, 1) powd. wh., dec. &300, inêam. in air, rapidly react. with H2O; 2) inact. form., a- stab. in air, slow. react. with H2O,

N2)

M4N8, M = Sr, Ba, blk.

K2[Ca(N3)4(H2O)4]

19)

Silicates Mg2SiO4, ("forsterite"); (Mg,Fe)2SiO4, ("olivine"); Mg2Si2O6, ("enstatite"); Mg3Si4O10(OH)2, ("talc"); CaMg(SiO3)2, ("diopside"); Ca2SiO4,
n H2O, ("hillebrandite"); CaSiO3
nH2O "solanite"; Ca3[Si2O7], ("rankinite"); Ca3[Si3O9], ("wollastonite"); BaSiO3,
6 H2O; 5) RaSi2O5

M; MO

M(HS)2
n H2O, n = 6 (Ca), 0 (Sr), 4 (Ba), readily sol. in H2O MS;, m. p.  2000 (dec.) DH=ë352 (Mg), ë460 (Ca), ë452 (Sr), ë443 (Ba); NaCl str. type © N2O > M(HS)2 + M(OH)2; MgS4; MgS5 SrS4
n H2O, n = 6, 4; SrS5, yel. BaS2, m. p. 925 BaS3, grn., m. p. 554; BaS4, red, readily sol. in H2O, dec. 300;
2 H2O

0 Mg M

2+ H+; H2O+NH4+ ( H2:) H2O (ëH2)

[Mg(H2O)6]2+, oct. ion

[M(H2O)n]2+, stab. BaHg sol. in dil. ac., alk., in dil. ac. NH4OH 0.40 E0 M2+/M 0.76 sld. dist. hex. cl. pack. a=2.66 2.97 c=4.94 5.61 MìM

EN

900

t (O )

ZnO, wh. (>yel.), m. p. 1969 (Ó), subl. 1725 (dec.), DH = 348, "zincite", wurtzite str. type, framework of tetrah.

m. p. 256;

130

; 262


2 H2O 

non volat. isostr. Be- anal. 29) M(HCOO)4,
2 H2O# n = 1, CN Cd 7 MC2O4, S² = 10 9, ¬dis. = 10 5;
2 H2O# dec. 340; n = 3, ¬dis. = 10 M2[SiO4], m. p. 1509, "villemite" m. p. 1252 MSiO3, m. p. 1437 m. p. 1242 Zn4O(BO2)6, m. p. 980, str. anal. of Zn4O(CH3COO)6; ì Zn(BO2)2 ì

4

82 N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_29, © Springer-Verlag Berlin Heidelberg 2011

c.

t) 1,6) Zincates, cadmates Na2[M(OH)4]
2 H2O; Na[Zn(OH)3] Ba2[M(OH)6], anion ë oct. Ba[Zn2(OH)6]
5 H2O, K4ZnO3, anion ë triangle M2(Zn/Cd)O2#, chains of tetrah. Na6[MO4], K2Cd2O3, K2Zn6O7

Li[Cd(ClO4)3]; Na[Cd2(ClO4)5] K2[M(S2O3)2]
H2O, Kstab = 105(Zn) 12) M2[Zn(NO3)4], M = NO, R4N [NO][Zn(NO3)3]; M2[Zn(NO2)4] M2[Cd(NO2)4], stab. >Zn-compl., KZn2H(PO4)2; MZnPO4, cycles of tetrah. [PO4] Ë [ZnO4], Na[Cd(HCOO)3], anion ë layers of oct. 10) Na2[M(C2O4)2]

ZnHal2
n Zn(OH)2
m H2O#, Hal = Cl ë I, n = 1, 4, layers of tetrah. 25) and oct. Zn5(OH)8Cl2
H2O 30) M(OH)Hal#, CdHal2
3Cd(OH)2#, layers of oct.

+

H

2O 2

MO2
n H2O#, M = Zn, Cd, powd. wh. or yel., exp. >200 26)

H

21)

O

M2+

ZnF2# ZnCl2 ZnBr2 ZnI2

m. p.

b. p.

DH

875 326 (b) 315 (a) 394 446

1502 733

765 414

670 624 (dec.)

327 209

str. type TiO2 ì CdCl2 CdI2, CdCl2


n H2O, n= 4 4, 3, 2.5, 1.5, 1 3, 2 2

m. p. CdF2# CdCl2 CdBr2 CdI2

1072 568 567 388

b. p. 1753 964 863 754

DH -698 389 314 201

str. type CaF2 CdCl2 CdCl2 CdI2

RbMF3; M2ZnF4,; K3Zn2F7, Sr4Zn3F14 K2[MCl4], M = Zn (anion tetrah.); Cd (layers of oct., stab. 4 [ZnCl4]2 KZn2Cl5; KMCl3
n H2O. M4[CdCl6], anion ë oct. N3ZnCl5 = N3[ZnCl4]Cl Na6CdCl8 RbMBr3; Rb2MBr4, tetrah. Rb4CdBr6 oct. KMI3
n H2O; chain of tetrah. 2,13) Li2[MI4]


n H2O, n= 2 1ë4 2, 4 ì

cr. colrl., hyg., ZnHal2 sol. in H2O > CdHal2, readily sol. in alc. Et2O, weak electrolytes, prone to autocomplexing, in s.: Cd2+ + 2 [CdHal3] > 3 CdHal2 > 3 [CdHal]+ + 3 Hal ; 2 CdHal2 > Cd2+ + [CdHal4]2 , in gas ë linear mol. MHal2. In str. ZnCl2 (a-, b-) ë net of dist. tetrah., in str. ZnBr2, ZnI2 ë framework of tetrah.; in layered str. CdI2 ë hex. cl. pack [ICdI], in rhombohedral str. CdCl2 ë [ClCdClClCd] [ZnHal2L2], L = NH3, Py (mol. tetrah.), N2H4; [CdHal2L2], L = NH3, Py (chains of oct.) [CdHal4/2N2] ë trans, CdI2
10 NH3 5,28) CdI2 str. Zn(CN)2;, wh., dec. 800 Cd(CN)2;, colrl., dec. 200 [Cd(CN)2]n
m H2O
m R2O, (n = 3, 8) Cd(CN)2
L, L=DMPA, DMSO, in str. linear canals

ZnSO4 BaS

ZnS;, wh., amorph., S² = 10

; H S (dry)

, sol. in HCl,

2

b-ZnS, "wurtzite", m. p. 1900 (p), subl. 1185, DH = 192, hex. cl. pack., [ZnS4] and [SZn4] ë tetrah.

