You are on page 1of 23

Chemical Engineering Laboratory Report

Heriot-Watt University

Stage 3

Chemical Engineering

Laboratory Report

Ruqiyya Israfilova
Authors Name:
H00206285

Group Number: CE03

Project Name: Liquid Phase Reactor

Date of Experiment: 24.02.2017

Submission Date:
10.03.2017

Supervisors Name Sanan Eminov

1
Chemical Engineering Laboratory Report

Contents
1. Abstract ....................................................................................................................... 3
2. Introduction ................................................................................................................. 3
3. Theory ......................................................................................................................... 4
4. Experimental Details ................................................................................................... 6
5. Results ........................................................................................................................ 9
5.1 Recorded data ....................................................................................................... 9
5.2 Derived data ........................................................................................................ 10
6. Discussion of results ................................................................................................. 21
7. Conclusion ................................................................................................................ 22
8. References ................................................................................................................ 22
9. Appendix ................................................................................................................... 22

2
Chemical Engineering Laboratory Report

1. Abstract
The main purpose of the experiment is to investigate saponification reaction and
determine its order. The reaction takes place in the batch reactor. Theoretically, the
reaction is second order and endothermic. To get homogenous solution agitator is used
in the reactor. At the three different agitator speeds (30, 50 and 100 rpms), the
experimental data is obtained. There are many methods to determine the order of the
reaction, but here one titration method is investigated and order of the saponification
reaction is found out. Reaction order based on each reactant (NaOH and Ethyl Acetate)
is defined one and overall order of reaction is two. Besides this, effect of temperature on
the conversion and rate constant is also investigated. The results illustrated that by
increasing temperature high values of rate constant and conversions can be obtained.
Also rate of reaction at different temperatures is calculated.

2. Introduction
The main aim of the chemical industry processes is to produce economically a desired
product by different treatment steps from various starting materials. Reactor design and
chemical kinetics are the most important section of these processes. Knowledge of
chemical reactor design and chemical kinetics distinguish chemical engineers from the
other engineers. Economic efficiency of the chemical plant depends on the safe
operations of reaction system.
What is a chemical reaction? Chemical reaction is the conversion of one type of
molecule to another type. Chemical reactions can be classified in different ways:
depending on the phase homogenous (takes place in one phase) and heterogeneous
(requires two or more phases). Reactions can also be catalytic and non-catalytic. Rate
of catalytic reactions is changed by adding some material (small amount) which is not
reactant or product in the reaction.
Simply rate of reaction can be defined as rate of formation of species per unit volume.
Rate of chemical reaction may be affected by some variables. In homogenous systems,
these variables are pressure, temperature and compositions. In heterogeneous
systems, this is more difficult. Heat and transfer also plays an important role in
considering rate of heterogeneous reactions. Reactions can be defined endothermic
and exothermic relating to heat transfer.
A chemical reactor is a kind of vessel used to convert raw materials to desired products.
Reactors provide enough time (residence time) for the reaction takes place. Because of
diversity of chemical reactions different types of chemical reactors are designed for
optimum processes. There are two main types of reactors: batch and continuous
reactors. Most prominent reactors used in chemical industry are continuous stirred tank
(CSTR), tubular and batch reactors which are classified based on their concentration
distributions. In batch reactors, raw materials are loaded at once. In mixing type batch
reactors, agitation is applied to increase heat transfer and mix separate materials. There
is also a semi-batch type of reactors where feed is supplied at once and product is
charged gradually. In CSTRs uniform condition occur due to perfect mixing and leaving
product has the same concentration as in inlet of vessel. In tubular reactors there is no
mixing in the axial direction, concentration decreases with the time.
Mass and energy balances are applied to the reactors in general form:

3
Chemical Engineering Laboratory Report

= + +
Batch reactors: are kind of tanks consisting agitators and some equipment to maintain
desired temperature in the vessel. They are simplest type of reactors which is based on
cook technology (not require much knowledge regarding to reaction kinetics, put the
feed and at the end take product). There are some assumptions are made for batch
reactors: it is well mixed, reaction stops when quenched, startup and filling procedures
are complete. Operations can take place either in homogenous or heterogeneous
systems. One of the advantages of batch reactors is that their design requires
integration over time. Reactor design makes batch reactors desirable for higher order
reactions. They are also advantageous for series reactions where intermediate can be
produced and react with the by-products. In batch reactors, it is easier to control
temperature compared to others. One of the main disadvantages of the batch reactors
is labor requiring for filling and emptying the vessel. Moreover, its dependence on the
type of reaction whether parallel or series limit use of these reactors.
Batch reactors are used in the industry where small-scale production required, also in
the laboratories. However, small-scale production and high cost controlling dont make
them economical.

