TITTLE OF EXPERIMENT:

Experiment 1 – Batch Reactor

OBJECTIVES:

 To determine the reaction rate of saponification reaction at given temperature

by measuring the conversion against reaction time.
 To evaluate the reaction rate constant at constant temperature using differential
and integral methods of analysis.
 To evaluate the rate constant at different temperature and activation energy
determination from Arrehenius Plot.

INTRODUCTION:

A batch reactor is a type of reactor where the reactants and catalyst for a certain
reaction are placed in the reactor and allowed to react for a given amount of time. At
the end of the time limit that was set, the mixture of unreacted material and the products
are withdrawn. Spatiality in concentration and temperature is an assumption that is
made for an ideal batch reactor. However, in reality, the conditions can be
approximately created by vigorous stirring or agitation. In terms of residence time, all
elements of the fluid amount the same because they have all spent the same amount of
time in the reactor. A batch reactor is what is considered to be a closed thermodynamic
system.

Small scale experiments and reactions are ideally carried out in a batch reactor
because of its simplicity and the lack thereof of supporting equipment. In the industry,
batch reactors are used to produce products that are produced in smaller amounts or
when the demand of a product varies. In this sense, batch reactors are prioritised in the
industry of pharmaceuticals, where high value products are made in small volumes.
 In batch reactions, there are no feed or exit streams and therefore the mass
balance equation for species A in an element of reactor volume V obeys the following
statement:

Rate of A produced within volume element = Rate of A accumulated within volume

element

In a batch reactor, the process in the reactor is at unsteady state by its nature. In this
process, one or more variables vary with time. The longer the reactant is in the reactor,
the more reactant is converted to product until either equilibrium is reached or the
reactant is exhausted.

A tank with an agitator and an integrated heating or cooling system comprises

a typical batch reactor. Solids and liquids are fed into the reactors through the
connections in the top cover of the reactors while the products, which are usually in
liquid or gaseous phase are discharged from both top and bottom covers, typically
liquids at the bottoms and gases at the top.

MATERIALS AND EQUIPMENTS:

1. Beaker 2L x 1, 1L x 1, 250mL x 2.
2. 100mL measuring cylinder.
3. Conductivity meter.
4. Electric agitator.
5. Batch reactor.
6. Water.
7. Stopwatch.
8. 5L of 0.1M sodium hydroxide, NaOH.
9. 2L of 0.1M ethyl acetate, Et(Ac), C4H8O2.
10. 1L of deionised water.
RESULTS AND CALCULATIONS

Experiment 1: Calibration Curve – Conductivity versus Conversion

Table 5.1: Conductivities for Different Conversion for the Reaction of 0.1M EtAc and
0.1M NaOH

Volume of Conductivity,
Volume of
Conversion, Ethyl
Sodium mS
Acetate
X Hydroxide,
(EtAc),
(NaOH), mL 1st reading 2nd reading Average
mL

0.9 10 90 1.76 1.80 1.78

0.8 20 80 2.98 3.02 3.00

0.7 30 70 5.14 5.22 5.18

0.6 40 60 7.62 7.58 7.60

0.5 50 50 13.16 13.22 13.19

Graph of Conductivity against Conversion

14

12

10
Conductivity, mS

6
y = -27.220x + 25.224
4

0
0.5 0.6 0.7 0.8 0.9
Conversion, X

Graph 5.1: The Graph of Conductivity against Conversion (Calibration Curve)

Experiment 2: Determine the Rate of Reactions

Table 5.2: Conductivity of Mixture at different temperature in the intervals of ten

seconds within 150 seconds

Temperature, °C 55 50 45 40
Time, s Conductivity, mS
0 0.00 0.00 0.00 0.00
10 15.70 14.53 8.05 5.61
20 15.20 13.02 8.70 4.89
30 15.13 12.70 8.54 4.78
40 14.88 13.57 8.65 4.67
50 14.76 12.99 8.60 4.88
60 14.70 12.54 8.53 5.40
70 14.50 11.83 8.41 5.37
80 14.46 11.97 8.27 5.38
90 14.23 12.36 8.18 5.35
100 14.25 12.09 8.06 5.33
110 14.25 12.31 8.13 5.36
120 14.23 12.08 8.11 5.32
130 14.26 11.78 8.08 5.31
140 13.99 11.24 8.13 5.27
150 14.13 11.87 8.12 5.28

Sample calculation

At temperature = 50°C, time = 40s, conductivity = 13.57mS

(i) Calculation of conversion, XA from the calibration curve

From Graph 5.1, the equation obtained from graph is y = -27.220x + 25.224, where x
is the conversion and y is the conductivity.

y − 25.224
x=
−27.220

13.57 − 25.224
=
−27.220
= 0.428141
(ii) Calculation of remaining concentration, CA
The initial concentration, CA0 of both solution = 0.1 mol/L
The remaining concentration is given by the equation,

𝐶𝐴 = 𝐶𝐴𝑜 (1 − X)
= 0.1(1 − 0.428141)
𝑚𝑜𝑙
= 0.057186
𝐿

𝑑𝑋𝐴
(iii) Calculation of the change in conversion of A with time, (𝑠 −1 )
𝑑𝑡

At t = 40s, 𝑋𝐴 = 0.428141 ; t = 30 s , 𝑋𝐴 = 0.460103

𝑑𝑋𝐴 0.428141 − 0.460103
=
𝑑𝑡 40 − 30
= −0.003196 𝑠 −1

(iv) Calculation of rate of reaction, -rA

The rate of reaction (disappearance of component A), is, in general given by

𝑑𝑋𝐴
−𝑟𝐴 = 𝐶𝐴𝑂
𝑑𝑡
= 0.1 × −0.003196

𝑚𝑜𝑙
= −0.00320 𝐿.𝑠
Table 5.3: Calculated conversion, remaining concentration, change in conversion of A
with time and rate of reaction at 55°C.

