TOPIC 2

Determination of Rate La
Method of Initial Rates
Method of Half-Lives
Varying-volume batch reactor
Method of Initial Rates

Determine reaction order and specific

rate constant
Series of experiments is carried out at
different initial concentration, CAO and -rAO is
determined for each run
Example:
 Exercise (a) :
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 r0 (M/s) CAo (M) CBo (M)
nt
1 1.25E-2 0.05 0.05
2 3.75E-2 0.15 0.05
3 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.
CHE594-Topic 2
 Exercise (b) :
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

Experime [ICl] [H2] Initial Rate

nt (mol/L) ( mol/L) (mol/(L*s))
1 0.10 0.01 0.002
2 0.20 0.01 0.004
3 0.10 0.04 0.008

CHE594-Topic 2
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
Taking the natural log of both sides

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

slope of (1-)
Example:
I.
Exercise (c) :
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.

(Answer : 35.38 mM; 1611.58s)

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 ttaken for the
reaction to be 80% complete, given that k, the
specific rate constant is 8.3x10-4s-1. What is the half-
life of the 2reaction?
CHE594-Topic
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

A accounts for both reaction stoichiometry

and the presence of inerts
Relationship between concentration and
conversion for isothermal varying volume
(varying density):