Figure 2.1: Batch reactor

3. Theory
As mentioned before, rate of reaction defines decomposition of a component (i) per unit
volume. Number of moles of this component changes during reaction:
1
= =
( )()
(),
= (),
()

4
Chemical Engineering Laboratory Report

Considering a single reaction with reactants A and B, rate of equation


(elementary reaction) can be given:
+


( ),


( ), ( )

Number of collisions of A and B molecules is proportional to rate of equation, as rate-
controlling mechanism defines collision and interacting of single A and B molecules.
Constant-volume batch reactor:
When the volume of the reaction mixture stays constant this is called constant-density
reaction system. Rate of reaction can be expressed:

1 ( )
= = = [1]

Rate change in the concentration of a component determines rate of reaction.


Conversion of a component over the reaction is determined by the following way:


= =1 =1 [1]
0 0 0

,
0 (),
(),
0

Integral method of analysis is a method to explore rate of equation and compare


concentration versus time. This is mainly useful for elementary reactions.
For the first order reactions:


= =



=
0 0

0
ln (
) =

The plot of ln(CA0/CA) versus time gives a straight line if it is not so, then order of the
reaction is not one.
For the second order reactions:
2

5
Chemical Engineering Laboratory Report


= = 2



2 =
0 0

1 1
=
0
1 1
Plotting against time gives straight line with slope equal to k for the second
0
order reaction.

Temperature dependency of rate of equation:


Temperature dependency of rate of equation is determined by using Arrhenius Law.
Rate expression depends on temperature and composition and formula can be derived
for many reactions (especially elementary reaction):
= 1 () 2 () = 2 () [1]

The rate constant where temperature dependence of rate expression is obvious can be
determined by using Arrhenius law:

= 0

0 , ,
, ()

For different temperatures Arrhenius law can be written like:


2 2 1 1
ln ( ) = ln ( ) = ( )
1 1 1 2

Activation energy for a reaction is constant.

4. Experimental Details
Equipment:
Batch reactor is a cylindrical tank consists of a heating coil inside of it and a baffle
pack. Heating coil is used to set temperature to desirable value and thermometer used
to control temperature. There is an agitator in the vessel to mix materials. Drainage
valve at the bottom of vessel is used to take samples during experiment and discharge
tank at the end of experiment.
A glassware and burette is used to store solution and measure amount of HCl solution
before titration, respectively.

6
Chemical Engineering Laboratory Report

Figure 4.1: Batch reactor scheme

Figure 4.2: Lab rig

7
Chemical Engineering Laboratory Report

Procedure: the reaction takes place in reactor is the saponification of ethyl


acetate with the sodium hydroxide:

3 2 2 5 + 2 5 2 + 3

Reaction is the irreversible reaction.


Order of reaction and rate constant, activation energy of reaction and effect of stirrer
speed on the reaction rate should be determined in the experiment.
1. 100ml of 1M NaOH solution is added to 900 ml water and 0.1M NaOH solution is
prepared.
2. 100ml of 1M HCl solution is added to 900ml water to prepare 0.1M HCl solution.
3. 10ml of 10M Ethyl Acetate solution is added to 990ml water to make 0.1M Ethyl
Acetate solution.
4. First NaOH solution (100 ml) is added to the vessel then Ethyl Acetate (100ml) is
mixed with it.
5. Time to time, 10 ml samples are taken from the reactor and HCl solution is added to
stop the reaction.
6. HCl is titrated with the unreacted NaOH and from this the amount of unreacted
reactant is determined.
+ + 2
7. Then conversion and final concentration of NaOH is calculated
8. Relative graphs are plotted and rate constants are determined, then activation energy
is calculated

8
Chemical Engineering Laboratory Report

5. Results
5.1 Recorded data

Set 1: 30 RPM
1 2 3
Time Titrate Vol. Temp Titrate Vol. Temp Titrate Vol. Temp
sec ml C ml C ml C
30 6.3 18.7 54 37.9 6.6 42.1
60 6.8 19 6.4 37.8 6.2 46.7
90 7.9 19.5 6.9 38.3 6.7 52.9
120 11.1 20.2 7.2 38.7 7 55
150 7 22.4 7.6 39.4 7.4 59.4
180 11.2 24.8 8.5 40.2 8.1 62.6
240 8.9 26.4 8.1 41 8.5 65.9
300 8.4 27.7 8.6 41.5 8.9 67.4
360 9.4 28.9 9.9 42.3 8.9 68.2
420 9.7 29.9 8.7 43.2 8.9 68.3
480 10.4 29 9.4 44.5 9.7 67.6
540 10.7 28.1 9.5 45 10 67.1
600 10.5 26.2 9.5 45.5 9.8 65.4
660 10.2 25.8 9.9 45.7 10.3 62.3
720 9.1 25.8 9.7 46.6 10.5 59.9
780 9.2 26 9.5 46.7 9.8 58.2
Table 5.1.1: Titrate volumes and three various temperatures range at 30rpm mixer
speed

