Abstract

In Batch reactor experiment, Saponification reaction is taken into consideration in order to study
the rate of reaction and calculate the rate constant using isothermal batch reactor. Also Different
conditions (reaction temperature and initial concentrations) are used to investigate their effect on
reaction constant. Rate constant is strongly dependent on temperature, it increases by increasing
temperature. Arrhenius Frequency Factor can be obtained using different values of K values.
1. Introduction
1.1 Objectives:
The main objectives of the experiment are to study the main specification of the batch reactor
and use the experimental result to find the rate constant of the reaction rate. Also it is considered
to study the effect of reaction temperature and inlet concentrations on the reaction constant.
Reaction rate will be written as a function of temperature.
1.2 Approach taken:
Pilot scale batch reactor is used for the experiment for the saponification reaction. Batch reactor
is provided with water jacket for heating and agitator. In addition, computerized system is used
to monitor all data including concentration of reactant and product with time, temperature and
concentrations.
1.3 General background:
Rate equation characterizes the rate of reaction; it is obtained from theoretical considerations or
simply using result of an empirical curve-fitting procedure. Batch reactor is used isothermally
with constant volume since it is easy to interpret the results for each run.[levenspeil] rate
constant at different condition is calculated and written as a function of temperature from
Arrhenius Equation.
2. Theory
2.1) Batch reactor.
Batch reactor is a type of vessel that is widely used in the process industries. In batch reactor
reactants and catalyst are placed allowed to proceed for a given time. Sometimes the reaction
mixture needs mixing using agitators. In an ideal batch reactor, the concentration and
temperature are assumed to be spatially uniform within the reaction, this assumption maybe
approximately realized by vigorous agitation or stirring. All the elements of the fluid spend the
same amount of time in the reactor, and hence have the same residence time. From the viewpoint
of thermodynamics, a batch reactor represents a closed system.

Batch reactors are simple and needs little supporting equipment, and are therefore ideal for small
scale experimental studies on reaction kinetics. Industrially it is used when relatively small
amounts of reactant are needed and when the product demand varies. Batch reactors are often
used in the pharmaceutical industry, where small volumes of high-value products are made.

A typical batch reactor consists of a tank with an agitator and integral heating/cooling system.
Liquids and solids are usually charged via connections in the top cover of the reactor. Vapors
and gases also discharge through connections in the top. Liquids are usually discharged out of
the bottom.

2.2) Reaction constant and rate of reaction

Researchers typically use a batch reactor to study reaction kinetics under ideal conditions. A
batch reactor can be used to find the reaction rate constant, activation energy and order of the
reaction. The data reflect the intrinsic kinetics for the reaction being investigated.

This experiment studies the rate of the reaction of ethyl acetate with base to give the acetate ion
and ethyl alcohol:
CH3COOCH2CH3 + OH- CH3COO- + CH2CH3OH (1)
This reaction is often called saponification. An application of saponification is the manufacture
of soaps. The base in this experiment is NaOH. For the purposes of this experiment, it can be
assumed that this reaction runs essentially to completion.
Rate law or rate equation for a chemical reaction is an equation which links the reaction rate
with concentrations or pressures of reactants and constant parameters; it can only be obtained
from experimental data. From the experimental rate expression, a detailed mechanism for the
reaction can be developed. In general, consider the rate of a general chemical reaction:
aA+bBcC+dD
The rates of appearance of the products or the disappearance of the reactants are related to the
overall reaction rate by:

Where: the brackets refer to concentrations generally in mol L-1. The rate expression often has
the form rate = k [A]n[B]m where k is the rate constant and n and m are the reaction order with
respect to each reactant. The concentrations of products and catalysts can also occur in the rate
law. The reaction is assumed to be elementary, experimental data will approve this result.

Assuming that, the reaction is an elementary reaction then, the rate equation become:

rA kCAC B (2)

If the initial concentrations for the two reactants are equal then the above equation can be simpli-

fied to be:

rA kCA
2
(3)

Mole balance around the batch reactor:

dN A
FAo FA rAV (4)
dt

dC A
Input and output flow are canceled in the batch reactor, kCA
2

dt

Estimation of rate constant, There are two classical approaches to the kinetic analysis of single
reactions: differential and integral methods.
Integral analysis can be used when the available data are in the form of concentration (or
conversion) versus time or space time. These kinds of data are obtained when an ideal batch
reactor or an ideal plug-flow tubular reactor is used. For these two reactors, use of the integral
method avoids the need for numerical or graphical differentiation which tends to introduce some
additional error into the experimental data.