:

1020

a-ZnS, "sphalerite" DH = 205, diamond cub. str., tetrah. Na2ZnS2 [ZnS4] and [SZn4]

ZnSe#, yel. ZnTe#, red 16)

17)

Zn(NCS)2;, colrl., in str. ë layers of tetrah. [Zn(NCS)2(N2H4)2], mol. ë oct. Cd(SCN)2, colrl., in str. ë oct. [CdS4N2] [Cd(SCN)2(N2H4)2], mol. ë oct.

24

m. p. DH 1575 130 CdSe#, red 1239 121 CdTe#, brn. semiconduct. 700 (dec.) 21 Cd(N3)2, yel. 9) ì Cd3N2, blk.

Zn3N2, blk. Zn(N3)2, colrl., exp.
2.5 H2O t, H+ CdS;, yel. ! red., m. p. 1475(p) ì Zn(NH2)2, wh. 27 DH ˆ 150, S² = 10 , sol. in conc. HCl, H 2 .) Zn3P2 420 a-, "greenockite", semiconduct., wurtzite str. type KN liq 3 As 1015 Zn H 3 2 b-, sphalerite str. type (N ì ZnC2, wh. Zn/Hg (ZnH2)n (?), wh., dec. 90 insol. in Et2O

ì ì ì ì ì 9)

M2[Zn(CN)4], anion ë tetrah., Kstab. = 1020 K[Zn(CN)3]
2.5 H2O = K2Zn[Zn(CN)6]
5 H2O, in str. ë oct. [ZnC6] and tetrah. [ZnN4] M2[Cd(CN)4], Kstab. = 1018; M[Cd(CN)3]

19)

K2[Zn(ëNCS)4]
3H2O, tetrah. [ZnN4], Kstab.=10 3 M2[Cd(ìSCN)4], anion ë dist. oct. [CdN2S4/2], Kstab. = 103 M[Cd(SCN)3], M = Rb, Cs, chains of alternate oct. [CdS2N4] ì [CdS4N2] (M = Rb), [CdS6] ì [CdN6] (M = Cs) Ba2[Cd(ìSCN)6]
7 H2O 7)

17)

m. p. DH 1250 (Ó) 105 1090 100 21 ì

+163 ì

Cd(NH2)2, wh. ì ì Cd3P2, grey CdP2, orange Cd3As2 721 ì CdC2;, +HCl ? C2H2" dec. 20 ì CdH2, wh., insol. in Et2O

K2[Zn(NH2)4]; LiZnN M2[Zn(N3)4], M = K, Cs Cs3[Zn2(N3)7]; Cs[Zn2(N3)5] 14) K[Zn3(N3)7] C2H4 (t)

K2[Cd(NH2)4] K[Cd(N3)3]
H2O K2[Cd(N3)4] Tl8Cd3(N3)14, 18)

Zn, Cd M

I, S

83

84 N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_30, © Springer-Verlag Berlin Heidelberg 2011

85

ALKALI METALS, FRANCIUM

5p

5d

6p

6d

Rb0

Caesium

Cs0

5s 6s

Cath. Red

Cath. Red Na

a

N

K

)

MCl

s ga

(

Ca (8008, vac.)

Rb

Cs golden

met. silver-wh. 0.6 0.4 0.5

0.3

0.2

Fr

M3N

1)

ì ì

va

Solidity (diamand ë 10)

0.8

;

NaCl+60% CaCl2 (m. p. 580)

Li

0.8

;

O2

Rubidium

LiCl + KCl

0.9

;

êa me )

4d

9)

(Na

4p

³s4O Cs7O Cs11O3

1.0

(t,

Ox in air with inê. 0.97 0.86 1.52 H2O (ë H2) 1.90 0.54 2.46 97.8 64 39 28.7 180 23 886 776 696 705 1337 669 2.71 2.92 2.92 3.04 2.92 ì +H2O ! [H:]; sol. in NH3 liq. (bl. s.), [M(NH3)6] > [M(NH3)6]++ [e(NH3)n] ë("polaron"); ! MNH2 + H2 a-Fe str. type (cub.) 4.28 5.33 5.62 6.08 a=3.50 3.80 4.70 4.96 5.34 ì MìM 3.10 :>195 cub. cl. pack 5.34 ì ì ì ì a=4.41 in gas ë mol. M and M2 (1000 400 DH 594 418

yel. 740 ì ì 340

t

Rb2O

Peroxydes, cr. colrl., hyg. (yel. at admix ®°2), diamagn., O ì O 1.50 ë 1.54 2)

Cs2O

M

t

! colour increase; ! M2O2 + M; in gas ë mol. linear

!




H2O

10ë22% in crust

LiOH m. p. b. p. dec. DH
n H2O Kdis.

NaOH

KOH

RbOH

473 321 405 925 1390 1320 600 >2000 >2000 487 428 427 n ˆ 1 1; 2; 3.5; 4; 7 1; 2; 4 1.5 3.4 5.1

382 ì ì 414

1; 2

ì

m. p. ì dec. 342 DH 636
n H2O2, n ˆ 2
n H2O, n ˆ 1; 2

Na2O2 596 675 510 4 8

K2O2

Rb2O2

Cs2O2

ì ì 494 4 ì

567 1010 422 4 ì

597 650 402 4 ì

t strong Ox.: + Fe ! M2FeO4; [M2O2 + CaCl(OCl)] ("oxylit") + ³O2 ! O2 + M2CO3

12)

Alkali, cr. colrl., subl. &400, sol. in ¯2°, alc. (CsOH 4 LiOH), liq. NH3. Melt react. with glass, (Pt + O2); insol. Ag, Ni, Fe, volat. (expect LiOH)