Set 2: 50 RPM
Time Titrate Vol. Temp Titrate Vol. Temp Titrate Vol. Temp
sec ml C ml C ml C
30 6.8 22.6 6 34.1 6.9 43.1
60 6.6 22.7 6.5 37.4 7.5 49.7
90 7 23 7.3 239.8 7.6 54.7
120 8.1 24.2 7.6 42 6.9 58
150 7.1 24.6 8.1 44.3 8.6 61.5
180 7.7 25.6 8.2 45.5 8.7 63.3
240 7.9 25.9 8.4 48 9.6 66.8
300 9.8 26.1 8.7 49.8 10.1 68.4
360 9 26.3 9 50.6 9.9 68.3
420 8.6 26.4 9.2 51.2 9.8 67.3

9
Chemical Engineering Laboratory Report

480 8.8 26.5 9.1 51.6 10.3 66.8


540 9.7 26.5 9.5 51.6 10.1 66
600 9.1 26.5 9.3 51.6 10.5 64.5
660 9.1 26.5 8.9 51.5 10.4 58.3
720 9.2 26.5 9.2 51.3 10.6 57.8
780 9.1 26.5 9.2 51.1 11 57.1
Table 5.1.2: Titrate volumes and three various temperatures range at 50rpm mixer
speed

Set 3: 100 RPM


Time Titrate Vol. Temp Titrate Vol. Temp Titrate Vol. Temp
sec ml C ml C ml C
30 6.2 18.3 5.7 30.6 6.6 44.2
60 5.8 18.1 5.8 33.4 7.3 48.1
90 6.4 19.8 6.5 34.7 7.2 53
120 6.5 21.2 7 36.5 6.4 57.1
150 7.1 22.7 6.9 37.7 8.4 62.4
180 7.1 23.8 7.7 39.1 7.8 61.2
240 7.7 25.2 8.3 40.7 9.9 60.8
300 8.4 26.3 8.7 41.6 10.3 60.3
360 8.5 27.1 8.7 42.3 9.9 60.4
420 8.8 27.7 8.6 42.5 9.9 60.4
480 8.7 28 9.2 42.6 9.8 62.6
540 9.2 28.4 8.6 42.7 10.3 66.3
600 9.3 28.4 9 42.6 10 67.6
660 9.2 28.5 8.6 42.5 9.9 70.1
720 9.7 28.5 9.6 42.4 11.1 72
780 9.3 28.5 9 42.3 11 68.9
Table 5.1.3: Titrate volumes and three various temperatures range at 100rpm
mixer speed

5.2 Derived data

Data set 1: 30 rpm

Final
Unreacted Reacted
Conversion / xA concentration/ Ln(CA0/CA) 1/CA-1/CA0
HCl/ ml NaOH/ ml
CA (M)
3.70 1.30 0.26 0.037 0.301105 7.027027
3.20 1.80 0.36 0.032 0.446287 11.25

10
Chemical Engineering Laboratory Report

2.10 2.90 0.58 0.021 0.867501 27.61905


- - - - -
3.00 2.00 0.4 0.030.510826 13.33333
- - - - - -
1.10 3.90 0.78 0.011 1.514128 70.90909
1.60 3.40 0.68 0.016 1.139434 42.5
0.60 4.40 0.88 0.006 2.120264 146.6667
0.30 4.70 0.94 0.003 2.813411 313.3333
- - - - - -
- - - - - -
- - - - - -
- - - - - -
0.90 4.10 0.82 0.009 1.714798 91.11111
0.80 4.20 0.84 0.008 1.832581 105
Table5.2.1: Calculations on temperature ranges between 18.3 and 28.3oC

