I = 1/2 [CK+ x I2 + CBrAC- x I2 + 2ck+ x I2 + CS2O32- x 22]

where cis the concentration and z the charge of each ion i in the mixture.

Log10kr / dm-3 -0,526 -0,510 -0,490 -0,465 -0,437

mol-1min-1

I / mol dm-3 0,0020 0,0028 0,0040 0,0056 0,0080

0,0447 0,00529 0,0633 0,0748 0,0894

√I / mol dm -3

A plot of log10 kr against √I is given in figure 8.4. The graph is linear with slope =
2.01dm3/2 mo-1/2, which is in good agreement with the predicted value for 2AzAzB of 2 x
2 x 0.51 dm3/2 moi-1/2= 2.04 dm3/2 mol-1/2 , and intercept= log10k0 = -0.615 = 1.385. This
gives

K0 = 0,243 dm3 mol-1 min-1

Rearrangement of equation 8.16 gives

Kr
log10 ( ) = 2Az AzB √I
K0

Therefore a plot of log10 kr/k0 against√I is linear. Figure 8.5 shows this plot

for the ionic reactions listed in table 8.1. It is seen that for reactions
Figure 8.5 Variation of log10 kr/k0 with √I for a number of ionic reactions

[ Co(NH3)s Br ]2++ Hg2+ CH2 BrCOOCH3 + S2 03 2-

CH2BrCOO- + S2O32 - [Co(NH3)sBr] 2++ OH-

CH2 CICOO- + OH

between ions of like charge the slope is positive. Such reactions show a positive salt
effect; that is, the reaction rate increases with increasing ionic strength. For reactions
between ions of opposite charge the slope is negative. This corresponds to a negative
salt effect and the reaction rate decreases with increasing ionic strength. A reaction
between an ion and a neutral molecule such as the acid or alkaline hydrolysis of an ester
does not exhibit a primary salt effect.

8.4 Effect of pressure on reaction rates

The field of high-pressure chemistry is still in its early years and apparatus capable of
measuring reaction rates over a wide range of pressure is rather expensive. While the
average student is likely to have investigated the effect of temperature on a reaction rate
in his laboratory programme, he is unlikely to have access to equipment that measures
the effect of pressure on reaction rates. Nevertheless the information gained from such
experients has proved invaluable to the understanding of many reaction mechanisms. In
particular it provides a method of measuring volumes of activation.

From the van't Hoff equation

∆G = -RT ln K

But volume and free energy are related by

 G 
v T
 P 

or

  G    d ln K 
V   T   RT  T
 P   dP 
Giving

 d ln K  V
 T  
 dP  RT

The volume of activation ∆V*is defined as the change in volume in going from the
reactant state to the activated state. Therefore

 d ln K *   V * 
 T    (8.18)
 dp   RT 

Since kr = (kT/h)K*, the variation of rate constant with pressure is given by

 d ln Kr  V *
   (8.19)
 dp  RT

This relationship predicts that if the rate constant increases with increasing pressure, the
volume of the activated state is less than that of the reactants; that is, ∆V* is negative.
Conversely, a rate constant that increases with increasing pressure corresponds to a
positive ∆V*.

Volumes of activation can be determined from measurements of the rate

constant carried out over a wide range of pressure at constant temperature. Integration
of equation 8.19 gives

V *
ln Kr   p
RT

That is

V *
Log 10 Kr = log10 K0  p (8.20)
2,303PT

A plot of log 10 kr against p is therefore linear and the slope is given by ∆V*/2.303RT,

from which ∆V*is determined.

Example8.2

The following data were obtained by Laidler and Chen (Trans. Faraday Soc. 54 (1958),
1026) for the alkaline hydrolysis of methyl acetate at 25° C
Pressure/MN m-2 0.1 27.6 55.2 82.7

Rate constant kr/dm3 mol-1s-1 0.146 0.163 0.181 0.203

Calculate the volume of activation.