Temperature (55˚C)
Change in
conversion of A Rate of
Time Conversion, Remaining concentration, CA 𝑑𝑋𝐴 -1 reaction,-rA
(s) X (mol/L) with time, (s ) (mol/L·s)
𝑑𝑡
0 0.000000 0.100000 0.000000 0.000000
10 0.349890 0.065011 0.034989 0.003499
20 0.368259 0.063174 0.001837 0.000184
30 0.370830 0.062917 0.000257 0.000026
40 0.380015 0.061999 0.000918 0.000092
50 0.384423 0.061558 0.000441 0.000044
60 0.386627 0.061337 0.000220 0.000022
70 0.393975 0.060602 0.000735 0.000073
80 0.395445 0.060456 0.000147 0.000015
90 0.403894 0.059611 0.000845 0.000084
100 0.403159 0.059684 -0.000073 -0.000007
110 0.403159 0.059684 0.000000 0.000000
120 0.403894 0.059611 0.000073 0.000007
130 0.402792 0.059721 -0.000110 -0.000011
140 0.412711 0.058729 0.000992 0.000099
150 0.407568 0.059243 -0.000514 -0.000051

Table 5.3: Calculated conversion, remaining concentration, change in conversion of A

with time and rate of reaction at 50°C.

Temperature (50 ˚C)

Change in
conversion of A Rate of
Time Conversion, Remaining concentration, CA 𝑑𝑋 reaction,-rA
(s) X (mol/L) with time, 𝑑𝑡𝐴 (s-1) (mol/L·s)
0 0.000000 0.100000 0.000000 0.000000
10 0.392873 0.060713 0.039287 0.003929
20 0.448347 0.055165 0.005547 0.000555
30 0.460103 0.053990 0.001176 0.000118
40 0.428141 0.057186 -0.003196 -0.000320
50 0.449449 0.055055 0.002131 0.000213
 60 0.465981 0.053402 0.001653 0.000165
70 0.492065 0.050794 0.002608 0.000261
80 0.486921 0.051308 -0.000514 -0.000051
90 0.472594 0.052741 -0.001433 -0.000143
100 0.482513 0.051749 0.000992 0.000099
110 0.474431 0.052557 -0.000808 -0.000081
120 0.482880 0.051712 0.000845 0.000084
130 0.493902 0.050610 0.001102 0.000110
140 0.513740 0.048626 0.001984 0.000198
150 0.490595 0.050940 -0.002314 -0.000231

Table 5.4: Calculated conversion, remaining concentration, change in conversion of A

with time and rate of reaction at 45°C.

Temperature (45 ˚C)

Change in
conversion of A Rate of
Time Conversion, Remaining concentration, CA 𝑑𝑋𝐴 -1 reaction,-rA
( s) X (mol/L) with time, (s ) (mol/L·s)
𝑑𝑡
0 0.000000 0.100000 0.000000 0.000000
10 0.630933 0.036907 0.063093 0.006309
20 0.607054 0.039295 -0.002388 -0.000239
30 0.612932 0.038707 0.000588 0.000059
40 0.608891 0.039111 -0.000404 -0.000040
50 0.610727 0.038927 0.000184 0.000018
60 0.613299 0.038670 0.000257 0.000026
70 0.617708 0.038229 0.000441 0.000044
80 0.622851 0.037715 0.000514 0.000051
90 0.626157 0.037384 0.000331 0.000033
100 0.630566 0.036943 0.000441 0.000044
110 0.627994 0.037201 -0.000257 -0.000026
120 0.628729 0.037127 0.000073 0.000007
130 0.629831 0.037017 0.000110 0.000011
140 0.627994 0.037201 -0.000184 -0.000018
150 0.628361 0.037164 0.000037 0.000004
Table 5.5: Calculated conversion, remaining concentration, change in conversion of A
with time and rate of reaction at 40°C.