Final
Unreacted Reacted
Conversion / xA concentration/ Ln(CA0/CA) 1/CA-1/CA0
HCl/ ml NaOH/ ml
CA (M)
4.6 0.40 0.08 0.046 0.083382 1.73913
3.6 1.40 0.28 0.036 0.328504 7.777778
3.1 1.90 0.38 0.031 0.478036 12.25806
2.8 2.20 0.44 0.028 0.579818 15.71429
2.4 2.60 0.52 0.024 0.733969 21.66667
1.5 3.50 0.7 0.015 1.203973 46.66667
1.9 3.10 0.62 0.019 0.967584 32.63158
1.4 3.60 0.72 0.014 1.272966 51.42857
0.1 4.90 0.98 0.001 3.912023 980
1.3 3.70 0.74 0.013 1.347074 56.92308
0.6 4.40 0.88 0.006 2.120264 146.6667
0.5 4.50 0.9 0.005 2.302585 180
0.5 4.50 0.9 0.005 2.302585 180
0.1 4.90 0.98 0.001 3.912023 980
0.3 4.70 0.94 0.003 2.813411 313.3333
0.5 4.50 0.9 0.005 2.302585 180
Table5.2.2: Calculations on temperature ranges between 30.6 and 42.3 C o

11
Chemical Engineering Laboratory Report

Final
Unreacted Reacted
Conversion / xA concentration/ Ln(CA0/CA) 1/CA-1/CA0
HCl/ ml NaOH/ ml
CA (M)
3.4 1.60 0.32 0.034 0.385662 9.411765
3.8 1.20 0.24 0.038 0.274437 6.315789
3.3 1.70 0.34 0.033 0.415515 10.30303
3 2.00 0.4 0.03 0.510826 13.33333
2.6 2.40 0.48 0.026 0.653926 18.46154
1.9 3.10 0.62 0.019 0.967584 32.63158
1.5 3.50 0.7 0.015 1.203973 46.66667
1.1 3.90 0.78 0.011 1.514128 70.90909
1.1 3.90 0.78 0.011 1.514128 70.90909
1.1 3.90 0.78 0.011 1.514128 70.90909
0.3 4.70 0.94 0.003 2.813411 313.3333
- - - - - -
0.2 4.80 0.96 0.002 3.218876 480
Table5.2.3: Calculations on temperature ranges between 42.1 and 58.2 C o

Determination of first order y = 0.0021x


R = 0.4698
4.5
y = 0.0038x
4 R = 0.63
y = 0.0045x
3.5 R = 0.9275
3
T=298 K
Ln(Ca0/Ca)

2.5 T=315K

2 T=333.7K
Linear (T=298 K)
1.5
Linear (T=315K)
1
Linear (T=333.7K)
0.5

0
0 200 400 600 800 1000
time (s)

Graph 5.2.1: Determination of first order

12
Chemical Engineering Laboratory Report

Determination of second order


1200 y = 0.17x + 29.309
R = 0.2302
1000
y = 0.5983x - 13.825
800 R = 0.2207

y = 0.707x - 82.344
1/Ca-1/Ca0

600 R = 0.8225

400 T=298K
T=315 K
200
T=333.7 K

0 Linear (T=298K)
0 200 400 600 800 1000 Linear (T=315 K)
-200 Linear (T=333.7 K)
time (s)

Graph 5.2.2: Determination of second order

Tav(1)K Tav(3) K k1 k3 Activation Pre-


1/s 1/s energy (J/mol) exponential
factor (A/ 1/s)
297.9 333.7 0.0021 0.0045 17650.18 2.607

Set 1: 30 RPM
1 2 3
Rate Rate Rate
Time constant Rate constant Rate constant Rate
sec Mol/(l s) Mol/(l s) Mol/(l s)
30 0.001807 6.6869E-05 0.002832 0.00013025 0.003101 0.00010544
60 0.001821 5.8266E-05 0.002825 0.00010171 0.003416 0.00012982
90 0.001844 3.8715E-05 0.002856 8.8551E-05 0.003876 0.00012791
120 0.001876 - 0.002882 8.0684E-05 0.004041 0.00012123
150 0.00198 5.9387E-05 0.002926 7.022E-05 0.004402 0.00011445
180 0.002097 - 0.002977 4.4655E-05 0.004678 8.8886E-05
240 0.002179 2.3967E-05 0.003029 5.7547E-05 0.004975 7.4628E-05
300 0.002247 3.5946E-05 0.003062 4.2861E-05 0.005114 5.6257E-05
360 0.00231 1.3863E-05 0.003114 3.1143E-06 0.00519 5.7085E-05
420 0.002365 7.0941E-06 0.003175 4.1269E-05 0.005199 5.7189E-05

