Compound Forming Extractants, Solvating Solvents and Inert Solvents

49 Pages·1977·2.444 MB·English

by  Y. Marcus, E. Yanir and A. S. Kertes (Auth.)

COMMISSION ON EQUILIBRIUM DATA (1975)
Titular Members: G. H. Nancollas (Chairman), S. Ahrland (Secretary),
G. Anderegg, M. T. Beck, E. Hogfeldt, A. S. Kertes, D. D. Perrin, J. Stary.
Associate Members: R. Battino, A. F. Clifford, H. Freiser, D. N. Hume,
Y. Marcus, H. Ohtaki, C. L. Young. National Representatives:
I. N. Marov (USSR), H. M. N. H. Irving (UK), A. E. Martell (USA)
INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY
ANALYTICAL CHEMISTRY DIVISION
COMMISSION ON EQUILIBRIUM DATA
IUPAC CHEMICAL DATA SERIES - No. 15
Equilibrium Constants of Liquid — Liquid Distribution Reactions
PART III: COMPOUND FORMING
EXTRACTANTS, SOLVATING SOLVENTS AND
INERT SOLVENTS
Prepared for publication by
Y. MARCUS, E. YANIR and A. S. KERTES
The Hebrew University of Jerusalem,
Jerusalem, Israel
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INTRODUCTION
This report represents the third part of the compilation of Equilibrium Constants of
Liquid-Liquid Distribution Reactions. The work has been sponsored by Commission V.6,
Equilibrium Data, Division of Analytical Chemistry, of the International Union of Pure and
Applied Chemistry (IUPAC). The work has been supported financially by the Office of Standard
Reference Data, the U.S. National Bureau of Standards, and is a part of its Standard
Reference Data Series.
The report consists of tables compiling equilibrium constants. All the solvents
included in the list in Appendix A of the Introduction to this Series (Part I) have been
looked up in the literature. In all cases, only systems in which equilibrium constants
have been calculated are included in this compilation. The tables on pages 2-17 are for
distribution reactions of carboyxlic and sulfonic acid extractants, for their dimerization
and other reactions in the organic phase, and for extraction reactions of metal ions from
aqueous solutions. The inorganic anions in these solutions are usually irrelevant, since
they do not participate in the extraction reaction, hence are not properly called ligands.
The extractants themselves are acids, which exchange their hydrogen ions (rarely also
alkali metal ions), for the extracted metal ions, which form compounds with extractants.
Since the extractants are monofunctional carboxylic or sulfonic acids, no chelates are
formed.
The tables on pages 18-30 deal with the distribution of inorganic acids, salts and
complexes between aqueous solutions and solvents which have oxygen donor atoms. Here the
anions may act as ligands, and have been specified as such. The tables on pages 33-46 deal
with the distribution of inorganic acids, salts and complexes between aqueous solutions and
inert solvents, which do not have donor atoms, and which are often employed as, hopefully,
inert diluents,
The literature searched covers the period 1947-1971 inclusive. The sources searched
have been specified in the general introduction to the series, in Part I. The general
arrangement of the tables is the same as used there and explained there in detail. In the
reactions, the extractants are denoted by HS for the carboxylic and sulfonic acid extrac­
tants, and by S for the solvating and inert solvents. The ligands, if present, are denoted
by A" for univalent anions. A bar over the symbols denotes the organic phase. The equilib­
rium constants are in the molar scale, unless otherwise noted. The temperature is in
degrees centigrade. Values of AH and AS for the extraction reactions are in kcal mol-1,
respectively in cal K^mol"1 (1 cal = 4.184J), and refer to the standard states of infinite
dilution of all solutes. The figures in the "conditions" columns are molar concentrations
(mol dm ),
1
2
REF. 69S,67S 70K 69S 68S 70K 70A 70A 69H 70K 69S 70K 70A 67S,69S 70K 69S S8S

