The Data Tables

II. The Data Tables

PART A - STABILITY CONSTANT DATA.

Medium

Temp, HYDROGEN

Log K

Me thod

Ref.

Remarks

H

RECOMMENDED

3(ΝαΟ.(\)

25

K

3.28

qh

6 3C

3(NaCl(V

25

Kl 3.29

qh

64F

3(NaCl(V

25

K

fe,qh

70K

SCNaCHV

25

l 3.33 Kl 3.33

fe

73K

2(NaC10i+)

25

K

2(NaC10 l+ )

25

K

KNaClO^)

25

K

KNaClOi^)

25

K

KNaClCV

25

K

KNaClO^)

25

l

3.13

fe ,qh

70K

l 3.14

fe

73K

2.98

qh

54A

l

2.96

qh

l

l

l

C o r r e c t e d from 20 ΔΗι from 71Ac.

using

54S

2.97

qh

l 2.97 K l 2.95

qh qh

64F

Kl 2.95 Kl 2 . 9 3

qh

65C

K

56A 58A

KNaClOi,)

25

KNaClOt,)

25

KNaC10 4 )

25

KNaClO^)

25

K

fe5qh

70K

KNaClOit)

25

K

qh

70W

fe ,qh

71A

fe

73K

l

2.98

fe,H

KNaClOi,)

25

l 2.95 Kl 2.95

KNaClOt,)

25

Kl 3.00

KNaCl)

25

Kl 2.89

fe,H

KNaCl)

25

Kl 2 . 8 4

fe

O^NaClO^)

25

K

O.öCNaClO^)

25

K

Molal u n i t s .

69M

Low v a l u e s (cf. KNaClO^)) may be due t o medium e f f e c t . 69M in molal u n i t s .

69M 74K/771

2.92

fe

69A

l 2.92

fe

73K

2.91

qh

43B

l 2.92

fe

73B

l

0.53(NaN0 3 )

25

K

0.5(NaN0 3 )

25

K

0.5(NaN0 3 )

25

K

l

2.88

fe

0 corr

25

K

l

3.17

Pb,H

47B

+ 0

25

K

l 3.18

ccn

63E

l

Molal u n i t s .

74S

63Ea/6 3Eb

+ 0

25

Kl 3 . 2 1

-* 0

25

K

l

3.21

fe,gl

+ 0

25

K

l

3.17

fe ,qh

0 corr

25

K

i

3.15

fe,gl

+ 0

25

K

l

3.16

fe

73K

0 corr

25

K

i

3.17

fe,qh

73Ka

con O r i g i n a l e x t r a p o l a t i o n (68V) r e j e c t e d ( c r i t i c i s e d 71P).

68V/7IP 69B+70Be

C o r r e c t e d from 20 ΔΗχ from 73V.

using

72C

(Continued)

19

The Data Tables

20

Temp.

Medium

HYDROGEN

H

Log K

Ref.

Remarks

Method

(cont. )

TENTATIVE fe,qh

70K

K 2 1.08

qh

63C

K 2 0.86

qh

64F

^CNaClOt,)

25

SCNaClO^)

25

SCNaCKV SCNaClO^)

25 25

K 2 0.94

fe,qh

3(KC1)

25

Kx 3.31; K 2 0.73

qh

2(NaC10 i+ )

25

K2 0 . 8 4

fe,qh

70K

KNaClO^)

25

K2 0.59

qh

54A

KNaClO^)

25

K2 0.71

qh

KNaClO^)

25

K2 0.50

qh

Kx 3 . 5 4 ; K2 1.05

70K Ki n o t Recommended b e c a u s e of p o s s i b l e medium e f f e c t s .

Corrected from 20 |

using ΔΗ 2 from 71Ac.

70N

54S 56A 58A

KNaClO^)

25

K2 0.44

KNaClOi*)

25

K2 0.58

qh qh

64F

KNaC10 4 )

25

K2 0.59

qh

65C

KNaClO^)

25

K2 0.86

fe,H

KNaClO^)

25

K2 0.73

fe,qh

KNaN0 3 )

25

Ki 2.90; K2 0 77

fe

0.53(KN03)

25

Ki 2.94; K 2 0 57 2.82; K 2 0 59

qh

Molal units.

69M 70K

Unusual KQ values (of. KNaClOit)) may be due to medium effect.

68S

42B 42B

0.53(NHi4N03)

25

0.5(NHUN03)

25

0.5(Na,HCl(V

25

0.53(NaN03)

25

Ki 2.75 K2 0.57

qh

0.5(NaN03)

25

K2 0.40

fe

0.3(NH^0 3 )

25

Ki 2.87

fe

69B

0.2(Na,HC10 4 )

25

Ka 2 . 9 3

fe,gl

68V

O.KNajHClOi^)

25

Ki 3.03

fe,gl

68V

0.1(ΝΗ^Ν0 3 )

25

Κα 2.94

fe

69B

0.08(NaN0q)

25

Kx 2 . 9 5 ; K2 0.56

fe

O.OSCNa^HClO^)

25

Kx 3.04

fe,gl

0.05(NaN0 3 )

25

K2 2.97

fe

0.01(ΝΗ^Ν03)

25

Kx 3.08

fe

2.84

qh

i

fe fe,gl

y

Low Ki values (cf. 0.5 (NaClOit)) may be due to medium effects.

69B 68V

43B Molal units.

Molal u n i t s .

74S

74G 68V

Molal u n i t s ; K2 r e j e c t e d .

74G

69B+70Be (Continued)

21

Stability Constants

Temp.

Medium

HYDROGEN TENTATIVE

H

Log K

Method

Remarks

Ref.

(cont.)

(cont.)

0 corr

25

K 2 0.59

Pb,H

47B

0 corr

25

K 2 0.53

con

63E

+ 0

25

K 2 0.70

fe

69B

0 corr

25

K 2 0.60

fe,qh

73Ka

2(HC101+)

25

Ka 2.80

fe,gl

KNaCl)

25

K 2 0.98

fe,H

KNaCl)

25

K 2 0.50

fe

0 corr

22(?)

K, 0.43 a

fe,gl

Kd ( 2 H F ^ ( H F ) 2 ) ; insufficient supporting evidence.

71Wa

0 corr

25

Ki 3.23

fe

Value at variance with other work; criticised 73Ka.

71P

DOUBTFUL

Insufficient exptl. detail. No allowance for liquid junction potentials. Very poor agreement. 69M in molal units.

71B

69M 771

REJECTED

05D, 25A5 25Aa, 32F5 37R (I var); 51D (method?, T?; criticised 58A) ; 67H (criticised 68Sb), 74G (K2 value different from all other studies), 70Aa (very poor estimations from literature values), 71Wa (T?, 0 corr procedure unclear). COMMENTS

Ki (HF) values well established over wide range of ionic strengths. Note minimum in plot of log Ki vs. I (70K). Variation in K 2 (HF2) probably due to low concentration in solution relative to HF concentration (IIP, 71Wa). K values contained in 54C/56C although widely cited in literature are not listed because experimental data from which they were obtained have apparently not been published. K^ values (1 = 0 corr, T = 25) have also been reported in D 2 0 (73Ka). More work is required at high ionic strengths and on medium effects particularly in the presence of HCIO^.

SODIUM (I)

Na

DOUBTFUL

KNaCl)

25

K^O.79

fe,calc.

(NaF)

25

Ki-0.27

fe,calc.

COMMENTS

Ion pairing probably occurs but data equivocal (72D).

Molal units

70Bc 71R

The Data Tables

22

Temp.

Medium

Log K

POTASSIUM ( I )

Method

Remarks

Ref.

K

COMMENTS

P o s s i b i l i t y of i o n - p a i r i n g h a s been s u g g e s t e d ( 6 6 S , 71R) b u t n o q u a n t i t a t i v e l o g K have been r e p o r t e d .

BERYLLIUM ( I I )

Be

values

2+

TENTATIVE

2(HC1(V

20

KÏ 1 . 9 9 ; K2 1 . 1 2 ;

dis

61H

κ | 0.38; HNaCKV

25

K* 2 . 0 6 ; K* 0 . 8 8 ;

fe,H

Molal u n i t s .

69M

fe ,H

Molal u n i t s .

69M

4-0.12; κ£-1Λ9 KNaCl)

25

K* 2 . 0 1 ; K* 0 . 8 7 ; K3-O.IO; Κ 4 - Ι Λ 6

0.5(ΝΗ 4 010 4 )

25

Κχ 1 . 8 0 ; κ£ 0 . 7 0 ;

red,qh

65B

K 3 - O . i l ; K4-O.6M·

REJECTED

49T, 60T, 61Ta ( I v a r . ) ; 51K ( I v a r , T ? ) ; 66Pc ( T ? ) ; 68F ( I v a r , i n a d e q u a t e m e t h o d ) ; 70H ( u n r e l i a b l e m e t h o d ) . COMMENTS

Unpublished data also available (I = 0.5, T = 25) in 52Y/55Y. Outer sphere complex (68B), and polymerization at high Be 2 + and F" concentrations (68F) suggested.

MAGNESIUM (II)

Mg

2+

RECOMMENDED

KNaClOt,)

25

Ki 1.32

25

Ki 1.38

fe fe

68T

l(NaCl04)

71Ba

KNaN0 3 )

25

Kl 1.30

fe

69G

l(NaN03)

25

Ki 1.32

fe

71C

0.5(NaCKV

25

Kl 1.30

red

54C

O.b(UaClO^)

25

Kl 1.32

fe

69A

O.SWaClO^)

25

Ki 1.33

fe

Corrected from 16° using ΔΗχ from 68T.

70Ba (Continued)

23

Stability Constants

Temp,

Medium

Method

Log K

Remarks

Ref.

Mg 2+ ( c o n t . )

MAGEŒSIUM ( I I ) TENTATIVE KNaCl)

25

fe

Kx 1.27

Value n o t Recommended b e c a u s e of p o s s i b l e medium e f f e c t s . Data a l s o r e p o r t e d at I ■ 0 . 1 , 0 . 4 , 0.7.

70E

REJECTED 70S ( d a t a and c a l c u l a t i o n s

inadequate).

2+ Ca

CALCIUM ( I I ) RECOMMENDED KNaClOit)

25

Κλ 0 . 6 3

fe

68T

KNaCHV

25

Kx 0 . 5 3

fe

71Ba

KNaCl)

25

Kx 0.56

fe

KNaN0 3 )

25

Κχ 0 . 5 7

fe

0.5(Να0104)

25

Κχ 0.70

fe

TENTATIVE Values not Recommended because of possible medium effects.

70E 71C

69A

REJECTED 54C (criticised 71Ba); 70S (data and calculations inadequate). COMMENTS NIo medium e f f e c t s a p p a r e n t in d a t a a t I = 1 b u t c o n f i r m a t o r y s t u d i e s r e q u i r e d . 70E a l s o r e p o r t e d a t I = 0 . 4 , 0 . 7 .

STRONTIUM ( I I )

Sr

Data in

2+

RECOMMENDED KNaClOi,)

25

Kx 0 . 1 5

fe

68T

KNaClCV

25

Kx 0 . 1 1

fe

71Ba

(Continued)

24

The Data Tables

Medium

Temp.

Log K

STRONTIUM ( I I )

Sr

2+

Method

Remarks

Ref.

(cont.)

TENTATIVE KNaN0 3 )

25

BARIUM (II)

Ki-0.03

fe

Value riot Recommended b e c a u s e of p o s s i b l e medium effects.

71C

2+ Ba'

RECOMMENDED

KNaClCV

25

Ki-0.22

fe

68T

KNaClO^)

25

Κχ-Ο.ΐδ

fe

71Ba

25

Ki-0.38

fe

TENTATIVE KNaN0 3 )

Value not Recommended because of possible medium effects.

71C

Ki(H ) 2 . 9 1

59K

+

69A

COMMENTS

Very weak conplex hard to determine precisely.

SCANDIUM (III)

Sc

3+

RECOMMENDED

O.öCNaClO^)

25

Ki 6.19

red

0.5(NaC10 4 )

25

Kl 6.22

fe

0.5(NaCl(V

25

K2 6.16

dis

25

Κ2 5 . 2 8 ; Κ3 4 . 0 8 ;

red

K!(H+)2.91

59K

Ki(H+)2.9l

69A

K!(H )2.91

69Aa

TENTATIVE 0.5(NaCl(V

2.85

O.SCNaClO^)

25

Κ2 Κ2 5 . 1 1 ; Κ3 3.90

fe

O.ôCNaClOt,)

25

Κ2 5 . 2 8 ; Κ3 4 . 0 2 ;

dis

Κ2

3.03

69Aa

25

Stability Constants Medium

Temp»

Log K

YTTRIUM ( I I I )

Y

Method

Remarks

Ref,

3+

RECOMMENDED

0.5(NaCl(V

25

Ki 3.88

red

Κχ(Η ) 2 . 9 4 . +

59S

0.5(NaC10h)

25

Ki 3 . 9 1

red

K!(H )2.91.

61P

0.5(NaCl(V

25

Ki 3 . 9 1

fe

K!(H+)2.91.

69A

+

25

Ki 3.89

dis

Ka(H )2.91.

69Aa

l(NaCl(\)

25

Ki 3.60

red

Κχ(Η ) 2 . 9 7 .

67W

O.SCNaClCV

25

K2 3 . 2 ; K3 3.2

red

Κχ(Η ) 2 . 9 1 .

6 IP

0.5(NaCl(V TENTATIVE

O.ôCNaClOi,)

25

K2 3.25

fe

O.ôtNaClO^)

25

K2 3 . 2 2 ; K3 3.2

dis

25

Ki* 3.92

red

+

Κχ(Η )2.91.

69A 69Aa

DOUBTFUL 0.b(NaClOk)

Converted from Κχ using Κχ(Η+) 2.92.

61P

COMMENTS

Ki+ difficult to detect because of precipitation of YF 3 (61P). K 2 and K 3 required before data can be Recommended.

LANTHANUM

(III)

La

More independent studies of

3+

RECOMMENDED

0.5(NaCl(V

25

Κχ 2 . 6 8

red

O^tNaCKV

25

Κχ 2.69

dis

KNaClOij)

25

Κχ 2.67

red

O.SCNaClO^)

25

K2 2.49 3

Κχ(Η ) 2 . 9 1 .

57K 70A

TENTATIVE

CERIUM ( I I I )

^3

2.68

K!(H ) 2 . 9 7 .

dis

67W 70A

Ce 3+

RECOMMENDED

O.SCNaClCV

25

Κχ 3.12

red

O.S(Na£10k)

24-5

Kx 3.15

dis

csos—c

Converted from Κχ using Κχ(Η+)2.92.

57K 67La (continued)

The Data Tables

26

Medium

Temp.

Log K

Method

Remarks

Ref.

3+ Ce (cent.)

CERIUM ( I I I ) TENTATIVE KNaCKV

25

Ki 2 . 8 1

red

Κχ(Η ) 2 . 9 7 .