13
Chemical Engineering Laboratory Report

480 0.002316 - 0.003263 1.9578E-05 0.005133 1.5399E-05


540 0.002268 - 0.003297 1.6487E-05 0.005086 #VALUE!
600 0.002169 - 0.003332 1.6661E-05 0.004929 9.8588E-06
660 0.002148 - 0.003346 3.3461E-06 0.004652 #VALUE!
720 0.002148 1.9333E-05 0.003409 1.0228E-05 0.004444 #VALUE!
780 0.002158 1.7266E-05 0.003416 1.7082E-05 0.004301 8.6029E-06
Table5.2.4: Rate constants and rates of reaction

Data set 2: 50 rpm


Final
Unreacted Reacted
Conversion / xA concentration/ Ln(CA0/CA) 1/CA-1/CA0
HCl/ ml NaOH/ ml
CA (M)
3.2 1.8 0.36 0.032 0.446287 11.25
3.4 1.6 0.32 0.034 0.385662 9.411765
3 2 0.4 0.03 0.510826 13.33333
1.9 3.1 0.62 0.019 0.967584 32.63158
2.9 2.1 0.42 0.029 0.544727 14.48276
2.3 2.7 0.54 0.023 0.776529 23.47826
2.1 2.9 0.58 0.021 0.867501 27.61905
0.2 4.8 0.96 0.002 3.218876 480
1 4 0.8 0.01 1.609438 80
1.4 3.6 0.72 0.014 1.272966 51.42857
1.2 3.8 0.76 0.012 1.427116 63.33333
0.3 4.7 0.94 0.003 2.813411 313.3333
0.9 4.1 0.82 0.009 1.714798 91.11111
0.9 4.1 0.82 0.009 1.714798 91.11111
0.8 4.2 0.84 0.008 1.832581 105
0.9 4.1 0.82 0.009 1.714798 91.11111
Table5.2.5: Calculations on temperature ranges between 22.6 and 26.5oC

Final
Unreacted Reacted
Conversion / xA concentration/ Ln(CA0/CA) 1/CA-1/CA0
HCl/ ml NaOH/ ml
CA (M)
4 1 0.2 0.04 0.223144 5
3.5 1.5 0.3 0.035 0.356675 8.571429
2.7 2.3 0.46 0.027 0.616186 17.03704
2.4 2.6 0.52 0.024 0.733969 21.66667
1.9 3.1 0.62 0.019 0.967584 32.63158
1.8 3.2 0.64 0.018 1.021651 35.55556

14
Chemical Engineering Laboratory Report

1.6 3.4 0.68 0.016 1.139434 42.5


1.3 3.7 0.74 0.013 1.347074 56.92308
1 4 0.8 0.01 1.609438 80
0.8 4.2 0.84 0.008 1.832581 105
0.9 4.1 0.82 0.009 1.714798 91.11111
0.5 4.5 0.9 0.005 2.302585 180
0.7 4.3 0.86 0.007 1.966113 122.8571
1.1 3.9 0.78 0.011 1.514128 70.90909
0.8 4.2 0.84 0.008 1.832581 105
0.8 4.2 0.84 0.008 1.832581 105
Table5.2.6: Calculations on temperature ranges between 34.1 and 51.1oC

Final
Unreacted Reacted
Conversion / xA
concentration/ Ln(CA0/CA) 1/CA-1/CA0
HCl/ ml NaOH/ ml
CA (M)
3.1 1.9 0.38 0.031 0.478036 12.25806
2.5 2.5 0.5 0.025 0.693147 20
2.4 2.6 0.52 0.024 0.733969 21.66667
3.1 1.9 0.38 0.031 0.478036 12.25806
1.4 3.6 0.72 0.014 1.272966 51.42857
1.3 3.7 0.74 0.013 1.347074 56.92308
0.4 4.6 0.92 0.004 2.525729 230
- - - - - -
0.1 4.9 0.98 0.001 3.912023 980
0.2 4.8 0.96 0.002 3.218876 480
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
Table5.2.7: Calculations on temperature ranges between 43.1 and 57.1 Co

15
Chemical Engineering Laboratory Report

Determination of first order


4.5 y = 0.0021x
R = 0.39
4
y = 0.0022x
3.5 R = 0.7591

3 y = 0.009x
ln(Ca0/Ca)

R = 0.8921
2.5

2
T=298.6 K
1.5 T=332.6 K
1 T=338.9 K
0.5 Linear (T=298.6 K)

0 Linear (T=332.6 K)
0 200 400 600 800 1000 Linear (T=338.9 K)
1/Ca-1/Ca0

Graph 5.2.3: Determination of first order

Determination of second order


1200 y = 0.1485x
R = 0.0852
1000 y = 0.1601x
R = 0.6667
800
y = 2.033x
1/Ca-1/Ca0