CONDITIONS, ORG. HS 0.3-3 in benzene HS in benzene HS 1.0, 0.3 in CHC1 3 HS 0.05-3.0 in CHC1 3 HS in 1,2 dichlorobenzene HS 0-0.2 in dodecane HS 0-0.2 in hexadecane HS in hexane HS in isopropylether HS 0.1-3.0 in 4-methyl-2- pentanone HS in nitrobenzene HS 0-0.2 in octane HS 0.3-3.0 in benzene HS in benzene HS 0.3, 1.0 in CHC13 HS 0.05-3.0 in CHC13
AQ. ts J
CONDITIONS, -Forming Extractan NaC10 0.1 4 ++(Na,H)C10" 0.14 NaClO. 0.1 4 NaClO, 0.1 4 ++(Na,H)C10~ 0.14 H0 2 H2° 0 H2 ++CNa,H)C10" 0.14 NaC10„ 0.1 4 ++(Na,H)C10~ 0.1 0 H2 NaC10„ 0.1 (?) 4 ++(Na,H)C10 0.1 4 NaC10 0.1 4 NaC10 0.1 4
d
n )
TEMP. ompou 27 25 27 27 25 20 20 25 25 27 25 20 27(? 25 27 27
C

:
LOG K Class 0.5 0.31 0.9 0.7 0.82 1.26 1.13 0.8 1.48 1.6 0.77 1.35 2.2 2.45 1.6 2.1
t
n
a
t
c
a
r
t
x
E
N
O
I
T
C S
H
A
E d,
R i
c
A
c 2
i )
o S
n H
a (
x S
e H =
H
= S
n n H
: o S o
t i H i 2
n t t
a u a
t b z
METAL ION, M Extrac Distri Dimeri
3

C C C C C
EF. a a a ,69 ,69 ,69 ,69 ,69
R K K K S S K S S S S S S S S S
0 0 0 9 9 0 9 9 9 9 8 8 8 8 8
7 7 7 6 6 7 6 6 6 6 6 6 6 6 6
-
a
CONDITIONS, ORG. 1,2 dichlorobenzene isopropylether nitrobenzene in 4-methyl 2-penta- in CHC13 in benzene -3 in benzene -3 in CHC13 -3 in 4-methyl-2-pent -3 in CHC13 5-3 in CHC13
0 0 0 3 3 1 3 0
n n n . . . . . . . .
i i i 1 e 1 1 0 0 0 e 0 0
n n
S S S S o S S S S S o S S
H H H H n H H H H H n H H
Q.
A
NS. 0.1
TIO ~ ~ ~
CONDI +,H)C10 4+,H)C104 +,H)C104 0 0.1 4 O, 0.1 4 +,H)C104 0 0.1 4 O, 0.1 4 0 0.1 4 O, 0.1 4 0 0.1 4
+Na +Na +Na aC1 aCI +Na aC1 aCl aC1 aCl aC1
( ( ( N N ( N N N N N
EMP. 25 25 25 27 27 25 27 27 27 27 27 27 27 27 27
T

K 19 19 96 9 9 48 3 3 6 6 5 6 3 0 0
OG 1. -0. 0. 7. 7. 11. 4. 4. 3. 1. 10. 9. 12. 14. 3.
L -
+
H
4

ON ) S)5 ) +2 ) S)"2 ) S)2 S)3
I S H S S H S H H
T H ( H H ( H ( (
EAC MS(3 = MS3 (MS-2 MS(2 = MS2 MS(3 = MS3 = MS3 S)3
R (HS) 2 3S + HS = 3S" + 5HS 3(HS) = 2 2S" + HS = + S" = MS 2S" + 2HS 3S~ + HS = 3S~ + 2HS 3S~ + 3HS ) = MS(H33
HS =2 +3M + +3M + +22M + +2M + +2 + M +3M + +3 + M +3 + M +3M + MS(HS3

n
L M io
META ION. tract +2 +2 +3
x u n n
E C Z l
4
REF. 69S 61A 69S 69S/65K 65P 58G/65P 69S 69S

e
n
e
z
n
e
b

CONDITIONS, ORG. _4HS 10 -6 in benzene HS (mix C-C) 6.4 in?g 4HS 10" -6 in CHC1 3 HS in decane HS in heptane HS 0.012 in heptane _4HS 10-6 in hexane _4HS 10-6 in hexanol

