UNIVERSITY OF ENGINEERING AND TECHNOLOGY, LAHORE

DEPARTMENT OF CHEMICAL ENGINEERING

The experiment performed by following group members:

Hafiz Muhammad Dilshad 2022-CH-1

K.M Arslan Khan Khilji 2022-CH-3

Saad Baig 2022-CH-27

Muhammad Rayan 2022-CH-35

“Open Ended Lab”

Submitted to
Ma’am Sobia Anwar
Ch.E-301L Chemical Reaction Engineering Lab
Title:
Determine Activation Energy for the Reaction between Oxalic Acid
and Sodium Hydroxide in a batch reactor via back titration.

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 Table of Contents
Objective....................................................................................................................................4
Reactor Type..............................................................................................................................4
Apparatus...................................................................................................................................4
Reagents/Chemicals...................................................................................................................4
Chemical Reaction.....................................................................................................................4
Batch Reactor.........................................................................................................................5
Types of Analyzing Kinetic Data...........................................................................................5
Integral Method...................................................................................................................5
Differential Method............................................................................................................6
Arrhenius Law........................................................................................................................6
Activation Energy and Temperature Dependency.................................................................7
Linear Form of the Arrhenius Equation..............................................................................7
Applications of Arrhenius Law...........................................................................................8
Determination of Rate Constant.............................................................................................8
Procedure..................................................................................................................................10
Observations and Calculations.................................................................................................11
Safety Precautions....................................................................................................................13
Result........................................................................................................................................14
Conclusion................................................................................................................................14
Interpretation of the result....................................................................................................14
References................................................................................................................................14

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Objective:
Determine the activation energy (Ea) for the reaction in a batch reactor by measuring
reaction rates or constants at different temperatures back titration.

Reactor Type:

 Batch Reactor

Apparatus:

 Burette (for back titration)

 Thermometer
 Beakers, pipettes, and a stopwatch

Reagents/Chemicals:

 Hydrochloric acid (HCl) 0.03 M solution.

 Oxalic acid (C2H2O4) 0.06 M solution.
 Sodium hydroxide (NaOH) 0.06 M solution.
 Distilled water
 Na2C03 Solution

Chemical Reaction:

C2H2O4+2NaOH→Na2C2O4+2H2O

Theory:
A rate equation characterizes the rate of reaction, and its form may either be suggested
by theoretical considerations or simply be the result of an empirical curve-fitting procedure.
In any case, the value of the constants of the equation can only be found by experiment;
predictive methods are inadequate at present. The determination of the rate equation is
usually a two-step procedure; first the concentration dependency is found at fixed
temperature and then the temperature dependence of the rate constants is found, yielding the
complete rate equation.

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Batch Reactor:
The batch reactor is simply a container to hold the contents while they react. All that has to
be determined is the extent of reaction at various times, and this can be followed in a number
of ways, for example:
 By following the concentration of a given component.
 By following the change in some physical property of the fluid, such as the electrical
conductivity or refractive index.
 By following the change in total pressure of a constant-volume system.
 By following the change in volume of a constant-pressure system.
The experimental batch reactor is usually operated isothermally and at constant volume
because it is easy to interpret the results of such runs. This reactor is a relatively simple
device adaptable to small-scale laboratory set-ups, and it needs but little auxiliary equipment
or instrumentation. Thus, it is used whenever possible for obtaining homogeneous kinetic
data.

Fig 1: Batch Reactor

Types of Analyzing Kinetic Data:

There are two procedures for analyzing kinetic data,
 Integral Methods
 Differential methods.

Integral Method:
In the integral method of analysis we guess a particular form of rate equation and,
after appropriate integration and mathematical manipulation, predict that the plot of a certain
concentration function versus time should yield a straight line. The data are plotted, and if a
reasonably good straight line is obtained, then the rate equation is said to satisfactorily fit the
data.

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The integral method is easy to use and is recommended when testing specific mechanisms, or
relatively simple rate expressions, or when the data are so scattered that we cannot reliably
find the derivatives needed in the differential method.

Differential Method:
In the differential method of analysis we test the fit of the rate expression
to the data directly and without any integration. The differential method is useful in more
complicated situations but requires more accurate or larger amounts of data. The integral
method can only test this or that particular mechanism or rate form; the differential method
can be used to develop or build up a rate equation to fit the data.
In general, it is suggested that integral analysis be attempted first, and, if not successful, that
the differential method be tried.

Arrhenius Law:
For many reactions, and particularly elementary reactions, the rate expression
can be written as a product of a temperature-dependent term and a composition- dependent
term, or

−r =f ( Temperature ) . f ( Composition )
−r =k . f ( composition )

For such reactions the temperature-dependent term, the reaction rate constant, has been found
in practically all cases to be well represented by Arrhenius' law:

−E
k =k 0 e RT

Where;

k0 is called the frequency or pre-exponential factor

E is called the activation energy of the reaction.
This expression fits experiment well over wide temperature ranges and is strongly suggested
from various standpoints as being a very good approximation to the true temperature
dependency.
At the same concentration, but at two different temperatures,

ln
() ( )
r2
r1
=ln
k 2 −E 1 1
k1
= ( − )
R T1 T2

Arrhenius' law indicates that provided that E stays constant.