Li2O2

O2 (t)

yel. Ñrange ì 495 ì ì 400 300 331 318

red

4s

0 Potassium K

3d

(L ië

3p

;

2

3s

°xides, cr., hyg., subl. vac. (10 5mm), Ânti-CaF2 str. type (CN ® 4); str. Cs2O ë Ânti-CdCl2 type (CN ³s 3)

ë ye l. ê a me )

1.0

2)

Na0

EN

;

O

Sodium

2s

N

Li0

c.,

Lithium

13)

CsOH 339 ì ì 407 0.5; 1; 2; 3 ì

O2 (K , Rb ì vl Cs ì bl. êa t., me)

O H2 ( H2 ol. ctr ele

MClO4, M = Li (m. p. 247, dec. 500), readily sol. in alc., Et2O;
3 H2O; Na (482 m. p., dec.)
H2O; K (610 m. p., dec), Rb;, Cs; ( 700 m. p., dec.), Fr; MClO3, M = Li (m. p. 129, dec. 270),
0.5 H2O; Na (262); K ("berthollet salt"), (m. p. 368, dec. 400), sol. in ¯2° Li 4 Cs MBrO3, M = Na (m. p. 381), K (434, m. p., dec.); Rb (430); Cs (420), sol. in ¯2° Na 4 K ë Cs, MIO3, M=Li ë K (m. p. 560), Rb;, Cs; MIO3
n HIO3 MIO4, M = Na, dec. 300 (
3 H2O), K; (m. p. 582), Rb;, Cs; See Tabl. "Hal"

MHSO4, M = Li (m. p. 170), Na (186,
H2O), K (210), ³s;
0.5 H2SO4
n H2SO4, (n ˆ 1, 2, 3) M = Na ë Cs 14) Li2SO4, m. p. 860;
H2O, v. readily sol. in H2O
M2SO4, M = Na, K, NH4;
2 M2SO4
9 H2O, M = Na, K Na2SO4, m. p. 884, b. p. 1430, ("tehnardit") DHsol.Na MOH + ROH; str. anal. of LiOH (M = Li, Na, R = Me, CN 4) or a-KOH (K ë Cs, ®Ç, CN 5).
n ROH, n = 2 (Li, Me, Et), 5, 4, 3 (Na, Me), 3, 2 (Na, Et, n-, i-Pr, n-, i-Bu); 5, 3, 1 (K, Me); 1 (K, Et), 7, 5, 2, 1 (Rb, Cs, Me), 1 (Cs, Et, Pr) 3, 7) [MOBu-t]4, M = K ë Cs ë cubane-like tetramers, CN 3; cat. react. polymerization, condensation, Red. ³=° gr. "MCO" = (MOC:)2, acetylendiolates, pyrophoric, CaC2 str. type


HF CsCl CsBr CsI

m. p.

b. p.

798 ì ì 726 692 656 ì

1430 ì ì 1395 1352 1327 ì

m. p.

b. p.

684

1302

531

ì ì ì 1295 1297 1280

ì ì ì 431 410 ì


n H2O, n = 2/3, 1/5

N2)

MNH2, amides, cr. colrl. or light grn.; m. p. 390 (Li), 210 (Na), 338 (K), 309 (Rb), 261 (Cs); subl. &400; sol. in liq. NH3; liq. > M+ + [NH2] ; +H2O ? MOH + NH3; chem. act. CsNH2 4 LiNH2 (See Tabl. "N")

RbF,
n H2O, n = 3, 3/2,
n HF, n = 1, 2, 3 RbCl RbBr RbI Rb[In], n=7, 9, brn. 16) Rb2(OH)I

CsF,

M3N, nitrides, cr. ruby-red., M = Li (m. p. 845, DH = 47), Na (dec. 200), K ë Cs (exp.); + H2O ! NH3 + MOH

;H

m. p.

ì 646 638 622

DH

24 22 20 18 16 14 12 10 8 6 4 2 0

MF

Sol., mol/l (188)

m. p. 900

MCl MBr MI Li Na K Rb Cs Solubility of ®Hal in ¯2°

CsCl str.

Hydrides, cr. colrl., insol. in NH3 liq., org. sol., NaCl str. type LiH NaH KH RbH CsH m. p. 691 &800 &400 &400 &400 (p H2, Na ë Cs) 56 DH 91 56 57 54 3.19 MìH 2.04 2.44 2.85 3.02 melt. > M+ + H ë, in gas ë mol. MH (Li ì H 1.60), mLiH = 5.88, v. strong Red; + H2O ! H2 + MOH; + CO2 ! HCOOM; chem. Âct. CsH 4 LiH Used for separation of MI and the allocation of Rb and Cs: 5) MBiI4, M = K ë Cs; MBiCl4; M2BiCl5; M3BiCl6; Rb3Bi2Cl9; Cs4BiCl7, M[Sb(OH)6], M = Li, Na;, K M3SbHal6, Hal = Cl, Br, M = Li, Na, K ë Cs; MHC4H4O6, hydrotartrates, M = Li, Na (sol. in. ¯2°), NH4, K ë Fr; (sol. in. ac., alk.) M2[SiF6], M = Li (
2 H2O, dec. 100, readily sol. in ¯2°, alc.), Na; ("mallardite"), K; ("hieratite"), Rb;, NH4, t Cs (v. readily sol. in ¯2°); ! MF + SiF4 M2[SnCl6], M = Li, Na (sol. in ¯2°), K ë Cs; M[BF4], M = Na (m. p. 384, readily sol. in ¯2°), K; (m. p. 530), M[BPh4], M = Li, Na (sol. in ¯2°), K ë Cs; M3[Co(NO2)6], cr. yel., M = Li, Na (sol. in ¯2°), NH4;, K ë Fr; M2[PtCl6], cr. yel., M = Li, Na (sol. in ¯2°), NH4, K ë Fr (poorly sol. in ¯2°, insol. in alc.) MZn(UO2)3(CH3COO)9
6 H2O, M = Li;, Na; M3P(Mo12O40)], M = Li ë Na (sol. in ¯2°), K ë Fr; M4[Si(W12O40)], M = K ë Fr;

M O Hal or N

87

[N O (2 ]Cl 00 0 O ) 4

Cu2O str.

