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Liquid Phase Reactor PDF
Liquid Phase Reactor PDF
SUMMARY
The topic investigated in this experiment was liquid phase chemical reactors with the
effect of temperature on reaction rate constant. This is significant in Chemical
Engineering because of the underlying importance it has in understanding how a
chemical reaction works ( i.e. chemical kinetics). In addition, knowing
the kinetics of a reaction will help chemical engineers in optimum
reactor design.
The major objective of this lab was to find the reaction rate constant in a batch
stirred tank reactor for the saponification ethyl acetate with dilute sodium hydroxide.
Another objective was to study the effect of temperature on reaction rate constant,
and also to find the values of the rate constant and the Arrhenius parameters;
activation energy, Ea and pre-exponential factor, A).
In carrying out the experiment, a chemical reactor service unit fitted with batch
chemical reactor was used (see figure 1 for the diagram of the experimental set up).
From the experiment, some key results were obtained. One of such result was that
for any given chemical reaction, the reaction rate is temperature dependent. Thus,
an increase in temperature causes an increase in the reaction. Also, the conductivity
of the reactants decreases with time as the reactants loses their ions and become
less conductive. Another important finding was that as the concentration of the
hydroxide reduces, the reaction rate increases.
Going by the objectives of the lab, the Arrhenius parameters were estimated to be
197.87 and 501.625 kJ/mol respectively (i.e. the pre-exponential factor and
activation energy). In addition, the reaction rate constant (k) for the reactions were
estimated to be 0.0101 M-1s-1 at 25°C, 0.2853 M-1s-1 at 30°C and 0.0089 M-1s-1 at
40°C respectively.
From the experiment, it can be concluded that temperature plays a major part in
chemical kinetics (rate increases as temperature increases). Also, in a chemical
reaction, as the reactant (s) are been converted into products, the conductivity
changes. Finally, in homogenous (same phase) reaction that is second order overall
(first order in both components) like the one done in the lab, the concentration of the
reactants also affects the reaction rate.
Page 1 of 22
B. INTRODUCTION:
One of the major objectives of this lab was to find the reaction rate constant using a
batch stirred tank reactor for the saponification ethyl acetate with dilute sodium
hydroxide. Another objective was to study the effect of temperature on reaction rate
constant, and also to find the values of the rate constant and the Arrhenius
parameters; activation energy, Ea and pre-exponential factor, A). In the course of the
experiment, the effect of concentration of reactants on a homogenous reaction was
also considered.
One of the three types of reactors in chemical processes is the batch reactor. In this
type of reactor, the total feed is introduced at the beginning and no withdrawal is
made until the reaction has reached the degree of completion desired; hence it is a
closed system reactor. It differs from a continuous stirred tank reactor (CSTR) which
has material exchange taking place during the reaction.
For this experiment, a stirred tank batch reactor was used; meaning it has a stirrer to
ensure continuous mixing of the reactants to aid in a homogenous concentration
throughout the mixture. Another important thing to note about this type of reactor is
that it works with an unsteady process (that is all variables change with time).
Also, the mixture in the volume is assumed to be perfectly mixed (that is there will be
uniform concentrations). In addition, temperature will be uniform throughout the
reactor; however it may change with time (Basu, 2012). Also, batch reactors are
often used for liquid-phase reactions particularly when the required production is
small (Smith, 1981).
Generally, the mass balance for a stirred tank reactor can be written as:
Rate of change within the reactor = Input – Output – Loss by reaction. For any liquid
phase chemical reactor with a constant volume such as the batch stirred tank
reactor, this can be rearranged to give: Rate of change within the reactor = loss by
reaction.