Temperature (40 ˚C)

Change in Rate of
conversion of A reaction,
Time Conversion, Remaining concentration, CA 𝑑𝑋𝐴 -1 -rA
( s) X (mol/L) with time, (s ) (mol/L·s)
𝑑𝑡
0 0.000000 0.100000 0.000000 0.000000
10 0.720573 0.027943 0.072057 0.007206
20 0.747024 0.025298 0.002645 0.000265
30 0.751065 0.024893 0.000404 0.000040
40 0.755107 0.024489 0.000404 0.000040
50 0.747392 0.025261 -0.000771 -0.000077
60 0.728288 0.027171 -0.001910 -0.000191
70 0.729390 0.027061 0.000110 0.000011
80 0.729023 0.027098 -0.000037 -0.000004
90 0.730125 0.026988 0.000110 0.000011
100 0.730860 0.026914 0.000073 0.000007
110 0.729758 0.027024 -0.000110 -0.000011
120 0.731227 0.026877 0.000147 0.000015
130 0.731594 0.026841 0.000037 0.000004
140 0.733064 0.026694 0.000147 0.000015
150 0.732697 0.026730 -0.000037 -0.000004

Graph of Conversion against Time

0.8
0.7
0.6
Conversion, X

0.5
0.4
0.3
0.2
0.1
0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Time (s)

55˚C 50˚C 45˚C 40˚C

Graph 5.2: The graph of conversion against time

 Graph of Concentration against Time
0.12

0.1
Concentration (mol/L)

0.08

0.06

0.04

0.02

0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Time (s)

55˚C 50˚C 45˚C 40˚C

Graph 5.3: The graph of concentration against time

Graph of Rate of Reaction against Time

0.008
0.007
Rate of reaction( mol/L·s)

0.006
0.005
0.004
0.003
0.002
0.001
0
-0.001 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Time (s)

55˚C 50˚C 45˚C 40˚C

Graph 5.4: The graph of rate of reaction against time at different temperature
Evaluate the rate constants for forward reaction, kf in saponification reaction.

(a) Integral Methods

In forward reaction, one mole of sodium hydroxide, NaOH will react with one mole of
ethyl acetate, Et(Ac) to form one more of sodium acetate, Na(Ac) and one mole of ethyl
alcohol, EtOH.

𝑁𝑎𝑂𝐻 + 𝐸𝑡(𝐴𝑐) ↔𝑁𝑎(𝐴𝑐) + 𝐸𝑡𝑂𝐻

𝑎𝐴 + 𝑏𝐵 ↔ 𝑐𝐶 + 𝑑𝐷

Where,

A = Sodium Hydroxide, NaOH a = Stoichiometric Coefficient of NaOH

B = Ethyl Acetate, Et(Ac) b = Stoichiometric Coefficient of Et(Ac)

C = Sodium Acetate, Na(Ac) c = Stoichiometric Coefficient of Na(Ac)

D = Ethyl alcohol (Ethanol), EtOH d = Stoichiometric Coefficient of EtOH

The rate of reaction (disappearance of component A) in batch reactor is given by:

𝑑𝐶𝐴
−𝑟𝐴 = = 𝑘𝐶𝐴 𝐶𝐵
𝑑𝑡

Since an equimolar feeds were used, CA = CB,

𝑑𝐶𝐴
−𝑟𝐴 = = 𝑘𝐶𝐴 2
𝑑𝑡

Rearrange and integrate the equation:

𝑑𝐶𝐴
= −𝑘𝐶𝐴 2
𝑑𝑡

𝐶𝐴 𝑡
𝑑𝐶𝐴
∫ = − ∫ 𝑘 𝑑𝑡
𝐶𝐴0 𝐶𝐴 2 0
 1 𝐶𝐴
[− ] = −𝑘 [𝑡]𝑡0
𝐶𝐴 𝐶𝐴0

1 1
[ − ] = −𝑘𝑡
𝐶𝐴0 𝐶𝐴

1 1
= 𝑘𝑡 +
𝐶𝐴 𝐶𝐴0

1 1
Where 𝑦 = 𝐶 ; 𝑥 = 𝑡; gradient, m = k; y-intercept, 𝑐 = 𝐶
𝐴 𝐴0

Table 5.6: Data required for plotting graph of 1/CA against time for the determination
of forward rate constant in integral method

Temperature (˚C) 55 50 45 40
Time (s) 1/CA (L/mol)
0 10.000000 10.000000 10.000000 10.000000
10 15.382007 16.471015 27.095361 35.787536
20 15.829263 18.127331 25.448766 39.529480
30 15.893962 18.522047 25.835232 40.171192
40 16.129415 17.486830 25.568289 40.834083
50 16.244927 18.163619 25.688939 39.586969
60 16.303306 18.725922 25.859776 36.803678
70 16.500970 19.687545 26.157986 36.953570
80 16.541079 19.490190 26.514709 36.903471
90 16.775545 18.960713 26.749214 37.054179
100 16.754894 19.324152 27.068417 37.155337
110 16.754894 19.026982 26.881296 37.003806
120 16.775545 19.337880 26.934494 37.206124
130 16.744587 19.759001 27.014688 37.257049
140 17.027399 20.565125 26.881296 37.462152
150 16.879573 19.630751 26.907869 37.410665
 60.000000
Graph of 1/CA against time
50.000000 y = 2.4846x + 10

40.000000

y = 1.5005x + 10
1/CA (L/mol)

30.000000

y = 0.8375x + 10
20.000000 y = 0.599x + 10

10.000000

0.000000
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Time (s)
55 50 45 40
Linear (55) Linear (50) Linear (45) Linear (40)

Graph 5.5: The graph of 1/CA against time at different temperature

In Graph 5.5, there are four linear equations which represented the relationship
between 1/CA and time at different temperature of 40°C, 50°C, 60°C, and 70°C
respectively. The reciprocal of constant initial concentration of reactant (0.1M) when
time = 0s make the y intercept of 10 can be obtained from the four linear equations.