67W

KNaClCV

25

Kx 2.72

dis

0.5(NaCl04)

25

K2 2 . 8 1

dis

25

Kx 3.68

cix

Reliability criticised.

red

Κ Χ (Η )2.97 ,

67W

red

K X (H )2.97.

67W

67La

DOUBTFUL 0.5(NaCl0 4 )

self-

5 IM

3+ Pr

PRASEODYMIUM (III) TENTATIVE KNaClO^)

25

Κλ 3.01

NEODYMIUM (III)

3+ Nd'

TENTATIVE KNaClO^)

25

3.09

PROMETHIUM (III)

3+ Pm'

TENTATIVE 25

KNaClO^)

Kx 3.16

SAMARIUM ( I I I )

dis

67W

3+ Sm

TENTATIVE KNaClOi,)

25

Kx 3.12

red

Κχ(Η ) 2 . 9 7 .

67W

Stability Constants

Medium

Log ϋ ^

Temp.

27

Method

Remarks

Ref.

3+ Eu'

EUROPIUM ( I I I ) TENTATIVE

Ki(H + ) 2 . 9 7 .

KNaCKV

25

Ki 3.19

KNaClO^)

25

Ki 3.20

dis

KNaClOi,)

25

Ki 3.33

dis

0.5(Νό£10ι*)

24-25

Ki 3 . 3 9 ; K2 3.10

dis,gl

O.SCNaClO^)

25

Ki 3.40

fe

Ki(H + ) 2 . 9 1 .

69A

red

Ki(H ) 2 . 9 1 .

57K

GADOLINIUM ( I I I )

red

67W 67W

Ki(H + )

2.94(7).

75C 66L

Gd'3+

RECOMMENDED 0.5(NaC10 i+ )

25

Ki 3.38

O.SCNaClC^)

25

Ki 3.36

fe

Ki(H ) 2 . 9 1 .

69A

KNaClOit)

25

Ki

red

Ki(H ) 2 . 9 7

67W

0.5(Ν<£1(ν

24-25

Ki 3 . 4 3 ; K2 3.28

dis

O.StNaClOi,)

25

K2 3.26

fe

Ki(H + )

^20

Κλ 4 . 0 4

nmr

Ki(H + )? C a l c u l a t i o n method approximate.

+

TENTATIVE 3.31

67La 2.91

69A

DOUBTFUL O.KNaCKV

6 7 Va

COMMENTS

Ki value in 67La not Recommended because T not constant.

TERBIUM (III)

3+ Tb'

TENTATIVE KNaCKV

25

Kx 3.42

red

ΚΧ(Η ) 2 . 9 7 .

67W

The Data Tables

28

Temp.

Medium

Log K

Remarks

Method

Ref.

3+ Dy'

DYSPROSIUM (III) TENTATIVE KNaCKV

25

iq

3.46

red

KX(H ) 2 . 9 7 ·

67W

O.ôtNaClO^)

25

Kx 3.56

red

Converted from K* using Κχ(Η+) 2.92.

681

red

Κχ(Η ) 2.97,

67W

Κχ(Η ) 2.97.

67W

HOLMIUM (III)

Ho

3+

TENTATIVE KNaClO^)

25

Kx 3.52

ERBIUM (III)

Er

3+

TENTATIVE KNaClCV

25

Ki 3.54

red

KNaClOit)

25

Kx 3.56

dis

0.5(NaC3J\)

25

Κχ 3.53

red

Converted from K* u s i n g Κχ(Η + ) 2 . 9 2 .

681

KX(H ) 2 . 9 7 .

67W

67W

3+ Ttn

THULIUM ( I I I ) TENTATIVE KNaClO^)

25

Κχ 3.56

red

KNaClOij)

25

Κχ 3.57

dis

YTTERBUIM ( I I I )

Yb

67W

3+

TENTATIVE KNaClOij)

25

Kx 3.58

red

KNaClO^)

25

Kx 3.60

dis

O.öiNaClO^)

25

Κχ 3.57

red

K X (H + ) 2.97 .

67W 67W

MH*)

2.91.

681

29

Stability Constants

Log K

Temp.

Medium

LUTETIUM ( I I I )

Method

Remarks

Ref.

3+ Lu

TENTATIVE KNaClOi»)

25

Κλ 3 . 6 1

red

Κχ(Η ) 2 . 9 7 .

67W

O-ôCNaClCV

25

Kx 3.47

red

Ki(H ) 2 . 9 1 .

681

ACTINIUM ( I I I )

3+ Ac

TENTATIVE 0.5(NaC104)

25

Kx 2 . 6 9 ; K2 2 . 4 9 i

70A

dis

K3 2 . 6 0

TiO'.2+

TITANIUM (IV) DOUBTFUL 25

SCNaClOi*)

K i > 5 . 3 8 ; K2 4 . 3 2 ;

qh

Κχ (H ) 3 . 2 7 ·

60C

cix,aix

Κχ (Η + ) 3 . 2 7 .

66N

K3 3 . 9 6 ; K4 3.72 0.2CHC1)

25

Kx 6 . 6 5 ; K2 5 . 0 9 ? K3 4 . 5 8 ; K4 4 . 0 6

REJECTED 67Pa ( i n s u f f i c i e n t experimental d e t a i l ) . COMMENTS Species have not been sufficiently characterized.

ZIROCNIUM (IV)

Zr4+

DOUBTFUL 4(Η010^)

20

K* 5.96; K2 4.54

cix

63A

HCHCKV

20

Kj 5.88; K2 4.36;

d i s ,red

67Nb+69Na

K3 3.00; κ£ 2.28; *

ΐ'ί

K5 1.53; K6 0.3 (Continued)

The Data Tables

30

Temp.

Medium

ZIRCONIUM (IV) DOUBTFUL

Method

Log K

Remarks

Ref.

Zr 4 + (cent.)

(oont. ) dis

149c

K* 5.81; K*2 3.57

cix

69Kc

25

K'I 5.79; K | 3.59

cix

69Kc

KHCIO^)

25

KÎ 5.32; K2 3.79

cix

69Kc

KHNO3)

25

K* 5.42;

κ£ 4.23

cix

69Kc

2(HC104)

25

2(Ηα(ν

25

2(HN03)

K* 5.80; ¥$ 4.32 ; K3 2.83

REJECTED

62B (pH too high to suppress Zr

hydrolysis), 66B (insufficient experimental detail).

COMMENTS

Insufficient independent data at comparable ionic strengths preclude higher classification. The extent of Zr4"1" hydrolysis in the presence of fluoride has not usually received sufficient attention.

HAINIUM (IV)

.4+

Hf

DOUBTFUL

4(Ηαθ 4 )

20

Ki 5.52; K 2 4.04;

67N

red,dis

K3 3.04; KÎ 2.20; Kg 1.7;

Kg 0.5

4(Η0104)

20

Κϊ 5.51; K2 3.7

cix

^(Να,ΗΟΙΟ^)

25

Ki 5.50

fe

Corrected for hydrolysis.

73N

3(Να,Η0104)

25

KÎ 4.09; K2 3.67;

dis,qh

Criticised 67N.

63V

HfFs negligible,

64V

67Na

Kg 2.97; KjJ 2.77; Kg 1.55; Kg 2.54 3(^10^)

25

Kï 4.16; K2 3.63; Kg 2.21;

4 1.94;

3g 12.62 2(HC1(V

27

KÎ 4.62

dis

65Da

REJECTED

67P ( T ? ) ; 75Va (K n e s t i m a t e d a t 1=0, T=25; b u t o n l y e m p i r i c a l and p o o r c h o i c e Κχ(Η + ) u s e d ) . (Continued)

31

Stability Constants

Medium

Temp.

Log i^

Method

Remarks

Ref.

Hf 4 * (cont.)

HAFNIUM (IV) COMMENTS

Recent study (73N) indicates hydrolysis of the metal ion is not as extensive as previously believed in the acidity range 0.5 M < [H+] < 4 M. However, confirmatory studies are required before a higher classification can be given. The large number of complexes also reduces the accuracy of the higher order constants.

4+

THORIUM (IV)

Th

RECOMMENDED

4 4.65;

O.StNaClOi,)

25

0.5(NaC10 4 )

25

KI

UQiCHV

20

K

4(HC10 4 )

K

red

49D

4 . 7 0 ; K2 2.76

dis

51Z

? 2.81

TENTATIVE fe

69N

20

4 . 6 8 ; K* 2.97 Ki 4.62

dis

69N

3(Ν ά ,Η010 4 )

25

KÎ 4 . 5 2 ;

fe

7 IK

2(HC104)

25

K, 4.43

dis

75P

I

K* 2.66

KNajHClCV

25

Kx 4 . 5 8 ; K2 2.76

fe

KHClOi,)

25

KÏ 4.49

dis

KHClOit)

25

Ki 4 . 5 1

fe

Values not Recommended because of possible medium effects.

0.5(HX)

25

Kx 4 . 6 3 ; K2 2.86

dis

Variable anion.

50D

0.01(ΝΗ4Ν03)

25

Kx 5.00; K 2 3.28

fe

Data converted from K^ using K!(H+) 3.08.

70Be

0 corr

25

Kx 5 . 2 7 ; K2 3.45

fe

Data c o n v e r t e d from 1^ u s i n g Κ 2 (Η + ) 3 . 1 7 .

70Be

3(^^010^)

25

K3 1.6

fe

7 IK

l(Na,HC10 4 )

25

K3

1.41

fe

7 IK

O.ötNaCHV

25

K3

1.51

red

49D

0.01(ΝΗ^Ν03)

25

K 3 1.49; K^ 0.20

fe

Data converted from 1^ using Κχ(Η+) 3.08.

70Be

0 corr

25

K 3 1.58; K^ 0.19

fe

Data converted from K n using K!(H+) 3.17.

70Be

7 IK 7C-p

75C

DOUBTFUL

(Continued)

32

The Data Tables

Temp.

Medium

Log i^

Method

Remarks

Ref.

Th 4 * (cont.)

THORIUM (IV) REJECTED

59T, 59Ta (criticised in 71K; insufficient experimental detail). COMMENTS D a t a g i v e n as l o g K^ v a l u e s t o f a c i l i t a t e c o m p a r i s o n . E x t e n s i v e c a l c u l a t i o n s (71K) i n d i c a t e t h e v a l u e of K3 i s d o u b t f u l . P r e c i p i t a t i o n o f ThF^ makes p r e c i s e d e t e r m i n a t i o n of Ki+ d i f f i c u l t .

VQ 2 *

VANADIUM (IV) TENTATIVE KNaCKV

25

KNaCKV

25

Kx 3 . 3 2 ; K2 2 . 1 8 ; K3

qh

1.71

Kx 3 . 3 7 ; K2 2 . 3 6 ;

Converted from 20 ΔΙ^ from 71Ac.

using

fe ,qh

58A 7]A

K3 1.56 DOUBTFUL KNaCKV

25

Kk

0.32

KNaCKV

25

Kh 0.79

qh

Converted from 20 ΔΗ^ from 71Ac.

using

f e ,qh

58A 71A

COMMENTS S l i g h t l y d i f f e r e n t r e s u l t s have been o b t a i n e d by r e c a l c u l a t i o n (61R) o f d a t a i n 58A. F o u r t h complex (V0F^~) d i f f i c u l t t o d e t e r m i n e p r e c i s e l y b e c a u s e of p r e c i p i t a t i o n . I n d e p e n d e n t s t u d i e s r e q u i r e d b e f o r e a h i g h e r c l a s s i f i c a t i o n can be a c c o r d e d .

VANADIUM (V)

V0 o

TENTATIVE KNaCKV

20

Kx 3 . 0 5 ; K2 2 . 5 5 ;

sp

691

K3 1.26 DOUBTFUL KNaCKV

20

Kx 3 . 6 7 ; K2 2.65

sp

KNaCKV

20

Kh ^ 0 . 2

sp

Data less precise than the later work (691).

671 691

33

Stability Constants

Medium

Temp. NIOBIUM (V)

Log K

Method

Remarks

Ref.

Nb5+

DOUBTFUL 0.5(Na,HCl(V

25

K 8 3.08; K 9 4.0

fe

72L

COMMENTS "Doubtful" classification used because of insufficient characterization of complexes in the presence of oxo and hydroxo species (72L, 70N).

Ta5+

TANTALUM (V) DOUBTFUL 3(Η0104)

25

Κι* 5.86; K 5 4.91;

dis

K 8 , K 9 rejected.

65V

K 6 4.90; K 7 4.48 KH,NaC10 4 )

25

Κ 5 4.8; Κ 6 3.6;

aix,qh

KNaClO^)

25

Κ6 3.75; Κ 7 3.10

qh

0.25(ΗΝ03)

18

Κβ 3.16

sol,cix, dis

62V

Κ 7 3.3 K 8 rejected.

66B 71N

REJECTED 72Ba (species doubtful). COMMENTS Higher order complexes (K 8 , Kg), have not been sufficiently characterized and Y^ have therefore been rejected. Lower order complexes are subject to severe hydrolysis (71N) and have also been rejected (72Ba).

PBOTACriNIUM (IV)

Pa4+

DOUBTFUL 301010^)

25

Κχ 4.73; κ£ 3.53

dis

66Ga

34

The Data Tables

Medium

Temp.

Log Kn

Method

Ref.

Remarks

5+

PROTACTINIUM ( V )

Pa

REJECTED

66B, 67K ( d o u b t f u l s p e c i e s , s e e 66Ga).

Cr'3+

CHROMIUM ( I I I ) DOUBTFUL

KLiClOu)

77

Kx 1.32

cix

65S

0.5(NaClO l+ )

25

Kj 1 . 4 2 ; Κ^ 0 . 4 0 ;

sp

52W

Κ3-ΟΛ6 COMMENTS

Conplexes a r e n o t s u f f i c i e n t l y w e l l c h a r a c t e r i z e d t o a l l o w h i g h e r

URANIUM (IV)

classification.

UA+

TENTATIVE

5.54;

25

4

4CHC10,,)

20

1.96

4(Na,HCl0 4 )

25

2(^10^)

20

KÎ 4 . 3 5 ;

2(Η010 4 )

20

κί

l(Na,HCl)

25

KÎ 4 . 5 0 ;

HHC1CV

25

KÎ 4.82

IKHCICV

20

^(HjNaClO,,)

? 3.18

fe

69N

Kl 5 . 3 7 ; *2 2.92

red

69Ga

4

fe

69N

red

69Ga

K

DOUBTFUL

K3 1.16 K2 2.46

2.6

nmr

Converted from B^ using K X (H + ) 2.80 (71B).

hyp

4 2.94

fe dis

63Va 63Va

No allowance for chloride complexing.

74K 75C

REJECTED

60 Sa (criticised in 69Ga) ; 62L, 66V (I var).

(Continued)

35

Stability Constants

Temp.

Medium

URANIUM ( I V )

Log Kn U4+

Method

Ref.

Remarks

(cont.)