3

0

70

: t(



al 2

uH

C ); + +

H 26)

m.p.

b.p.

DH

SP

Cu ì Hal 7

Alloys 90% Cu + 10% Sn ë bronze; 90% Cu + 10% Zn ë tombak; 60% Cu + 40% Zn ë brass; 50% Cu + 45% Al + 5% Zn ë Dewar alloy; 95% Cu + 4% Sn + 1% Zn ë mint alloy

O2+SiO2 (ë FeSiO3 ë SO2 :) ; in production of H2SO4

electrolytic raéning in s. CuSO4

H3PO2; NaBH4 CuSO4

88

Fe

[CuHal(PR3)]4, in mol.ë cub ë [Cu-eHal]4 [CuI(C5H11N)]4, in mol.ë tetrah. [Cu4]

27)

CuCN;, colrl., m.p.. 473, SP = 10 20 Cu2 ë xS;, grey, SP = 10 50, "copper glance", m.p. 1130; DH = 79 CuIFeIIIS2, "cooper pyrites", "chalcopyrite", in str. ë tetrah. [CuIS4], [FeIIIS4], [SCu2Fe2], sphalerite str. type Cu2Se, bl., m.p. 1112; Cu2Te, blk., m.p. 855 Cu3N, grn., dec. 300, DH = +75

CuH;, cr., red-brn., dec. 20, DH=+21, wurtzite str. type

Cu

CuCl; 450 1212 136 10 2.16 CuBr; 504 1345 105 10 9 ì 12 CuI; 605 1336 68 10 2.44 CuHal, wh., sol. in surp. NH3, MCN, M2S2O3. Str. CuHal sphalerite type, CN Cu 4 (sp3), in gas ëtrimer cycles.

hn

CuN3; ! Cu + N2 Cu3P, m.p. 1022; Cu3As; Cu3Sb; Cu2Sb Cu2C2, acetylide, red-brn.,
H2O

S CuFeS2 str.

C

al

2;

H

H

HCuCl2, KCuCl2; K2CuCl3 MCu2Cl3, anions ë chains of HCl tetrah. M2CuBr3; [R4N]3[Cu2Br4] H2O chains of triangels or tetrah. M2[CuI3], Cs3Cu2I5, M[Cu2I3], [PyH]2[Cu5Hal7], Hal=Br,I [NO]+[CuX2]-, X=Hal,CN,SEN,blk., sol. 2) in ROH

al

+

+O

2

Cu

O

2;

O

N

C

31)

X, H20

ia

³u ì Hal m.p. dec. CuF2, colrl., 950 ì CuCl2, yel. 596 1000 290 CuBr2, blk. ì

DH 536 216 134


n H2O,

ax.

equ.

n=

2.27 2.95 3.18

1.93 2.30 2.40

2, bl. 2, bl. 2, brn.

CuHal2 (Hal=Cl,Br), sol. in H2O, ROH, Py, ac.; str. CuF2 ë dist. rutile type, in str. CuCl2, CuBr2 ë ribbon of squares. 21) [CuHal2(NO)]2

M[Cu(CN)2], colrl., Kstab=1024 K3[Cu2(CN)4]
H2O, CN Cu=3: anion ë tetrah., Kstab.=1024 M3[Cu(CN)4] CS[Cu(SCN)2], Kstab.=1012 16) K2[Cu(SCN)3]; Na3[Cu(SCN)4]
4H2O KCuS, anion ë zigzag chain KCu4S3, bl., semiconduct., layer of tetrah. [CuS4]

Cu(CN)2;, powd., yell.-brn. 20

! CuCN + (CN)2:; + H2O ! CuCN; + O2 (slow.)

+

Cu2+

+H

H 2S

CuS;, blk., dec. 220, SP = 10 38, sol. in ac.-Ox, M2Sn, "covellite", 200 DH = 53, conduct. ! Cu2S + S CuS3; Cu2S5; CuSe; CuSe2 Cu(N3)2;, cr., brn., exp. CuC2;, acetylide

N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_32, © Springer-Verlag Berlin Heidelberg 2011

3)

31)

CuHal2
3Cu(OH)2, CdI2 str. type; Cu2OCl2, Cu(OH)Cl, in str. ë layers of elongated oct.

aq

.r eg

H2O)

[Cu(CH3COO)2(H2O)]2, grn., cluster, diamagn. t (N ) CuC2O4
H2O;, bl.; !2 Cu + CO2 + H2O Cu6[Si6O18]
6 H2O, "dioptase" 12)

3)

2.64

nc (co O

N

, (-C

H

l4

CN 12 (cubooct.), ³u ì ³u 2.56

OH

O H 3C

H

7)

Cu(IO3)2; ! CuO+I2+O2;
n H2O, n=1, 2/3, Cu2HIO6;,
n H2O;, n = 1, 2 258 CuSO4, colrl., dec. 550,
n H2O, n=1, 3, 5 ("vitriol"), bl., 7 Cu(NO3)2, bl., subl. 200, m.p. 226, in gas ë planar mol. 23) 1.
n H2O, n ˆ 9; 6; 2.5; 1 95 Cu(NO2)2, m.p. 147 68 ³u3(PO4)2
n H2O;, n = 1, 3; Cu4H(PO4)3; 120 CuHPO4
n H2O; Cu(H2PO4)2 24) n CuCO3
Cu(OH)2;, "malachite" (n ˆ 1), "azurite" (n ˆ 2), in str. oct. [CuO6]; + CO2 (p, t) ! ³uCO3; Cu(CH3COO)2, grn., sol. in ¯2° and org. solv.

4

M[CuSO3]; M3[Cu(SO3)2]; Kstab=108 109

Zn; Fe; cath. Red.

Cu(OH)2;, bl., sol. in ac., NH4OH, in str. layers of 30) oct.; + MOH (conc.) ! vlt. coll. s.

290

.)