Based on four linear equation obtained in Graph 5.5, the forward rate constants
for saponification reaction, the slope of the line (gradient of the graph) can be used to
determine the forward rate constants for saponification reaction, k f and the values are
tabulated in table below.

Table 5.7: The forward rate constant for the saponification reaction at different
temperature.

Temperature (°C) 40 45 50 55

Forward rate constant, kf (L/mol.s) 2.4846 1.5005 0.8375 0.599

Determine the Activation Energy for Forward Saponification Reaction using
integral method.

Arrhenius equation is used to show the effect of a change of temperature on the rate
constant.

Arrhenius equation,

𝑘 (𝑇) = 𝐴𝑒 −𝐸⁄𝑅𝑇

Where k = Reaction rate constant

A = pre-exponential factor of frequency factor

E = Activation energy, kJ/mol

R = Gas constant (8.314 J/mol.K)

T = Absolute temperature

By taking logarithm on both sides of equation,

𝐸
ln 𝑘 = ln 𝐴 −
𝑅𝑇

1 𝐸
Where 𝑦 = ln 𝑘; 𝑥 = 𝑇; gradient, 𝑚 = − 𝑅; y-intercept, 𝑐 = ln 𝐴

Table 5.8: Data required in the determination of the activation energy at different
temperature in forward saponification reaction.

Temperature Temperature Forward rate constant, kf

(˚C) (K) -1
1/T (K ) (L/mol.s) ln k
40 313.15 0.003193 2.4846 0.910112
45 318.15 0.003143 1.5005 0.405798
50 323.15 0.003095 0.8375 -0.17733
55 328.15 0.003047 0.599 -0.51249
 Graph of ln k against 1/T
1
0.8
0.6 y = 9984.7x - 30.991

0.4
ln k

0.2
0
0.00302 0.00304 0.00306 0.00308 0.0031 0.00312 0.00314 0.00316 0.00318 0.0032 0.00322
-0.2
-0.4
-0.6
-0.8
1/T (K-1)

Graph 5.6: The graph of ln k against 1/T

From graph in Graph 5.6, a linear equation of 𝑦 = 9984.7𝑥 − 30.991 was obtained.
Based on the linear equation, the activation energy can be calculated from the slope of
the graph.

𝐸
𝑚=− = 9984.7 𝐾
𝑅

𝐸
− = 9984.7 𝐾
𝐽
8.314 𝑚𝑜𝑙. 𝐾

𝐽
𝐴𝑐𝑡𝑖𝑣𝑎𝑡𝑖𝑜𝑛 𝑒𝑛𝑒𝑟𝑔𝑦, 𝐸 = 9984.7 𝐾 × 8.314
𝑚𝑜𝑙. 𝐾

= 83012.80 𝐽/𝑚𝑜𝑙

Determine the Pre-exponential Factor, A

Pre-exponential factor, A can be determined from the y-intercept of the graph in Graph
5.6.

y − intercept, c = ln 𝐴 = − 30.991

𝑃𝑟𝑒 − 𝑒𝑥𝑝𝑜𝑛𝑒𝑛𝑡𝑖𝑎𝑙 𝑓𝑎𝑐𝑡𝑜𝑟, 𝐴 = exp(−30.991)

𝐿
= 3.4736 × 10−14 𝑚𝑜𝑙.𝑠
(b) Differential Methods

Rate law equation:

−𝑟𝐴 = 𝑘𝑓 𝐶𝐴 𝛼

Batch reactor design equation:

𝑑𝐶𝐴
−𝑟𝐴 = − = 𝑘𝑓 𝐶𝐴 𝛼
𝑑𝑡

By taking the logarithm of the equation on both side:

𝑑𝐶𝐴
ln(− ) = ln 𝑘𝑓 + 𝛼 ln 𝐶𝐴
𝑑𝑡

𝑑𝐶𝐴
Where y = ln(− ), 𝑥 = ln 𝐶𝐴 , 𝑔𝑟𝑎𝑑𝑖𝑒𝑛𝑡, 𝑚 = 𝛼 and 𝑦 − 𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡, 𝑐 = ln 𝑘𝑓
𝑑𝑡