0
.
Q. J 3
A 5 H
6 p
CONDITIONS. , U.S.A., 1967. A. Vol. 70, 1095 7 (1970). 33 (1970). y0.1(NaC10) 4 NaN0 0.0-6.0, 3 yO.l (NaC10) 4 HS dil. -> oo y0.16, pH 7.5 yO.l (NaC10) 4 yO.l (NaClC>) 4
. . 8 3
LOG K TEMP. References ennessee, Knoxville, Tenn him. Acta, 41, 23 (1968). , (4), 1565 (1969). ehti B, 4_2, 113 (1969); C him. Acta, 45_, 57 (1969). im. Acta, 47, 19 (1969). ay Soc., 66, 37 (1970). norg. Nucl. Chem., 32_, 9 norg. Nucl. Chem. 32_, 1 1.60 25 1.07-1.65 25 2.17 25 4.3 25 -1.92 23 0.63 23 0.7 25 3.3 25
T C 0 l C h d I I
3 i C a
f . t . r . .
rsity o ., Anal Int. B, , Kemis ., Anal , Anal. ans. Fa , M. , J , M. , J
ve .M . om .C M. Tr ka ka
i M s u F . a a
ON , Un on, . Ab ., S rd, i, S .W., Tan Tan , HS
CTI esis ders Diss a, E iffo ngha l, R and and H)0T
A h n l l a l . . (
RE .R., M.Sc. T , G.K. and A dward Chinn, K. and Tommi , G.K. and C , G.K. and S . and Mitche , Yoshida, M , Yoshida, M anoic acid, HS
V r E r r R . . t
e , e e I I c =
, z e n z z , O
y t c e t t d , , : S
e i n n i i r a a n H
r e e o e e a m m : o
b w r r w w y i i t i
w h a i h h e j j n t
a c l e c c v o o a u
METAL ON. M S S S S C C H H S S Sa S A A K K Ka K tract strib
I 7 8 9 9 9 9 0 0 0 x i
6 6 6 6 6 6 7 7 7 E D
5
B G B K P
8 1 4 5 5
F. a /2 /3 /3 /6 ,6 a
RE 1A 9S 7S 7S 9S 9S 7S 9S 9S 9S 9S 8S 8S 8S 8S 8E 1A 9S 9S
6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 5 6 6 6

) e
^ n
C a
- x e
^ l e n )
CONDITIONS, ORG. n kerosene (mix C 40"-6 in MiBK .01-1.0 in octano .0 in 1-octanol n olive-oil n petroleum-ether .0 undil. HS -4 0 -6 in benzene 40"-6 in CHC13 .01-0.2 in cycloh -4 0 -6 in decane .12 in dekaline -5 -3 0 -10 in hepta n kerosene (C^-Cg -4 0 -6 in hexane -4 -6 in hexanol 0
i 1 0 3 i i 7 1 1 0 1 0 1 i 1 1

S S S S S S S S S S S S S S S S
H H H H H H H H H H H H H H H H
Q.
A
CONDITIONS. HS ^ 0 yO.l (NaC10) 4 yO.l (NaC10) 4 ) yO.l (NaC104 H0 2 H0 2 yO.l (NaC10) 4 yO.l (NaC10) 4 ) UO.l (NaC104 - yO.l CNaC10) 4 - - - - y0.16, pH 7.5 HS + 0 yO.l (NaC10) 4 yO.l (NaC10) 4
TEMP. 25 25 27 25 ? ? 27 25 25 25 25 20 75 100 140 23 25 25 25

8 4 9
. . .
2 0 3
LOG K 1.11 3.07 2.9 2.5 ^2 1.65 2.1 2.5 2.46 2.4- 0.0- 3.50 2.61 2.0 2.22 3.76 0.63 3.6- -1.7
N
O
I
T
C
A
E
R