600 R = 0.6837

400 T=298.6 K

200 T=332.6K

T=333.9 K
0
0 200 400 600 800 1000 Linear
-200 (T=298.6 K)
time (s)

Graph 5.2.4: Determination of second order

Tav(1)K Tav(3) K k1 k3 Activation energy Pre-exponential


1/s 1/s (J/mol) factor (A/ 1/s)
298.6 333.9 0.0021 0.009 30381.91 416.84

16
Chemical Engineering Laboratory Report

Set 2: 50 RPM
1 2 3
Rate Rate Rate
Time constant Rate constant Rate constant Rate
sec Mol/(l s) Mol/(l s) Mol/(l s)
30 0.001794 5.74046E-05 0.002849 0.000113948 0.003996 0.000123881
60 0.001801 6.12477E-05 0.003232 0.000113137 0.005061 0.000126524
90 0.001824 5.47225E-05 0.335747 0.009065163 0.006015 0.000144349
120 0.001917 3.64272E-05 0.003838 9.21168E-05 0.006721 0.000208355
150 0.001949 5.65249E-05 0.004175 7.93172E-05 0.007543 0.000105607
180 0.002031 4.67101E-05 0.00436 7.84717E-05 0.007997 0.000103963
240 0.002056 4.31749E-05 0.004767 7.62661E-05 0.008943 3.57735E-05
300 0.002073 4.14562E-06 0.005079 6.60235E-05 - -
360 0.00209 2.08978E-05 0.005223 5.22274E-05 0.009376 9.37585E-06
420 0.002098 2.93764E-05 0.005333 4.26635E-05 0.009086 1.81714E-05
480 0.002107 2.52825E-05 0.005407 4.86671E-05 - -
540 0.002107 6.32062E-06 0.005407 2.70373E-05 - -
600 0.002107 1.89619E-05 0.005407 3.78522E-05 - -
660 0.002107 1.89619E-05 0.005389 5.92762E-05 - -
720 0.002107 1.6855E-05 0.005351 4.28119E-05 - -
780 0.002107 1.89619E-05 0.005314 4.25155E-05 - -
Table5.2.8: Rate constants and rates of reaction

Data set 3: 100rpm


Final
Unreacted Reacted
Conversion / xA concentration/ Ln(CA0/CA) 1/CA-1/CA0
HCl/ ml NaOH/ ml
CA (M)
3.8 1.2 0.24 0.038 0.274437 6.315789
4.2 0.8 0.16 0.042 0.174353 3.809524
3.6 1.4 0.28 0.036 0.328504 7.777778
3.5 1.5 0.3 0.035 0.356675 8.571429
2.9 2.1 0.42 0.029 0.544727 14.48276
2.9 2.1 0.42 0.029 0.544727 14.48276
2.3 2.7 0.54 0.023 0.776529 23.47826
1.6 3.4 0.68 0.016 1.139434 42.5
1.5 3.5 0.7 0.015 1.203973 46.66667
1.2 3.8 0.76 0.012 1.427116 63.33333
1.3 3.7 0.74 0.013 1.347074 56.92308
0.8 4.2 0.84 0.008 1.832581 105

17
Chemical Engineering Laboratory Report

0.7 4.3 0.86 0.007 1.966113 122.8571


0.8 4.2 0.84 0.008 1.832581 105
0.3 4.7 0.94 0.003 2.813411 313.3333
0.7 4.3 0.86 0.007 1.966113 122.8571
o
Table5.2.9: Calculations on temperature ranges between 18.3and 28.5 C (1)

Final
Unreacted Reacted
Conversion / xA concentration/ Ln(CA0/CA) 1/CA-1/CA0
HCl/ ml NaOH/ ml
CA (M)
4.3 0.7 0.14 0.043 0.150823 3.255814
4.2 0.8 0.16 0.042 0.174353 3.809524
3.5 1.5 0.3 0.035 0.356675 8.571429
3 2 0.4 0.03 0.510826 13.33333
3.1 1.9 0.38 0.031 0.478036 12.25806
2.3 2.7 0.54 0.023 0.776529 23.47826
1.7 3.3 0.66 0.017 1.07881 38.82353
1.3 3.7 0.74 0.013 1.347074 56.92308
1.3 3.7 0.74 0.013 1.347074 56.92308
1.4 3.6 0.72 0.014 1.272966 51.42857
0.8 4.2 0.84 0.008 1.832581 105
1.4 3.6 0.72 0.014 1.272966 51.42857
1 4 0.8 0.01 1.609438 80
1.4 3.6 0.72 0.014 1.272966 51.42857
0.4 4.6 0.92 0.004 2.525729 230
1 4 0.8 0.01 1.609438 80
Table5.2.10: Calculations on temperature ranges between 30.6 and 42.3oC