Cu2SO4, grey, m.p. *400; + H2O ! Cu; + CuSO4; strong Red, damb-bell 25) [CuO2];
2NH3 Cu2SO3
H2O;, wh.; CuCH3COO;, needles, colrl., chains of 8-member cycles 1)

: t (under s.) 5)

Cu(ClO4)2, yel.-grn., dec. 130, volat.,
n H2O, n = 6, 2 Cu(ClO3)2
6 H2O; Cu(BrO3)2
n H2O, n=6, 2 (bl.),

14) Cuprates (I), MCuO, M = Li ë K, chains of squares [Cu4O4]4 M3[CuO2], yel., +H2O ! Cu;+CuII

O

H2SO4 (200 )

CuO, "blk. oxyde", m.p. 1335 (p O2), dec. 1026, DH = 1565, in str. ë squares [CuO4] (dsp2 )

Cu4O3=CuI2[CuII 2 O3], "paramelaconit" 22)

2S

M

, (t) O 2 (t) O 2

00 )

( CO  ) 2; H 0 M; (>20 O2

2

 ); C 250

CC

Cu, met. yel-red., ductile, high electro- and heat conduct., d ˆ 8:9, m.p. 1085, b.p. 2540, sol. in ac.-Ox., NH4OH, KCN, Ox in air. E0 Cu2+/Cu =+0.34 sld. E0 Cu+/Cu = ‡0:52 sld. diamagn., in str. ë facecentred cube, a=3.61 (cub. cl. pack., Cu str. type)

d CuCl2 Re

16

;

Fe

Cu2O;, "red oxyde", m.p. 1236, dec. 1800, DH = 167, CN ³u 2 (sp), dumb-bell; [CuO2], [OCu4] ë tetrah., SP = 10 15, sol. in NH4OH, HHal (conc.)+ + H2SO4 (dil.) ! Cu; + CuSO4 M

; Zn

.

h cat

1.8

4(

;

EN

4d

O

:; :; :; :; :;

4p

3) 2S

4s

H

3d

(C

Cu

0

2+(d 9)

1+(d 10)

H

COPPER

3+(d 8)

K2S2O8(OHë)

4+(d 7)

M

2O n+

O

Cuprates (II) 4) 3 MOH Na2II[Cu(OH)4], bl. IIanion ë tetrah. (sp ), paramagn. M2 [Cu(OH)6], M = Sr, Ba, bl.; anions ë oct. (sp 3 d 2 ) or (conc.) squares (elongated oct.), Cu ì O 1.95 (equ.) and 2.8 (ax.) H2O MI2CuO2, red, Ca2CuO3 YBa2Cu3O7 ëx, high-temperature superconduct. 5)

18)

M[Cu(ClO4)3], (NO2)2[Cu(ClO4)4] ; Ba2[Cu(TeO6)] Na6[Cu(HIO6)2]
13 H2O, Na4H2[Cu(H2TeO6)2], 5) in anions ë squares [CuO4] [NO]+[Cu(NO3)3] ë (= "Cu(NO3)2
N2O4"), bl.ëgrn., 6) sol. in org. solv., anion ë net of elongated oct. M4[Cu(NO2)6], anion ë oblate oct. 13) K3[Cu(NO2)5], Rb4[Cu3(NO2)10], Ba2Cu(PO4)2 K2[Cu(CO3)2], in str. ë net of square, 13)
3 H2O, bl., in str. ë tetr. pyram. [CuO4(H2O)] 32) K2[Cu2(CH3COO)4][Cu(CH3COO)4] 17) M2[Cu(C2O4)2]
2 H2O, anion ë elongated oct.

H2O

Cuprates (III) 15) K[Cu(OH)4], red, dec. 20 MCuO2#, M = Na ë Cs, blk. or bl., diamagn. (d8), anion ë ribbons of squares (dsp2) Ba(CuO2)2#, red, stab. M6[CuO3]2, M = Li, Na, diamagn., anion ë 2 squares sharing a edge, semiconduct.

MClO; MBrO(Ohë) K2S2O8

O

4;

K

2S 2O 8;

lO

+

CuF3, red. F 2(p,

}

KI

O

4

HF ( 60 ) t)

X:; H2O

[CuX2] ë, colrl., diamagn. (d 10), linear

t

2ë

Cl

Xë O2

H2O

[Cu(H2O)6]2+, bl., paramagn. H2O [Cu(H2O)5(OH)]+ H2O [Cu2(OH)]3+, 7 (d 9) cation, elongated oct. Kstab.=106 20) H+ Kstab. = 10 H+

OH (pH&5)

Cu(OH)2#, bl., SP = 10 20, s. in ac., NH4OH, K2bas. = 10 7; K1ac. = 10 10, K2ac. = 10 13 H

H+ Cu2O# yel. (gel), ! red., SP = 10 15, sol. in NH4OH, HHal (conc.), KCN

NH2OH; As33 ; C6H12O6

OH

OHa ë l (OH ë )

[Cu(OH) 4 )] ë , red., diamagn. (d 8 ), square

OH

[Cu(OH)4]2 ë . [Cu (OH)6)]4 ë, 15 H2 O bl., oct. (sp 3d 2), Kstab. = 10 bl., paramagn., paramagn. tetrah.

Cu O Fe

H+ NH3 +

[Cu(NH3)2] , colrl., diamagn. (d 10 ), linear (sp) ion, ex. only in s., Kstab. = 1011

11)

3+

Clë

+

)

9)

! F2 + . . .

[CuCl4] , orange, paramagn. [CuCl4(H2O)2] , grn., para(d 9) ion, oblate tetrah. (sp 3) H O magn. ion, oblate oct. (sp 3d 2) 2

H2SO4; HNO3; HCl+O2; CH3COOH+O2

OH

M[Cu(N3)3]; M2[Cu(N3)4]; M4[Cu(N3)6]

( 78 )

2+ 2ë

Zn; Fe

NH 3(

M[CuS4], M = NH4, K ë Cs, red.

+ HF

F2(p, t) + CsCl

X = CN SCN I Br Cl K.stab = 1024 1011 109 106 105

H 2O+

M2[CuS4], Kstab. = 106

Cs2CuF6, orange, rapidly react. with H2O, meff = 1.77 (1 unpair. el.), low-spin oct. (t62g e1g),

K3CuF6, grn., paramagn., high-spin oct. (sp3d 2); + H2O ! F2 + . . . Cs[CuF4], anion ë square, diamagn. (dsp2) 28)

CuX#, X = Hal, CN, SCN, SO3, colrl.

