TOPIC 2 (PART 2)

Determination of Rate Law

Constant-volume

of batch reactor
3. Method of Initial Rates
4. Method of Half-Lives
Varying-volume batch reactor

Method of Initial Rates

Determine

reaction order and specific

rate constant
Useful when the reaction is reversible
Series of experiments is carried out at
different initial concentration, CAO and -rAO
is determined for each run

Example 1:

Example 2:

A series of experiments is carried out at different initial

concentrations of each reactants, Cio and the initial rate of
reaction, -ro is determined in each run. For the reaction:
3A + 2B products
The following data on initial rates were obtained
experimentally:
Experime
nt

r0 (M/s)

CAo (M)

CBo (M)

1.25E-2

0.05

0.05

3.75E-2

0.15

0.05

5.00E-2

0.05

0.10

a) Determine the kinetic orders with respect to A and B

b) Determine the rate constant and write the rate law.

Example 3:
Determine the reaction order for the reactants in the
reaction below given the table of data on initial rate.
Write the rate law for the reaction and determine the
value of the rate constant k.
Reaction: 2ICl +

H2

I2 + 2HCl

Experimen
Initial Rate
[ICl] (mol/L) [H2] ( mol/L)
t
(mol/(L*s))
1
2
3

0.10
0.20
0.10

0.01
0.01
0.04

0.002
0.004
0.008

Method of Half Lives

The

half-life reaction, t1/2, is defined as the

time it takes for the concentration of the
reactant to fall to half of its initial value.

Time required
for the
concentration
to fall to 1/n of
the initial
value

 Taking

Plot

the natural log of both sides

ln t1/2 as a function of ln CA0 will get

the slope of (1-)

Example 1:
I.

Compound A undergoes a decomposition reaction,

which obeys 1st order kinetics, with a specific rate
constant, k= 5.14x10-4 s-1. Determine the
concentration of A that remains 780s after it
commences to decompose at 83oC, if the initial
concentration of A is 53 mM. Determine also the
time taken for the concentration of A to decrease
from 53mM to 23 mM at the same temperature.

II. Given that the initial concentration of a compound A,

being consumed in a reaction obeying first order
kinetics, is 13.7 mM, determine the taken for the
reaction to be 80% complete, given that k, the
specific rate constant is 8.3x10-4s-1. What is the halflife of the reaction?

Example 3:
The following reaction is first-order in N2O3 and has
a half-life of 19.25 minutes
N2O5 (g) 2NO2 (g) + O2 (g)
How long will it take for the concentration of N2O5
to decrease from 0.050 mol/L to 0.030 mol/L
The half life for the second order decomposition of
HI is 15.4 s when the initial concentration of HI is
0.67 M. What is the rate constant for this reaction?
The first order decomposition of N2O5 at 328 K has
a rate constant of 1.70x10^-3 s^-1. If the initial
concentration of N2O5 is 2.88 M, what is the
concentration of N2O5 after 12.5 minutes?

Example 4:
For an elementary reaction of
2A B
Prove that the half life of this reaction to be
t1/2 = 2/CAO with rate constant of 0.5 L/mol.s
(10 marks)

arying volume of batch reacto

Much

complex than simple constant-volume batch reactor.

Usually main use would be in micro processing field where
a capillary tube with a moveable bead would represent the
reactor.

This

reactor is used for isothermal constant pressure

operations for reactions having a single stoichiometry.

 For

this system, the volume is linearly

related to the conversion

Differentiating

to produce

which A is fractional change in volume of

the system between no conversion and
complete conversion of reactant A, thus

 For

example

Another

example

accounts for both reaction stoichiometry

and the presence of inerts

 Relationship

between concentration and

conversion for isothermal varying volume
(varying density):