The effect of added electrolytes (up to 2M) on the reaction between persulfate and iodide ions was reinvestigated, utilizing the absorption of I3— in the near ultraviolet to follow the reaction. The effect could be represented very well by the empirical relation over the entire range, where A, B, and D are constants specific for the cation (uni‐, di‐, or trivalent) employed, and k0 and k are the rate constants in the absence and in the presence of added electrolyte at concentration c.
The inapplicability of the concept of ionic strength to the reaction between two anions is discussed and contrasted with the behavior of reactions between ions of unlike sign.
REFERENCES
1.
2.
Miryam
Bobtelsky
, B.
Perlmutter‐Hayman
, and G.
Stein
, Bull. Res. Council Israel Sect.
A9
, 195
(1960
).3.
4.
5.
C. V.
King
and M. B.
Jacobs
, J. Am. Chem. Soc.
53
, 1704
(1931
)., J. Am. Chem. Soc.
6.
7.
W. G. Howells, J. Chem. Soc. 1939, 463;
1941, 641;
1940, 203.
8.
V. Carassiti and C. Dejak, Atti Accad. Sci. Ist. Bologna, classe Sci. Fis., Rend., 11, 2 (1955);
Ann. Chim. (Rome)
49
, 233
(1959
).9.
10.
A. Indelli and J. E. Prue, J. Chem. Soc. 1959, 107.
11.
12.
see, however, F. A. Westheimer in A Symposium on Enzyme Action, edited by W. D. McElroy and B. Glass (The John Hopkins Press, Baltimore, Maryland, 1954), p. 335.
13.
14.
Y. Katzhandler, M.Sc. thesis, Jerusalem, 1958.
15.
H. A.
Benesi
and J. H.
Hildebrand
, J. Am. Chem. Soc.
71
, 2703
(1949
).16.
A. O.
Allen
, C. J.
Hochanadel
, J. A.
Ghormley
, and T. W.
Davis
, J. Phys. Chem.
56
, 575
(1952
).17.
T. C.
Allen
and R. M.
Keefer
, J. Am. Chem. Soc.
77
, 2957
(1955
); , J. Am. Chem. Soc.
18.
M.
Davies
and E.
Gwynne
, J. Am. Chem. Soc.
74
, 2748
(1952
) , J. Am. Chem. Soc.
L. I.
Katzin
and E.
Gebert
, J. Am. Chem. Soc.
77
, 5814
(1955
) , J. Am. Chem. Soc.
19.
D.
Meyerstein
and A.
Treinin
, Trans. Faraday Soc.
57
, 2104
(1961
). We are indebted to J. Jortner for suggesting this method of analysis of nitrate solutions.20.
A. R.
Olson
and T. R.
Simonson
, J. Chem. Phys.
17
, 348
, 1322
(1949
).21.
22.
G. B.
Bonino
and E.
Rolla
, Att. Accad. Nazl. Lincei Mem. Classe Sci. Fis. Mat. Nat.
3
, 445
(1947
).23.
24.
Similarly, a plot of the type of Gryder’s Fig. 6 will be linear at sufficiently high concentrations, where the changes in logk are due mainly to the term Dc in our Eq. (2). A sensitive test for Gryder’s Eq. (9) [obtained by using Eq. (8) twice] is provided only if the slope has the correct value of Unfortunately, the value of for the persulfate‐iodide and bromoacetate‐thiosulfate reactions, used by Gryder to illustrate his Eqs. (8) and (9), seems somewhat uncertain.
25.
C. W. Davies, Ion Association (Butterworths Scientific Publications, Ltd., London, 1962), (a) p. 39;
26.
A.
Indelli
, G.
Nolan
, and E. S.
Amis
, J. Am. Chem. Soc.
82
, 3233
(1960
);27.
Ion‐pair formation is probably the reason why negative values of b sometimes fit the data for activity coefficients, as, e.g., in E. A. Guggenheim and J. E. Prue, Physico‐Chemical Calculations (North‐Holland Publishing Company, Amsterdam, The Netherlands, 1956), pp. 228 and 446; Guggenheim, Ref. 25.
28.
29.
J. C. Lalor and E. A. Moelwyn‐Hughes, J. Chem. Soc. 1963, 1560 [We recalculated these results and found that they fitted Eq. (3) at least as well as they fit the slightly different expression proposed by the authors.];
F.
Bell
, R.
Gill
, D.
Holden
, and W. F. K.
Wynne‐Jones
, J. Phys. Colloid Chem.
55
, 874
(1951
).30.
B. Perlmutter‐Hayman and Y. Weissmann (to be published).
31.
A.
Indelli
, G.
Nolan
, and E. S.
Amis
, J. Am. Chem. Soc.
82
, 3237
(1960
).32.
According to
Healy
and Kilpatrick
[J. Am. Chem. Soc.
77
, 5258
(1955
)], the kinetic results cannot be accounted for by a single reaction between and and the salt effect consists in a competition between and to form either or the former being hydrolyzed more rapidly.33.
J. N. Brønsted, ibid. 44, 877 (1922).
34.
E. A. Moelwyn‐Hughes, The Kinetics of Reactions in Solution (Oxford University Press, London, 1947) p. 102;
S. Glasstone, K. J. Laidler and H. Eyring, The Theory of Rate Processes (McGraw‐Hill Book Company, Inc., New York 1941), p. 423 ff.
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