Cu#, red.

( 2 NH3)

Na5[Cu(HIO6)2]
3.8 H2O; Na5[Cu(H2TeO6)2]
11.5 H2O, brn., diamagn., in anions ë square [CuO4], strong Ox. 24)

O 2+

K2[Cu(CN)4], colrl., stab., + CN ! vlt. cyanides whith high CN of Cu at.



1+

)

MCuF3, colrl. framework or layers elongated oct. M2CuF4, HCuCl3
3 H2O, CsCuCl3, red, chains of oct. Cs2CuCl4, orange, anion ë oblate tetrah. 7) M2[CuCl4(H2O)2], M = K ë Cs, grn. Rb3[Cu2Cl7], layers of oct. [Cr(NH3)6][CuCl5], trig. bipyr. HCuBr3
10 H2O; MCuBr3, blk. M2CuBr4, red Cs2CuBr4, blk., oblate tetrah., all polyhedra are dist. (Jahn-Teller effect, d9)

; 200

[Cu(NH3)2X2], X = Hal, N3, ribbons. of oct. [CuDipy2I ]I, trig. bipyr. (CN 5) [CuPy4]X2, square (dsp2). 30 [Cu(NH3)2](NO2)2, purp., ! grn. 19) CuI2
n NH3, n = 5, 6, 10, 35

6ë H2O IO5ë 6 ; TeO6

KC

2 (H +

Cu ì Hal equ. ax. ì ì 1.95 2.08 2.39 2.5-2.7 2.23 ì 2.28 2.89 2.30 2.87 2.41 2.30 ì ì ì ì ì ì

[Cu(NH3)6]Hal2, cation ë oblate oct. [Cu(NH3)5]SO4. [Cu(NH3)4(H2O)2]X2, elongated oct. [Cu(NH3)4]X2, X = OH, Hal, NO3, SCN

MOH

12)

8)

Halogenocuprates (II)

! CuO + O2; + HCl ! Cl2 + CuCl2

CuX

[R4N]4[Cu4OCl10]

400

)

2.5+ Li3Cu2O4, 29)

MI

¡mmines of Cu (II), cr., bl.

Cu2O3#, garnet red;

2 (t

S O2 N2H4

2+

2+

[Cu(NH3)4(H2O)2] , dark bl., NH3 [Cu(NH3)5] , elongated oct., Kstab.=1013 Kstab. = 1011 2+ [Cu(NH3)4]X2 H2 O [(NH3)2Cu](m-OH)]2

20)

89

SILVER Ag

0

4d

5s

;: ;: ;: ;: ;:

;

5p

5d

EN

2+(d 9 ) or "2+"

1+(d 10)

3+(d 8)

1.4

"4+" 5+(d 6 )