COMMENTS D a t a c o n v e r t e d t o Kn t o f a c i l i t a t e c o m p a r i s o n . H i g h e r o r d e r complexes d i f f i c u l t t o measure b e c a u s e of p r e c i p i t a t i o n of U F . . I n d e p e n d e n t s t u d i e s r e q u i r e d b e f o r e h i g h e r c l a s s i f i c a t i o n can be a c c o r d e d .

URANI UM ( V I )

2+ UOg

TENTATIVE 4(H,NaCl(V

25

κ[

1.48

red

69Ga

2(NaC10l+)

25

Kx

1.42

dis

54D

2(Η010 4 )

25

KÎ 1.56

dis

76P

KNaClO^)

25

Κχ

1.43

dis

1(HC1(\)

25

Kj

1.52

cix

KNaClO^)

25

K]_ 1 . 5 7 ; K2 0.46

fe

Converted from 1^ u s i n g Κχ(Η + ) 2 . 9 7 .

73A

KNaClCV

20

Κχ 1 . 5 7 ; K2 0 . 3 7

qh

Converted from l·^ u s i n g K!(H + ) 2 . 9 7 .

56A

KNaCl)

25

K* 1 . 5 5 ; K2 0 . 5 4

fe

Converted from K^ u s i n g Κλ(Ε+) 2.84 ( 7 7 1 ) . No allowance f o r c h l o r i d e complexing.

771

0.2(Η01(ν

25

Κχ 1.57

cix

KNaCKV

20

K3-O.4O

qh

Converted from K^ u s i n g Κχ(Η + ) 2 . 9 7 .

56A

KNaClO^)

25

K3-O.52

fe

Converted from 1^ u s i n g Κχ(Η + ) 2 . 9 7 .

71A

KNaCl)

25

K3-O.78; Kil-1.86

fe

Converted from l·^ u s i n g Kj(H ) 2.84 ( 7 7 1 ) . No allowance f o r c h l o r i d e complexing.

771

0.2(^10^)

25

K2 0 . 0 7 ; K3 0 . 0 3

cix

25

K,

dis

Values a l s o r e p o r t e d 1=0.5, 0.25, 0.05.

54D

at

6 8K

68K

DOUBTFUL

1.71

6 8K E x t r a p o l a t i o n procedure u n c l e a r . Data e r r a t i c .

54D

REJECTED 50M, 51B, 54B ( I v a r ) ; 61C ( i n s u f f i c i e n t e x p e r i m e n t a l d e t a i l s ) ; 61K, 61T ( I ? ) 74B ( I v a r , inadequate method, values a t variance with o t h e r d e t e r m i n a t i o n s ) .

(Continued)

The Data Tables

36

Medium

Temp, URANIUM ( V I )

Log Έ^

2+

UOg

Method

Remarks

Ref.

(cont.)

COMMENTS

More independent studies under i d e n t i c a l conditions required before higher c l a s s i f i c a t i o n can be accorded. Evidence for polynuclear comglexes a t high concentrations in U02F2 solution (52J, 54J, 74B). Data converted t o K" t o f a c i l i t a t e comparison.

NEPTUNIUM ( I V ) Np 4+ TENTATIVE HCHClOi,)

20

66A

20

A 4.82; A 2.75 2.69; K3 2.34; A 1.30

cix

4(HC104)

aix

66A

2(Η010ι>)

25 25

Â

Â

2.89

cix dis

69K

2{¥C10^)

A 4.56 4.60;

2(HC1(V

25

dis

25

 A 4.70; 4.11

2.68

2(HNf03)

KHCIO^)

25

KHCIO^)

25

1(HN03)

25

Ki

A 4.70 4.60 AKi 4.23

cix

Considerable variation in reported values.

75P

No allowance for nitrate complexing.

69Ka

76Bb

cix

69K

dis cix

75C No allowance for nitrate complexing.

69Ka

COMMENTS Further independent studies at coiiparable ionic strengths required before higher classification can be accorded.

NEPTUNIUM ( V )

NpOg

DOUBTFUL 2(NaC10 l+ )

25

Kx 0.99

COMMENTS

E a r l i e r work (70Aa) i n d i c a t i n g no complex formation probably incorrect (78V, 78P) but further characterization required before higher c l a s s i f i c a t i o n can be accorded.

78V

37

Stability Constants

Medium

Temp.

NEPTUNIUM ( V I )

^9

*n

Method

Remarks

Ref.

NpO!2 +

DOUBTFUL

2.1KHCKV

25

Κ'ι 2 . 1 1

cix

68K

2(HC1(V

25

KÏ 1.12

dis

76P

l.OUCHClO^)

25

Ki 2 . 2 0

cix

68K

KHClOi»)

21

Ki 0 . 9 3 ; K2 0 . 1 8

dis

68A

0.5(Η<:ΐ(\)

25

Κχ 1 . 1 1 ; K2 0 . 0 3

red

■* 0

25

Kx 1 . 4 1 ; K2 0 . 0 4

red

Data a l s o r e p o r t e d a t I = 0.4, 0 . 3 , 0.2, 0.1 . Poor c h o i c e of ^ ( H F ^ makes ί^ values very doubtful.

70Aa

COMMENTS

F u r t h e r work n e c e s s a r y t o r e c o n c i l e d i f f e r i n g v a l u e s . U n p u b l i s h e d d a t a (2(NaC10 I t ), 2 5 ° ) q u o t e d i n 78P a l s o a v a i l a b l e i n n o t v e r y good agreement w i t h above d a t a .

PLUTONIUM ( I V )

Pu

4+

DOUBTFUL

2(HN0 3 )

20

Ki 3.78

cix

No allowance for nitrate complexing.

69Kb

2(HC10 if )

20

ΚΪ 4 . 4 5

cix

69Kb

2CHCKV

25

KÏ 4 . 6 4 ; K2 2.97

dis

76B

KHCICV

25

Κχ 4 . 2 0

cix

1(HN0 3 )

20

KÏ 4 . 0 4

cix

69Kb No allowance for nitrate complexing.

69Kb

REJECTED 72P (criticised 76B). COMMENTS

U n p u b l i s h e d d a t a (C.K. McLane, N a t . N u c l e a r Energy S e r . , 1949 IV-14B, 414) a l s o a v a i l a b l e ( I = 1 ( H N 0 3 ) , T=25) i n p o o r agreement w i t h t h e above d a t a b u t p r o b a b l y i n c o r r e c t . Complexes n o t s u f f i c i e n t l y w e l l c h a r a c t e r i z e d t o p e r m i t h i g h e r c l a s s i f i c a t i o n . More work i s needed p a r t i c u l a r l y on t h e e f f e c t s o f " h o l d i n g o x i d a n t s " (76B) and pH e f f e c t s .

The Data Tables

38 Medium

Temp.

Log K

PLUTONIUM ( V I )

PuOp

Method

Remarks

Ref.

+

DOUBTFUL

2CHCKV)

25

KÏ 2 . 0 0 ; K*2 1 . 8 2 ;

2(^10^)

25

K* 1.12

KHCHV

25

Kj 2 . 1 1 ; K2 2.OU;

cix

68K

Kg 1 . 7 0 ; K* 1.16 76P

K3 1 . 9 3 ; ]ζ

cix

68K

0.22

COMMENTS

Further work required t o reconcile differing values. pH dependence also require i n v e s t i g a t i o n .

AMERICIUM ( I I I )

Use of "holding oxidants" (76P) and

Am3+

DOUBTFUL

1.0(NaC104)

25

0.5(ΝΟ£1(\)

25

ddis is

Κχ 2.49 2.49 Κχ Kxx K

3.39; 3.39;

Κ3

2.89

Κ22 2.72; 2.72; K

Κχ(H+) 2.94(?).

dis dis

75C 69Aa

COMMENTS

Unpublished data (I = 0.1 (HCIO4), T = 23°) for K3 also available (54F) in poor agreement with above data. Note also abnormal dependence of Κχ on i o n i c s t r e n g t h . Further investigation required before higher c l a s s i f i c a t i o n can be accorded.

CURIUM ( I I I )

Cm 3+

DOUBTFUL

KNaClCV

25

Κχ 2 . 6 1

dis

O.StNaCKV

25

Κλ 3 . 3 4 ; K2 2 . 8 3 ;

dis

Κ Χ (Η + ) 2.94 (?) .

75C 69Aa

K3 2.90 COMMENTS

Unpublished data (I = 0.1 (HCIO4); T = 23°) also available (54F) in poor agreement with above data. Note also abnormal dependence of Kx on ionic strength. Further investigation required before higher classification can be accorded.

39

Stability Constants

Medium

Temp,

Log K

BERKELIUM ( I I I )

Bk

Method

Remarks

Ref.

3+

DOUBTFUL KNaClCV

25

Kx 2.89

dis

Κχ(Η + ) 2.94?

75C

COMMENTS Complex n o t s u f f i c i e n t l y

c h a r a c t e r i z e d t o allow h i g h e r

CALIFORNIUM ( I I I )

Cf

classification.

3+

DOUBTFUL KNaClOit)

25

Κχ 3.03

dis

Ki(H + )

2.94?

75C

COMMENTS Complex n o t s u f f i c i e n t l y

MANGANESE ( I I )

c h a r a c t e r i z e d t o allow higher

Mn

classification.

2+

TENTATIVE KNaCHM

25

Ki 0.79

H,qh

KNaClOij)

25

Κχ 0.62

fe

SCNaClO^)

25

Κχ 1.0

fe

See Comments b e l o w .

76K

KNaClOi»)

25

Κχ 1.0

pol

P r e c i s i o n lower t h a n above studies.

71Bc

Value may be high (72B).

65C 72B

DOUBTFUL

COMMENTS Outer sphere complex suggested (68M) but further confirmation required. Data in 76K not Tentative because insufficient experimental detail to assess possible influence of higher oxidation state species (of. 72B).

The Data Tables

40

Temp.

Medium

Log K

MANGANESE ( I I I )

Mn

Method

Remarks

Ref.

3+

TENTATIVE 6.KHC1CV

23

K* 2 . 7

sp

64Fa

6(HC10 4 )

25

KÏ 2 . 8 8

sp

69D

5.3(HCHV

25

Ki 2 Λ

sp

64Fa

2CHC1CV

25.2

Kj 2 . 5 1

sp

2(H 2 S0 4 )

25

03 5 . 1

oth

Coulometric method. No allowance for sulphate complexing.

fe

Value may be slightly high 72B due to Fe(III) contamination.

DOUBTFUL

IRON ( I I )

48T 72K

F e 2+

TENTATIVE

KNaCKV

25

Kx 0.83

REJECTED

A value of log 3 2 = 2.30 has been obtained by a kinetic method (67Wa). This contradicts the well known relative complexation of Fe(III) and Fe(II) used in the "ferri" method (42Ba, 49D) and is also contrary to chemical expectations (72B5 74H).

IRON (III)

Fe 3+

RECOMMENDED

KNaClCV

25

K x 5.19

red

Converted from Kx using Ki(H + ) 2.97.

67W

KNaClO^)

25

K x 5.15

fe

Converted from Kx using K!(H+) 2.97.

75J

O^CNaClOi,)

25

Κχ 5.20; K 2 3.94

red

49D

0.5(NaC^)

25

K x 5.17; K 2 3.92;

red

56C

K 3 2.91 0.5(NaCl(V

25

Κχ 5.16; K 2 3.91;

fe

K X (H ) 2.91.

69A

red

KX(H ) 2.91.

69A

K 3 2.93 O.öCNaCICV

25

Kx 5.19; K 2 3.93; K 3 2.93

O.SCNaClOO

25

Κχ 5.18

fe

Converted from Κχ using l( H + ) 2 ·92·

K

75J (Continued)

41

Stability Constants

Medium

Temp. IRON ( I l l )

Log K Fe

3+

itewarfcs

Method

Ref.

(cont. )

TENTATIVE 0.53(KN0 3 )

25

Κχ 5 . 1 5 ; K2 4 . 0 0

red

Ο.52(Η01Ο^)

25

ΚΊ 5 . 1 4 ; K

3.95

sp

Ο.δΐΗΟΙΟ^)

25

K. 5 . 1 7 ; K

3.95

red

0.5(Na,HC10i,)

25

Κχ 5 . 1 2 ; K2 4 . 0 1 ;

1

'

1

K

3

'

2

2

kin

3.19

Values n o t Recommended b e c a u s e of p o s s i b l e medium effects.

42Ba

Converted from 2 6 . 7 u s i n g ΔΗ from 56C. n Converted from 0 u s i n g ΔΗ n from 56C. Data n o t Recommended b e c a u s e of p o s s i b l e medium e f f e c t s .

61Y

53S

53Ha

DOUBTFUL KNaClO^)

25

Kj 5.06

fe

Κχ(Η ) 2.90 too low; Κχ a t v a r i a n c e w i t h above v a l u e s .

68Sa

0.5(NaC10O

25

K3 2.68

red

At v a r i a n c e w i t h above values.

49D

REJECTED 47Ba ( I ? , T ? ) , 57S (no e x p t l . d e t a i l s ) , 64B ( I ? ) , 76Ka ( T ? ) . COMMENTS U n p u b l i s h e d d a t a ( I = 0 . 5 , T = 25) a l s o a v a i l a b l e i n 52Y/55Y i n r e a s o n a b l e agreement w i t h 49D.

COBALT ( I I )

Co 2+

TENTATIVE 3(NaC10h)

25

Κχ 0 . 6 4

fe

76K

KNaClO^ )

25

Ki 0 . 4 0

fe

72B

fe

76K

NICKEL ( I I )

Ni2*

DOUBTFUL StNaClOt,)

25

Kx 0.76

KNaClOit)

20

Kj 0.66

qh

56Aa

KNaClOit)

25

iq

pol

71Bc

KNaClOit)

25

Κλ 0 . 3 4

fe

72B

0.5(NaN0 3 )

16

Ki 0 . 1 8

fe

70Ba

0Λ8

(Continued) CSOS

I)

The Data Tables

42 Medium

Temp. NICKEL ( I I )

Log K N i "2 +

Method

Remarks

Ref.

(cont.)

COMMENTS

D a t a i n NaClO^ do n o t j u s t i f y " T e n t a t i v e " c l a s s i f i c a t i o n b e c a u s e a l a r g e p e r c e n t a g e v a r i a t i o n i n t h e Kj v a l u e a t 1=1 i s o b s c u r e d by p r e s e n t a t i o n i n l o g K form.

COPPER ( I I )

Cu

2+

TENTATIVE

3(NaCl(V

25

Kx 1.06

fe

76K

KNaClCV

25

Kx 0 . 8 3

pol

63Ma

KNaClO^)

25

Κχ 0 . 8 4

fe

72B

KNaClO^)

30

Κλ 0 . 6 1

pol

69Bc

0.5(NaCl(V

25

Kx 0 . 7 1

red

58C

0.5(NaN0 3 )

25

Κλ 0 . 7 3

0.08(NaN0 3 )

25

Κχ 0 . 8 7

0.05(NaN0 3 )

25

Kj 0 . 9 3

KNaClO^)

20

Kx 0 . 9 5

qh

0.08(NaN0q)

25

K2-0.87

fe

73B

fe fe fe

Molal u n i t s .

