Kinetics of Chlorate-chloride reaction

Chlorine dioxide is used as an oxidizing species in large scale industrial processes such as pulp and
textile bleaching. One of the most important preparation method is the reaction between chlorate and
chloride in strong acidic condition.
23 + 2 + 4 + 2 + 22 + 22
The kinetics of the reaction was studied using UV-vis spectrophotometry at 25.0 C. It is considered to
have a simple rate law equation (Sant Anna et al., 2012):
2
= [3 ] [ ] [ + ]

The effect of initial hydrogen ion concentration on the initial rate of reaction was studied using method
of initial rates. Note that HCl and HClO4 are strong acids.
Run [3 ] , [] , [] , [4 ] ,
1
2

0.2
0.2

0.2
0.3

0.3
0.2

3.3
3.3

2
, /

1.79510-5
1.65010-5

1. Determine the initial concentration of chlorate, chloride and hydrogen ion in each run.
2. Determine the order of the reaction with respect to hydrogen ion.
The change in the concentration of chlorate and chloride with respect to time was studied. For the first
experiment, the initial concentration of chloride and hydrogen ion was very large with respect to the
initial concentration of chlorate (thus keeping their concentrations approximate constant):
,
0
60
180
300
600

[3 ],
0.0500
0.0476
0.0433
0.0393
0.0308

3. Determine the order of the reaction with respect to chlorate.

For the second experiment, the initial concentration of chlorate and hydrogen ion was very large with
respect to the initial concentration of chloride (thus keeping their concentrations approximate constant):
,
0
60
180
300
600

[ ],
0.0500
0.0471
0.0419
0.0372
0.0276

4. Determine the order of the reaction with respect to chloride.

5. Determine the rate constant k.
6. Determine the initial concentrations of each fixed species per experiment if the fixed species have
the same initial concentration.
7. If the rate law must be expressed for the overall expression, what must be the value of the rate
constant?