𝑑𝐶𝐴
By applying numerical method, − can be obtained by using the formula.
𝑑𝑡

𝑑𝐶𝐴 −3𝐶𝐴0 + 4𝐶𝐴1 − 𝐶𝐴2

𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑃𝑜𝑖𝑛𝑡: ( )𝑡0 =
𝑑𝑡 2∆𝑡

𝑑𝐶𝐴 𝐶𝐴2 − 𝐶𝐴0

𝐼𝑛𝑡𝑒𝑟𝑖𝑎𝑙 𝑃𝑜𝑖𝑛𝑡: ( )𝑡1 =
𝑑𝑡 2∆𝑡

𝑑𝐶𝐴 𝐶𝐴3 − 𝐶𝐴1

𝐼𝑛𝑡𝑒𝑟𝑖𝑎𝑙 𝑃𝑜𝑖𝑛𝑡: ( )𝑡2 =
𝑑𝑡 2∆𝑡

𝑑𝐶𝐴 𝐶𝐴4 − 𝐶𝐴2

𝐼𝑛𝑡𝑒𝑟𝑖𝑎𝑙 𝑃𝑜𝑖𝑛𝑡: ( )𝑡3 =
𝑑𝑡 2∆𝑡

𝑑𝐶𝐴 𝐶𝐴5 − 𝐶𝐴3

𝐼𝑛𝑡𝑒𝑟𝑖𝑎𝑙 𝑃𝑜𝑖𝑛𝑡: ( )𝑡4 =
𝑑𝑡 2∆𝑡

∙
 ∙

𝑑𝐶𝐴 𝐶𝐴𝑛 + 4𝐶𝐴(𝑛−1) − 𝐶𝐴(𝑛−2)

𝐿𝑎𝑠𝑡 𝑃𝑜𝑖𝑛𝑡: ( )𝑡𝑛 =
𝑑𝑡 2∆𝑡

Table 5.9: Data required to determine the forward rate constant using differential
method at 55°C.

Remaining ln -dCA/dt (mol/L.s)

concentration, CA
Time, s (mol/L) ln CA -dCA/dt (mol/L.s)
0 CA0 0.100000 -2.30259 0.0103 -4.57561
-2.7332
10 CA1 0.065011 0.0018413 -6.29728
-2.76186 0.0001047 -9.16441
20 CA2 0.063174
-2.76594 5.875E-05 -9.74222
30 CA3 0.062917
-2.78064 0.00006795 -9.59674
40 CA4 0.061999
-2.78778 3.31E-05 -10.316
50 CA5 0.061558
-2.79137 4.78E-05 -9.94848
60 CA6 0.061337
-2.80343 0.00004405 -10.0302
70 CA7 0.060602
-2.80584 4.955E-05 -9.91253
80 CA8 0.060456
-2.81992 3.86E-05 -10.1623
90 CA9 0.059611
-2.81869 -3.65E-06
100 CA10 0.059684 #NUM!
-2.81869 3.65E-06 -12.5208
110 CA11 0.059684
-2.81992 -1.85E-06 #NUM!
120 CA12 0.059611
-2.81807 4.41E-05
130 CA13 0.059721 -10.0291
-2.83482 2.39E-05 -10.6416
140 CA14 0.058729
-2.82611 0.00293645 -5.83055
150 CA15 0.059243
Table 5.10: Data required to determine the forward rate constant using differential
method at 50°C.

ln -dCA/dt
Remaining concentration, CA (mol/L.s)
Time, s (mol/L) ln CA -dCA/dt (mol/L.s)

0 CA0 0.100000 -2.30259 0.0044835 -5.18214

-2.8016
10 CA1 0.060713 0.00224175 -6.1005
-2.89743 0.00033615 -7.99795
20 CA2 0.055165
-2.91896 -0.00010105 #NUM!
30 CA3 0.053990
-2.86145 -5.325E-05 #NUM!
40 CA4 0.057186
-2.89942 0.0001892
50 CA5 0.055055 -8.57271
-2.92991 0.00021305 -8.45398
60 CA6 0.053402
-2.97998 0.0001047 -9.16441
70 CA7 0.050794
-2.96991 -9.735E-05 #NUM!
80 CA8 0.051308
-2.94236 -2.205E-05 #NUM!
90 CA9 0.052741
-2.96135 9.2E-06
100 CA10 0.051749 -11.5963
-2.94586 1.85E-06 -13.2003
110 CA11 0.052557
-2.96207 9.735E-05 -9.2372
120 CA12 0.051712
-2.98361 0.0001543 -8.77661
130 CA13 0.050610
-3.0236 -1.65E-05 #NUM!
140 CA14 0.048626
-2.97711 0.0024313
150 CA15 0.050940 -6.01933
Table 5.11: Data required to determine the forward rate constant using differential
method at 45°C.

ln -dCA/dt (mol/L.s)
Remaining concentration,
Time, s CA (mol/L) ln CA -dCA/dt (mol/L.s)
0 CA0 0.100000 -2.30259 0.009583 -4.64776
-3.29935
10 CA1 0.036907 0.00303525 -5.79746
-3.23666 -9E-05 #NUM!
20 CA2 0.039295
-3.25173 9.2E-06
30 CA3 0.038707 -11.5963
-3.24135 -1.1E-05 #NUM!
40 CA4 0.039111
-3.24607 2.205E-05
50 CA5 0.038927 -10.7222
-3.25269 3.49E-05 -10.263
60 CA6 0.038670
-3.26416 4.775E-05 -9.94953
70 CA7 0.038229
-3.2777 4.225E-05 -10.0719
80 CA8 0.037715
-3.28651 3.86E-05 -10.1623
90 CA9 0.037384
-3.29838 9.15E-06 -11.6018
100 CA10 0.036943
-3.29142 -9.2E-06 #NUM!
110 CA11 0.037201
-3.29341 9.2E-06
120 CA12 0.037127 -11.5963
-3.29638 -3.7E-06 #NUM!
130 CA13 0.037017
-3.29142 -7.35E-06 #NUM!
140 CA14 0.037201
-3.29241 0.00186005
150 CA15 0.037164 -6.28715
Table 5.12: Data required to determine the forward rate constant using differential
method at 40°C.