74G

Molal u n i t s .

74G

Evidence f o r a r e a c t i o n between Cu 2 + and qh ( 6 9 P ) .

56Aa

DOUBTFUL

74G Existence of CuF2 (aq.) very doubtful. Molal units.

0.05(NaN03)

25

K2-0.08

fe

74G

COMMENTS

Values at I = 0.5 are in good agreement, but variation at other ionic strengths suggests more investigation is required before a recommended value can be given.

SILVER

(I)

Ag

TENTATIVE

KNaCKV

25

O.ötNaClOi,) 0.5(NaN0 3 )

Kj-0.32

Ag

52L

25

Ki-0.17

Ag

61C

16

Κι-ΟΛ

fe

70Ba

43

Stability Constants

Medium

Log Kn

Temp. ZINC

(II)

Zn

Method

Ref.

Remarks

2+

TENTATIVE 3(NaCl(V

25

Κχ 0 . 8 5

est

69Gb

3(NaCl(\)

25

Kx 0 . 8 8

fe

76K

2(NaClO l+ )

25

Κχ 0 . 8 5

pol

63Ma

KNaCKV

25

Κχ 0.79

qh

KNaClOi,)

25

Κχ 0 . 5 2

fe

72B

O.ôtNaClO^)

25

Κχ 0 . 7 4

red

58C

0 corr

25

Kx

1.14

emf

71Ca

1.0

C o r r e c t e d from 20 ΔΗχ from 69Gb.

using

56Aa

DOUBTFUL 70Bg

HNaClCV

25

Kx

pol

Non-rigorous

1(KN0 3 )

25

Κχ 0 . 9 8

pol

C o r r e c t e d from 30 ΔΗχ from 69Gb.

0.5(NaN0 3 )

25

Kx 0.49

fe

C o r r e c t e d from 16 u s i n g ΔΗ]_ from 58C.

70Ba

0.3(NaN0 3 )

25

Kx 0 . 9 2

pol

No allowance for nitrate complexing.

67V

calculation. using

69Bd

REJECTED 65Sb (at variance with all other determinations).

CADMIUM

(II)

Cd

2+

TENTATIVE 2(^010^)

25

Kj 0.81

pol

KNaClO^)

25

Κχ 0.72; K2-0.1

pol

C o r r e c t e d from 30 u s i n g ΔΙ^ from 66G.

69Bb

3(NaN0 3 )

25

Ki 0.46

fe

No allowance f o r n i t r a t e complexing.

76Ba

KNaCKV

30

Κλ 0 . 3 ; K 2 0 . 2 ;

dis

L i t t l e experimental d a t a ; CdF 3 u n l i k e l y .

65H

63Ma

DOUBTFUL

(Continued)

The Data Tables

44

Medium

Temp*

Remarks

Ref.

Cd2+ ( c e n t . )

CADMIUM ( I I ) DOUBTFUL

Method

Log K

(oontj

0.5(NaN03)

25

Kx 0.57

fe

Corrected from 30 using ΔΗ η from 66G. No allowance for nitrate compexing.

70Ba

0.05(NaN03)

16

Kx 1.11

fe

No allowance for nitrate complexing.

70Ba

COMMENTS

Unpublished data also available (I = 3 & 1 (NaClO^), T = 25°) in 43L, in reasonable agreement with the above studies.

MERCURY (II)

Hg

2+

COMMENTS

No published work available. Unpublished data (I = 0.5 (NaClO^), T = 25°) in 55P would seem to be reasonable (74H).

METHYL MERCURY (II)

CH3Hg

TENTATIVE 0.1(KN03)

20

gi

Κ Χ (Η + ) 2.85.

Ki 6.11; K2 4.96

qh

Converted from Kn Κχ(Η+) 2.97.

Ki 1.50

ALUMINIUM (III)

Al

65Sa

3+

TENTATIVE KNaClO^)

25

0.53(KN03)

25

Ki 6.13; K2 5.02;

qh,red

25

K 3 3.85 Ki 6.08; K2 4.93;

fe

Data also given at I = 0.3, 0.1, 0.01.

69B

25

K 3 3.69 Ki 6.14; K2 5.09;

fe,qh

K ^ H F ^ from 68V. Data also given at I = 0.2, 0.1, 0.05.

71Aa

0.5(NH4N03) 0.5(KN03)

K 3 3.93

using

71W

43Ba

(Continued)

45

Stability Constants

Temp.

Medium

Log Ί^

ALUMINIUM ( I I I ) TENTATIVE

Method

Remarks

Ref.

Al3+ (cont.)

(oont.)

+ 0

25

Κ2 6 . 9 8 ; K2 5,, 6 2 ;

fe

69B

+ 0

25

K3 4 . 0 5 Κ2 6 . 8 9 ; K2 5,. 3 5 ;

fe,qh

7IAa

qh,re<

43Ba

*3 3.68 DOUBTFUL

0.53(KN0 3 )

25

Κ2 2 . 7 4 ; K5 1.. 6 3 ; Κ2 0 . 4 7

0.5(ΝΗ 4 Ν0 3 )

25

^ 2.50

fe

69B

0.5(KN0 3 )

25

κ^ 3.68

fe,qh

71Aa

+ 0

25

K, 2 . 3 8

fe

69B

+ 0

25

K4 2.75

fe,qh

71Aa

REJECTED 49L, 57T, 59B, ( I v a r ) ; 50K ( T ? ) ; 64Ba ( T ? , I v a r ) ; 67Y, 70M, 74B ( I v a r , t e c h n i q u e u n s a t i s f a c t o r y , a t v a r i a n c e w i t h o t h e r w o r k ) . R e c a l c u l a t i o n s i n 59Kb a r e n o t c o n s i d e r e d satisfactory. COMMENTS

No Recommended d a t a ( a t I = 0 . 5 ) b e c a u s e Kg(HF n ) v a l u e s chosen f o r c a l c u l a t i o n s a r e n o t "Recommended" v a l u e s ( s e e u n d e r H*). S p a r i n g s o l u b i l i t y o f A1F 3 and t h e weakness of t h e h i g h e r o r d e r complexes makes l ^ ( A l F n ) f o r n > 4 d o u b t f u l w i t h o u t f u r t h e r i n v e s t i g a t i o n .

GALLIUM ( I I I )

Ga'3+

DOUBTFUL

KNaClCV

25

Kx 4 . 4 0 ; K2 3.80

qh

Converted from 1^ u s i n g K!(H + ) 2 . 9 7 .

71W

l(Na,HC10 4 )

25

Kj 3 . 3 3 ; K+ 1.79

oth

Amperometric method; Κχ(Η + ) from 70W.

7 4M

K f ( G a 3 + + HFr^GaHF 3 " 1 ") · 0.5(NaC10 4 )

25

Kx 5.02

sp

KX(H ) 2 . 9 4 .

52W

(Continued)

46

The Data Tables

Temp.

Medium

Log Ί^

GALLIUM ( I I I )

Remarks

Method

Ref.

Ga 3 + ( c o n t . )

REJECTED 59B (T?, I var); 60K (I var, HF neglected); 60Kb (I var). COMMENTS Complexes have not been s u f f i c i e n t l y well c h a r a c t e r i s e d t o permit higher c l a s s i f i c a t i o n . Unpublished data (I = 0.5 (NaClO^) , T = 25°) i s also a v a i l a b l e (52Y), and in f a i r agreement with the above.

INDIUM ( I I I )

In 3+

RECOMMENDED KNaClO^)

25

Ki 3.72

H,In,c

KNaClOi,)

25

dis

Corrected from 20 , using AHj from 74V.

54S

KNaClO^)

25

Ki 3.67 *1 3.69

KNaClO^)

25

Ki 3.75

qh

Converted from Κχ using K!(H+) 2.97.

71W

K2 2 . 5 5 ; K3 2 . 3 6 ;

H,In,c

Corrected from 20 using ΔΚ^ from 74V.

54S

68Aa

fe,qh

69R

TENTATIVE KNaClOi,)

25

K, 1.13 KNaClCV

25

K2 2 . 5 9 ; K3 2 . 3 5

dis

68Aa

KNaClO^)

25

K2 2 . 8 3 ; K3 2 . 1 1 ;

fe,qh

69R

KNaClOi,)

25

K2 2.97

qh

Converted from K 2 using Κχ(Η+) 2.97.

71W

O.oiNaClO^)

25

Kl 3 . 7 6 ; K2 2 . 6 2

red

Converted from K^ using Κ Χ (Η + ) 2.92.

54H

0.5(NaN0 3 )

25

Ki 3 . 7 2 ; K2 2 . 6 7

fe

No allowance for nitrate complexing.

73B

cix

At variance with above studies.

5USa

K, 1.27

DOUBTFUL KNaClO^)

25

3 . 0 0 ; K2 2 . 7 8 ; K3 2.82

COMMENTS Further independent studies at comparable ionic strengths necessary to reconcile differing values particularly of higher order complexes.

47

Stability Constants

Medium

Temp.

Log K

THALLIUM (I)

Method

Remarks

Ref.

Tl

REJECTED

53B (inaccurate determination) COMMENTS

Independent studies (70Ba, 70Bd, 73J) indicate that no complex can be detected within the limits of experimental error. The most likely value for K ^ T I F ) is 0.00 ± 0.06 at I = 1, T = 25 (73J) and thus no value can be given for log Κχ (since log x -*- - « as x + 0 ) .

SILICON (IV)

Si

4+

REJECTED

36R, U6R (Calculations in 62C indicate dependence of stability constant on solution molarity), 68P (T?).

ŒRMANIUM (IV)

4+

Ge

DOUBTFUL

0.4(NaCl)

20

Kg 0.58

ana

6 MR

54Sb

REJECTED

68P (T?).

TIN (II)

Sn

2+

DOUBTFUL

2.5(KN0 3 )

25

3 3 9.92

pol

KNaClOit)

25

K x *\Λ; K 2 2.8;

pol

Poor choice Κχ(H + ),

70Bf

K 3 2.6 l(Na,HCl0 4 )

25

KÎ 1.51; K* 0.03;

pol

70Bf

MHg,fe

68H/71Bd

K3 0.22 0.85(^10^)

25

Κχ 4 . 5 ;

K2 3 . 7 ;

K3 2 . 1 (Continued)

The Data Tables

48

Medium

Temp. TIN ( I I )

Log J^

Method

Remarks

Ref.

Sn2* ( c e n t . )

DOUBTFUL (oont.) 0.8(NaN0 3 )

25

3 3 10.96

pol

0.1(Na 2 S0 t + )

25

Kx 3 . 6 0 ; K2 4 . 4 4 ; y- -. qfi 3 *

fe

54Sb No allowance f o r s u l p h a t e complexing. Inappropriate Kn(H+).

75N

REJECTED

61C (doubtful complexes), 6 ID (I var), 68H (criticised and recalculated in 71Bd). COMMENTS

This system w a r r a n t s a thorough

TIN (IV)

re-investigation.

Sn4+

REJECTED

54Sb ( n o n - r e v e r s i b l e p o l a r o g r a p h i c w a v e s , I v a r ) .

METHYL TIN (IV)

Me„Sn ( 4

n )

+

DOUBTFUL

0.5(Να010^)

25

Kx 5 . 1 0 ; K2 4 . 7 5 ;

red

n - 1.

67C

K3 4 . 1 2 ; Κ^ 3 . 0 9 ; Κ5 2.2 KNaClO^)

25

Κχ 3 . 7 0 ; Κ2 2 . 8 7 ; £ ^ 47

qh

η = 2; other data r e j e c t e d (I var) .

67C

KNaClOi,)

25

Kx 2 . 2 7 ; K2 0 . 6 1

qh

n - 3.

67C

Kj 2 . 2 9 ; K2 0 . 6 0

sol

COMMENTS

Organo t i n (IV) i o n s n o t s u f f i c i e n t l y c h a r a c t e r i z e d i n aqueous s o l u t i o n t o p e r m i t "tentative" classification.

49

Stability Constants

Temp.

Medium

LEAD ( I D

Log K

Remarks

Method

Ref.

Pb' Z~r

RECOMMENDED KNaCKV

25

KNaCHV

25

Ki 1.48 Kl 1.40

KNaCKV

25

KNaClCV

25

2(NaCl0 4 )

MHg,qh

Ki(H + ) 2 . 9 5 .

65Ba

pol

71Bb

Ki 1.40

fe

72H

Ki 1.46

MHg

73Ba

25

Ki 1 . 2 6 ; K2 1.29

pol

63M

KNaClCV

15

Kl 1 . 5 3 ; K2 1.06

pol

70Bb

KNaCKV

25

K2 1.14

pol

71B

KNaClO^)

25

K2 1.06

MHg

72H

15

Kx 1.62

fe

TENTATIVE

DOUBTFUL KNaCHV O.KNaClCV

15

fe

Κχ 1 . 7 3

70Bb P r e c i s i o n lover than the above s t u d i e s (72H).

70Bb

REJECTED 56T (cheiTiically u n l i k e l y ) ; 58C (method i n a p p l i c a b l e , c r i t i c i s e d 70Bb); 77B (Kj^ d e p e n d e n t on [ P b ( I I ) ] ) .

ORGANO-LEAD (IV)

R n Pb

(4-n)+

DOUBTFUL KNaCKV

25

Kx 1 . 7 3 ; K2 1.16

qh

Κ2

Me2

Kx 1 . 5 4 ; K 2 1 . 0 1

Κ2

Et2

Κχ 1 . 6 1 ; K 2 0 . 9 3

Κ2

n - Pr2

Κχ 0.81

Κ2

Me3

Kx 0 . 5 4

Κ2

Et3

70P

COMMENTS Organo-lead (IV) ions not sufficiently characterized to permit "tentative" classification.

The Data Tables

50

Medium

Temp.

Log K

Method

Remarks

Ref.

Sb3*

ANTIMONY ( I I I ) DOUBTFUL

2(H,NaCl0i4)

30

K^ 3.0; κ£ 2.7;

pol

K3 2.6; Ki; 2.7

Complexing species?; non-rigorous method.

70B

REJECTED

58P (very doubtful method and calculations)

PHENYL ANTIMONY (V)

Ph^Sb*

REJECTED

73Ab (insufficient experimental d e t a i l s ) : Κχ given for reaction Phi+Sb + F~ ^r^Phi+SbF.

Bi3+

BISMUTH (III) DOUBTFUL

1.89(Η0Κν

25

2(Η^0104)

30

Ki 1.70; κ£ 0.60

cix

Ki 1 Λ 2 ; Κ£-1.12; pol

67L Non-rigorous method.