The steps in the integral method are as follows: a rate equation is assumed, the material balance
is integrated to generate a relationship between concentration and time, the relationship is
linearized, the data are plotted so as to test the linearized equation, if the equation fits the data,
the values of the slope and the intercept are used to estimate the unknown parameters in the rate
equation.

Rate laws for irreversible homogeneous reactions are often constructed via power-law model:

r = k (T) 11 22 = k(T)

k (T) is the reaction rate constant . The exponents i a are the partial orders with respect to
reactant i . The reaction order is the sum of partial reaction orders.

It should be noted that k is a function of Concentration. It also depends on the solution

temperature. The dimension of the specific conductivity is S cm-1.In aqueous electrolyte
solutions k is as a first approximation proportional to the electrolyte concentration.

It is important to distinguish between elementary and non elementary reaction rates. For
elementary reactions, it specifies the number of molecules involved in an elementary step. On a
practical level are almost never elementary. Therefore, the reaction is not in accordance with the
stoichiometric equation. If a reaction is of zero order then the rate is independent of all reactant
concentrations.

This differential equation is integrated to calculate K value of the reaction rate.

 1 1 dC A
kt rA kCAo (1 X A )( X )
2
>>>
CA C Ao dt

This equation is also integrated to result in a linear equation in the form of y ax b with

intercept of zero.

XA
ln C Ao ( 1)kt (6)
(1 X A )

The rate constant ( k ) is a function of temperature, this dependency is expressed in Arrhenius

Equation as below:

E
k k 0 exp A (7)
RT

Where:

k o : is the rate constant at a reference temperature.

The equation above can be linearized in order to calculate K0 to be in the form:

EA
ln k ln k o (8)
RT

Where:
ko: represents a proportionality constant between the total number of molecule collisions and the
reaction rate.
EA: the minimum energy a molecule must possess to make a simple collision a reactive one. The
exponential e-EA /(RT)
describes the fraction of molecules which for a specified temperature T
exhibit this required energy according to the BOLTZMANN probability distribution. ko and EA
are characteristic quantities for each reaction.
3. Experimental Methods
3.1) Procedure of the experiment
Part 1:
1. Both NAOH and Ethyl Acetate are diluted from 0.2 M to 0.08 M.
2. 0.25 Liter of NAOH and Ethyl Acetate is prepared.
3. Computerized system is run at isothermal reaction conditions.
4. Reactor jacket is prepared at the reactor temperature to ensure uniform distribution of
temperature.
5. Batch reactor is fed with sodium hydroxide solution. Agitator is set the reactor to 54,
power is pressed on to start the agitation. 'Hot Water Circulator' is pressed and water
starts to circulate through jacket of the reactor.
6. Sample time interval is specified to be about 30 second and the data collection period is
30 minutes.
7. 0.25 Liter of ethyl acetate solution is also added to the reactor.
8. These steps are repeated again at different concentration.
Part 2:
This part is carried out under a fixed concentration of (0.08,0.08) but at two other temperatures
of 35C, 45C .
3.2) Equipment
The main equipment is a batch reactor (a glass vessel with a water jacket). Agitator is driven
with electric motor to ensure uniform mixing; it is driven by an electric motor and controlled
using the Armfield software. The speed can be varied using
the up/down arrows or by typing in a value between 0-100%.
Computer system with temperature controller of PID type is
used. Thermocouples are provided to the reactor to measure
temperature of liquid inside the vessel and the temperature
of water jacket. Conductivity probe is used to measure the
conductivity of reactants as an indication to the amount of
reactant that converts through the reaction period.

Figure (1.1): Reactor Setup.

4. Results and Discussion.

4.1 Batch Reaction of 0.08 M Ethyl Acetate and 0.08 M Sodium Hydroxide.

1) Dilution of ethyl acetate and NAOH solutions

. = .

0.2*V1= 0.08*0.25

V1 = 0.1 Litre of distilled water must be added.

2) Estimation of rate constant at 250C.

Both concentrations are the same, so the rate of reaction is considered to be second order in
component A= NAOH.

Figure (1.2): Concentration of NAOH with time at 25 C.

In order to calculate rate constant K, 1/CA is blotted with time, the linear equation is
y=0.1089x+20.032

Figure (1.3): 1/CA vs. time to find the rate constant at 25 C.

The slope is the rate constant and equal to 0.1089
This calculation is repeated for operating temperature of 35C and 45C. Results are shown in
table (1.1)
Table (1.1): Values of rate constant (K) at different temperature.

Operating temperature 25 C 35 C 45 C
Rate constant 0.1089 0.25 0.98

It is noticed that the rate constant increases with increasing temperature, since rate constant is
function of temperature.