2
)
S
H
(
S
H =
=
S
S H
H
n 2
o
i
t
L M za
META ION. meri
i
D
C.F.E.S.I.S. C
6

S S G
EF. /57 /57 /31 a
R S S S S P D K M M M M A K
9 9 9 9 5 6 0 7 7 7 7 1 0
6 6 6 6 6 6 7 6 6 6 6 6 7
-
r e
a n e
l e n
u e e z e
c n n n z e
e a e e n n
G. ol pt nz e b be ze
R m r e e n n n
NS, O MiBK igh- in ethe in h in b enze 87 i 8 in n be
CONDITIO 410"-6 in 0.05m in h ght paraff in petrol- -5 -3 10 -10 -5 -4 10 -10 < 1.0 in b (C-C) 2.7g (C-C) 0.79 0.01-1.0 i
i
S S e S S S S S S S
H H w H H H H H H H

0
.
2
-
AQ. " 4 3.0 0.1
CONDITIONS. (NaC10) 4 , pH 7.5 ++(Na, H)C10 5, MOH < 1.0 0.0-6.0 pH + H, C10") 4
yO.l — - - y0.16 - yO.l pH 5. NaN03 +(Na,

TEMP. 25 46 179 ? 25 25 ? ? ? ? 25 25 ces 1931). 1957).
n ( (
e
0 r 1 8
. e 2 2
G K 2.0 2.11 0.4 2.4-3 1.0 4.31 1.6 7.00 6.62 6.07 6.16 2.5 1.65 Ref 85_, 3 6
LO - - < -1 - - - - - -1 . Chem., (1934). Chim.,
REACTION 2 HS = (HS)2 2 S" 2 •V!f HS + S = HSS 1,3 Diphenyl guanidine S' = tion + +2 + 3 (HS) = (MS.HS) + 4H2M222 + +(HS) = MS.HS + HM + 2 -i-+4 (HS) = MA.7HS + H M + 2 + +2 + 3 (HS) = (MS.HS) + 4H2M222 Bodansky, M., J. Biol. Chem., 79, 241 (1928) Grossfeld, J. and Miermeister, A., Z. Anal. Broughton, G., Trans. Faraday Soc, 30, 367 Sarbadi*, D.S. and De Baer, J.H., Rec. Trav.
c
METAL ION. M Extra +2 Cu + Li + Na + K + Cs +2 Cu 28B 31G 34B 57S
7
REF. REF. Ab Ab Ab Ab
8 8 8 8
6 6 6 6

RG; RG; kerosene kerosene
OO m
o o
TIONS, TIONS, 0 fr frm2
DIDI °
CONCON = CH in ction CH=i324 ct ion
a a
S r S r
H f H f
TIONS, AQ. TIONS, AQ. . . H09162 H012222
CONDICONDI _3, 272 (1961) 3_, 284 (1961) 33 (1965). (1967). . ). , 1333 (1970). 0, HS CH E2 H0, HS = C2
TEMP. imiya, imiya, SSSR, 1628 (1967) (1969 ., 32_ ? ? ? ?
h h , 5 m
k k . £ 6 6 e
REACTION LOG K Goodman, D.S., J. Amer. Chem. Soc, 80, 3887 (1958). Adamskii, N.M,, Karpacheva, S.M. and Sorokin, S.I., Radio Adamskii, N.M., Karpacheva, S.M. and Sorokin, S.I., Radio Pasupati Mukerjee, J. Phys. Chem., 2821 (1965). 69_, Kholkin, A.I. and Gindin, L.M., Izv. Sib. Otd. Akad. Nauk Davis, M.M. and Paabo, M., J. Org. Chem., 3JU 1804 (1966) Mikhailichenko, A.I. and Rozen, A.M., Zh. Neorg. Khim., 1 Schweitzer, G.K. and Howe, L.H., Anal. Chim. Acta, 37_, 31 Sterk, H., Monatsh. Chem., 99, 457 (1968). Schweitzer, G.K. and Morris, D.K., Anal. Chim. Acta, 45, Kojima, I., Uchida, M. and Tanaka, M., J. Inorg. Nucl. Ch tant: Naphthenic Acid(s), HS iation ^-4.3 + + S HS = H^-5.0 -7.5 HS = H* - S -6.4
METAL ION, M ION, M 58G 61A 61Aa 65P 65K 66D 67M 67S 68S 69S 70K Extrac Dissoc