ln -dCA/dt (mol/L.s)
Remaining concentration,
Time, s CA (mol/L) ln CA -dCA/dt (mol/L.s)
0 CA0 0.100000 -2.30259 0.01068 -4.53938
-3.57759
10 CA1 0.027943 0.0037351 -5.58998
-3.67703 0.0001525 -8.78835
20 CA2 0.025298
-3.69317 0.00004045 -10.1154
30 CA3 0.024893
-3.70953 -0.0000184 #NUM!
40 CA4 0.024489
-3.67849 -0.0001341 #NUM!
50 CA5 0.025261
-3.60561 -9E-05 #NUM!
60 CA6 0.027171
-3.60966 3.65E-06
70 CA7 0.027061 -12.5208
-3.6083 3.65E-06 -12.5208
80 CA8 0.027098
-3.61236 9.2E-06 -11.5963
90 CA9 0.026988
-3.61511 -1.8E-06 #NUM!
100 CA10 0.026914
-3.61103 1.85E-06
110 CA11 0.027024 -13.2003
-3.61648 9.15E-06 -11.6018
120 CA12 0.026877
-3.61782 9.15E-06 -11.6018
130 CA13 0.026841
-3.62332 0.00000555 -12.1017
140 CA14 0.026694
-3.62197 0.0013347 -6.61905
150 CA15 0.026730
Sample Calculation (First 5 point + last point)

At T = 55°C,

𝑑𝐶𝐴 −3𝐶𝐴0 + 4𝐶𝐴1 − 𝐶𝐴2

𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑃𝑜𝑖𝑛𝑡: ( )𝑡0=0𝑠 =
𝑑𝑡 2∆𝑡

−3(0.1) + 4(0.065011) − 0.063174

=
2(10)

mol
= −0.0103
𝐿∙𝑠

𝑑𝐶𝐴 𝐶𝐴2 − 𝐶𝐴0

𝐼𝑛𝑡𝑒𝑟𝑖𝑎𝑙 𝑃𝑜𝑖𝑛𝑡: ( )𝑡1=10𝑠 =
𝑑𝑡 2∆𝑡

0.063174 − 0.1
=
2(10)

mol
= −0.001841
𝐿∙𝑠

𝑑𝐶𝐴 𝐶𝐴3 − 𝐶𝐴1

𝐼𝑛𝑡𝑒𝑟𝑖𝑎𝑙 𝑃𝑜𝑖𝑛𝑡: ( )𝑡2=20𝑠 =
𝑑𝑡 2∆𝑡

0.062917 − 0.065011
=
2(10)

= −0.0001047

𝑑𝐶𝐴 𝐶𝐴4 − 𝐶𝐴2

𝐼𝑛𝑡𝑒𝑟𝑖𝑎𝑙 𝑃𝑜𝑖𝑛𝑡: ( )𝑡3=30𝑠 =
𝑑𝑡 2∆𝑡

0.061999 − 0.063174
=
2(10)

mol
= 5.87E − 05
𝐿∙𝑠
 𝑑𝐶𝐴 𝐶𝐴5 − 𝐶𝐴3
𝐼𝑛𝑡𝑒𝑟𝑖𝑎𝑙 𝑃𝑜𝑖𝑛𝑡: ( )𝑡4=40𝑠 =
𝑑𝑡 2∆𝑡

0.061558 − 0.062917
=
2(10)

mol
= 0.00006795
𝐿∙𝑠

𝑑𝐶𝐴 𝐶𝐴15 + 4𝐶𝐴14 − 𝐶𝐴13

𝐿𝑎𝑠𝑡 𝑃𝑜𝑖𝑛𝑡: ( )𝑡15=150𝑠 =
𝑑𝑡 2∆𝑡

0.059243 + 4(0.058729) − 0.059721

=
2(10)

mol
= 0.03838125
𝐿∙𝑠

Graph of ln(-dCA/dt) against ln CA

0
-4.5 -4 -3.5 -3 -2.5 -2 -1.5 -1 -0.5 0
-2
y = 4.3134x + 9.317

y = 4.591 + 9.2466 -4
ln(-dCA/dt)

y = -0.4763x - 6.6033
-6

y = -2.0648x - 11.381 -8

-10

-12

-14
lnCA

Graph 5.7: The graph of ln(-dCA/dt) against ln CA.

From Graph 5.7, the value of ln kf at each temperature can be determine from the y-
intercept of the linear equation respectively.

At temperature = 55°C,

ln 𝑘𝑓 = 9.317

𝑘𝑓 = 1.11 × 104
At temperature = 50°C,

ln 𝑘𝑓 = −6.6033

𝑘𝑓 = 1.356 × 10−3

At temperature = 45°C,

ln 𝑘𝑓 = 9.2466

𝑘𝑓 = 1.037 × 104

At temperature = 40°C,

ln 𝑘𝑓 = −11.381

𝑘𝑓 = 1.141 × 10−5

Table 5.13: The forward rate constant for the saponification reaction at different
temperature using differential method.