69Ba

4 2.4

MIXED COMPLEXES CONTAINING FLUORIDE

CHROMIUM ( I I I )

[Cr en3]

; for e n 2 C l 2 ]

+

REJECTED

65Sc (I var)■

IRON (III) 0.b(HClOk)

26.7

Fe3+ Kf 3.13

red

K*(Fe 3+ + SCN" + F" r=* FeSCNF+).

61Y

51

Stability Constants

Temp.

Medium

Log Kn

Remarks

Ref.

Outer sphere complex: K' (M1 + F~"v=*MfF"~) .

68Ba

68Ba

Method

MIXED COMPLEXES (CONT.) RHODIUM ( I I I )

[Rh(NH3)sOH2J

3+

(= Mf )

DOUBTFUL O^CNaClOi»)

45

K1 0 Λ 2

75

Kf 1.06

kin

[Rh ei^BrOHj 2 + (= M')

RHODIUM ( I I I ) DOUBTFUL O^NaClO^)

75

TIN (IV)

K?

1.04

kin

Outer sphere complex: Κ' (Μ1 + F ^ ^ M T " ) .

K ! 2.72

pol

K' (Pb 2 + + Cl" + F>=* PbCIF) 71Bb

Sn 4+

REJECTED 68D ( I v a r ) .

LEAD

(ID

Pb' d-r

DOUBTFUL KNaClO^)

25

KNaClOi^)

25

K

2.78

fe,M(Hg)

K f ( P b 2 + + Cl" + F%=*PbClF) 72H

KNaClO^)

25

K' 2.86

fe,M(Hg)

K ' ( P b 2 + + Br~ + F~
!

COMMENTS None of the mixed complex systems have been sufficiently well characterized to permit higher classification.

PART B - ENTHALPY AND ENTROPY DATA Temp.

Medium

HYDROGEN

ΔΗη

Method

àSvL

Ref.

Remarks

H

TENTATIVE KNaClOi*)

25

ΔΗχ 13.5

ASX

102

cal

KNaClO^)

25

ΔΗχ 12.2; ΔΗ2 2.9

Δδχ AS 2

97 ; 20

cal

Kn from 71Aa.

71Ac

KNaClCV

25

ΔΗ! 12.0; ΔΗ2 3.6

àSx 97; AS 2 2 3

cal

Kn est. from literature; ΔΟ 88. Pi

73V

HNaClCV

25

ΔΗχ 13.6

ASj 103

cal

0.5(NaC104)

25

ΔΗ! 12.2

AS2 97

T

O.ôCNaClO^)

25

ΔΗχ 13.0

69A

25

ΔΗΧ

13.2

ASx 100 LSi 99

T

0.5(NaN03)

T

74S

0 corr

25

ASX 105 ASX 102

cal T

Kn from 47B.

53H

Kn est. from literature values; àC 96. PI ASx calculated by compilers.

73V

1^ est. from literature; AC 84. Pi

73V

0 corr

25

ΔΗΧ 13.3 ΔΗχ 12.7

+ 0

25

ΔΗχ 13.3

ASx 105

cal

+ 0

25

ΔΗχ 13.0

ASX 104

cal

25

ΔΗχ 9.9 ; ΔΗ2 3.5

AS2 28

70W

73K 47B/54C/56C/67A

70Be

73K

DOUBTFUL 3(NaC10h)

97 ;

cal

SCNaClOi,)

25

ΔΗι 11.9

AS! 104

cal

3(NaCl)

25

ΔΗχ 6.7 ; ΔΗ2 2.0

ASX AS 2

86 ; 23

cal

K_ est.; AC 84. T* Pi

73V

2(NaC10u)

25

ΔΗχ 11.0; ΔΗ 2 4.1

ASi 96 ; AS 2 28

cal

Κ^ est. from literature; AC 92. PI

73V

2(NaC10it)

25 25

ΔΗχ 14.6

ASi 109

cal

2(NaCl)

ΔΗΧ ΔΗ2

ASX AS 2

cal

KNaClO^)

25

KNaClO^)

25

KNaCl)

8.7 ; 2.6

89 ; 22

73K

73K K^-, est.; ACp i 92.

73V

ΔΗχ 11.5 ΔΗχ 14.6

ASX 94

T

AS: 105

T

Less reliable than calorimetric values (70W).

70W

25

ΔΗι 10.6; ΔΗ2 3.3

ASX 92 ; àS2 22

cal

IL· il est.; àCP l 88.

73V

0.5(NaN03)

25

ΔΗ2 6.3

AS2 29

T

dil

20

ΔΗι 12.7

ASi 29

cal

69M

74S 47B+53H

(Continued) 52

53

Enthalpy and Entropy Temp

Medium

HYDROGEN DOUBTFUL

Wn H

àS

Method

AS 2 23

cal

AS 2 22

cal

Remarks

Ref.

(cont.)

(oont.)

0 corr

25

+ 0

25

ΔΗ2 4 . 3

47B+53H Kn est. from literature.

73V

REJECTED

ΔΗ2 d a t a i n 39R and 69M ( c h e m i c a l l y u n l i k e l y , d i s a g r e e w i t h a l l o t h e r s t u d i e s ; 39R c r i t i c i s e d i n 73V). C o n v e r s i o n of d a t a o f 53H t o I = 0 . 5 i n 59K u n s a t i s f a c t o r y . COMMENTS

D a t a o f 73V o b t a i n e d i n NaCl media g i v e n a l o w e r c l a s s i f i c a t i o n b e c a u s e o f p o o r c h o i o e o f Kn (no a l l o w a n c e made f o r p o s s i b l e media e f f e c t s - s e e PART A ) . F u r t h e r d a t a c o u l d b e o b t a i n e d from 39R and 63E by ( l o g K 5 T) method.

BERYLLIUM ( I I )

Be 2 +

DOUBTFUL

KNaCl)

25

ΔΗΧ ΔΗ 2 ΔΗ 3 ΔΗ 4

-1.5; -4.8; -1.2; -1.9

ASx AS 2 AS 3 AS 4

89 ; 56 ; 49 ; 21

τ

Doubtful AH(HFn) used (see a b o v e ) .

69M

REJECTED

68F(I v a r , inadequate method). COMMENTS

Unpublished data (1=0.5(NaC10i+), T=25°) in 55Y in reasonable agreement with the above.

MAGNESIUM

(II)

Mg

2+

DOUBTFUL

25

KNaClCV

25

ΔΗχ 11.3

ASx 63

cal T

KNaN0 3 )

25

ΔΗχ 6.3

ASx 47

T

71C

0.5(NaCKM

25

ΔΗχ 16.7

ASi 79

T

54C

KNaC10 4 )

ΔΗΧ 13.4

ASX 70

68T 68T

54

Medium

Temp.

àSy,

àHy,

CALCIUM ( I I )

Ca

Method

Ref.

Remarks

2+

DOUBTFUL KNaClCV)

25

ΔΗχ 1 4 . 6

ASx 63

cal

68T

KNaClOi,)

25

ΔΗχ 15.9

ASi 66

T

68T

KNaN0 3 )

25

ΔΗχ 9.6

ASX 43

T

71C

STRONTIUM ( I I )

Sr

2+

DOUBTFUL KNaClCV

25

ΔΗχ 1 6 . 7

ASX 59

cal

68T

KNaCICV

25

ΔΗχ 1 6 . 7

ASx 59

T

68T

KNaN0 3 )

25

ΔΗχ 9.6

ASi 31

T

71C

2+ Ba'

BARIUM ( I I ) DOUBTFUL KNaClO^)

25

ΔΗι 0

ASx - 4

T

68T

KNaN0 3 )

25

ΔΗχ 1 7 . 1

ASi 50

T

71C

COMMENTS Extremely weak carp lex introduces large e r r o r s i n t o ΔΗ value obtained from temperature v a r i a t i o n of log K.

Sc

SCANDIUM ( I I I )

3+

DOUBTFUL 0.5(Ν ά 010^)

25

ΔΗΧ 1.7 ; ΔΗ2 - 5 ; ΔΗ3 - 5 . 3

YTTRIUM ( I I I )

Y

ASX 12 3 ; Δε 2 83 ; àS3 60

T

55Ρ/59Κ/67Α

3+

DOUBTFUL KNaClOit)

25

ΔΗχ 3 4 . 8

LSl 186

cal

Criticised in 74H.

0.5(NaC10 l+ )

25

AEl 9 . 2

AS X 105

T

Ι^ data for higher complexes not precise enough to calculate Δϊ^ for n > 1.

O.StNaClO^)

25

ΔΗχ 5.1 ; ΔΗ 2 -5.0

àSx 92 ; ΔΞ 2 46

T

67W 61P/67A

69A

55

Enthalpy and Entropy

Medium

Temp»

LRn

LANTHANUM ( I I I )

LSn

Method

Remarks

Ref.

La3+

DOUBTFUL HNaClOt,)

25

ΔΗχ 16.7

ùSx 107

cal

C r i t i c i s e d in 74H.

67W

ASX 121

cal

C r i t i c i s e d in 74H.

67W

ASX 138

cal

C r i t i c i s e d in 74H.

67W

àSx 154

cal

C r i t i c i s e d in 74H.

67W

191

cal

C r i t i c i s e d in 74H.

67W

67W

Ce3*

CERIUM ( I I I ) DOUBTFUL KNaCKV

25

ΔΗΧ 2 0 . 1

Pr3+

PRASEODYMIUM ( I I I ) DOUBTFUL KNaCKV

25

ΔΗΧ 2 4 . 0

NEODYMIUM ( I I I )

Nd3+

DOUBTFUL KNaCKV

25

ΔΗχ 28.5

SAMARIUM ( I I I )

Sm3+

DOUBTFUL KNaClCV

25

ΔΗΧ 39.2

EUROPIUM ( I I I )

àSl

Eu3+

DOUBTFUL KNaCl(\)

25

ΔΗΧ 38.5

ASx 190

25

ΔΗχ 38.5

ASi 193

cal T

Criticised in 74H.

KNaClO^)

AS X 171

cal

Criticised in 74H.

GADOLINIUM ( I I I )

75C

Gd3+

DOUBTFUL KNaClO^)

25

ΔΗχ 37.2

67W

56

Medium

Temp.

Method

Remarks

Ref.

171

cal

C r i t i c i s e d i n 74H.

67W

LSX 165

cal

C r i t i c i s e d i n 74H.

67W

ASi 169

cal

C r i t i c i s e d i n 74H.

67W

ASX 172

cal

C r i t i c i s e d i n 74H.

67W

ASX 190

cal

C r i t i c i s e d i n 74H.

67W

203

cal

C r i t i c i s e d i n 74H.

67W

ASi 203

cal

C r i t i c i s e d i n 74H.

67W

LSn

ΔΗη

TERBIUM ( I I I )

Tb

3+

DOUBTFUL

KNaClO^)

25

DYSPROSIUM

ΔΗχ 3 1 Λ

(III)

bS\

Dy

3+

DOUBTFUL

KNaCl
25

ΔΗχ 29 A

HOLMIUM ( I I I )

Ho

3+

DOUBTFUL

KNaCKV

25

ΔΗχ 3 0 . 3

ERBIUM ( I I I )

Er

3+

DOUBTFUL

KNaCKV

25

ΔΗχ 31.0

THULIUM ( I I I )

Tm

3+

DOUBTFUL

KNaClOi,)

25

ΔΗχ 36.2

YTTERBIUM ( I I I )

Yb

3+

DOUBTFUL

KNaClO,,)

25

ΔΗχ 4 0 . 0

LUTETIUM ( I I I )

Lu

bSl

3+

DOUBTFUL

KNaClCV

25

ΔΗχ 39.1

57

Enthalpy and Entropy

Δ# η

Temp.

Medium

ZIRCONIUM

(IV)

Method

àSn

Zr

Remarks

Ref.

4+

DOUBTFUL 25

dil

ΔΗ!_ 3 -25 ; 50.5; ΔΗ4 ΔΗ5 -18.0; ΔΗ 6 15.9

AS X _ 3 àSk àS5 àS6

552; 96 ; 25 ; 121

cal

Ι ^ e s t . from

literature.

76V

COMMENTS Very p o o r agreement w i t h p r o b a b l y r e l i a b l e u n p u b l i s h e d work q u o t e d i n 73A ( 1 = 4 ; T=25) s u g g e s t s l i t t l e r e l i a n c e s h o u l d be p l a c e d on t h e above v a l u e s .

HAFNIUM ( I V )

Hf

4+

DOUBTFUL 25

dil

ΔΗχ.5 1 2 . 5 ; ΔΗ!_ 6 2 4 . 7

ASi_ 6 773

cal

Kn from 67N/75Va; ΔΙ^ (Η + )?

77V

COMMENTS Unpublished work ( 1 = 4 , T=25) on l o w e r o r d e r c a r p l e x e s a l s o a v a i l a b l e : q u o t e d i n 73A.

THORIUM ( I V )

Th

4+

DOUBTFUL KNaClOt,)

25

ΔΗχ

KNaClCV

25

ΔΗχ 2 . 3

KNaCKV

25

AHj 3.0

0 corr

25

ΔΗΐ ΔΗ2 ΔΗ3 ΔΗ4

1.1

5.0; 3.3; 3.3; 3.8

145

T

75C

ASX 150

T

75C

cal

75C

T

70Be

àSx

Δ^! àS2 AS 3 ASh

163; 130; 79 ; 50

COMMENTS Unpublished d a t a ( 1 = 4 , T=25) q u o t e d i n 73A a l s o a v a i l a b l e .

VANADIUM ( I V )

VO

2+

DOUBTFUL KNaClO^)

C'SOS

I

25

ΔΗχ ΔΗ2 ΔΗ3 ΔΗ^

7.9; 6.5; 5.8; 6.2

ASx 9 1 ; àS2 6 7 ; AS 3 4 9 ; ASÎ+

36

cal

1^ from 71A.

71Ac

58

Medium

Temp,

ΔΗη

LSn

Method

Remarks

Ref.

Cr3+

CHROMIUM ( I I I ) DOUBTFUL

KLiCKV

77

ΔΗχ 5 . 4

Ο.δΐΗΟΙΟ^)

25

ΔΗΧ 1.38

URANIUM ( I V )

U

ASX 25

Τ

65S

cal

76D

T

75C

4+

DOUBTFUL

KHCKV

25

ΔΗΤ

0.8

LSl

151

COMMENTS

U n p u b l i s h e d d a t a a v a i l a b l e ( 1 = 4 , T=25 ) , q u o t e d i n 73A.

URANIUM ( V I )

UOQ*

DOUBTFUL

2(NaCl<\)

25

ΔΗΪ - 2 2 . 6

ASx

-50

T

2(NaC10 l+ )

25

ΔΗι - 8 . 4

ASX

54

T

KNaClOit)

25

ΔΗχ ΔΗ2 ΔΗ3 ΔΗ^

ASi AS2 AS 3 ASit

92; 67; 48; 21

cal

NEPTUNIUM ( I V )

1.7 0.4 0.3 -2.0

l o g Kx υ β . T" 1 p l o t shows pronounced c u r v a t u r e .