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Activation Energy and Temperature Dependency:
The temperature dependency of reactions is determined by the activation
energy and temperature level of the reaction as illustrated in above figure. These findings are
summarized as follows:
 From Arrhenius' law a plot of ln(k) vs 1/T gives a straight line, with large slope for
large E and small slope for small E.
 Reactions with high activation energies are very temperature-sensitive; reactions with
low activation energies are relatively temperature-insensitive.
 Any given reaction is much more temperature-sensitive at a low temperature than at a
high temperature.
 From the Arrhenius law, the value of the frequency factor k, does not affect the
temperature sensitivity.

Linear Form of the Arrhenius Equation:

The logarithmic form of the Arrhenius equation is used to

experimentally determine the activation energy and pre-exponential factor:

−E 1
ln ( k )=ln ( k 0 ) + ( )
R T

This equation represents a straight line when ln (k) vs 1/T (an Arrhenius plot), where:

−E
 Slope =
R
 Intercept = ln ( k 0 )

From the slope of this graph, activation energy can be calculated:

E=−slope × R
Where
R is the universal gas law constant.

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 Fig 2: General Arrhenius plot

Applications of Arrhenius Law:

Determining Activation Energy

 The Arrhenius law provides a method to calculate the activation energy of a chemical
reaction by analyzing the temperature dependence of the rate constant.
 Experimentally, ln(k) vs 1/T(Arrhenius plot) yields a straight line, and the slope gives
–E/R

Temperature Dependence of Reaction Rates

 Arrhenius law explains how reaction rates change with temperature.

 Useful in predicting the behavior of chemical processes in different environments.

Catalysis

 Catalysts lower the activation energy of reactions, increasing the reaction rate. The
Arrhenius law quantifies this effect by showing how a smaller “E” leads to a faster
rate constant (k).

Stability of Substances

 Used in shelf-life predictions of chemicals, pharmaceuticals, and food.

 For example, by studying the degradation rate constant of a drug at different
temperatures, its stability at room temperature can be estimated.

Chemical Kinetics in Industrial Processes

 Essential in chemical engineering to design reactors and optimize reaction conditions.

 Determines the ideal temperature for maximum efficiency and safety of reactions.

Predicting Reaction Rates in Environmental Chemistry

 Helps predict the rates of atmospheric reactions, such as the breakdown of pollutants
or ozone layer depletion, based on temperature.

Determination of Rate Constant:

Consider an elementary reaction which is given as:
2A + B = Products
The reaction between the oxalic acid and the sodium hydroxide is the second order reaction
as per data available in the literature.
So rate law is written as;
−dC A
−r A = =k C A C B
dt

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As from the reaction stoichiometry;
1
C A0 X A= CB0 XB
2
C A=C A 0 ( 1− X A )

( 1
C B=C B 0 ( 1−X A ) C A 0 M − X
2 A )
Now write rate law equation in the terms of conversion;

( )
dX A 1
=k C A 0 ( 1− X A ) M − X
dt 2 A

As;
CB0
M=
CA 0

If we use in the stoichiometric proportions;

CB0 1
M= =
CA 0 2

Put in the equation

( )
dX A 1 1
=k C A 0 ( 1− X A ) − X
dt 2 2 A

dX A 1 2
= k C A 0 ( 1− X A )
dt 2

XA t
1 1
∫ 1−X 2 dX A = 2 k C A 0∫ dt
0 ( A) 0

After integration we found; also putting limits;

1 1
−1= k C A 0 t
1−X A 2

XA 1
= kt
C A 0 ( 1−X A ) 2

CA
1−
CA 0 1
= kt
CA 2

1 1 1
− = kt
CA C A0 2

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 1 1 1
= + kt
CA C A0 2

Now the equation is in the form of;

y=c+ mx

Fig 3: Determination of rate constant via integral method

Procedure:
 Prepare 1000 mL of standard solutions of all chemicals written above.
 Dump 1000 mL of NaOH and 500 mL of oxalic acid in the batch reactor.
 Extract the sample from the reactor after every 5 minutes.
 Note down the temperature of the reactor.
 Find the concentration of the NaOH in the sample using back titration.
 Find a rate constant at this temperature.
 Repeat above steps 3 to 4 times.
 Turn on circulate hot water and raise the temperature to 10 0C from the previous one.
 Repeat above steps and find the concentration of NaOH and rate constant at this
temperature.
 Using these rate constant, find the activation energy.