; + ) (H x. O3 . O an

AgO# = AgIAgIIIO2, blk., cub., dec. 100 …a†, Ag3O4 = Ag2O3, blk., 178 …b†; DH = 13, sol. in HNO3, HClO4; 20 AgIIIAgIIO , 19) Ag2O, brn., dec. 300, DH = 29, SP = 10 8, sol. in ac., an. Ox. (OH ) dec. 20, SO ! Ag SO +O "; + H 2 4 Ag O, 2 4 2 4 2 3 Ag, met., wh., ductile, NH4OH, KCN; +H2O > Ag++ OH (pH>7), K2S2O8 (90 ); O3 (OH ) v. Ox., semiconduct., diamagn., in str. a-form blk. 17) isostr. to conduct., 4 with high thermal and K = 10 ; cub., isostr. to Cu2O (CN Ag 2, sp) dumb-bells [AgIO2] and squares [AgIIIO4], Au2O3 13, 17) in str. ë M electrical conduct., OH I,III 8,17) ] oct. [Ag  in str. b-form ë tetrah. [Ag O ] 6 4 H2O (> 50 ) d=10.5, m.p. 962, ) (co ) Ag M2 O OH 12 nc Ag 300 ) b.p. 2210, sol. in ac.-Ox., .) H 4 9) > AgOH 2 ( 0 2 ; M H2O (t) HX (dil.) C H (20 (KCN+O2), 2O N p 2 ( 2 O H E0 Ag+/Ag = 0.80; Argentates 7) M5[Ag(HIO6)2]
n H2O Ag7O8X, X = HF2, ClO4, HSO4, NO3, sol. AgClO4, colrl., dec. 486, readily sol. in H2O, org. solv. 2) K[Ag(OH)2], ex. in s. pH 4 7 Na5[Ag(H2TeO6)2]
12.5 H2O blk., with met. lustre, conduct. cub. cl. pack., a ˆ 4:08, + ! AgCl; + O2 AgClO3, colrl., m.p. 230, dec. 270; + H t M4[Ag4O4], M = Li ë Cs, yel., light yel., diamagn. (d 8 ), Ag ì Ag 2.88 + H2O ! AgO# + O2 + AgNO3, in str. ë AgBrO3, poorly sol. in H2O, stab. in H+>AgClO3 I III anion ë square anion ë square (dsp 2) 15) Coll. Ag, grn. or blk. 10 cubes [Ag O8] and squares [Ag O4] AgIO3#, SP = 10 , insol. in ac. (t) M3[AgO2], dumb-bell (sp), HX leaves with met. lustre Ag2H3IO6#, yel.; Ag5IO6#, blk. Na4Ag2O3; Na2Ag4O3 ("collargol"), powd. Cs[Ag(SO3F)3], 1000 Ag2SO4#, cr., colrl., m.p. 660; ! Ag + SO2 + O2; MAg3O2; +H2O ! Ag+O2+... yel.-brn. ("protargol"), Ag(SO3F)2, dec. 210; K2[Ag(SO3F)4] 4 SP = 10 , in str. CN Ag 6; +H2SO4 ! AgHSO4 have sterillizing effect. + ) Hal Py + H2O ! O2 + ... , x. (Pt Ag2S2O3#, wh., + H2O ! Ag2S# + H2SO4 2 an. O ) [AgPy4]X2, X = NO3, S2O8/2, orange., 0 Ag CrO #, red-brn.; Ag Cr O #, dark-red 2 4 2 2 7 25 14 v. strong Ox., cation ë square [AgN4] 1 ( Na [Ag(S O ) ], K = 10 3 2 3 2 stab AgNO3#, cr., colrl., m.p. 212, dec. 444, sol. in H2O, alc., " 14) MNO2 Ag3(PO4)2, AgCrO4 Zn K[Ag(NO2)2], Kstab = 103 Py, MeCN, liq. NH3, coagulated protein Ag Cs3Ba[Ag(NO2)6]
2 H2O Alloys AgNO2#, [= AgONO + Ag ì NO2], light yel., dec. 140, 3 + K[Ag(CO3)], in str. ë chain of 90% Ag + 10% Cu ë silver-, SP = 10 ;
NH3 = [Ag(NH3)2] [Ag(NO2)2] tetrah. [AgO4] 90% Au + 10% Ag ë gold, AgPO3#, colrl., m.p. 482, sol. in dil. ac. MF+F2 monetary alloys Ag4P2O7#, colrl., m.p. 585 F2; ClF3 19 Amalgams, is easily formed, Ag3PO4#, yel., m.p. 849, SP = 10 Cs2[AgF6], AgF2, cr., colrl., m.p. MAgF3, containes Ag4Hg3, Ag5Hg8 Ag3AsO4#, red; Ag3AsO3#, yel. AgF3#, 6) MIIAgF3, 1) K2PtCl6 12 690, DH = 347, M = K ë Cs (m.p. 276 and 127). In system Ag2CO3#, light yel., dec. 100; SP = 10 , in str. ë tetrah. [AgO4] red-brn., M[AgCl2], anion ë tetrah., str. type, oct. paramagn. (< 110 ), M2AgF4, M= diamagn., Ag ë Zn ë Pb ë delamination, AgCH3COO, sol. in H2O 1%, Kdis = 0.2 21) Kstab = 106 [AgIIIF6], 200 ! ferromagn., strongest 6 =K ë Cs, Ag sol. in Zn-layer (over) Ag[BF4]; Ag[¿F6], E = P, As, Sb, Nb, Ta M[AgBr2], Kstab = 10 d 8(t62ge2g) and 22) AgF2+F2 F-agent; + H2O ! Ca ë Ba/2, Ag3BO3, in str. ë chains of dumb-bells [AgO2] MAgI , M AgI , in 2 2 3 [AgVF6] 16) Zn (t) Ag2O + O3 + HF, Cd/2, Hg/2, Ag[EH4], E = B (wh.), Al (yel.), Ga (orange), dec. 30, 50, 75; str. ë chain of tetrah.  in str. ë squares [AgF4] anion ë M[AgF4],
n PR3, stab. >100 "Rough Pb" KAg3I4
8 H2O; CsF+F2 (p) Ag[MIVF6], MIV = square 5) M=K ë Cs, [Ag3Hal](NO3)2, Hal = Cl ë I, CN, SCN 11) [R4N]2Ag13I15, RbAg4I5 Ge ë Pb, Ti ë Hf, Rh, Ba2AgF6 [O2], yel., ionic conduct., in str. ë AgF m.p. b.p. DH SP Solv. Pt, Pd, stab. AgCl > AgI. Str. AgHal (Hal = F ë Br) Ag H2O ( O2) v. strong Ox. SO antibakterial 10) 2 NaCl type (CN Ag 6), AgI ë sphalerite or wurtzite types. 0 ;H H+ OH pH 4 7 ; O3 50 18) N 11 S S#, blk., m.p. 827, sol. in HNO (t), KCN; SP = 10 , in Ag ë Pb ores Ag 2 3 H 2 O ± H AgNO3 2 14 [Ag(OH) ] , colrl. linear, 2 2 AgCN#, wh., stab. to hn-vis, SP = 10 , in str. ë linear chains H Ag#, [AgAm4]2+, square NH conc. s. Kstab=104, strong bas. 12 ] 3 AgSCN#, wh., SP = 10 12 ³ " coll. s. [AgAm6]2+, oct., brn. M[Ag(CN)2], linear ion, 9 20) H [ Ag3N#, nitride, exp., brn., DH=+225, SP = 10 or orange, paramagn. Kstab ˆ 1021 + o + ë 20) [Ag(NH3)2] , linear, AgN3#, azide, m.p. 252, exp. 300 , ì Ag ì N=N =N ì (d 9), v. strong Ox. Mn[Ag(SCN)n+1], n ˆ 1 5, 7 = 10 K AgONC, fulminate, exp., detonator; AgOCN, cyanat stab 9, 18) 8 Kstab ˆ 10 CuAg3S2, "jalpaite"; Ag8GeS6, "argirodite" 2

O

Zn

+

K

C

N

O2 (ëSO2, baking)

K

2C

O

3

OH 8) K + 2S 2O 4 IO .; K Ox n.

(a

K

90

N. Turova, Inorganic Chemistry in Tables, DOI 10.1007/978-3-642-20487-6_33, © Springer-Verlag Berlin Heidelberg 2011

:;

GOLD Au

0

1+(d 10)

5d

6s

;: ;: ;: ;: ;:

;

6p

6d

EN 1.4

>260 ; H2; CO (100 )

2O

AuOCl;, red, sol. in conc. HCl;

; Br 2 (20  )

M[AuCl2], Kstab. = 109, M[AuBr2], Kstab. = 1013 M[AuI2], anions diamagn., linear (sp), + H2O ! ! Au+[AuHal4]ë

[Au(SO3F)3]2 Au2(SeO4)3, yel. Au(TeOF5)3 14)

290

! Au + Cl2 + O2;

AuCl2, red, diamagn., I 0 [AuIII 2 Au2Cl4] , [AuIIICl2Cl2/2]0 [AuICl2/2]0 ë chair, square, dumb-bell 16)

t

DH

500 150

348 117

100 20

54 ì

AuHal3 ! AuHal + Hal2. In str. AuF3 ë spirals from squares. In str. and gas ë Au2Hal6 (Hal = Cl ë I) ë êat 7,8) dimeres

