View Article Online / Journal Homepage / Table of Contents for this issue

160 J. Chem. SOC. (A), 1969

Published on 01 January 1969. Downloaded by University of Windsor on 22/10/2014 05:36:18.

The Kinetics of the Oxidation of Iodide Ions by Octacyanomolybdate(v)

Ions in Aqueous Solution
By M. H. Ford-Smith' and J. H. Rawsthorne, The Chemical Laboratory, The University of Sussex, Brightorr
BN1 9QJ, Sussex

The kinetics of the reaction ~ M O ( C N ) ~ ,+- 31- +~ M o ( C N ) , ~ +

- I,- have been studied as a function of temper-
ature and ionic strength. The reaction is first-order with respect to both the octacyanomolybdate(v) and iodide
concentrations and there is evidence of retardation by product octacyanomolybdate(Iv). The second-order rate
constant is kob6= 3.52 f 0.13M-' set.-' in the expression -d[M~(CN),~-l/dt= kobs[M~(CN)s3-] [I-] and the
activation energy and entropy of activation have the values , = 5.68 f 2-57 kcal./mole and AS* = -39 f 8.5 e.u.
at 25.7"Cand / = 0.1 M. The plot of log kobsagainst d / i s linear with a slope of +3.12,which suggests that ion-pairs
may not play an important role in this reaction.

MOST reported examples of the oxidation of iodide by I t is presumed that the reaction proceeds by an outer-
transition-metal ions involve complicated mechanisms sphere mechanism.
(which often include the formation of a metal ion-iodide
complex) and consequently have complicated rate ex- EXPERIMENTAL
pressions. The rate expression for the reaction 2Fe3+
+ 21- +
2Fe2+ I, has been shown to be:
The reaction was followed by manual spectrophotometric
measurement at 350 or 288 m p of the I,- produced by the
Rate = k,[Fe3+][I-I2/(1 + k2[Fe2+J/[Fe3+J) reaction in the presence of an excess of iodide. The cell
compartment of the Unicam SP 500 spectrophotometer was
and the rate expression for the reaction 2Fe(CN)63-$- thermostatted to better than & 0.05".
+
21- __t 2Fe(CN)64- I, has been the subject of many Solid K4Mo(CN),,2H,0 was prepared by the method of
publication^,^*^ but there seems to be general agreement Willard and Thielke and was recrystallised several times
that the reaction is first-order in [Fe(CN),,-] and from ethanol-water mixtures. Titration with ceric sul-
second-order in [I-]. The Cr,0,2- +
I- reaction has a phate showed it to be 100% pure. Aqueous solutions of
complicated rate expression4*5 and the Np(v) I- + K,Mo(CN), were prepared by the anodic oxidation of
reaction is fifth-order.6 The Mn0,- +
I- and aqueous K,Mo(CN), using a platinised titanium anode.
+
Co(NH3),12+ I- reactions7p8 are both first-order in Solutions of K,Mo(CN), were carefully protected from
light since light induces a rapid reduction of Mo(CN),~-
each reagent but slow steps are followed by a series of to Mo (CN)84-. Spectrophotometry and titration with ceric
fast subsequent reactions. sulphate indicated that 100yo conversion to Mo(CN),~-
We report that the reaction 2Mo(CN),,- +
31- _+ was obtained.
~Mo(CN),~- + I,- appears to be a simple second-order Our measurements of the spectra of Mo(ChT),,- and
reaction with the rate expression : Mo(CN),~- in aqueous solution gave the following results,
in fair agreement with previously published results.1-12

