School of Chemical and Materials Engineering (SCME)

Chemical Reaction Engineering Lab (CHE-347L)

ASSIGNMENT 1- METHODS OF DETERMINING REACTION

KINETICS

Submitted by: Rida Riaz

Roll No: 215628
Introduction
Chemical reaction kinetics deals with the rates of chemical processes. Any chemical
process may be broken down into a sequence of one or more single-step processes
known as elementary reactions. Elementary reactions usually involve either a single
reactive collision between two molecules, which we refer to as a bimolecular step, or
dissociation/isomerisation of a single reactant molecule, which we refer to as a
unimolecular step.
The huge variety of chemical species, types of reaction, and the accompanying
potential energy surfaces involved means that the timescale over which chemical
reactions occur covers many orders of magnitude, from very slow reactions, such as
iron rusting, to extremely fast reactions, such as the combustion reactions occurring
in flames.
A study into the kinetics of a chemical reaction is usually carried out with one or both
of two main goals in mind:
 Analysis of the sequence of elementary steps giving rise to the overall reaction.
i.e. the reaction mechanism.
 Determination of the absolute rate of the reaction and/or its individual
elementary steps.
A kinetics experiment consists of measuring the concentrations of one or more
reactants or products at a number of different times during the reaction. We will now
look at the methods that allow us to use the experimental data to determine the
reaction orders with respect to each reactant, and therefore the rate law.
The rate law is an expression relating the rate of a reaction to the concentrations of
the chemical species present, which may include reactants, products, and catalysts.
Many reactions follow a simple rate law, which takes the form
ν = k [A]a [B]b [C]
The rate is proportional to the concentrations of the reactants each raised to some
power. The constant of proportionality, k, is called the rate constant. The power a
particular concentration is raised to is the order of the reaction with respect to that
reactant.
Methods of determining reaction kinetics
1. INITIAL RATE METHOD
The method of initial rates is a commonly used technique for deriving rate laws. As
the name implies, the method involves measuring the initial rate of a reaction. The
measurement is repeated for several sets of initial concentration conditions to see
how the reaction rate varies. This might be accomplished by determining the time
needed to exhaust a particular amount of a reactant. The method of initial rates
allows the values of reaction orders to be found by running the reaction multiple
times under controlled conditions and measuring the rate of the reaction in each
case. All variables are held constant from one run to the next, except for the
concentration of one reactant.
Consider a sample set of data below for the reaction:
A + B→ products
Run [A] M [B] M Rate
1 0.01 0.01 0.0347
2 0.02 0.01 0.0694
3 0.02 0.02 0.2776

The analysis of this data involves taking the ratios of rates measured where one of the
concentrations does not change. For example, assuming a rate law of the form

Rate = k [A]α[B]β

The ratio of runs will generate the following relationship:

𝛽
𝑟𝑎𝑡𝑒𝑖 𝑘[𝐴]𝛼𝑖 [𝐵]𝑖
= 𝛽
𝑟𝑎𝑡𝑒𝑗 𝑘[𝐴]𝛼𝑗 [𝐵]𝑗

By plugging in the values of the rates and concentrations respectively, we can eliminate
the values of ‘k’ and the concentrations (and their subsequent powers) that are in
excess and so the order of the reaction with respect to the reactant may be calculated.

The rate constant can then be evaluated by substituting one of the runs into the rate
law (or using all of the data and taking an average).
 2. INTEGRAL METHOD
The integral method of analysis always puts a particular rate equation to the test by
integrating and comparing the predicted C versus t curve with the experimental C
versus t data. If the fit is unsatisfactory, another rate equation is guessed and tested.

Consider the following reaction that occurs in a constant volume batch reactor: (We
will withdraw samples and record the concentration of A as a function of time.)

𝐴 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
𝑑𝑁
Mole balance: 𝐴 = 𝑟𝐴 𝑉
𝑑𝑡
Rate law: −𝑟𝐴 = 𝑘𝐶𝐴𝛼
From stoichiometry we know that, V =Vo
𝑑𝐶𝐴
∴ − = 𝑘𝐶𝐴𝛼
𝑑𝑡

We could integrate the above equation to plot reaction rate data in terms of
concentration vs. time for 0, 1st, and 2nd order reactions.

When n = 0, the integrated rate equation is CA-CAo= -kt . If provided data fits this
model, order of reaction is 0.

When n=1, the integrated rate equation is ln(CA/CAo)= -kt . If provided data fits this
model, order of reaction is 1.

When n=2, the integrated rate equation is (1/CA)-(1/CAo)= kt . If provided data fits
this model, order of reaction is 2.
When n=3, the integrated rate equation is (1/CA2)-(1/CAo2)= 2kt . If provided data
fits this model, order of reaction is 3.

