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CHE151-1L Chemical Engineering Laboratory 2

4th Quarter AY 2016-2017

Continuously-Stirred Tank Reactor (CSTR)

Evora, Micaella Francesca1, Gomez, Ricky Jay1, Santiago, Camille1


1
Student, Mapúa University, School of Chemical Engineering and Chemistry

ABSTRACT
Continuous-Stirred Tank Reactor consists of a well-stirred tank into which there is a continuous flow of reacting
material. It is operated in steady-state and is assumed that it has a perfect mixing condition. A CSTR is different from
a batch reactor in the fact that it is not closed when operating the mass flows in and out of the system. In this experiment,
the CSTR was used to calculate the reaction rate constant, the Arrhenius constant (A) and activation energy (E) of the
reaction. From the results of the experiment, it was observed that the specific reaction rate decreases as the temperature
increases where in it should be increasing. From the graph, the activation energy calculated has a negative value and
the value of the Arrhenius constant is too small. Based on the theoretical concepts, the activation energy should have
a positive value and the value of Arrhenius constant should be logical enough. Possible sources of error are that the
conditions of the equipment might not be well established that is why there are problems in data gathering.

Keywords: CSTR, Arrhenius constant, activation energy

INTRODUCTION

Continuous-Stirred Tank Reactor (CSTR),


shown in Figure 1, consists of a well-stirred
tank into which there is a continuous flow of
reacting material, and from which the
partially reacted material passes
continuously[1]. This is because these kinds of
vessels are squat in shape that are good
stirring if their contents are essential.
Otherwise there could be an occurrence of a
bulk streaming of the fluid between the inlet
and outlet and much of the volume of the
vessels would be essentially dead space. The
CSTR configuration is widely used in
industrial applications and in wastewater
Figure 1. Line Diagram of a CSTR [1]
treatment units.
Stirring is an important characteristic of a rate of reaction, it will lead the following
CSTR. The most appropriate first equation:
approximation to an estimation of its
performance is based on the assumption that 𝐹𝑗𝑜 − 𝐹𝑗
𝑉= (2)
its contents are perfectly mixed. As a −𝑟𝑗
consequence the effluent stream has the same
composition as the contents and it The CSTR design equation gives the reactor
differentiates the CSTR and the tubular volume V necessary to reduce the entering
reactor. It is not difficult to attain the fair flow rate of species j from Fj0 to the exit flow
approximation to perfect mixing in a CSTR, rate Fj, when species j is disappearing at a rate
given that the fluid phase is not too viscous[1]. of –rj. Wherein, Fj is equal to Cj multiplied by
v. And will obtain the ideal CSTR mole
A CSTR is operated at steady state where the balance equation that is algebraic and not a
accumulation is equal to zero and are differential equation given in equation 3:
assumed to be perfectly mixed [3]. The main
assumption in this case is that the 𝑣𝐶𝐴𝑜 − 𝑣𝐶𝐴
𝑉= (3)
concentration of the incoming fluid will −𝑟𝐴
become instantaneously equal to the outgoing
upon entering the vessel. Figure 2 visually Furthermore, an advantage of a CSTR is its
explains the concept. This makes the openness of the construction compared to the
temperature, concentration, and reaction rate tubular reactor. It makes it very easy to clean
independent of position in the reactor. the internal surfaces and this is important
because in the case of the reactions where
there is a tendency for the solid matter to be
deposited such as polymerization processes
and reactions in which tarry material is a by-
product.

The reaction:

NaOH + H3COOC2H5  CH3COONa


+C2H5OH

Figure 2. Concept of a CSTR [2] can be considered equimolar and first order
with respect to both sodium hydroxide and
A CSTR differs from a batch only in the fact ethyl acetate with a second order overall
that it is not closed. Thus, the mass flows in within the limits of concentration (0-0.1M)
and out of the reactor is given in equation 1: and temperature of 20oC to 40oC. The
reaction carried out in a CSTR will
𝑑𝑚 eventually reach steady state when a certain
= 𝑄 (𝑐𝑖𝑛 − 𝑐𝑜𝑢𝑡 ) + ∫ 𝑟𝑑𝑉
𝑑𝑡 𝑣 (1) amount of conversion amount of conversion
=0 of the starting reagents has taken place.

Since the CSTR is steady-state and has a Both sodium hydroxide and sodium acetate
perfect mixing condition, accumulation is contribute conductance to the reaction
equal to zero and no spatial variations in the solution whilst ethyl acetate and ethyl alcohol
do not. The conductivity of a sodium
hydroxide solution at a given concentration
and temperature, however, is not the same as
that of a sodium acetate solution at the same
molarity and temperature and a relationship
has been established allowing conversion to
be inferred from conductivity.

The purposes of the experiment are to use


graphical analysis in calculating reaction rate
constant at different temperatures and to
calculate the Arrhenius constant (A) and
activation energy (E) of the reaction.