54D 54D/67A

Κ^ from 71A.

71Ac

Np4+

DOUBTFUL

KNaClOit)

25

ΔΗχ 3.2

NEPTUNIUM ( V I )

àSx

155

T

2+ NpOg

COMMENTS

TWo sets of unpublished data in very poor agreement available (quoted in 78P).

75C

Enthalpy and Entropy

Medium

Temp.

ΔΗη

LSn

Method

LS\ 67

T

59 Remarks

Ref.

Pu4+

PLUTONIUM ( I V ) DOUBTFUL

2(Η0Κ\)

25

ΔΗΪ -5.9

ί^ partly from 76B.

77Ba

REJECTED

ΔΗχ, ASi (77Ba) u n j u s t i f i e d a s s u n p t i o n of ΔΗ(Η ) and AS(H ) v a l u e s .

Mn2*

MANGANESE ( I I ) DOUBTFUL

3(NaClO^)

25

ΔΗχ 1 5 . 0

AMERICIUM ( I I I )

àSl

44

cal

Doubtful K2 v a l u e used in c a l c u l a t i o n s . (See PART A ) .

76K

Am3+

DOUBTFUL

KNaCKV

25

CURIUM ( I I I )

ΔΗι 27.6

ASX 141

T

75C

141

T

75C

ASX 146

T

75C

149

T

75C

Cm 3 *

DOUBTFUL

KNaCKV

25

ΔΗχ 27.2

BERKELIUM ( I I I )

àSx

Bk3+

DOUBTFUL

HNaCKV

25

ΔΗχ 2 7 . 1

CALIFORNIUM ( I I I )

Cf3+

DOUBTFUL

KNaCKV

25

ΔΗΧ 27.2

àSl

60

Temp.

Medium

IRON ( I I I )

àSy,

LHn Fe

Method

Ref.

Remarks

3+

TENTATIVE 0.5(NaC10 4 )

25

ΔΗχ 9.7 ; ΔΗ2 7.4 ; ΔΗ3 12.5

ASx 1 3 0 ; AS2 1 0 0 ; AS 3 96

T

53K/55P/56C

COMMENTS Unpublished d a t a ( Ι = 0 . 5 ( Ν ε £ 1 0 ι , ) , T=25°) i n 55Y (method=T) and 59Sa (method=cal) agreement w i t h t h e above s u g g e s t s " t e n t a t i v e " c l a s s i f i c a t i o n i s r e a s o n a b l e .

COBALT ( I I )

Co

i n good

2+

DOUBTFUL 25

3(NaCl(V

ΔΗχ 1 3 . 8

76K

ASX 59

cal

ASj 33

cal

65

cal

76K

τ

58C

Ni2*

NICKEL ( I I ) DOUBTFUL 3(NaC10 4 )

25

ΔΗχ 5.9

COPPER ( I I )

Cu

Outer s p h e r e complex suggested.

76K

2+

DOUBTFUL 3(Νό£Κν

25

ΔΗχ 1 3 . 4

àSx

0.5(NaCl0 l + )

25

ΔΗχ 3.8

ASX 2 5

SILVER

(I)

Ag

DOUBTFUL 0.5(Ν<£1(\)

25

ZINC ( I I )

ΔΗχ - 1 1 . 7

ASX -42

τ

61C

Ζη

TENTATIVE

3(NaClOn)

25

ΔΗχ 7.6

ASx 42

cal

3(NsC10h)

25

ΔΗχ 9.2

ASx 48

cal

Ι^ estimated.

69Gb 76K (Continued)

Enthalpy and Entropy

Medium

Temp. ZINC ( I I )

àSn

LHn Zn2*

61

Method

Ref.

Remarks

(cont.)

DOUBTFUL 69Gb

KNaCKV

25

ΔΗχ 8.3

ASX 42

cal

0.5(NaCl04)

25

ΔΗχ 6 . 3

ASX 33

τ

58C

0 corr

25

ΔΗχ 15.9

ASi 75

τ

71C

CADMIUM ( I I )

Cd

Ι ^ from 56Aa.

2+

DOUBTFUL 3(Να010 4 )

KNaClO^)

KNaClO^)

25

ΔΗχ 4 . 3

ASx 25

25

ΔΗΧ 5 . 0 ; ΔΗ2 - 2 . 9

ASX 26 AS2 - 8

25

ΔΗχ 6 . 4

àSx

MERCURY ( I I )

Hg

cal

;

30

l·^

from 43L.

66G

cal

Ι ^ from 43L.

66G

cal

Ι ^ from 43L4, AC

54.

75V

2+

COMMENTS U n p u b l i s h e d d a t a (I=0.5(NaC10 1 + ), T=25°) a v a i l a b l e i n 55P.

ALUMINIUM ( I I I )

Al

3+

DOUBTFUL

KNaCKV)

25

ΔΗχ 3.0

àSx 127

cal

0.5(Na,HC104)

25

ΔΗχ 2.7 ; ΔΗ 2 4.9 ; ΔΗ 3 5.3

ASi 127; Δ3 2 104; àS3 77

cal

Kn from 71Aa; Δϋ 100; Pl Δ0 118. P2

0.07

25

ΔΗι 4.4 ΔΗ 2 3.8 ΔΗ3 0.7 ΔΗ^ 0.2; ΔΗ5-1.5

àSi 141 ; AS 2 115 ; àSs 80; àSi+ 52; àS5 20

cal

Kn from 43Ba.

71W 75V

53L/59Ka

REJECTED 53L ( I v a r ) ; 59Sa ( u n p u b l i s h e d r e c a l c u l a t i o n o f 5 3 L ) . (Continued)

62

Δ# η

Temp.

Medium

àSn Al3*

ALUMINIUM ( I I I )

Remarks

Method

Ref.

(cont.)

COMMENTS

F u r t h e r d a t a oould be o b t a i n e d from 71Ac by ( l o g K,T) method.

GALLIUM ( I I I )

Ga

3+

DOUBTFUL

KNaClOif)

25

ASx 119

cal

71W

ΔΗχ 9.2; ΔΗ 2 7.6

AS! 101;

cal

69R

ΔΗΧ 9.0;

AS! 101;

ΔΗ2 8.2

àS2

82

87

AHj 10.5

INDIUM ( I I I )

In

3+

TENTATIVE

KNaClO^)

25

KNaClO^)

25

àS2

80

cal

Δ0 105 74V,74Va Pi Δ0 37. P2 Data a l s o given at 1=0, 0 . 5 , 2.0(NaC10O ; Kn from 69R or e s t i m a t e d .

DOUBTFUL

KNaClOit)

25

ΔΗ3 13.8

kS3

KNaClO^)

25 25

ΔΗι 12.5

ASx 114

ΔΗ 3 6.9;

àS3

63;

ΔΗ 4 9.6

àSit

57

ΔΗι 1 0 . 3 ; ΔΗ2 16.7

àSx 105 ; AS2 105

KNaC10 4 )

O.SCNaClO^)

25

69R

cal cal cal

71W Δ0 63 5 P3 Δ0 50 74V,74Va P4 Data alLso given at I==0, 0.5, 2..OCNaClO^); Ι^ from 69R or estimated.

τ

54H/55P

COMMENTS

I n a d e q u a t e a p p a r a t u s used i n 71W make v a l u e s l e s s r e l i a b l e .

GERMANIUM ( I V )

Ge

4+

DOUBTFUL

0.4(NaCl)

25

ΔΗι 1 0 . 8

ASx - 2 6

64R

63

Enthalpy and Entropy

Medium

Δ#

Temp. TIN ( I I )

àSn

Method

Remarks

Ref.

ΔΗ'(Mf + F ' P ^ M ' F " ) -outer sphere complex.

68Ba

Sn2+

REJECTED 68H ( c r i t i c i s e d in 71Bd).

MIXED COMPLEXES CONTAINING FLUORIDE RHODIUM ( I I I )

trans

[Rh e n 2 B r O H 2 ] 2 + = Μ'

DOUBTFUL 0.2(NaCl(V

45

ΔΗ' 46

ASf 160

T

PART C - SUMMARY OF "BEST" VALUES Remarks

Log Kn

Ion

Medium

Temp.

H!

LKNaClCV

25

K

3 . 5 4 ( 2 0 ; K2 1.05(20

3(^010^)

25

K

3 . 3 1 ( A ) ; K2 0.90(2')

2(NaC10 4 )

25

K

3 . 1 3 0 ? ) ; K2 0.84(20

HNaClCV

25

K

2 . 9 7 0 ? ) ; K2 0.63(20

a

a

0.5

25

K

2 . 9 2 0 ? ) ; K2 0.54(2')

b

0

25

K

3 . 1 9 0 ? ) ; K2 0.61(20

a

Na*

1

25

Ki -0.56(D)

Ββ^

KNaClCV

25

Ki 2 . 0 6 ( 2 ' ) ; K2 0 . 8 8 ( 2 0 ; K3 - 0 . 1 2 ( 2 ' ) ; KL\ - 1 . 4 9 ( 2 0

1

25

Ki 1.33(A)

b

CfLl

KNaClCV

25

Ki 0.58(A)

a

sxf:

KNaClOij)

25

Ki 0 . 1 3 0 ? )

a

**:

KNaC10 4 )

25

Ki - 0 . 1 9 0 ? )

a

Sç^

0.5(NaC10 4 )

25

Ki 6 . 1 9 ( A ) ; K2 5 . 2 2 ( 2 ' ) ; K3 4 . 0 0 ( 2 ' ) ; Kk 2.94(20

a

0.5(NaCl04)

25

Ki 3 . 9 0 0 ? ) ; K2 3 . 2 2 ( 2 ' ) ; K3 3.2(20; Kk

a

T 3+

La

O.SiNaClOi,)

25

Kl 2 . 6 9 ( A ) ; K2 2 . 4 9 ( 2 0 ; K3 2.68(20

a

a£

O.ôtNaClO^)

25

Ki 3 . 1 4 0 ? ) ; K2 2.81(20

a

KNaClOi,)

25

KI

N^:

HNaClOi*)

25

Ki 3.09(20

Pm 3+

KNaC10 4 )

25

Ki 3.16(20

a^

KNaClO^)

25

Ki 3.12(20

^ 3+ Eu

KNaClCV

25

Ki 3.19(20

a

Gd 3+

0.5(NaC10i,)

25

Ki 3 . 3 7 0 ? ) ; K2 3.27(20

a

T^l

KNaClOi,)

25

Ki 3.42(20

TV 3+

KNaClOi,)

25

Ki 3.46(20

u

2+

γ 3+

T5

+ 3

Pr

b

3.92(D)

3.01(20

64

65

Summary of 'Best' Values

Log Kn

Temp.

Remarks

Ion

Medium

Ho

KNaClOi,)

25

Kx

3.52(7

Er^

KNaClO^)

25

Kx

3.55(7

a

WÜ

KNaClOi,)

25

Kx

3.57(7

a

Yb^

KNaClOi,)

25

Ki

3.59(7

a

l£L

KNaCl(\)

25

Kx

3.61(7

b^L

O.SCNaClO^)

25

K2 2 . 6 9 ( 7

Ί102+

SCNaClO^)

25

Kx 5 . 3 8 ( 0 ; K2 4 . 3 2 ( 0 ) ; K3 3 . 9 6 ( 0 ) ; K4 3 . 7 2 ( 0 )

Zr4+

4(HC1(V

20

Kj 5 . 9 2 ( 0 ; K2 4 . 4 5 ( 0 ) ; K3 3 . 0 0 ( 0 ) ; κί| 2 . 2 8 ( 0 ) ;

K2 2 . 4 9 ( 7 ) ; K3 2 . 6 0 ( 7 )

a

Kg 1 . 5 3 ( 0 ; K6 0 . 3 ( 0 )

Hf

.4+

4(Η010 4 )

20

Ki 5 . 5 2 ( 0

K2 4 . 0 4 ( 0 ) ; K3 3 . 0 4 ( 0 ) ; K^ 2 . 2 0 ( 0 ) ;

K5

Kg 0 . 5 ( 0 )

1.7(D)

Th^

O.öCNaClOi,)

25

Κχ 4.65(f? ; K2 2 . 8 1 ( A ) ; K3 1 . 5 1 ( 0 )

VP 2 *

KNaClOt,)

25

Kx

*£

KNaC10 4 )

25

Κχ 3 . 0 5 ( 7 ; Κ2 2 . 5 5 ( 7 ) ; Κ3 1 . 2 6 ( 7 ) ; Κ4 0 . 2 ( 0 )

Nb 5 *

O^CNaClOi,)

25

K8 3 . 0 8 ( 0 ; Κ9 4 . 0 ( 0 )

Ί^Ι

3CHC104)

25

Kk 5 . 8 6 ( 0 ; Κ5 4 . 9 1 ( 0 ) ; Κ6 4 . 9 0 ( 0 ) ; Κ7 4 . 4 8 ( 0 )

Εί£

3(^10^)

25

Κχ 4 . 7 3 ( 0 ; Κ2 3 . 5 3 ( 0 )

O.SCNaClO^)

25

K* 1 . 4 2 ( 0 ; Κ2 0 . 4 0 ( 0 ) ; Κ 3 - Ο . 4 6 ( 0 )

4(Η010 4 )

20

K* 5 . 5 4 ( 7 ; Κ2 3 . 1 8 ( 7 ) ; Κ3 1 . 9 6 ( 0 )

*f

1

25

ΚΪ 1 . 5 2 ( 7 ; Κ2 0 . 5 0 ( 7 ) ; Κ3 - 0 . 5 7 ( 0 )

b

Np

4(Η010 4 )

20

Ki 4 . 8 2 ( 7 ; Κ2 2 . 7 2 ( 7 ) ; Κ3 2 . 3 4 ( 7 )

a

NpOp

2(NaC10i,)

25

Kj 0 . 9 9 ( 0

Npof

KHCIO4)

21

ΚΪ 0 . 9 3 ( 0 ; Κ2 0 . 1 8 ( 0 )

cil £

a

3 . 3 7 ( 7 ; Κ2 2 . 3 6 ( 7 ) ; Κ3 1 . 5 6 ( 7 ) ; Kk 0 . 7 9 ( 0 )

66

Medium

Ion 4+

Temp.