Temperature (°C) 40 45 50 55

Forward rate constant, 1.141 × 10−5 1.037 × 104 1.35 × 10−3 1.11 × 104
kf (L/mol.s)

To determine the Activation Energy for Forward Saponification Reaction

Arrhenius equation is used to show the effect of a change of temperature on the rate
constant.

Arrhenius equation,

𝑘 (𝑇) = 𝐴𝑒 −𝐸⁄𝑅𝑇

Where k = Reaction rate constant

A = pre-exponential factor of frequency factor

E = Activation energy, kJ/mol

 R = Gas constant (8.314 J/mol.K)

T = Absolute temperature

By taking logarithm on both sides of equation,

𝐸
ln 𝑘𝑓 = ln 𝐴 −
𝑅𝑇

1 𝐸
Where 𝑦 = ln 𝑘𝑓 ; 𝑥 = 𝑇; gradient, 𝑚 = − 𝑅; y-intercept, 𝑐 = ln 𝐴

Table 5.14: Data required for the determination of activation energy at different
temperature in forward saponification reaction using differential method.

Temperature Temperature 1/T (K- Forward rate constant, kf

1
(°C) (K) ) (L/mol.s) ln kf

40 313.15 0.00320 1.141 × 10-5 -11.381

45 318.15 0.00314 1.037 × 104 9.2466

50 323.15 0.00310 1.35 × 10-3 -6.6033

55 328.15 0.00300 1.11 × 104 9.317

Graph of ln kf against 1/T

15

10

5
ln kf

0
0.00295 0.003 0.00305 0.0031 0.00315 0.0032 0.00325
-5

-10

-15
1/T (k-1)

Graph 5.8: The graph of ln kf against 1/T

From graph in Graph 5.8, a linear equation of 𝑦 = 55614𝑥 − 161.14 was obtained.
Based on the linear equation, the activation energy can be calculated from the slope of
the graph.

𝐸
𝑚=− = 55614 𝐾
𝑅

𝐸
− = 55614 𝐾
𝐽
8.314 𝑚𝑜𝑙. 𝐾

𝐽
𝐴𝑐𝑡𝑖𝑣𝑎𝑡𝑖𝑜𝑛 𝑒𝑛𝑒𝑟𝑔𝑦, 𝐸 = 55614 𝐾 × 8.314
𝑚𝑜𝑙. 𝐾

= 4.62 × 105 𝐽/𝑚𝑜𝑙

Determine the Pre-exponential Factor, A

Pre-exponential factor, A can be determined from the y-intercept of the graph in Graph
5.8.

y − intercept, c = ln 𝐴 = − 161.14

𝑃𝑟𝑒 − 𝑒𝑥𝑝𝑜𝑛𝑒𝑛𝑡𝑖𝑎𝑙 𝑓𝑎𝑐𝑡𝑜𝑟, 𝐴 = exp(−161.14)

𝐿
= 1.0418 × 10−70 𝑚𝑜𝑙.𝑠

Calculation for the Time Required for 95% Conversion

Table 5.15: Time needed for 95% conversion at different temperature in forward
saponification reaction.

T (oC) L t95 (s)

k ( mol∙s )

40 1.141 × 10−5 16652059.6

45 1.037 × 104 0.01929

50 1.35 × 10−3 148148.148

55 1.11 × 104 0.018018

Sample Calculation

1 𝑋𝐴
𝑡= [ ]
𝑘𝐴 𝐶𝐴𝑂 1 − 𝑋𝐴

For the temperature = 40oC,

1 0.95
𝑡95 = [ ]
−5 𝐿 𝑚𝑜𝑙 1 − 0.95
(1.141 × 10 𝑚𝑜𝑙 ∙ 𝑠) (0.1 𝐿 )

= 16652059.6s

DISCUSSIONS

According to particle theory, when the temperature increases, the molecules in

the system will gain more energy and have higher chance to break the bonds as well as
they will collide with each other so that the reaction occurs. In a simple word,
theoretically, as the temperature increases, the time taken for a reaction to reach certain
conversion will be shorter. In this experiment, the time taken to reach 95% conversion
is calculated for 4 different temperatures, which are: 40 oC, 45 oC, 50 oC, and 55 oC. For
the 40 oC experiment, the time is 16652059.6s. For the 45 oC experiment, the time has
been shorten until 0.01929s while for the 50 oC experiment, the time increases back to
148148.148s. Meanwhile for the 55 oC experiment, the time taken is 0.018018s. The
trend is not following the theory and physics it should be. It is impossible to get
0.01929s for 45 oC while 148148.148s for 50 oC. There should be error occurred while
carrying this experiment.

“Esters can be cleaved back into a carboxylic acid and an alcohol by reaction
with water and a base. The reaction is called a saponification from the Latin sapo which
means soap. The name comes from the fact that soap used to me made by the ester
hydrolysis of fats. Due to the basic conditions a carboxylate ion is made rather than
a carboxylic acid.” (Steven Farmer, 2014)

Kinetic data is the data that obtained from every certain time interval for
monitoring the process. Batch reactor will be used when performing and study of the
kinematics of chemical reaction. There are advantage and disadvantage of obtaining
kinetic data in a batch reactor. For the advantage of obtaining kinetic data, by analysing
the kinematic parameters, various properties of the mixture such as concentration of
components, total volume of the system, physical properties can be identified. In the
other hand, by using kinetic data, there will occur with inaccurate result in the
experiment. This is because in practical the properties will not be constant from time to
time so this will affect the change of concentration of component to be in not constant
rate and lead to inaccurate of result.