Equation 8.20 predicts that a plot oflog10 kr against p will be linear.

log10 kr/dm3 mor-1 s-1 1,164 1,212 1,258 1,308

p/MN m-2 0,1 27,6 55,2 82,7

The graph is drawn in figure 8.6. From the graph

V *
Slope = = 1,74 x 10-3m2 (MN)-1
2,303RT

that is

∆V* = -1,74 x 10-3 x 10-6 x 2,303 x 8,314 x 298 m3 mol-1

=-9,93 x 10-6 m3 mol-1 = -9,93 cm3 mol-1

Figure 8.6 Variation of rate constant with pressure for the alkaline hydrolysis of methyl
acetate

Problems

1. The reaction between persulphate ions and iodide ions is as follows

 SzO82- + 21- 2SO42-+ I2

Using an initial concentration of 1.5 x 10-4 mol dm-3 potassium persulphate, King and
Jacobs (J. Am. chem. Soc., 53 (1931), 53) obtained the following values of the rate
constant kr at the concentrations of potassium iodide given

103 [KI] /mol dm- 3 1,6 2,0 3,2 4,0 6,0 8,0 10,00

10 kr/dm3mol-1 min-1 1,03 1,05 1,12 1,16 1,18 1,26 1,32

Estimate zAzB for this reaction and calculate the rate constant when the activity
coefficients are unity.

2. Bnmsted and Livingstone (1. Am. chem. Soc., 49 (1927), 435) found rate constant at
l5°C of 1.52 dm3 mol-1 s-1 for the reaction

[CoBr(NH3)5] 2+ + OH- [Co(NH3)sOH]2+ + Br-

measured during an experiment when the initial concentration of [CoBr(NH3)5] ion

(present in the form of the bromide)was 5 x 10-4 mol dm-3 and the OH- ion concentration
(present as sodium hydroxide) was 7.05 x 10-4 mol dm- 3. Calculate (a) the rate constant
at zero ionic strength, and (b) the rate constant when the reaction mixture is made 5x
10-3 mol dm-3 with respect to sodium chloride.

3. The data below relate to the first-order hydrolysis of 2-chloro-2-methylbut-

3-yne in aqueous ethanol at 25° C.

(CH3)2CCIC≡CH + H2O (CH3)2(OH)C≡CH + HCI

Rate constant x 106/s-1 0,23 0,38 0,74 1,27 2,04

Pressure/MN m-2 0 107 213 317 421

Calculate the volume of activation

[University of Salford, B.Sc. (Part 2) 1968]

Further reading

References

1. E. Rabinovitch. Trans. Faraday Soc., 33 (1937), 1225.

2. J. N. Br.0nsted. Z. phys. Chern., 102 (1922), 169.

3. N. Bjerrum. Z. phys. Chern., 108 (1924), 82.

4. J. A. Christiansen. Z. phys. Chern., 113 (1924), 35; G. Scatchard.

Chern. Rev., 10 (1932), 229.

Reviews

C. W. Davies. Salt effects in solution kinetics. Progr. Reaction Kinetics,

1(1963),161.

B. Perlmutter-Hayman. The primary kinetic salt effect in aqueous solution.

Pro gr. Reaction Kinetics, 6 (1971 ), 239.

C. H. Rochester. Salt and medium effects on reaction rates in concentrated

solutions of acids and bases. Pro gr. Reaction Kinetics, 6 (1971), 143.

G. Kohnstam. The kinetic effects of pressure. Progr. Reactio'n Kinetics,

5 (1970), 335.

Books

E. A. Moelwyn-Hughes. Chemical Statics and Kinetics of Solution,

Academic Press, London ( 1971 ).

E. A. Moelwyn-Hughes. Kinetics of Reactions in Solution, Clarendon

Press, Oxford ( 194 7).

S. D. Hamann. Physico-Chemical Effects of Pressure, Butterworths,

London (1959), ch. 9.