Remarks

Log Κ^

2(Η010^)

25

Κχ 4 . 5 5 ( D ) ; K2

Puo;

KHC1CV

25

Κχ 2 . 1 1 ( D ) ; Κ2 2 . 0 4 ( D ) ; Κ3 1 . 9 3 ( D ) ; Κ^ 0.22(D)

3+ Am"

O.SCNaClO^)

25

Κχ 3 . 3 9 ( D ) ; Κ2 2 . 7 2 ( D ) ; Κ3 2.89(D)

3+ On"

O.ötNaClOi,)

25

Κχ 3 . 3 4 ( 2 0 ; Κ2 2 . 8 3 ( 7 ) ; Κ3 2 . 9 0 ( 7 )

3+ Ek'

l(NaC10 4 )

25

Κχ 2.89(D)

3+

KNaClO^)

25

Κχ 3.03(D)

2+ Ma"

KNaClOt,)

25

Κχ 0 . 6 2 ( 7 )

6(HC^)

25

ΚΪ 2 . 8 8 ( 7 )

KNaClOi,)

25

Κχ 0 . 8 3 ( 7 )

Ο.δίΝοΟΙΟι,)

25

Κχ 5 . 1 8 ( A ) ; Κ2 3 . 9 3 ( i ? ) ; Κ3

KNaClOit)

25

Κχ 0 . 4 0 ( 7 )

KNaCl04)

25

Κχ 0.49(D)

a

KNaClOi,)

25

Κχ 0 . 8 3 ( 7 )

a

KNaClOi,)

25

Κ1-0.32(Γ)

KNaClOit)

25

Κχ 0 . 7 7 ( 7 )

2+ Cd'

KNaClOi,)

25

Κχ 0 . 7 2 ( 7 ) ; Κ 2 - 0 . 1 ( 7 )

O^Hg*

0.1(ΚΝ0 3 )

20

Κχ 1 . 5 0 ( 7 )

0.53(KN0 3 )

25

Pu

2+

Cf

3+

MQ"

Fe

2+

Fe'

3+

2+ Co' Ni'

2+

eu

2+

Ag Zn

Al

2+

3+

a

2.91(D)

2.92(A)

a

a

K 2 6.13(20; Κ 2 5.02(Τ); Κ 3 3.85(20; Κ^ 2.74(D); Κ 5 1.63(D); Κ 6 0.47(D)

3+

KNaClOt,)

25

Κχ 4.40(D); Κ 2 3.80(D)

3+ In'

KNaClO^)

25

Κχ 3.71(A); Κ 2 2.74(20; Κ 3 2.28(20; Κ 4 1.19(20

4+ Ge

0.4(NaCl)

20

Kg 0.58(D)

2+ Sn'

KNaClOi*)

25

ΚΪ 1.51(D); Κ 2 0.03(D); Κ3 0.73(D)

Ga

a

Summary of 'Best' Values

Ion

Medium

2+ Pb'

KNaClCV

25

Κχ 1 . 4 4 0 ? ) ; Κ2 1 . 0 9 ( 7 )

Sb3+

2(Ν ά ,Η010 4 )

30

KÎ 3 . 0 ( D ) ; Κ2 2 . 7 ( D ) ; Κ3 2 . 6 ( D ) ; }ζ

Ι.βθΟΚΙΟ^)

25

Kj 1 . 7 0 ( D ) ; Κ2 0 . 6 0 ( D ) ;

2(Na,HC10 1+ )

30

Κ3 2.4(D)

Bi^l

67

Remarks

L°g «η

Temp,

a 2.7(D)

REFERENCES 05D 25A 2TA 32F 36R 37R 39R 1+2B l*2Ba I+3B U3Ba 1+3L U6R 1+7B UTBa 1+8T 1+9C U9D 1*9L U9T 50D 50K 50M 51B 51D 51K 51M 51Z 52J 52L 52T 52W 52Y 53B 53H 53Ha 53L 53S 5^A

5*+B

5*+C 5^D 5^F 5*+Η 5^ 5^S 5USa 5^Sb 55P 55Y 56A 56Aa 56C 56T 57K 57S 57T 58A 58C 58P 59B 59K

E. Deussen, Z. Anorg, Chem., 1905 44 300. J.D.C. Anthony and L.J. Hudleston, J. Chem. Soo., 1925 127 1122. M. Aumeras, Compt, Rend., 192? 184 165O. K. Fredenhagen and M. Wellmann, Z. Phys, Chem,, 1932 162 k^k, A.G. Rees and L.J. Huddleston, J. Chem, Soo., 1936 133U. 1937 43 350. W.A. Roth, H. Pahlke, A. Bertram, and E . Borger, Z, Elektroohem., W.A. Roth, Liébig's Ann, Chem,, 1939 542 35. C. Brosset, Svensk Kern, Tidskr., 19*+2 54 155. C. Brosset and B. Gustaver, Svensk Kern, Tidskr., 19^2 54 185. C. Brosset and U. Wahlberg, Svensk Kern, Tidskr., 19^3 55 335C. Brosset and J. Orring, Svensk Kern. Tidskr., 19^3 55 101. I. Leden, Dissertation, Lund, 19I+3 p. ^9. I.G. Ryss, Zh. Obshohei Khim., 19h6 16 331. H.H. Broene and T. DeVries, J. Amer, Chem, Soc, 19^7 69 l6hh. Khim,, 19^7 1? 1259. A.K. Babko and K.E. Kleiner, Zh, Obshohei H. Taube, J. Amer, Chem, Soo,, 19^8 70 3928. R.E. Connick and W.H. McVey, J. Amer, Chem, Soo,, 19^9 71 3182. H.W. Dodgen and G.K. Rollefson, J, Amer, Chem, Soo,, 19U9 71 26ΟΟ. S. Lacroix, Ann, Chim, (France) , 19^9 4 5. I.V. Tananaev andE.N. Deichman, Izvest, Akad, Nauk S.S.S.R., Otdel. Khim. Nauk, 1949 lM+. R.A. Day and R.W. Stoughton, J. Amer. Chem. Soo., 1950 72 5662. K.E. Kleiner, Zh. Obshohei Khim., 1950 20 17U7. G.E. Moore and K.A. Kraus, O.R.N.L. - 795, 1950. C A . Blake, R.S. Lowrie, and K.B. Brown, A.E.C.D. - 3212, 1951. L.P. Ducret, Ann. Chim. (France), 1951 6 705. K.E. Kleiner, Zh. Obshohei Khim., 1951 21 ±8. S.W. Mayer and S.D. Schwartz, J, Amer. Chem. Soo., 1951 73 222. E . L . Zebroski, H.W. Alter, and F.K. Heumann, J. Amer. Chem. Soo., 1951 73 561+6. J.S. Johnson and K.A. Kraus, J. Amer. Chem. Soo., 1952 74 kk36.

I. Leden and L.E. Marthen, Aota Chem. Soand., 1952 6 1125, M.S. Tsao, Thesis, Univ. of California, Berkeley, 1952, quoted in refs. 5*+C 56C and 55P. A.S. Wilson and H. Taube, J. Amer. Chem. Soo., 1952 74 3509. L.M. Yates and H.W. Dodgen, Amer. Chem. Soc., 122nd meeting, Sept., 1952 Abstracts 18P. R.P. Bell and J.H.B. George, Trans. Faraday Soo., 1953 49 619. L.G. Hepler, W.L. Jolly, and W.M. Latimer, J. Amer. Chem. Soo., 1953 75 2809. J. Hudis and A.C. Wahl, J. Amer. Chem. Soo., 1953 75 1+153. W.M. Latimer and W.L. Jolly, J. Amer. Chem. Soo., 1953 75 15I+8. G. Saini, Gazzetta, 1953 83 677. S. Ahrland and R. Larsson, Aota Chem. Soand., 195^4 # 35I+.

R.D. Brown, W.B. Bung er, W.L. Marshall, and C.H. Secoy, J. Amer. Chem. Soo., 195*+ 76 I58O. R.E. Connick and M.S. Tsao, J. Amer. Chem. Soo., 195^ 76 5311. R.A. Day and R.M. Powers, J. Amer. Chem. Soo., 195*+ 76 3895. - 25^7. D.C. Feay, Thesis, Berkeley, 195^, U.C.R.L. L.G. Hepler, J.W. Kury, and Z.Z. Hug us , J. Phys. Chem., 195*+ 58 26. J.S. Johnson, K.A. Kraus and T.F. Young, J. Amer. Chem. Soo., 195I+ 76 1U36. N. Sunden, Svensk Kern. Tidskr., 195^ 66 50. J.A. Schufle and H.M. Eiland, J. Amer. Chem. Soo., 195*+ 76 96Ο. W.B. Schaap, J.A. Davies, and W.H. Nebergall, J. Amer. Chem. Soc, 195^ 76 5226. A.D. Paul, Thesis, Univ. California, Berkeley, 1955, U.C.R.L. - 2926. L.M. Yates, Thesis, State Coll., Washington, 1955, Univ. Microfilms 15662. S. Ahrland, R. Larsson and K. Rosengren, Aota Chem. Soand., 1956 10 705. S. Ahrland and K. Rosengren, Aota Chem. Soand., 1956 10 727, R.E. Connick, L.G. Hepler, Z.Z. Hugus , J.W. Kury, W.M. Latimer, and M.S. Tsao, J, Amer, Chem, Soo,, 1956 78 1827. Sh. T. Talipov and O.F. Kutumova, Dokl. Akad. Nauk Uzbek. S.S.R., 1956 (8) 23. J.W. Kury, Z.Z. Hugus and W.M. Latimer, J. Phys. Chem., 1957 61 1021. W.M. Smith, Proc Chem. Soo., 1957 207. I.V. Tananaev and A.D. Vinogradova, Zh. Neorg. Khim., 1957 2 21+55. S. Ahrland and B. Noren, Aota Chem. Soand., 1958 12 1595. R.E. Connick and A.D. Paul, J. Amer. Chem. Soo., 1958 80 2069. D. Pavlov and D. Lazarov, Dokl. Akad. Nauk S.S.S.R., 1958 118 103; Zh. Neorg. Khim., 1958 3 2099. A.K. Babko and L.G. Shimadina, Zh. Neorg. Khim., 1959 4 1060. J.W. Kury, A.D. Paul, L.G. Hepler, and R.E. Connick, J. Amer. Chem., Soo., 1959 81 U185.

68

References

59Ka 59S 59Sa 59T 59Ta 60C 60K 60Ka 60S 60T 6lC 6lD 6lH 6lK 6lP 6lR 6lT 6lTa 6lY 62B 62C 62L 62V 63A 63C 63E 63Ea 63Eb 63M 63Ma 63V 63Va 64B 64F 64Fa 64R 64V 65B 65Ba 65C 65D 65H 65S 65Sa 65Sb 65Sc 65V 66A 66B 66G 66Ga 66L 66N 66P 66S 66Y 67A 67c 67H 67I 67K 67L 67La

69

E.L. King and P.K. Gallagher, J. Phys. Chem., 1959 63 1073. G.B. Seifer, Zh. Neorg. Khim., 1959 4 2832. P.C. Scott, Thesis, 1959, Univ. of Minnesota, Univ. Microfilms 59-3764. I.V. Tananaev and C-D. Lu, Zh. Neorg. Khim., 1959 4 2122. I.V. Tananaev, Aota Chim. Sinioa, 1959 25 391. V. Caglioti, L. Ciavatta, and A. Liberti, J. Inorg. Nuolear Chem. , i960 15 115. K.E. Kleiner, Zh. Fiz. Khim., i960 34 4l6. K.E. Kleiner and G.I. Gridchina, Zh. Neorg. Khim., i960 5 202. A.W. Savage and J.C. Browne, J. Amer. Chem. Soo., i960 82 4817. I.V. Tananaev and A.D. Vinogradova, Zh. Neorg. Khim. , I960 5 321. R.E. Connick and A.D. Paul, J. Phys. Chem., 196l 65 1216. T.F. D'yachenko, Nauohnye Trudy Dnepropetrovsk Khim-tekh. Inst. , 196l 12(2) 87. C.J. Hardy, B.F. Greenfield, and D. Scargill, J. Chem. Soo., 1961 174. A.F. Kuteinikov, Radiokhimiya, 1961 3 706. A.D. Paul, L.S. Gallo, and J.B. Van Camp, J. Phys. Chem., 1961 65 44l. J. Rydberg, Aota Chem. Soand., 1961 15 1723. Sh. T. Talipov, V.S. Podgornova, and G.N. Zinina, Uzbek. Khim. Zh., 196l(4), n . I.V. Tananaev and E.N. Deichman, Radiokhimiya, 1961 8 712. R.G. Yalman, J. Amer. Chem. Soo., 196l 83 4l42. Yu. A. Buslaev, Zh. Neorg. Khim., 1962 7 1204. J.R. Cooke and M.J. Minski, J. Appl. Chem., 1962 12 123. Yu. A. Lukfyanychev and N.S. Nikolaev, Atomnaya Energiya, I962 13 179. L.P. Varga and H. Freund, J. Phys. Chem., 1962 66 21. S. Ahrland, D. Karipides, and B. Noren, Aota Chem. Soand., 1963 17 Uli. L. Ciavatta, Arkiv Kemi, 1963 21 129. A.J. Ellis, J. Chem. Soo., 1963 4300. T. Erdey-Gruz, L. Majthenyi, and E. Kugler, Aota Chim. Aoad. Soi. Hung., 1963 67 393. T. Erdey-Gruz, L. Majthenyi and E. Kugler, Magyar Kern. Folyoirat, 1963 69 68. S.S. Mesaric and D.N. Hume, Inorg. Chem., 1963 2 788. S.S. Mesaric and D.N. Hume, Inorg. Chem., 1963 2 IO63. L.P. Varga and D.N. Hume, Inorg. Chem., 1963 2 201. V.M. Vdovenko, G.A. Romanov and V.A. Shcherbakov, Radiokhimiya, 1963 5 581. W. Brendel and A. Swinarkski in 'Theory and Structure of Complex Compounds' (Symposium Papers, Wroclaw, 1962) , Pergamon, Warszawa, 1964 p. 497· H.N. Farrer and F.J.C. Rossotti, J. Inorg. Nuolear Chem.> 1964 26 1959. J.P. Fackler and J.D. Chawla, Inorg. Chem., 1964 3 1130. I.G. Ryss and N.F. Kulish, Zh. Neorg. Khim., 1964 9 1103. L.P. Varga and D.N. Hume, Inorg. Chem., 1964 3 77Yu. A. Buslaev and M.P. Gustyakova, Zh. Neorg. Khim., 1965 27 1524. E. Bottari and L. Ciavatta, J. Inorg. Nuolear Chem., 1965 27 133. L. Ciavatta and M. Grimaidi, J. Inorg. Nuolear Chem., 1965 27 2019. R.G. Deshpande, P.K. Khopkar, C.L. Rao, and H.D. Sharma, J. Inorg. Nuolear Chem., 1965 27 2171. H.E. Hellwege and G.K. Schweitzer, J. Inorg. Nuolear Chem., 1965 27 99. T.W. Swaddle and E.L. King. Inorg. Chem., 1965 4 532. G. Schwarzenbach and M. Schellenberg, Helv. Chim. Aota, 1965 48 28. A. Swinarski and A. Grodzicki, Roozniki Chem., 1965 39 3. T.R. Stengle and C.H. Langford, J. Phys. Chem., 1965 69 3299. L.P. Varga, W.D. Wakley, L.S. Nicolson, M.L. Madden, and J. Patterson, Analyt. Chem., 1965 37 1003. S. Ahrland and L. Brandt, Aota Chem. Soand., 1966 20 328. M.N. Bukhsh, J. Flegenheimer, F.M. Hall, A.G. Maddock and C. Ferreira de Miranda, J. Inorg. Nuolear Chem., 1966 28 421. P. Gerding, Aota Chem. Soand., 1966 20 79. R. Guillaumont, Rev. Chim. Minerale, 1966 3 339. S.J. Lyle and S.J. Naqyi, J. Inorg. Nuolear Chem., 1966 28 2993. B.I. Nabivanets, Ukrain. Khim. Zht, 1966 32 886. O.E. Presnyakova and R.S. Prishchepo, Zh. Neorg. Khim., 1966 11 l436. CG. Swain and D.F. Evans, J. Amer. Chem. Soo., 1966 88 383. V.M. Vdovenko, G.A. Romanov, and V.A. Shcherbakov, Zh. Neorg. Khim., 1966 11 252. S. Ahrland, Helv. Chim. Aota, 1967 50 306. A. Cassol, L. Magon, and R. Barbieri, Inorg. Nuolear Chem. Letters, 1967 3 25; Gazz. Chim. Ital. 1966 96 1734; 1752; 1764. R. Haque and L.W. Reeves, J. Amer. Chem. Soo., 1967 89 250. A.A. Ivakin, Zh. Neorg. Khim., 1967 12 1787. R.T. Kolarich, V.A. Ryan, and R.P. Schuman, J. Inorg. Nuolear Chem., 1967 29 783. H. Loman and E. van Dalen, J. Inorg. Nuolear Chem., 1967 29 699. S.J. Lyle and S.J. Naqyi, J. Inorg. Nuolear Chem., 1967 29 244l.

