Chapter-3: Development of rate equation for single reactions:

General Considerations

• Establishing the form of a rate law experimentally for a particular

reaction involves determining values of the reaction rate parameters, such as
reaction orders α, β and γ 𝑎𝑛𝑑 Arrhenius parameters (kA and EA).
• The general approach for a simple system would normally require the
following choices, not necessarily in the order listed:
(1) Choice of a species (reactant or product) to follow the extent of reaction for
specification of the rate
(2) Choice of type of reactor to be used and certain features relating to its mode
of operation (e.g., a BR operated at constant volume)
(3) . Choice of method to follow the extent of reaction with respect to time or a
time related quantity (e.g., by chemical analysis).
1
 Cont’d
4. Choice of experimental strategy to follow in light of points (1) to (3) (i.e.,
how to perform the experiments, the number and type required).
5. Choice of method to determine numerically the values of the parameters,
and hence to establish the actual form of the rate law
• Determination of Rate Equations from the Experimental Data
• The chemical engineer needs rate equation for

 Designing of reactors

 Boosting the performance of a reactor.

1) To find the concentration dependency of the substance on time at a fixed

temperature for determining the order of the reaction

2) To find the temperature dependency for evaluating the rate constant to

yield the complete rate equation for some reaction parameters.

2
 Cont’d
The experimental methods used in kinetics may be classified into two categories
Physical Analysis (by measuring the changes in an observable physical property)

• Physical measurements can be performed on a system while it is reacting. These

measurements have the advantage of not disturbing the system, and they can be taken
during the reaction. Examples of these measurements are changes in volume,
temperature, and absorption of a solution.

 The physical change during the course of reaction that does not require removal
successive samples from the reaction mixture is continuously measured.

 Theoretically, any property that undergoes sufficient change may be used to follow the
course of the reaction.

• Chemical analysis (by taking samples of the reaction solution and measuring
concentration directly)

Determine directly the concentration of one of the reacting substances or products

against time (or more specifically of residence time).
3
 Cont’d

 The advantages of application of physical methods, as a rule are their

measurement rapidity.

 They also make it possible to obtain a large number of experimental data in

a given time interval.

 The experimental measurement can often be performed directly in reaction

vessel itself. The vessel is distinct in two types of process, namely batch
and flow reactors.

Among physical methods the following may be mentioned:

 Dilatometric methods:- based on the change in volume due to reaction

 Optical methods:- such as polarimetry, refractometry, colorimetric

 Electrical methods:- such as conductimetry, potentiometry, polarography,

and mass spectroscopy
4
 Cont’d
• As a criteria to implement a physical method is that one has to know the
linear relationship between physical properties and concentration, i.e,
concentration on the one hand and the electrical conductivity, optical density,
rotation of the plans of polarization and the pressure of gaseous, on the other.

• The most difficult part in kinetic is to find the rate after having the
experimental data.

• Raw Data obtained from the batch or flow reactor experiments are analyzed in
one of the following ways

The differential method

 The integral method

 The initial rate method

 The half-life method

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 The least-square method
 Differential Methods
 In this method, it requires differentiation of the experimental data to obtain
a rate derived from the experiment.

 Restriction for application for such method is that it should only be applied
for irreversible reactions with a single reactant A
 P
The kinetic expression for such type of reaction is given by
  k C
dC A
 r   r  k C and 
A A A dt A

ln  
dC A 
  ln k   ln C A
 dt 

𝑑𝐶𝐴
ln − can be determined from concentration
𝑑𝑡
versus time data using
Graphical area differentiation, Numerical Method
6
,(Finite Difference ) and Non-linear Least Square etc.
Procedure to carry out Graphical differential method:
• Measure concentration versus time
• Arrange the differential equation in a natural logarithmic form

Example

• Differentiate the CA versus t data either numerically or graphically.

• Plot the natural logarithmic form of the rate equation


ln  
dC A 
ln C A
• Observe a straight line graph of  V-s
 dt 

ln  
dC A 
• Obtain the slope of the graph  V-s ln C A
 dt 
𝑑𝐶𝐴
• observe that the slope of a plot of ln − as a function of ln 𝐶𝐴 is
𝑑𝑡
the reaction order, 𝜶.
7
8
 .
• .

Care must be taken in choosing the order of the polynomial. If the order
is too low, the polynomial fit will not capture the trends in the data and not go
through many of the points. If too large an order is chosen, the fitted curve can
have peaks and valleys as it goes through most all of the data points, thereby
producing significant errors when the derivatives, dCA/dt, are generated at the
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various points.
Method of excess : More Complex Reactions (Dependence on CA and CB)
• We can use the approach of pseudo-order reactions or method of excess. If
we take the general rate equation for two species, A and B reacting with
orders α and β respectively:

• where 𝛼 𝑎𝑛𝑑 𝛽 are both unknown, the reaction could first be run in an
excess of B so that CB, remains essentially unchanged during the course of
the reaction and;

Once 𝛼 𝑎𝑛𝑑 𝛽 are determined.

ln (−𝑟𝐴 ) = 𝑙𝑛𝑘′′ + 𝛽𝑙𝑛𝐶𝐵 kA, can be calculated from the
measurement of -rA, at known
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concentrations of A and B:
 Integral methods

• The integral method follows a trial and error approach to find reaction
order

• General procedure

• Guess the reaction order and integrate the mole balance equation

• Calculate the resulting function for the data and plot this against function of
time.