1A. J. Fudge and K. W. Sykes, J . Chem. SOC.,1952, 119.
3A. Indelli and G. C. Guaraldi, J . Chem. Soc., 1964, 36.
3 Y . A. Majid and K. E. Howlett, J . Chem. Soc. ( A ) , 1968,
679, and references therein.
R. F. Beard and N. W. Taylor, J . Anzer. Chem. Soc., 1929,
51, 1973.
K. E. Howlett and S. Sarsfield, J . Chem. SOC. ( A ) , 1968,
683.
N. K. Shastri, J. 0. Wear, and E. S. Amis, J . Ilnorg. Nuclear
Chem., 1962, 24, 535.
7 L. J . Kirschenbaum and J. R. Sutter, J . Phys. Chem., 1966,
70, 3863.
8 R. G. Yalman, Inorg. Chem., 1962, 1, 16.
H. H. Willard and R. C. Thielke, J . Amer. Chem. Soc., 1935,
57, 2609.
10 J. R . Perumareddi, A. D. Liehr, and A. W. Adamson, J .
Amer. Chem. SOC.,1963, 85, 249.
11 P. C. H. Mitchell and R. J. P. Williams, J . Chem. SOC.,1962,
4670.
la R. M. Golding and A. Carrington, Mol. Phys., 1962, 5 , 377.
 View Article Online

Inorg. Phys. Theor. 161

Mo(CN)84- are in Table 1. The second-order rate constant was
A,., (mp) ........,...... 239 368 4 1Osh measured at four temperatures and the results are in Table
E., (M-, cm.-l) ...... 13,000 f 1000 160 & 5 91 2. A plot of log /cobs against 1/T yielded E, = 5.68 f 2.97
MO(CN)83-
A,, (mp) ............... 254 268 388
smX. (M-1 cm.-l) ...... 2630 2550 1280
The required ionic strength in reaction mixtures was
obtained using sodium perchlorate as the ' inert ' electro-
lyte. Reagent concentrations of Mo(CN),~-were 6 x l O d 5 ~
Published on 01 January 1969. Downloaded by University of Windsor on 22/10/2014 05:36:18.

in all runs and were prepared by suitable dilution of stock

solutions. Iodide concentrations were in the range
5 x 10-4-5 x 1 0 - 3 ~ .

RESULTS
9 O.Ot
*o
0,
-0
9
Iodide was present in reaction mixtures in at least a ten- -0-
fold excess over the octacyanomolybdate(v), and under
these conditions the reaction was pseudo-first-order with
respect to Mo(CN),3-. Plots of log,, (O.D., - O.D.,)
against time (where O.D., was the optical density after
about ten half-lives and O.D.t was the optical density a t 0 0.05 0.10
time t ) gave straight lines up to about 70% reaction. A J7
typical plot is shown in Figure 1. FIGURE
3 Pla of log,, hob8 against 1 / I ; t = 29.8"~

kcal./mole and AS* = -39 f 8.5 e.u. a t 2 9 8 . 2 " ~ . The

divergence of the log,, (O.D., - O.D.,) uewysus t plots from
linearity a t high yo reaction suggested that some re-
tardation by product Mo(CN),4- might be occurring. Runs

TABLE 1
Pseudo-first-order rate constants (K,) and second-order rate
constants (I&) a t various iodide ion concentrations
[Mo(CN),3-] = 5 x ~ O + M ; I = 0 . 1 0 ~ ;t = 2 9 . 8 " ~
lO4rI-l (M) A (mp) lO3k, (sec.-l) kobe ( M - ~sec.-l)
5.0 350 2-00 4.00
t (min.) 5.0 288 2-00 4.00
FIGURE1 Plot of log,, (O.D., - 0.D.J against time; 7.5 350 3.05 4.07
[Mo(CN),~-] = 5 x 1 0 - 6 ~ ; [I-] = 1 x 1 0 - 3 ~ ; I = 4.90 x 7.5 288 3-00 4.00
1 0 - 3 ~ ;t = 29.80~ 10.0 350 3.93 3.93
10.0 350 3.9 1 3.92
25.0 350 10.46 4.18
A plot of the logarithm of the pseudo-first-order rate 25.0 350 10.36 4-15
constant K, against log,, [I-], shown in Figure 2, gave a 50.0 350 20.75 4-15
50.0 350 18.28 3-65

6
50.0 350 23-50 4.70
-"7- 10.0 a 350 3.88
Average: 4-07 f 0.24
3.88

-2.0 L 10.0 b
a [Mo(CN),4-]
350 2.95 2-95
initially = 5 x 1 0 - 5 ~ .a [Mo(CN),~-] ini-

*-Q I /
/ tially = 1 x 1 0 - 4 ~ .