Fig 4: Laboratory Batch reactor

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Observations and Calculations:
“T = 25 0C”
M1 (Molarity of Na2CO3) = 0.03M
M2 (Molarity of HCl) = 0.06M
Total acid added = 30 mL
Volume of NaOH = Va = 10 mL

Sr. Volume Amount of free Amount of Concentration 1 t

No of acid after acid used of NaOH Ca
Na2CO3 neutralization by NaOH “Ca (mol/L)” (min)
used “V2 (mL)” (L/mol)
“V1 [V= total [Ca = M2V / Va]
(mL)” [V2 = 2M1V1 / acid added
M2] - V2]
1. 22.0 22.0 8.0 0.0480 20.833 5
2. 23.3 23.3 6.7 0.0402 24.876 10
3. 24.5 24.5 5.5 0.0330 30.303 15
4. 25.0 25.0 5.0 0.0300 33.333 20

Graph

35
f(x) = 0.85854 x + 16.6045
30

25
1/Ca (L/mol)

20

15

10

0
4 6 8 10 12 14 16 18 20 22

t (min)

K298 = 0.42925

“T = 35 0C”

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M1 (Molarity of Na2CO3) = 0.03M
M2 (Molarity of HCl) = 0.06M
Total acid added = 30 mL
Volume of NaOH = Va = 10 mL

Sr Volume of Amount of free Amount of Concentration 1 t

. Na2CO3 acid after acid used of NaOH Ca
No used neutralization by NaOH
“Ca (mol/L)”
(min)
“V1 (mL)” “V2 (mL)”
(L/mol)
[V= total
[Ca = M2V / Va]
acid
[V2 = 2M1V1 /
added -
M2]
V2]
1 24 24 6 0.036 27.78 5
2 24.3 24.3 5.7 0.0342 32.00 10
3 25.5 25.5 4.5 0.027 37.04 15
4 26 26 4 0.024 41.67 20

Graph

45.00
40.00 f(x) = 0.934074074074074 x + 22.9444444444445
35.00
30.00
1/Ca (L/mol)

25.00
20.00
15.00
10.00
5.00
0.00
4 6 8 10 12 14 16 18 20 22

t (min)

K308 = 0.46705

Activation Energy:
Sr. T (K) 1/T × 10-3 Rate Constant ln(K)
No “K”
1 298 3.36 0.42925 -0.8457
2 308 3.25 0.46705 -0.7613

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 Graph
3.20000 3.30000 3.40000 3.50000
-0.7
-0.72
-0.74
-0.76
ln (K)

f(x) = − 0.767243804920665 x + 1.73222340532888

-0.78
-0.8
-0.82
-0.84
-0.86

1/T *10^-3

So data extracted from the graph;

Intercept
ln (K0) = 1.7322
K0 = 5.65
Slope
−Ea
=−0. 7672
R
−E a=−0.7672 ×0.08206
−E a=−0.06296
E a=0.06296 L.atm mol-1
E a=0.06296 ×101.325 J
E a=6.37 J

These are the proposed values not actual values.

Safety Precautions:

 Wear appropriate personal protective equipment (PPE), including lab coat, gloves,
and safety goggles.
 Ensure the batch reactor is in good working condition and securely sealed to avoid
leaks.
 Handle oxalic acid and NaOH with care as they can cause skin and eye irritation;
avoid direct contact.
 Work in a well-ventilated area or under a fume hood to prevent inhalation of vapors.

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  Use precise measuring tools to avoid adding excess reactants, which could lead to
uncontrolled reactions.
 Add NaOH slowly to oxalic acid to minimize the risk of splashing or excessive heat
generation.
 Keep emergency equipment, such as an eyewash station and fire extinguisher, readily
accessible.
 Avoid ingestion by not eating or drinking in the lab; wash hands thoroughly after
handling chemicals.
 Dispose of waste chemicals properly, following local disposal regulations.
 Be prepared for spills with a neutralizing agent for NaOH (e.g., dilute acid) and
absorbent materials.

Result:
The activation energy for the reaction has found to be 6.37 Joules. To initiate this
reaction we give this energy to the reaction.

Conclusion:

The activation energy of a reaction refers to the minimum energy required for reactants to
undergo a chemical reaction and form products. In this case, the activation energy has been
determined to be 6.37 Joules. This value represents the energy barrier that must be overcome
for the reaction to occur.

Interpretation of the result:

 A value of 6.37 Joules is relatively low for the activation energy of many reactions,
especially in comparison to reactions that involve the breaking and forming of
complex bonds. This suggests that the reaction may occur relatively easily once the
energy is provided, meaning it doesn't require a lot of energy to initiate.

 To initiate this reaction, you would need to supply at least 6.37 Joules of energy to the
system. This could be in the form of heat, light, or some other form of energy. Once
this energy is supplied, it allows the reactants to reach the transition state, where they
can then proceed to form products.

 Since the activation energy is relatively low, once the activation energy is supplied,
the reaction could proceed more quickly. This is because fewer energy barriers need
to be overcome for the reactants to transition to the products.

 It's important to note that activation energy is a kinetic concept, referring to the
energy required for the reaction to begin. It doesn't tell us anything about the overall
energy change (enthalpy) of the reaction. For example, even with low activation
energy, the reaction could be exothermic or endothermic depending on the overall
energy difference between reactants and products.

References:

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 Octave Levenspiel, “Chemical Reaction Engineering” 3rd Edition, John Wiley and
Sons. Inc (1999)
 Charles G. Hill and Thatcher W. Puchigian “Introduction to Chemical Engineering
Kinetics & Reactor Design" 2nd Edition, Wiley (2007)
 H. Scott Fogler “Elements of Chemical Reaction Engineering" 5 th Edition, Prentice
Hall (2016)

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