Thus for any given reaction in constant volume, the rate equation can be given as:
(1)
Where:
is the rate of disappearance of reactant ‘A’ among the reacting species
is the concentration of reactant ‘A’ in the exit stream
Page 2 of 22
t is the time in seconds it takes for reactant ‘A’ to disappear
For a bimolecular reaction like the one in the experiment; the saponification of ethyl
acetate with dilute sodium hydroxide which is given as:
Generally several factors could influence the rate of a chemical reaction. Some of
these factors include:
(i) Temperature
(ii) Concentration (if homogenous)
(iii) State of reactants (that is if they are solid, liquid or gas)
(iv) Order of reaction
(v) Pressure
Out of the above mentioned factors, the effect of temperature on the reaction rate
was the one studied. Though, the effect of concentration was also observed because
the reaction that was studied was a homogenous reaction. The relationship between
reaction rate and temperature is explained by Arrhenius equation which is given as:
⁄ (3)
Where:
is the reaction rate constant
is the universal gas constant (8.314 J mol-1K-1)
is temperature (K)
is the activation energy (J mol-1)
is Arrhenius constant or pre-exponential factor (s-1) for a first order reaction
By applying natural logarithm to both sides, equation (3) can be re-written as:
(4)
Page 3 of 22
From equation (4), a plot of against 1/T would yield a straight line graph from
which ‘A’ can be obtained as the intercept of the line at 1/T = 0. The activation
energy (Ea) can be obtained from the slope of the graph which is given as .
Thus if the slope, S = , then the activation energy can be estimated as:
(5)
It is noteworthy to mention here that reactions with low activation energy are
relatively temperature-insensitive while those with high activation energies are very
temperature sensitive. Therefore, any given reaction is much more temperature-
sensitive at a low temperature than at a high temperature (Levenspiel, 1999).
From the above, it shows that the reaction rate constant has to be obtained first
before applying Arrhenius equation to find the Arrhenius parameters. This can be
done by referring to reaction to be studied:
The rate of the reaction can be said to depend on the concentrations of both reactant
‘A’ ( and reactant ‘B’ ( . The order of the reaction studied is
known to be first order with respect to both ‘A’, and ‘B’ , hence second order overall.
Thus by combining equation (1) and (2), an expression for the reaction rate constant
in terms of the concentration of A and B can be obtained as:
(6)
Where:
All the parameters are as defined in equation (2)
If the initial concentration of reactant A (CA0) and reactant B (CB0) are made to be
equal, then equation (6) can be reduced to:
(7)
(8)
Where:
Page 4 of 22
and are as defined before.
From equation (8), it can be seen that a graph of against will give a straight line
For the experiment, to calculate , the conductivity of the one of the reactants; in this
case reactant ‘A’ (Sodium hydroxide) can be measured at various time intervals.
With this, the concentration of the hydroxide can be calculated as:
(9)
Where:
is the concentration of reactant ‘A’ in the exit stream at time t
is the initial concentration of NaOH
is the conductivity of the solution at time t
is the conductivity of the solution at the end of reaction
is the initial conductivity at time t = 0
Note:
can be found by plotting a graph of the measured conductivity (k) against time
and extrapolating to t = 0.
C. EXPERIMENTAL EQUIPMENT
Page 5 of 22
The major equipment used in the experiment was a chemical reactor service unit
fitted with batch chemical reactor. A diagram of the experimental set up is shown in
figure 1. Other equipment used include; thermostatic bath to control the temperature
stability of the two reactants to be added in at any time, 1 litre glass flasks containing
the reactants, conductivity meter to measure the conductivity of the solution,
stopwatch and stock solutions of 0.1M solution of sodium hydroxide and 0.1M of
ethyl acetate.
This type of reactor is mostly used for liquid-phase chemical reactions, especially on
a small scale. Thus when used for liquid-phase reactions, the reactor volume does
not change significantly with the extent of reaction. For a gas-phase reaction, it may
be constant pressure sometimes. In addition, since the mixture in the tank is
assumed to be perfectly mixed, there will be uniform concentrations, and
temperature will also be uniform throughout the reactor; however with time it may
change. See figure 1 and 2 for a schematic diagram of a batch stirred tank reactor
and the experimental set-up respectively. The picture of the experimental set up is
also shown in figure 3.