Saponification is a chemical process which ester is being added into alkaline

condition to produce alcohol and carboxylic acid. In this experiment, ethyl acetate acts
as the ester while sodium hydroxide is the alkaline. Two methods can be used to
continuous monitoring the concentration of reactants during saponification: electric
conductivity method and titration method. Electric conductivity is used in this
experiment which the conductivity meter is placed into the beaker containing the
mixture of ethyl acetate and sodium hydroxide. When the reaction occurred, hydroxide
ions which are more conductivity are replaced by acetate ions which are the lower
conductivity one. Other ions can be ignored as they are not being ionised except for
those hydroxide and acetate ions. Since the conductivity is reducing over the time
recorded as they are being used up. Electrical conductivity method is a simple and
practical method as it just simply places the meter into the mixture and can measure the
conductivity from time to time. It does not required any withdrawal of sample or any
specific conditions to measure the conductivity.

Besides, there is another method which is the titration method. Unlike the
electric conductivity method, this method needs the withdrawal of sample from the
experiment. The ethyl acetate has to be titrated with sodium hydroxide and then the
sample has to be taken out for concentration measurement from time to time. This can
measure reaction rate from the unreacted sodium hydroxide in the mixture by plotting
unreacted sodium hydroxide volume versus time graph. However, there are
disadvantages for this method which is high error and requires the withdrawal of sample
from time to time.

In this experiment, batch reactor was used to carry out saponification reaction
between sodium hydroxide ethyl acetate. Batch reactor was used because of the small
scale operation in this experiment. The effect of the temperature on the extent of
reaction was also determined during this experiment. Besides, the rate constants and
activation energy for the forward reaction were also obtained. The reaction can be
represented by the following stoichiometric equation:

CH3 COOC2 H5 + NaOH → CH3 COONa + C2 H5 OH

Sodium hydroxide and ethyl acetate are used as reactants in this experiment to
react to form sodium acetate and ethanol which is known as ethyl alcohol. During this
experiment, the reactants that have the same initial concentration were mixed up to form
the product with different ratio of volume of its solution to achieve different conversion.
The conductivity of the mixture was determined by using conductivity meter while the
mixture was being stirred. The purpose of these procedure was to create a calibration
curve based on the data obtained. According to the data obtained, the conversion and
the conductivity had a relationship of inversely proportional to each other. This is
because the some of reactant sodium hydroxide has been used up to form the sodium
acetate and ethanol. When the mixing of ethyl acetate and sodium hydroxide is done,
the high concentration of sodium hydroxide ions Na+ and OH − will present in the
mixture. These ions will be consumed when saponification reaction takes places and
thus the conversion will be increase whereby the conductivity decreases.

Based on the graph of ln k against that plotted as shown in Graph 5.6, the

reaction rate constant, k can be obtained by using calculation. However, there is a

negative value of reaction rate constant which during 55℃ and 50℃. Based on the
Arrhenius equation that has been used to calculate the activation energy in this
experiment, 𝑘 (𝑇) = 𝐴𝑒 −𝐸/𝑅𝑇 it is obvious that the exponential, 𝑒 −𝐸/𝑅𝑇 has a range
only defined over the non-negative real numbers. Therefore, there might be some error
that had been occurred in this experiment. Theoretically, the reaction rate constant will
be increased when the temperature increases. The major factor of this is due to the
collision theory. When temperature increases, the molecular energy will also increase
causing the molecule collide each other and result a faster reaction. Therefore, the rate
of reaction increases.

There are some precautions steps that should be taken when carrying out this
experiment. Firstly, wear gloves when handling chemicals to ensure the chemicals not
contact with skin. If the chemicals come into contact with the skin, rinse off
immediately with the water and inform the officer in charge and seek for medical
treatment if the symptoms persist. Besides, do not touch the heating coil of the reactor
when the reactor is in operating mode to prevent any burnt to skin. In addition, make
sure that the blade of mixer not touching the beaker when the blades are moving to
prevent breaking of beaker during the experiment.

CONCLUSION

In conclusion, in this experiment the rate constant fluctuates at 50°C and 55°C. This is
because of the errors that have occurred during commencement of reaction.
Theoretically, the reaction rate constant increases with increasing temperature. This is
because, at higher temperature, the molecules will vibrate and move in a very vigorous
way, increasing its energy and the possibility of the said molecules to collide.

REFERENCE

 Anne Marie Helmenstine. (2017, May 12). Saponification Definition and

Reaction. Retrieved from https://www.thoughtco.com/definition-of-

saponification-605959

 Steven Farmer. (2014, July 24). Saponification - Chemistry LibreTexts.

Retrieved from

https://chem.libretexts.org/Core/Organic_Chemistry/Esters/Reactivity_of_Esters/

Saponification