• If the resulting plot is linear, the reaction order is probably guessed correctly.

• If the plot is not linear, guess another order and repeat the procedure

• The integral method is mostly used for known order of reaction and it is
best used to evaluate the rate constant at different temperatures in order to
determine the activation energy.
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 Zero order of reaction

• .

A plot of the concentration of A as a function of time will be linear (Fig. below)

with slope ( - k ) far a zero-order reaction carried out in a constant-volume batch
reactor.

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Finding the Reaction Order from the Integrated Rate Law: Zero Order Reactions

• Integrated rate law:

 At   A0  kt
• Straight-line form:
 At  kt   A0
y = mx + b

• A plot of [A] vs. time gives a straight line for a zero-order

reaction.

• If a reaction is zero-order, a plot of [A]t vs. t will yield a straight

line with a slope of -k.
 Integrated Method for Finding Reaction Order for first order

Consider a simple 1st order rxn: A B

Differential form:

Integrated rate law:

 A 0
ln  kt
A t
Straight-line form:
ln  At  kt  ln  A0
y = mx + b
If a reaction is first-order, a plot of ln [A]t vs t will yield a straight line with a
14
slope of -k.
 Cont’d
The integrated form of first order rate law:

or

[A]0 is the initial concentration of A (t=0).

[A]t is the concentration of A at some time, t, during the course of the

reaction.

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 Integrated Method for Finding Reaction Order for Second-Order
Reaction
Similarly, integrating the rate law for a process that is second-order in
reactant A:

Integrated rate law and rearrange

in Straight-line form:

also in the form y = mx + b

So if a process is second-order in A, a plot of 1/[A] vs. t will yield a straight
line with a slope of k.

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Example-Determine the order of reaction for the decomposition of N2O5:
Data Table

Time (min) 0 10 20 30 40 50 60
[N2O5], M 0.0165 0.0124 0.0093 0.0071 0.0053 0.0039 0.0029

Solution: zero order, 1st order 2nd order

Time (min) [N2O5] ln[N2O5] 1/[N2O5]

0 0.0165 -4.104 60.6
10 0.0124 -4.390 80.6
20 0.0093 -4.68 110
30 0.0071 -4.95 140
40 0.0053 -5.24 190
50 0.0039 -5.55 260
60 0.0029 -5.84 340
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 cont’d

• The concentration data is used to construct three different plots.

• Since the plot of ln [N2O5] vs. time gives a straight line, the reaction is first
order.
 Initial rate methods
• In this method,
 a series of experiments is conducted at different initial concentration

 Then the initial rate of reaction is determined for each test.

 The initial rate can be found by differentiating the data and

extrapolating to zero time. In other words, (say) the initial rates of
reaction are found by plotting the concentration-vs-time curve and
finding the slopes at t = 0 as shown in Fig. below.

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 Example
• The experimental concentrations of reactants A and B are given with the
initial rate of reaction in Table below.

Run Concentration of A Concentration of B Initial rate

(M) (M) (M*min-1)
1 0.2 0.2 0.4
3 0.2 0.4 1.6
3 0.4 0.2 0.8

a) Determine reaction order and rate law

b) Calculate the value of rate constant

c) What will be the initial rate, at the concentration of reactants A and B are
0.5M and 0.8M respectively ?
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 Half – life reaction
The half-life is the time required for the reactant concentration to drop to one –
half of its initial value, or the time taken for 50% reaction to occur (CA = 0.5CA0)
Half–life reaction for a first-order reaction
ln 2 0.693
t1/2   : (Rate = k[A])
k k
Half-life is independent of initial concentration of the reactant for a first-order.

Half-life reaction for 2st order

t1/2 
1
k  A 0
second-order process; rate  k  A  2

For a second-order reaction, t1/2 is inversely proportional to the initial concentration

Half-life reaction for zero order reaction order

 A 0
t1/2   zero-order process; rate  k 
2k
For a zero-order reaction, t1/2 is directly proportional to the initial concentration
cont’d

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 (Least-square methods)
If a rate law depends on the concentration of more than one species and it is
not possible to use the method of excess, we may choose to use a linearized
least-squares method. This method of data analysis is also useful to determine
the best values of the rate law parameters from a series of measurements when
three or more parameters are involved (example: reaction order, frequency
factor, A; and activation energy, Ea).

There are three techniques in use for the least-square method:

 Linearized of rate law You can use

 Non-Linearized Least-square and Excel, Polymath or MATLAB software

 Weighted Least-Squares
The method of least-squares can give the order of the reaction with respect to
all the components at once.
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 The Least-Square method requires having a series of measurements
Example linearized least square (rate law)

• .

Let,
𝑑𝐶
𝑌 = ln − 𝐴 , 𝑎 = 𝑙𝑛𝑘, 𝑎1 = 𝛼, 𝑎2 = 𝛽, 𝑋1 = 𝑙𝑛𝐶𝐴 𝑎𝑛𝑑 𝑋1 = 𝑙𝑛𝐶𝐵
𝑑𝑡 0
Then 𝑌 = 𝑎0 + 𝑎1 𝑋1 + 𝑎2 𝑋2 and you can get each parameter using any
software or by your hand calculation. Read the remaining from your 24
references.