Figure (1.4): 1/CA vs. time to find the rate constant at 35 C.

Figure (1.5): 1/CA vs. time to find the rate constant at 45 C.

4.2 Batch Reaction of 0.06 M Ethyl Acetate and 0.08 M Sodium Hydroxide.
1) Dilution of ethyl acetate.

. = .

0.2*V1= 0.06*0.25

V1 = 75 mille Litre of distilled water must be added to Ethyl Acetate.

0.2*V1= 0.08*0.25

V1 = 100 mille Litre of distilled water must be added to NAOH.

2) Estimation of rate constant at 250C.

dC A
Using this equation: rA kCAo (1 X A )( X ) and equation (6), linear equation will
2

dt
produce.

Figure (1.6): Linearization of reaction rate to find rate constant at 0.08 M NAOH and 0.06 M
Ethyl Acetate.

Slope equals to CA0 ( 1)K = -0.0008

Where: = /

K value = -0.107

4.3 Batch Reaction of 0.08 M Ethyl Acetate and 0.06 M Sodium Hydroxide.

1) Dilution of ethyl acetate.

. = .
 0.2*V1= 0.06*0.25

V1 = 75 mille Litre of distilled water must be added to NAOH

0.2*V1= 0.08*0.25

V1 = 100 mille Litre of distilled water must be added to Ethyl Acetate.

2) Estimation of rate constant at 250C.

dC A
Using this equation: rA kCAo (1 X A )( X ) and equation (6), linear equation will
2

dt
produce.

Figure (1.7): Linearization of reaction rate to find rate constant at 0.06 M NAOH and 0.08 M
Ethyl Acetate.

Slope equals to CA0 ( 1)K = 0.0011

K value = -0.12256

4.5 Estimation of Arrhenius Frequency Factor K0.

Arrhenius Frequency factor is strongly dependent on operating temperature. From the
linearization of equation (7), equation (8) is obtained. Ln (k) is plotted vs. (1/T) as below:
Table (1.2): Estimation of Arrhenius constant at different reaction temperature.

Tempreature
K linearization equation Ca Cb Ca0 a1 k abs(k) ln(k) 1/T
318 y=0.9807x-323.08 0.08 0.08 0.0328 1 0.9807 0.9807 0.9807 -0.01949 0.003145
308 y=0.25x-25.987 0.08 0.08 0.0327 1 0.25 0.25 0.25 -1.38629 0.003247
298 y=0.1089x+20.032 0.08 0.08 0.0341 1 0.1089 0.1089 0.1089 -2.21733 0.003356
298 y=-0.0008x 0.06 0.08 0.0224 1.33333333 -0.0008 -0.10714 0.107143 -2.23359 0.003356
298 y=0.0011x 0.08 0.06 0.0359 0.75 0.0011 -0.12256 0.122563 -2.09913 0.003356
 1/T (Kelvin^-1)
0
0.0034 0.00335 0.0033 0.00325 0.0032 0.00315 0.0031
-0.5

Ln (K)
-1

-1.5

y = -10383x + 32.526 -2

-2.5

Figure (1.8): Estimation of K0 from 1/T vs. Ln (k)

The slope is (-E/R) = -10383 and the intercept is ln K0=32.526
So K0 equals to 1*10^(14)
-E/R = -10383, So Activation energy E equals to (-10383*-8.314) = 86324.262 Joul/mole.
5. Conclusion and Recommendations
Batch reactor is a closed system, there is no inlet and outlet streams during the reaction. Rate of
reaction is expressed as a function of concentration; it is strongly dependent of temperature. It is
noticed that Rate constant increases by increasing temperature. The reaction is second order
reaction. In addition, Rate of reaction decreases with time due to the consumption of reactant.
Batch reactor must be cleaned periodically after each run. Any deviation in the result is due to
the experimental and personal errors.

6. References
1. Manual of Laboratory 4.
2. Octave Levenspiel. Chemical Reaction Engineering. (2nd Edition), john Wiley and Sons,
1972.
3. Prof. Dr.-Ing. Andreas Seidel-Morgenstern, Dr.-Ing. Christof Hamel,, Dipl.-Ing. Tino
Lehmann, ESTIMATION OF KINETIC PARAMETERS IN A BATCH REACTOR
4. http://solve.nitk.ac.in/dmdocuments/theory_batch%20reactor.pdf
Contents

1. Introduction
2. Theory.
3. Experimental Method
4. Results and Discussion.............................
5. Conclusion and recommendations.....................................
6. References
7. Appendix...

Figures

Figure 1.1 Reactor Setup.