Final
Unreacted Reacted
Conversion / xA concentration/ Ln(CA0/CA) 1/CA-1/CA0
HCl/ ml NaOH/ ml
CA (M)
3.4 1.6 0.32 0.034 0.385662 9.411765
2.7 2.3 0.46 0.027 0.616186 17.03704
2.8 2.2 0.44 0.028 0.579818 15.71429
3.6 1.4 0.28 0.036 0.328504 7.777778
1.6 3.4 0.68 0.016 1.139434 42.5
2.2 2.8 0.56 0.022 0.820981 25.45455
0.1 4.9 0.98 0.001 3.912023 980
- - - - - -
0.1 4.9 0.98 0.001 3.912023 980
0.1 4.9 0.98 0.001 3.912023 980

18
Chemical Engineering Laboratory Report

0.2 4.8 0.96 0.002 3.218876 480


- - - - - -
- - - - - -
0.1 4.9 0.98 0.001 3.912023 980
- - - - - -
- - - - - -
Table5.2.11: Calculations on temperature ranges between 44.2 and 68.9oC

Determination of first order


6
y = 0.003x
R = 0.9217
5
y = 0.0023x
R = 0.7656
4

y = 0.007x
ln(Ca0/Ca)

R = 0.7099
3

2 T=298.2 K

T=312.8 K
1
T=334.1 K

Linear (T=298.2
0 K)
0 200 400 600 800 1000 Linear (T=312.8
time (s) K)

Graph 5.2.5: Determination of first order

19
Chemical Engineering Laboratory Report

Determination of second order


1400 y = 0.257x
R = 0.6597
1200 y = 0.167x
R = 0.5546
1000
y = 1.846x
800 R = 0.62
1/Ca-1/Ca0

T=298K
600

400 T=312.8 K

200 T=334.1 K

0 Linear (T=298K)
0 200 400 600 800 1000
-200
time (s)

Graph 5.2.6: Determination of second order

Tav(1)K Tav(3) K k1 k3 Activation energy Pre-exponential


1/s 1/s (J/mol) factor (A/ 1/s)
298 334.1 0.003 0.007 19476.3 7.78

Set 3: 100 RPM


1 2 3
Rate Rate Rate
Time constant Rate constant Rate constant Rate
sec Mol/(l s) Mol/(l s) Mol/(l s)
30 0.004213 0.00016 0.005606 0.000241 0.007505 0.000255
60 0.004192 0.000176 0.005965 0.000251 0.008125 0.000219
90 0.004367 0.000157 0.006137 0.000215 0.008954 0.000251
120 0.004515 0.000158 0.006381 0.000191 0.009692 0.000349
150 0.004678 0.000136 0.006548 0.000203 0.010708 0.000171
180 0.0048 0.000139 0.006746 0.000155 0.010472 0.00023
240 0.004959 0.000114 0.006978 0.000119 0.010394 1.04E-05
300 0.005086 8.14E-05 0.007111 9.24E-05 - -
360 0.00518 7.77E-05 0.007215 9.38E-05 0.010316 1.03E-05
420 0.005251 6.3E-05 0.007246 0.000101 0.010316 1.03E-05
480 0.005287 6.87E-05 0.007261 5.81E-05 0.010748 2.15E-05
540 0.005335 4.27E-05 0.007276 0.000102 - -
600 0.005335 3.73E-05 0.007261 7.26E-05 - -

20
Chemical Engineering Laboratory Report

660 0.005347 4.28E-05 0.007246 0.000101 0.012313 1.23E-05


720 0.005347 1.6E-05 0.007231 2.89E-05 - -
780 0.005347 3.74E-05 0.007215 7.22E-05 - -
Table5.2.12: Rate constants and rates of reaction

