Documente Academic
Documente Profesional
Documente Cultură
Heriot-Watt University
Stage 3
Chemical Engineering
Laboratory Report
Ruqiyya Israfilova
Authors Name:
H00206285
Submission Date:
10.03.2017
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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
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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:
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= + +
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.
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
= =
( )()
(),
= (),
()
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( ),
( ), ( )
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]
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
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= = 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.
The rate constant where temperature dependence of rate expression is obvious can be
determined by using Arrhenius law:
= 0
0 , ,
, ()
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.
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3 2 2 5 + 2 5 2 + 3
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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
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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
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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
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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
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)
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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)
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
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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
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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
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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
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)
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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
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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
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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)
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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)
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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
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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
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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
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