TABLE2
The variation of the second-order rate
constant with temperature
Number of runs Temp. ("c) kobs (M-, sec.-l)

-3.2 -2.8 -2.4 6 25.7" 3.52 f 0.13

11 29.8 4.07 f 0.24
'og,, [I-I 8 37.5 4.67 f 0.23
4 45.4 6.54 f 0.34
2 Plot of log,, k, against log,, [I-] ; t = 2 9 . 8 ";~
FIGURE
I = 0.1M
were accordingly carried out in which various concentra-
straight line of slope 1-02 f 0.05, which is the order of the tions of Mo(CN),~-were added, and some of the results for
reaction with respect to iodide. Thus it is clear that the these runs are included in Table 1. It is seen that there is
reaction is accurately first-order with respect to iodide and evidence that Mo(CN),4- does retard the reaction.
approximately first-order with respect to octacyanomolyb- The variation of rate constant with ionic strength was
date(v) concentrations. investigated for a range of ionic strengths from I = 1.6 x
The calculated second-order rate constants, kobs, a t 2 9 . 8 " ~ to I = 1 x 10-ZM. A plot of log,, bobs against d1 is
 View Article Online

162 J. Chem. SOC. (A), 1969

shown in Figure 3. A straight line was obtained of slope
+3.12 with an intercept of kobs = 0-68h1-lsec.-l, the second-
order rate constant extrapolated to zero ionic strength.
Using the expression log k = log k , + 2QZ,Z,dI (where
Q has the value 0.51 a t 25c) we calculate that ZAAB =
+-3-06.
DISCUSSION
+
Since the rate of the reaction ~Mo(CN),~- 31- _t
+
Published on 01 January 1969. Downloaded by University of Windsor on 22/10/2014 05:36:18.
+3-06 for the plot of log kobs against 2/1 is very close
to that expected for this reaction. Secondly, after this
work was completed, Majid and Howlett published
their interpretation of the observed salt effects for the
hexacyanoferrate(1x1)-iodide reaction. They success-
fully interpret many apparently conflicting results for
the reaction by assuming that s+eci$c salt effects are
operating and that every cation and anion affects the
rate to a different degree. In the present work the

~Mo(CN),~- I,- obeys the rate expression
2d [I3-]/dt = -~ [ M (CN),3-]
o /dt = kobs [MO(CN)83-1 [I-]
the mechanism of the reaction must presumably be :
ionic strength was varied using sodium perchlorate and
we find that one can equate the change in rate as a
function of ionic strength satisfactorily with the change
in a+].
One can write the rate expression:

-
k,
Mo(CN),3- + I- + Mo(CN),~-+ I. (1)
k-2 -d[Mo (CN),3-] /dt = k,[Mo(CN) 2-1[I-1 a+]
k
21. I, (2) corresponding to the mechanism :
I, + I- +I,- fast (3) Mo(CN):- Na+ + Mo(CN),Na2- (4)
in which case kob; = 2k,. The deviations of the first- MO(CN),Na2- 1- +
+ Mo(CN),Na3-
, -t I* (5)
order plots from linearity and the results for those runs A plot of kobsagainst a+] is shown in Figure 4 and it is
in which Mo(CN),~-was added suggest that reaction (1) seen that a straight line results, the slope of which
is reversible and that there is competition between
Mo(CN),~- and iodine atoms for reaction with iodine
atoms. Unfortunately the system of reactions (1) +(2)
is not amenable to quantitative analysis so it has not
been possible to obtain an estimate of k-,/k from the
available data.
The rate expression is in marked contrast to that for
the formally very similar ferricyanide-iodide reaction,
where rate a CI-12. The second-order dependence on
[I-] of both the Fe3+-I- and Fe(CN),3--I- reactions has
been attributed to inner-sphere complex formation
followed by oxidation of co-ordinated iodide in a re- I I I I I 1
action with the second iodide ion to yield the 1,- ion- 2 4 6 8 10
radical.1-3 lo3[NO] (M)
Fe(CN):- + I- Fe(CN),14- 4 Plot of hobs against a+] ; t
FIGURE = 29.8~
Fe(CN),14- + 1- +Fe(CN)2- + 1,- -
yields k, = 53 M-, set.-,, with an intercept of ktobs 0.90
Fe3+ + I- +Fe12+ M-l sec.-l a t a+] = 0. A plot Of log10 (hobs.- ktobs)
Fe12+ + I- +Fe2++ I,- against log,, a+] produces a straight line of slope 4 . 9 ,
the order with respect to a+].
It must be presumed that octacyanomolybdate(v) does
The value of kobs in the absence of sodium ions,
not react by a similar mechanism because Mo(v) is
ktobs-0.90 M - ~ sec.-l can either be attributed to a
reluctant to expand its co-ordination number from 8 to 9,
cation independent reaction mechanism [reactions
even though 10-co-ordinated Mo(xv)-CN- compounds
(1)-(3)] or t o the potassium ions present in solution
have been reported.13 Instead, Mo(CN),3- appears to
react uia an outer-sphere mechanism which does not
[arising from KI and K,Mo(CN),. Since [K+] lo-, M,
this gives a value of k, - -
900 M-, set.-, for k, in the
necessarily involve the formation of I,- as an inter-
expression :
mediate.
The results for the variation of rate constant with ionic -d [Mo (CN2-]/dt = k, [Mo(CN)2-1[I-] [K+]
strength can be interpreted in two ways. Firstly, one can
assume that the variation is caused by a general salt effect The result that k,/k,
of the results obtained by
-
17 seems unreasonable in view
Majid and Howlett that I(+
on the rate of the Mo(CN)Z--I- reaction, due to the effect
of changes in ionic strength on ionic activities, and that was only about twice as effective as Na+ in catalysing
outer-sphere complexes such as N~MO(CN),~- do not the Fe(CN),3- - I- reaction, and similar results for
play a significant role in the reaction. The slope of other cations obtained by Wahl and his co-workers l4for
13 W. Jacob, A. Samotus, and 2. Stasicka, Proc. 7th Inter- 14 R. J. Campion, C. F. Deck, P. King, and A. C. Wahl, Inorg.
national Conference on Coordination Chemistry, 1962, 238. Chenz., 1967, 6, 672.
 View Article Online

Inorg. Phys. Theor. 163

the Fe(CN),3- to Fe(CN),4- exchange reaction, and leads Mo(CN),3- and I-, although the entropy change for
us to prefer the explanation in terms of a general salt reaction (4) is not known so the mechanism involving
effect on the rate of the reaction. NaMo(CN)i2- cannot be rejected.
The value of AS* = -40.4 & 8.5 e.u. corresponding
to k , for the reaction Mo(CN),3- +I- MO(CN),~- We wish to acknowledge with thanks the receipt of a
+ I. is in quite good agreement with the value of Research Studentship (for J. H. R.) and a grant for appara-
-30 e.u. calculated from the equation AS* = - 1 0 2 ~ 2 ~tus, both from the S.R.C.
which assumes, among other things, that the only con-
[S / 1235 Received, August 23rd, 19681
tribution to the entropy of activation arises from the
Published on 01 January 1969. Downloaded by University of Windsor on 22/10/2014 05:36:18.

electrostatic free energy term.15 This is slight evidence 16 A. A. Frost and R. G. Pearson, ' Kinetics and Mechanism,'
in support of the mechanism involving reaction between 2nd edn., Wiley, London, 1961, p. 146.