16)

M3[AuS2], colrl., anion dumb-bell 10) MAuS K[Au(C:CH)2]

Hal2 + CN Au(CN)3
3 H2O;, colrl. Au(SCN)3;, red, v. unstab.  Au2S3, blk., hydr.; 200 ! Au + S

[Au2O3
x NH3 +Au(NH2)nXm(NH)p];, "fulminic gold", yel.-brn., exp., sol. in KCN [Au(NH3)4]X3;, X = NO3, CrO4/2, insol. in conc. ac. [Au(NH3)4]3+, colrl. ion, Kstab. = 1030

M[AuF4]n, light-yel., anion ë elong. oct. MAuCl4, M = Na ("Au-salt"), K (
H2O), Cs;, yel., diamagn. HAuCl4
4 H2O, "Au-chloride", light-yel.,hyg.,needles, Kstab. =1022

AuF5,red-brn., AuF7, cr. [F] yel., volat. m. p. 75, diamagn., H2O DH = 473, 100 Au2O3+Au in str. ë cycle 4) [AuF5]4, in gas [AuF5]2 3)

#

120

! AuCl3 + H2O + HCl KAuBr4
2 H2O, purp., anion ë square, Kstab. = 1031 K3AuBr6, yel., anion ë dist. oct. KAuI4, blk., strong Ox. 2) HAuI4, unstab. H[Au(CN)4]
3H2O, sol. in alc., Et2O 200 K[Au(CN)4],
H2O, colrl., anion ë square, Kstab. = 1056 K[Au(SCN)4], orange, Kstab. = 1042 NaAuS2
4 H2O, colrl., dec. 30 H2 S

NH

gas

K

60

Br

2

rF

2

M[AuF6]n, yel., diamagn., anion ë oct. (d 2 sp3 ) 3)

Cl +H

M2Au2Hal6, in str. ë dumb-bell [AuIHal2] and squares [AuIIIHal4]

dec. AuF3, orange AuCl3, red., m. p. 288 (p) AuBr3, brn. AuI3;, grn.

8)

13) Na5[Au(HIO6)2]
3.5 H2O M[Au(SO3F)4]; M[Au(SO4)2], yel.; K5[Au(SO3)4], colrl. M[Au(NO3)4], yel. H[Au(NO3)4]
3 H2O, yel. K2H[Au(NO3)6], M[Au(CH3COO)4], anion ë square

Cl 2

240

H

08); C l2 (200 8)

H+ (pH&7)

¡urates (III), K[Au(OH)4]
H2O, yel. MII[Au(OH)4]2, M = Ca ë Ba (
5 H2O, grn.), anion ë square (dsp2 ) NaAuO2, M6[Au2O6], anion ë 2 squares 12) sharing a edge

NaNO3 (ë NO)

Ox H2SeO4; HSO3F; an.

[Au4L4(m-I2)]; [Au6L8]X2; Au5L4Cl=[AuI(Au0L)4]+Cl ; [Au8L7]X2 = [AuI(Au0L)7]X2; [Au9L8]X3; [Au11L7X3]; L = PR3; clusters ë [Aun], n = 4 (tetrah.), 6 (Ñct.), etc. 11)

2

OHë

M3[Au(S2O3)2]
H2O, colrl., anion ë linear [S ë Au ë S] 9)

sol. in aq. regia; ! Au + S Au2S2;, blk.-brn. Au3N, nitride, exp.;
NH3 AuN3, azide, colrl., sol. in ¯2°, DH = +280, exp. even in s. 18) Au2C2, yel., exp. [Au(NH3)2]+, colrl., linear cation, Kstab. = 1027 [Au(H2O)2]+

1 ë (s ) 0 (d s )

3,

Au2O3
2 H2O;, "auric ac.", yel.-brn., sol. in ac., alk., Kac = 10 12 (I), 10 14 (II), 10 16 (III) >Kbas.

M+Auë, M = K ë Cs M3OAu 19)

10 1

7+(d 4)

100

¡urates (I), Cs[AuO], in str. ë anions [Au4O4]4 6) Na3AuO2,

F2 (35

5+(d 6)

AuO(OH) ëH2O(P2O5)

AuCN;, yel., isostr. to AgCN HCl M[Au(CN)2], colrl., AuSCN;, dec. 140; anion ë linear, + H2O ! Au(SCN)3 + H2 Kstab. = 1039 M[Au(SCN)2], Kstab. = 1023 Au S;, grey or brn. powd.,

2

Au2O3, powd., brn., DH = net of squares 5)

AuO = AuI[AuIIIO2], powd., grn.

Au2O
x H2O;, dark-vlt.; + MOH ! bl. sol. MOH

Au, met. yel., d = 19.32, m. p. 1064.4; b. p. 2947, volat. >1000 , does not react. with O2, N2, C, S; sol. in aq. regia, electrolytic ë reéning (Cl2 + HCl), in s. HAuCl4 (H2SO4 + HNO3), (H2SO4 + HMnO4), H2SeO4 (t), (KCN + O2); Zn[ M2Zn(CN)4] K[Au(CN)4] E0 Au+/Au = 1.68, sld. E0 Au3+/Au = 1.50 sld. Cub. cl. pack. (Cu str. type), a=4.08, Au ì Au 2.88 Cl 2( 3 electroI2 50  (5 ); dispergating 0ë B 10 r2 ( "Coll. gold" (negativ), is 0  70  ) formed in v. dil. s., with ); increasing particle size 1,17) color changes as follows: DH red ("Cassius purple"), AuF, ex. only in gas ì bl., vlt., blk. AuCl;,cr.,lightyel.,unstab. 33 AuBr;, cr., yel. 18 AuI;, cr., light-yel. +1 Alloys Au Amalgam contain In str.ë chains Hal AuHg2, AuHg3, Au3Hg Au t (m. p. 124, 310, 421) AuHal ! Au + Hal2; In the system Cu ì Au t; hn…vis† + H2O ! Au + [AuHal4] continuous series of sld. stab. AuI>AuCl; s.,