6. Discussion of results
As previously discussed, the main purpose of the experiment is to determine the order
of saponification reaction, then relative rate constants and rates of equations at the
given temperatures. For this, after the titration conversion of NaOH (unreacted in
titration) was determined. Then final concentrations of NaOH at different temperatures
are calculated. There are some errors in the data sets where excess volume HCl is
higher than the given measurement value. This is due to some misreading in the
apparatus.
Reaction order describes the mathematical form where it is possible to demonstrate
results of the changes. It can only be calculated in experiment and overall order of
reaction is calculated by sum of the orders based on each reactant. It should be noted
that order of reaction is not same as stoichiometric coefficients of reactants.
Analysis of data set 1: It is obvious from the Table 5.2.1 that as the time increases the
converted volume of NaOH is also increases and the volume of HCl decreases. Hence
conversion of NaOH in the reaction also rises and as a result of this final concentration
of NaOH drops. There are three temperature ranges in the reactor that are investigated.
As the temperature range increases conversion of NaOH gets bigger (from 0.84 to
0.96). To determine whether the reaction is first or second order, graphs of ln(CA0/CA)
and (1/CA 1/CA0) versus time was plotted. Here for different range of temperatures
various rate constants- slopes (ranges between 0.0021- 0.0045) are obtained (Graph
5.2.1). For high temperature range results get more linear form. The same results are
also obtained for second order determination reaction (Graph 5.2.2). However, in the
first order determination graph the results are more linear than the second order
determination graphs. Taking average temperatures and rate constants, activation
energy is calculated (17650 J/mol). Reactions have their constant activation energy
value. As the third temperature range is highest and straight line is obtained, pre-
exponential factor is calculated using its rate constant. After this, rate constants and
reaction rates are calculated for different temperatures. At the highest temperature, high
value of rate constant is obtained, for this reason rate of reaction is also high at the
relative time (Table 5.2.4).
Analysis of data set 2: rate of agitator is increased from 30 to 50 rpm. As in set 1,
highest conversion of NaOH is obtained in the high reaction temperature. More straight
line is obtained in first order determination graph (Graph 5.2.3). Then rate constant are
observed from the slope of the lines (k1=0.0021/s, k3=0.009/s). As the agitation speed
increased, rate of reactions also rise. Rate constant gets higher as the temperature
increases (based on Arrhenius law). In homogenous solutions, reactant molecules
collide with each other easily and this increases rate of reactions. Stirring solution
makes it more homogenous. For this reason, at the higher agitator speed high rate
constant is obtained. Calculated activation energy is 30382 J/mol and exponential factor
21
Chemical Engineering Laboratory Report

is 416.8/s. Firstly, rate of reaction increased as time passed then it decreased


as the NaOH consumed.
Analysis of data set 3: The same results are also derived for the data which obtained at
100 rpm stirrer speed. Reaction is observed as first order (Graph 5.2.5). The highest
rate is calculated when the agitator speed is 100rpm (0.000176 mol/ l s). The activation
energy is 19476.3 J/mol and exponential factor is 7.78/s.
The results shows that the order of reaction based on whether NaOH or Ethyl Acetate is
one, so overall order of reaction is two. Theoretically order of saponification reaction is
two. As the temperature increased rate constant and conversion of reactants also get
bigger. At high stirrer speed, higher rate of reaction is determined.

7. Conclusion
In conclusion, the aim of the experiment is achieved: order of the saponification reaction
is determined. Moreover, rate of reaction and rate constant is calculated after finding
activation energy for the reaction. Titration method is investigated and order of the
saponification reaction is found out and overall order of reaction is two. Besides this,
effect of temperature on the conversion and rate constant is also investigated. The
results illustrated that by increasing temperature high values of rate constant and
conversions can be obtained. Also rate of reaction at different temperatures is
calculated.

8. References
[1] Octave Levenspiel, Chemical Reaction Engineering, third edition
[2] Perry, Chemical engineering handbook
[3] - https://dissa4ict.wordpress.com/2013/01/09/determination-of-reaction-rate-and-
reaction-rate-constant/

9. Appendix
Unreacted HCl:
10 6.8 = 3.2
Reacted NaOH:
5 3.2 = 1.8
Initial concentration of NaOH:
100 0.1
= = 0.05
200

Conversion and final concentration of NaOH:


1.8
= = 0.36
5

= 0.05 (1 0.36) = 0.032


Activation energy:

22
Chemical Engineering Laboratory Report

0.021
ln ( )
= 0.0045 8.314 = 17650.2
1 1

333.7 298

Pre-exponential factor:
0.0045 1
= = 2.61
17650.2
exp ( 8.314 333.7)
Rate constant at t=19oC:
17650.2 1
= 2.61 exp ( ) = 0.0018
8.314 292
Rate of reaction:

= = 0.0018 0.032 = 5.81 05

23