Figure 1.2 Concentration of NAOH with time at 25 C.
Figure 1.3 1/CA vs. time to find the rate constant at 35 C.
Figure 1.4 1/CA vs. time to find the rate constant at 35 C.
Figure 1.5 1/CA vs. time to find the rate constant at 45 C.
Figure 1.6 Linearization of reaction rate to find rate constant at 0.08 M
NAOH and 0.06 M Ethyl Acetate.
Figure 1.7 Linearization of reaction rate to find rate constant at 0.06 M
NAOH and 0.08 M Ethyl Acetate.
Figure 1.8 Estimation of K0 from 1/T vs. Ln (k)
 The University of Jordan
Faculty of Engineering and Technology
Chemical Engineering Department
Chemical Engineering Laboratory IV

Experiment Name: Batch Reactor.

Experiment Number: 3.
Group Members:
1. Aishah Abu Zer 0100498
2. Hadeel Naqawa 0100515
3. Rana Hussein 0100482
4. Samah Alhyari 0100494

Principal supervisor: Prof. Menwer attrakih.

Date of performing Experiment: Monday, 21/11/2014.

Date of Submitting Report: Monday, 28/11/2014.

Report Type: Full Report.

7. Appendix
7.1 Change of concentration with time.

Figure (1): concentration vs. Time for .08 NaOH and 0.06 Eth. @ 25

Figure (2): concentration vs. Time for .06 NaOH and 0.08 Eth. @ 25
Figure (3): concentration vs. Time for .08 NaOH and 0.08 Eth. @ 25

Figure (4): concentration vs. Time for .08 NaOH and 0.08 Eth. @ 35

Figure (5): concentration vs. Time for .08 NaOH and 0.08 Eth. @ 45
 7.2 Calculation results.