It is recommended to move onto a differential method of analysis if the models for

n=0 to n=3 do not apply since for higher values of n, the integrals become less
accurate and fitting of data becomes more difficult.

3. DIFFERENTIAL METHOD
The differential method of analysis deals directly with the differential rate equation to
be tested, evaluating all terms in the equation including the derivative dC/dt, and
testing the goodness of fit of the equation with experiment.
The procedure is as follows. Plot the CA vs. t data, and then by eye carefully draw a
smooth curve to represent the data. Determine the slope of this curve at suitably
selected concentration values. These slopes dC/dt = r, are the rates of reaction at
these compositions.
Now search for a rate expression to represent this data, either by picking and testing
a particular rate form, -rA = kf (C)

Or testing an nth-order form -rA = kCAn : by taking logarithms of the rate equation

In the above case, the slope of the line will give the order of the reaction.

4. HALF LIFE METHOD

Another way of determining the reaction order is to investigate the behaviour of the
half life as the reaction proceeds. Specifically, we can measure a series of successive
1
half lives. t = 0 is used as the start time from which to measure the first half life, 𝑡1/2 .
 1 2
Then 𝑡1/2 is used as the start time from which to measure the second half life, 𝑡1/2 and
so on.
Zeroth order: t1/2 = [A]0 /2k.
1
Since at 𝑡1/2 the new starting concentration is ½[A] 0, successive half-lives will decrease
by a factor of two for a zeroth order reaction.
First order: t1/2 = ln2/k
There is no dependence of the half-life on concentration, so t1/2 is constant for a first
order reaction.
Second order t1/2 = 1 /k [A]0
The inverse dependence on concentration means that successive half-lives will double
for a second order reaction.
For a reaction
𝐴 + 𝐵 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
We may write the rate equation as
𝑑𝐶𝐴 𝛽
−𝑟𝐴 = − = 𝑘𝐶𝐴𝛼 𝐶𝐵
𝑑𝑡
If the reactants are present in their stoichiometric ratios, they will remain at that ratio
𝐶 𝛽
throughout the reaction. Thus, for reactants A and B at any time 𝐵 = and we may
𝐶𝐴 𝛼
write:
𝑏
𝑑𝐶𝐴 𝛽 𝛽 𝑏
−𝑟𝐴 = − = 𝑘𝐶𝐴𝛼 ( 𝐶𝐴 ) … . = (𝑘 ) … . . 𝐶 𝑎+𝑏+⋯
𝑑𝑡 𝛼 𝛼
Collecting the terms,
𝑑𝐶𝐴
− = 𝓀𝐶𝐴𝑛
𝑑𝑡
Integrating gives,
𝐶𝐴1−𝑛 − 𝐶𝐴0
1−𝑛
= 𝓀 (1 − 𝑛 )𝑡

Defining the half-life of the reaction, t,, , as the time needed for the concentration of
reactants to drop to one-half the original value, we obtain:

0.51−𝑛 − 1 1−𝑛
𝑡1/2 = 𝐶
𝓀(𝑛 − 1) 𝐴0

This expression shows that a plot of log t vs. log CAo gives a straight line of slope 1 – n.
The half-life method requires making a series of runs, each at a different initial
concentration, and shows that the fractional conversion in a given time:
 rises with increased concentration for orders greater than one
 drops with increased concentration for orders less than one
  and is independent of initial concentration for reactions of first order.

5. NON LINEAR LEAST SQUARE ANALYSIS

We want to find the parameter values (alpha, k, E) for which the sum of the squares of
the differences, the measured parameter (Pm), and the calculated parameter (Pc) is a
minimum.
𝑛
2
(𝑃𝑚𝑖 − 𝑃𝑐𝑖 )2
𝜎 =∑
𝑁−𝐾
𝑖=1

(we want 𝜎 2 to be a minimum)

For concentration-time data, the measured parameter P has concentration CA.
𝑑𝐶𝐴
= −𝐶𝐴𝛼
𝑑𝑡
We can integrate the combined mole balance equation and rate law to obtain:
1
1−𝛼
𝐶𝐴 = [𝐶𝐴0 − (1 − 𝛼)𝑘𝑡]1−𝛼
We now guess k and alpha, calculate each CACi at different times, and then compare it
with the measured concentration by taking the difference and squaring it.
We then sum up the differences for all the data points.
𝑁 𝑁
1 2
2 2 1−𝛼
[𝐶𝐴𝑜
𝑆 = ∑(𝐶𝐴𝑚𝑖 − 𝐶𝐴𝑐𝑖 ) = ∑ (𝐶𝐴𝑚𝑖 − − (1 − 𝛼)𝑘𝑡𝑖 ] )
1−𝛼
𝑖=1 𝑖=1

We continue to guess k and alpha until we find the values of alpha and k, which
minimize S2 (usually calculated using software)