Reactant components
Stirrer
Source: http://www.rpi.edu/dept/chem-eng/Biotech-Environ/IMMOB/stirredt.htm
Page 6 of 22
Figure 2: Schematic diagram of the experimental set up
Page 7 of 22
Ethyl acetate
NaoH
Temperature
adjuster Reaction
vessel
Conductivity
probe
Conductivity Temperature
meter probe
For safety reasons safety goggles and protective gloves were worn
during the course of the experiment advised to wear safety goggles and
protective gloves. After this, 0.1M sodium hydroxide and 0.1 M ethyl acetate
were provided to run the experiment. Then the reaction temperature was set to 25°C
on the thermostatic bath.
Then the two 1 litre flasks were filled to the mark with sodium
hydroxide solution and ethyl acetate solution respectively and placed in
a bath. The reaction temperature was then set on the reactor control
panel. After this, the conductivity meter was set and the probe end was
placed in the bath to get to get to the reaction temperature. The flasks
were also allowed to reach the reaction temperature.
Page 8 of 22
The 1 litre of sodium hydroxide solution was added to the reactor,
followed by the 1 litre of ethyl acetate solution, and the clock was
started when ca. 50% of ethyl acetate solution was added. After waiting
for about 30 seconds, ca. 200ml was withdrawn an d the conductivity
was measured, and then the sample was returned to the reactor while
the probe was returned to the bath.
The results (both experimental and calculated, and extrapolated results) obtained in
the experiment are shown in table 1- 4 below. The graphs are shown in figures 3 - 9
Page 9 of 22
Conductivity, k Conductivity, k Conductivity, k
t (s) @ 25°C (S/m) @ 30°C (S/m) @ 40°C (S/m)
30 1.511 0.601 1.698
60 1.398 0.544 1.511
90 1.308 0.498 1.386
120 1.246 0.462 1.304
150 1.188 0.431 1.246
180 1.140 0.407 1.199
210 1.100 0.387 1.161
240 1.066 0.37 1.13
270 1.037 0.355 1.105
300 1.011 0.343 1.084
330 0.988 3.33 1.065
360 0.968 0.324 1.049
390 0.950 0.317 1.035
420 0.934 0.31 1.022
450 0.918 0.305 1.011
480 0.906 0.3 1.001
510 0.893 0.296 0.984
540 0.882 0.292 0.976
570 0.871 0.289 0.969
600 0.862 0.287 0.955
780 0.818 0.276 0.936
960 0.787 0.271 0.913
1140 0.765 0.268 0.896
1320 0.748 0.266 0.882
1500 0.735 0.265 0.87
Page 13 of 22
1.600
1.400
1.200
Measured conductivity, k (S/m)
1.000
0.800
0.600
y = -0.0004x + 1.209
0.400
0.200
0.000
0 200 400 600 800 1000 1200 1400 1600
Time, t (seconds)
Page 14 of 22
0.700
0.500
0.400
0.300
0.200
y = -0.0002x + 0.4346
0.100
0.000
0 200 400 600 800 1000 1200 1400 1600
time, t (seconds)
1.800
1.600
Measured Conductivity, k (S/m)
1.400
1.200
1.000
0.800
y = -0.0004x + 1.2843
0.600
0.400
0.200
0.000
0 200 400 600 800 1000 1200 1400 1600
time, t (seconds)
Page 15 of 22
16
y = 0.0101x + 8.5495
14
12
10
1/CA (M)
0
0 100 200 300 400 500 600 700
time, t (seconds)
200
100
1/CA (M)
50
0
0 100 200 300 400 500 600 700
-50
time, t (seconds)
Page 16 of 22
16.000
12.000
10.000
8.000
6.000
4.000
2.000
0.000
0 100 200 300 400 500 600 700
time, t (seconds)
0
0.00329 0.0033 0.00331 0.00332 0.00333 0.00334 0.00335 0.00336
-0.5
-1
-1.5
-2
In k
-2.5 Series1
Linear (Series1)
-3
-3.5
-4
-4.5
y = -60335x + 197.87
-5
1/T (K)
Figure 10: Graph of In (k) against 1/T showing the effect of temperature on reaction
rate constant.