70

6ΤΝ 6TNa 67Nb 6TP 6TPa 6TV 6TVa 6TW 6TWa 67Y 68A 68Aa 68B 68Ba 68D 68F 68H 68I 68K 68M 68P 68S 68Sa 68Sb 68T 68V 69A 69Aa 69B 69Ba 69Bb 69Bc 69Bd 69D 69G 69Ga 69Gb 691 69K 69Ka 69Kb 69M 69N 69Na 69P 69R 70A 70Aa 70B 70Ba 70Bb 70Bc 70Bd 70Be 70Bf 70Bg 70E 70H 70K 70M 70N 70P 70S 70W 71A 71Aa 71Ab 71Ac 71B 71Ba

Β. Noren, Acta Chem. Scand., 196T 21 2^35. B. Noren, Acta Chem. Scand., 19 67 21 2UU9. B. Noren, Acta Chem. Soand., 196T 21 2^57. N.A. Parpiev, I.A. Maslennikov and Yu. A. Buslaev, Uzbek. Khim. Zh., 1967 11(3) 9. N.A. Parpiev, I.A. Maslennikov and Yu. A. Buslaev, Uzbek. Khim. Zh., 1967 11(6) 21, S. Varvicka and J. Koryta, Coll. Czech. Chem. Comm.3 196T 22 23h6. V.M. Vdovenko, O.B. Stebunov, and V.A.Shcherbakov, Zh. Neorg. Khim., 1967 12 1706. J.B. Walker and G.R. Choppin, Adv. Chem. Series, 196T 71 127. C F . Wells and M.A. Salam, Trans. Faraday Soc, 1967 ^ 620. M. Yamazaki and T. Takeuchi, Kogy Kagaku Zasshi 1967 70 656. S. Ahrland and L. Brandt, Acta Chem. Scand., 1968 22 106. A. Aziz and S.J. Lyle, J. Inorg. Nuclear Chem., 1968 30 3223. W.G. Baldwin and D.R. Stranks , Austral. J. Chem., 1968 21 2l6l. H.L. Bott, A.J. Poe and K. Shaw, Chem. Comm., 1968 793. P.A.W. Dean and D.F. Evans, J. Chem. Soc. (A), 1968 1151»·. J. Feeney, R. Haque, L.W. Reeves and C.P. Yue, Canad. J. Chem., 1966 46 1389F.M. Hall and S.J. Slater, Austral. J. Chem., 1968 21 2.663. B.N. Ivanov-Emin, V.A. Zaitseva, and A.M. Egorov, 7k. Neorg. Khim., 1968 13 2655· V.N. Krylov, E.V. Komarov, and M.F. Pushlenkov, Radiokhimiya, 1968 10 717, 719, 723. D.C. McCain and R.J. îtyers , J. Phys. Chem., 1968 72 Ull5. N.A. Parpiev and I.A. Maslennikov, Uzbek. Khim. Zh., 1968(2) 6, K. Srinivasan and G.A. Rechnitz, Analyt. Chem., 1968 40 509. K. Srinivasan and G.A. Rechnitz, Analyt. Chem., 1968 40 1818. K. Schaumburg and C. Deverell, J. Amer. Chem. Soc, 1968 90 2*+95. S.P. Tanner, J.B. Walker and G.R. Choppin, J. Inorg. Nuclear Chem., 1968 30 2067. N.E. Vanderborgh, Talanta 1968 15 1009. A. Aziz and S.J. Lyle, Anal. Chim. Acta, 1969 47 U9A. Aziz and S.J. Lyle, J. Inorg. Nuclear Chem., 1969 31 3^71. E.W. Baumann, J. Inorg. Nuclear Chem., 1969 31 3155. A.M. Bond, J. Electroanal. Chem., 1969 23 269. A.M. Bond, J. Electroanal. Chem., 1969 20 223. A.M. Bond, J. Electroanal. Chem., 1969 23 277. A.M. Bond, J. Electroanal. Chem., 1969 20 109. H. Diebler, Z. Phys. Chem. (Frankfurt), 1969 68 6k. H. Gamsjaeger, P.S. Schindler and B. Kleinert, Chimia, 1969 23 229. I. Grenthe and J. Varfeldt, Acta Chem. Scand., 1969 23 988. P. Gerding, Acta Chem. Scand., 1969 23 1695. A.A. Ivakin and E.M. Voronova, Zh. Neorg. Khim., 1969 14 1557. V.N. Krylov and E.V. Komarov, Radiokhimiya, 1969 11 105. V.N. Krylov, E.V. Komarov and M.F. Pushlenkov, Radiokhimiya, 1969 11 2hh. V.N. Krylov and E.V. Komarov, Radiokhimiya, 1969 11 101, 103, R.E. Mesmer and C F . Baes, Inorg. Chem., 1969 8 6l8. B. Noren, Acta Chem. Scand., 1969 23 931. B. Noren, Acta Chem. Scand., 1969 23 379. L. Pajdowski and Z. Karwecka, Roczniki Chem., 1969 43 1817. T. Ryhl, Acta Chem. Scand., 1969 23 2667. A. Aziz and S.J. Lyle, J. Inorg. Nuclear Chem., 1970 32 1925. N.S. Al-Niami, A.G. Wain and H.A.C. MacKay, J. Inorg. Nuclear Chem., 1970 32 2331. A.M. Bond, J. Electrochem. Soc., 1970 117 11U5 A.M. Bond and T.A. O'Donnell, J. Electroanal. Chem., 1970 26 137· A.M. Bond and G. Hefter, Inorg. Chem., 1970 9 1021. J.N. Butler and R. Huston, Anal. Chem., 1970 42 1308. A.M. Bond, J. Phys. Chem., 1970 74 331. E.W. Baumann, J. Inorg. Nuclear Chem., 1970 32 3823. A.M. Bond and R.J. Taylor, J. Electroanal. Chem., 1970 28 207. A.M. Bond, J. Electroanal* Chem., 1970 28 1+33. B. Elgquist, J. Inorg. Nuclear Chem., 1970 32 937. M.G. Hogben, K. Radley and L.W. Reeves, Canad. J. Chem., 1970 48 2960. K. Kleboth, Monatsch. Chem., 1970 101 767. N.A. Matwiyoff and W.E. Wageman, Inorg. Chem., 1970 9 1031. G. Neumann, Arkiv Kemi, 1970 32 229. G. Pilloni and F. Magno, Inorg. Chim. Acta, 1970 4 105. S. Scholle, Chem. Prum., 1970 20 hl6. J.B. Walker, J. Inorg. Nuclear Chem., 1970 32 2793. S. Ahrland and L. Kullberg, Acta Chem. Scand., 1971 25 3^57. R.P. Agarwal and E.C Moreno, Talanta, 1971 18 873. D. Aulangnier, H. Chermette, C. Martelet, J-P.Schlienger and J. Tousset, Bull. Soc. Chim. France, 1971 1135* S. Ahrland and L. Kullberg, Acta Chem. Scand., 1971 25 3^71. E.W. Baumann, Anal. Chim. Acta, 1971 54 189. A.M. Bond and G. Hefter, J. Inorg. Nuclear Chem., 1971 33 U29.

References

TIBb 71Bc 71Bd 71C 71Ca 71K 71N 71P 71R 71W 71Wa 72B 72Ba 72C 72D 72H 72K 72L 73A 73B 73Ba 73J 73K 73Ka 73N 73V 7^B 7*+G 7UH 7*+K 7^M 7^S 7I+V 7UVa 75C 75J 75N 75P 75V 75Va 76B 76Ba 76D 76K 76Ka 76P 76V 77B 77I 77V 76Bb* 77Ba* 78P* 78V*

A.M. Bond, Anal, Chim. Acta, 1971 53 159. A.M. Bond, J. Phys. Chem., 1971 75 261+0. A.M. Bond, Coord. Chem, Rev., 1971 6 377. J. Cadek, J. Vesely and Z. Sulcek, Coll. Czech. Chem. Comm., 1971 36 3377. 1971 3 907. R.O. Cook, A. Davies and L.A.K. Stavely, J. Chem. Thermodyn., P. Klotz, A. Mukherji, S. Feldberg and L. Newman, Inorg. Chem., 1971 10 lh0. B.I. Nabivanets and V.V. Lukachina, Ukr. Khim. Zh., 1971 37 581. Sect. A, 1971 P.R. Patel, E.C. Moreno and J.M. Patel, J. Res. Nat. Bur. Stand., 75 205. R.A. Robinson, W.C. Duer and R.G. Bates, Analyt. Chem., 1971 43 1862. Nuclear Chem., 1971 33 l8l3. J.B. Walker, C.R. Twine and G.R. Choppin, J. Inorg. L.J. Warren, Anal. Chim. Acta, 1971 53 199. A.M. Bond and G. Hefter, J. Inorg. Nuclear Chem., 1972 34 603. E.W. Baumann, J. Inorg. Nuclear Chem., 1972 34 687. A.K. Covington and J.M. Thain, J. Chem. Educ., 1972 49 55^. I, 1972 68 W.C. Duer, R.A. Robinson and R.G. Bates, J. Chem. Soc. Faraday Trans. 716. G. Hefter, J. Electroanal. Chem., 1972 39 3^5. M. Katoh and T. Yoshimori, Talanta, 1972 19 hoi. J.E. Land and C.V. Osborne, J. Less-Common Metals, 1972 29 1U7. S. Ahrland, Structure and Bonding, 1973 15 167. N. Bottazzini, V. Crespi and F. Perini, Chim. Ind. (Milan) 1973 55 697. Chem., 1973 42 1. A.M. Bond and G. Hefter, J. Electroanal. L. Johansson, Acta Chem. Scand., 1973 27 1832. Yu. A. Kozlov, V.V. Blokhin, V.V. Shurukhin and V.E. Mironov, Zh. Fiz, Khim., 1973 47 2386. A.J. Kresge and Y. Chiang, J. Phys. Chem., 1973 77 822, B. Noren, Acta Chem. Scand., 1973 27 1369. V.P. Vasil'ev and E.V. Kozlovskii, Zh. Neorg. Khim., 1973 18 2902. Yu. A. Buslaev, V.V. Peshkov and R.L. Davidovich, Dokl. Akad. Nauk SSSR, 197^ 214 1101. S. Gifford, W. Cherry, J. Jecnen and M. Readnour, Inorg. Chem., 1974 13 1434. G. Hefter, Coord. Chem. Rev., 19lh 12 221.. H. Kakihana and S. Ishiguro, Bull. Chem. Soc. Japan, 197^ 47 1665. Y U . I. Mikhailyuk and V.l. Gordienko, Zh. Neorg. Khim., 197^ 19 2033. M. Salomen and B.K. Stevenson, J. Chem. Eng. Data, 197^ 19 U2. V.P. Vasil'ev and E.V. Kozlovskii, Zh. Neorg. Khim., 197^ 19 l48l. V.P. Vasil'ev and E.V. Kozlovskii, Zh. Neorg. Khim., 1971*· 19 178l. G. Choppin and P.J. Unrein, in "Transplutonium Elements", (W. Müller and R. Lindner, Eds.) North-Holland, Amsterdam, 1976, p.97. L. Johansson, Acta Chem. Scand., 1975 A29 365. K.G. Nelson and K.N. Amin, J. Pharmaceut. Sei., 1975 64 350. S.K. Patil and V.V. Ramakrishna, Inorg. Nucl. Chem. Lett., 1975 H ^21. V.P. Vasil'ev and E.V. Kozlovskii, Zh. Neorg. Khim., 1975 20 II96. 1975 20 18. V.P. Vasil'ev, L.A. Kochergina and A.I. Lytkin, Zh. Neorg. Khim., S.V. Bagawde, V.V. Ramakrishna and S.K. Patil, J. Inorg. Nuclear Chem., 1976 38 1339. P. Beutler, K. Christen and H. Gamsjager, Chimia, 1976 30 10U. I. Dellien and L.G. Hepler, Canad. J. Chem., 1976 54 1383. L.A. Kul'vinova, V.V. Blokhin and V.E. Mironov, Zh. Fiz. Khim., 1976 50 1287. O.B. Khachaturyan and A.A. Belyakova, Zh. Fiz. Khim., 1916.50 26Ul. S.K. Patil and V.V. Ramakrishna, J. Inorg. Nuclear Chem., 1976 38 1075. V.P. Vasil'ev, E.V. Kozlovskii and G.L. Kokurina, Zh. Neorg. Khim., 1976 21 331^. C. Birraux, J-C. Landry and W. Haerdi, Anal. Chim. Acta, 1977 90 51. S. Ishiguro, C-F. Kao and H. Kakihana, Denki Kagaku, 1977 45 651. V.P. Vasil'ev, E.V. Kozlovskii and G.L. Kokurina, Zh. Neorg. Khim., 1977 22 1526. S.V. Bagawde, V.V. Ramakrishna and S.K. Patil, J. Inorg. Nuclear Chem., 1976 38 2085. S.V. Bagawde, V.V. Ramakrishna and S.K. Patil, Radiochem. Radioanal. Lett., 1977 31 56. S.K. Patil, V.V. Ramakrishna and M.V. Ramaniah, Coord. Chem. Rev. 1978 25 133. P.R. Vasudeva Rao, N.M. Gudi, S.V. Bagawde and S.K. Patil, J. Inorg. Nucl. Chem., 1978 40, in p r e s s .

* References added in proof.

71