NaOH 0.08
ETH 0.08 NaOH 0.08
Temp. 25 ETH 0.08
time concentration 1/ca Xa Temp. 35
60 0.0341 29.32551 0 time concentration 1/Ca
120 0.0288 34.72222 0.155425 60 0.0327 30.58104
180 0.0247 40.48583 0.27566 120 0.0269 37.17472
240 0.0215 46.51163 0.369501 180 0.0223 44.84305
300 0.0189 52.91005 0.445748 240 0.0188 53.19149
360 0.017 58.82353 0.501466 300 0.0159 62.89308
480 0.0139 71.94245 0.592375 360 0.0137 72.9927
540 0.0128 78.125 0.624633 420 0.012 83.33333
600 0.0118 84.74576 0.653959 480 0.0106 94.33962
660 0.011 90.90909 0.677419 540 0.0095 105.2632
720 0.0103 97.08738 0.697947 600 0.0085 117.6471
780 0.0096 104.1667 0.718475 660 0.0078 128.2051
840 0.0091 109.8901 0.733138 720 0.007 142.8571
900 0.0086 116.2791 0.747801 780 0.0065 153.8462
960 0.0081 123.4568 0.762463 840 0.0059 169.4915
1020 0.0077 129.8701 0.774194 900 0.0055 181.8182
1080 0.0073 136.9863 0.785924 960 0.005 200
1140 0.0069 144.9275 0.797654 1020 0.0047 212.766
1200 0.0066 151.5152 0.806452 1080 0.0044 227.2727
1260 0.0064 156.25 0.812317 1140 0.004 250
1320 0.0061 163.9344 0.821114 1200 0.0037 270.2703
1380 0.0058 172.4138 0.829912 1260 0.0035 285.7143
1440 0.0056 178.5714 0.835777 1320 0.0033 303.0303
1500 0.0055 181.8182 0.83871 1380 0.0031 322.5806
1560 0.0052 192.3077 0.847507 1440 0.0029 344.8276
1620 0.0051 196.0784 0.85044 1500 0.0027 370.3704
1680 0.0049 204.0816 0.856305 1560 0.0025 400
1740 0.0048 208.3333 0.859238 1620 0.0024 416.6667
1800 0.0046 217.3913 0.865103 1680 0.0023 434.7826
1740 0.0022 454.5455
1800 0.0021 476.1905
NaOH 0.08
ETH 0.08
Temp. 45
time concentration 1/Ca
60 0.0328 30.4878
120 0.026 38.46154
180 0.0203 49.26108
240 0.0159 62.89308
300 0.0126 79.36508
360 0.0102 98.03922
420 0.0084 119.0476
480 0.007 142.8571
540 0.0059 169.4915
600 0.0051 196.0784
660 0.0044 227.2727
720 0.0038 263.1579
780 0.0033 303.0303
840 0.003 333.3333
900 0.0027 370.3704
960 0.0023 434.7826
1020 0.0022 454.5455
1080 0.0019 526.3158
1140 0.0017 588.2353
1200 0.0015 666.6667
1260 0.0014 714.2857
1320 0.0013 769.2308
1380 0.0011 909.0909
1440 0.001 1000
1500 0.0009 1111.111
1560 0.0008 1250
1620 0.0007 1428.571
1680 0.0006 1666.667
1740 0.0006 1666.667
1800 0.0005 2000
NaOH 0.08 0.75
ETH 0.06 a1 0.0013
Temp. 25
time concentration Xa (-xa)/(*(1-xa)) ln(-xa/(*(1-xa)))
60 0.0359 0 1 0
120 0.0315 0.122562674 0.953439153 -0.04767967
180 0.0281 0.217270195 0.90747331 -0.097091124
240 0.0255 0.289693593 0.864052288 -0.146121994
300 0.0233 0.35097493 0.819742489 -0.198765026
360 0.0215 0.401114206 0.776744186 -0.252644216
420 0.0202 0.437325905 0.740924092 -0.299857098
480 0.019 0.470752089 0.703508772 -0.351674934
540 0.0181 0.495821727 0.672191529 -0.397211966
600 0.0172 0.520891365 0.637596899 -0.450049015
660 0.0164 0.543175487 0.603658537 -0.504746578
720 0.0157 0.562674095 0.571125265 -0.560146714
780 0.0152 0.576601671 0.546052632 -0.605039913
840 0.0148 0.587743733 0.524774775 -0.644786109
900 0.0144 0.598885794 0.502314815 -0.688528235
960 0.014 0.610027855 0.478571429 -0.736949803
1020 0.0137 0.618384401 0.459854015 -0.776846199
1080 0.0133 0.629526462 0.43358396 -0.835669822
1140 0.013 0.637883008 0.412820513 -0.884742374
1200 0.0127 0.646239554 0.391076115 -0.938853069
1260 0.0125 0.651810585 0.376 -0.978166136
1320 0.0123 0.657381616 0.360433604 -1.020447516
1380 0.0121 0.662952646 0.344352617 -1.066089097
1440 0.0119 0.668523677 0.327731092 -1.115561847
1500 0.0117 0.674094708 0.310541311 -1.169438341
1560 0.0116 0.676880223 0.301724138 -1.19824213
1620 0.0114 0.682451253 0.283625731 -1.260099759
1680 0.0114 0.682451253 0.283625731 -1.260099759
1740 0.0112 0.688022284 0.264880952 -1.32847479
1800 0.0111 0.690807799 0.255255255 -1.365491233
NaOH 0.06 1.333333333
ETH 0.08 a1 -0.0008
Temp. 25
time concentration Xa (-xa)/(*(1-xa)) ln(-xa/(*(1-xa)))
60 0.0224 0 1 0
120 0.0186 0.169642857 1.051075269 0.049813706
180 0.0156 0.303571429 1.108974359 0.103435587
240 0.0133 0.40625 1.171052632 0.157903029
300 0.0114 0.491071429 1.24122807 0.216101269
360 0.0099 0.558035714 1.315656566 0.27433583
420 0.0087 0.611607143 1.393678161 0.331946411
480 0.0076 0.660714286 1.486842105 0.396654478
540 0.0067 0.700892857 1.585820896 0.461102188
600 0.0059 0.736607143 1.699152542 0.530129622
660 0.0052 0.767857143 1.826923077 0.602633173
720 0.0046 0.794642857 1.967391304 0.676708454
780 0.0041 0.816964286 2.115853659 0.749458352
840 0.0037 0.834821429 2.263513514 0.816918258
900 0.0033 0.852678571 2.446969697 0.894850401
960 0.003 0.866071429 2.616666667 0.961901243
1020 0.0027 0.879464286 2.824074074 1.038180549
1080 0.0024 0.892857143 3.083333333 1.126011263
1140 0.0021 0.90625 3.416666667 1.228665417
1200 0.002 0.910714286 3.55 1.266947603
1260 0.0018 0.919642857 3.861111111 1.350954995
1320 0.0017 0.924107143 4.044117647 1.397263392
1380 0.0015 0.933035714 4.483333333 1.500366817
1440 0.0013 0.941964286 5.057692308 1.620910314
1500 0.0012 0.946428571 5.416666667 1.68948062
1560 0.001 0.955357143 6.35 1.848454813
1620 0.0009 0.959821429 6.972222222 1.941934001
1680 0.0008 0.964285714 7.75 2.047692843
1740 0.0008 0.964285714 7.75 2.047692843
1800 0.0007 0.96875 8.75 2.1690537