Page 17 of 22
Note: When plotting the graph of ln (k) against 1/T, the value of the reaction rate
constant (k) gotten when the reaction temperature was 40 °C as shown in figure 9
was not used. This was because from the readings gotten from the experimental as
shown in table 1, an experimental error was suspected to have occurred thereby
giving wrong readings. This error could possibly be in the reading of the conductivity
meter.
SAMPLE CALCULATIONS:
= 0.1250 M
Using same procedure, the hydroxide concentration (CA) and its reciprocal (1/CA) at
30°C and 40°C at various time intervals were also calculated.
A graph of In (k) against 1/T as shown in figure 8 will yields a straight line with
intercept ‘A’
Arrhenius parameter (A) = 197.87
Activation energy (Ea):
From equation (5):
Where slope in figure 8 = - 60335, R = 8.314 *10-3 kJ mol K-1
8.314 *10-3) = 501.625 kJ/mol = 501625.19 J/mol
F. DISCUSSION OF RESULTS:
Page 18 of 22
From the results obtained in the experiment, it shows that reaction rate is dependent
on temperature, through the dependence of reaction rate constant on ‘k’ on
temperature ‘T’. This can be seen from figure 9 where a plot of In (k) against 1/T
gave a straight line graph. This can also be seen from table 1 where at a
temperature of 25 °C, the reaction rate constant was 0.010 M-1s-1, while at 30 °C it
was 0.2853 M-1s-1 . At 40 °C, the reaction rate constant was 0.0089 M-1s-1.
Thus when a graph of In (k) was plotted against 1/T to estimate the Arrhenius
parameters, the values of the reaction rate constant (k) obtained when the
temperature was 40 °C was not used so as to obtain a straight line (linear) graph.
From figures 3, 4 and 5, it shows that conductivity decreases with time. This is could
be due to loses of some ions. This can also explain why at the start, only sodium
hydroxide would contribute to the conductivity. As reaction proceeds, sodium acetate
would start forming after consumption of sodium hydroxide resulting in different
conductivity results (Fogler, 1999).
Hence in the experiment carried out, there was a reduction in the concentration of
the hydroxide (NaOH) at various time intervals. The reason for this could be that
since it is a batch reactor, the reactants would be converted into products while
remaining in the reactor since there is no inflow or outflow; thus as the reactants are
been converted into products, there would be less and less reactant and more and
more products.
It can then been inferred that close to time t = 0, there would be a lot of reactant and
little product while close to time = infinity, there would be more product and less
reactant (Missen et al, 1999).
Page 19 of 22
Finally, this goes to show that for a second order reaction (first order in each reacting
components) like the saponification of ethyl acetate with dilute sodium hydroxide, the
reaction rate is also dependent on one or both of the reactants concentrations; in this
case that of the sodium hydroxide. For the reaction studied in this experiment, a
decrease in one of the reactant concentrations; in this case sodium hydroxide
causes and increase in the reaction rate. This is in line with the collision theory.
G. CONCLUSIONS:
Nomenclature
A Arrhenius parameter
(pre-exponential factor)
Page 20 of 22
CA M exit concentration of reactant
‘A’ in the exit stream
input concentration of ‘A’ in the
CA0 M input stream
Conductivity of solution at
k S/m various time intervals
T °C Reaction temperature
References:
Denbihh, K. G., and Turner, J. C. R. (1971) Chemical Reactor Theory. 2nd ed.
Cambridge: Cambridge University Press.
Fogler, H.S. (1999) Elements of Chemical Reaction Engineering. 3rd ed .New Jersey:
Prentice Hall.
Page 21 of 22
Levenspiel, O. (1999) Chemical Reaction Engineering. 3rd ed. New York: John
Wiley & Sons, Inc.,
Smith, J.M. (1981) Chemical Engineering Kinetics. 3rd ed .New York: McGraw-Hill.
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