METHODOLOGY Figure 4. Label of the Set-up of the CSTR[4]

Materials and Set-up Experimentation

The equipment that was utilized for this The reagents were filled in the apparatus by
experiment is a Continuous-Stirred Tank the laboratory assistant. The set point of the
Reactor (CSTR), illustrated in Figure 3 and 4 temperature controller was set to
which depicts its schematic diagram, approximately 30oC and then to 40 oC.
provided by Armfield. As for the chemicals
involved 0.1 M of sodium hydroxide and Every 5 seconds the conductivity data was
0.1M ethyl acetate with both contained of 2.5 recorded until it reached its steady-state
litres each. condition in the reactor. The data were
gathered at approximately 30 to 45 minutes.

Both feed pumps and the agitator motor were


switch on, and instigated the data logger
program. After a few minutes the temperature
sensor tip is covered (about 25mm of liquid
in reactor) – switch on the hot water
circulator [4]. The Armfield data logger
provided the set of readings of conductivity
with time and stored in an excel file. Figure 4
displays the Armfield Data Logger or
software interface of the apparatus.
Figure 3. Set-up of the CSTR
dependence of the specific rate constant and
the estimation of the value of specific rate
constant at various temperature ranges.

According to the Arrhenius principle, as the


temperature increases, the rate constant
decreases. This can be seen when the plot of
the natural logarithm of specific rate of
Figure 5. Armfield Data Logger reaction versus the inverse of temperature
was done. The Arrhenius equation shown in
Treatment of Results (4), correlates the activation energy,
The degree of conversion of the constituents Arrhenius constant and the variables, k and T.
can be converted with the conductivity of the The plot shows a linear relationship between
contents of the reactor that were recorded
over a period of the reaction. the variables mentioned. Figure 6 shows the
relationship of the treated data from the
From the given data by the software, by
graphical analysis, the rate constant can be experiment.
solved and calculated.

The calculation of the Arrhenius constant the


following equation is to be utilized: k = f(T)
−𝐸𝐴 -1.13
ln 𝑘 = + ln 𝐴 (4) 0.0032
-1.14
0.00321 0.00322 0.00323 0.00324 0.00325
𝑅(𝑇)
Where k is the rate constant, R is the gas -1.15
constant, A is the Arrhenius constant, E is the -1.16
ln k

activation energy and T is the temperature.


-1.17
-1.18
y = 1124.1x - 4.7883
-1.19 R² = 0.6988
RESULTS AND DISCUSSIONS
-1.2
1/T

In this experiment, graphical analysis is Figure 6. Estimation of k as a function of


incorporated in the estimation of the different temperature (T = 40 oC).
parameters such as the activation energy and
Arrhenius constant (A). It is also used to In this plot, as the reciprocal of temperature
generated a plot relating the temperature increases, the value of the natural logarithm
of k also increases. Take into note that the Table 1. Calculated results from the
Arrhenius equation gives the form where the graphical method.
slope is the negative of E/R, the y-intercept Ea -10,177.2 J / mol
being the natural logarithm of A, natural A 0.008327
logarithm of k as y variable and reciprocal of
temperature as x variable. From the curve Another data interpretation done was the
fitting equation, the slope has a positive value, determination of the temperature dependence
showing the direct relationship of the of the specific reaction rate constant. Figure
variables. Theoretically, the value should be 2 shows the trend of the treated data from the
negative given the fact that rate constant experiment.
decreases with the increase in temperature.
Also, the trend of the curve is ambiguous and
does not follow the theoretical assumptions
Temperature Dependence
of k
and considerations.
0.325
0.320
Possible error for this part is that it might be 0.315
k

0.310
that the conditions of operation of the y = -0.0036x + 1.4423
0.305
R² = 0.6984
equipment is not established well, or it might 0.300
also be a reason that there is a problem with 308.00000000
309.00000000
310.00000000
311.00000000
312.00000000
T,K
the data gathering capability of the
equipment. Figure 7. Plot of T versus k (T = 40 oC).

Ambiguous results also arise in this part, Arrhenius principle shows that the specific
where the value of the activation energy has reaction rate constant should be decreasing
a negative value and the value of the with the increase in the temperature, that is
Arrhenius constant was too small, to the point due to the form of the linear equation wherein
that having this certain value is not logical at natural logarithm is incorporated. However,
all. Table 1 shows the calculated activation in reality the reaction rate constant should
energy and the Arrhenius constant. increase with the increase in the temperature.
This is due to the improved activities of the
molecules, due to the fact that increase in
temperature refers to the increase in energy
Temperature Dependence
contained by the molecules, and so the
of k
movements of the molecules should be rapid.
0.734
0.732
0.730
In Figure 7, opposite trend was observed
0.728
from the theoretical assumptions and 0.726

k
0.724
considerations. Instead of specific reaction
0.722
rate increases, it actually decreases with the 0.720
0.718
increase in temperature. Again, possible
0.716
source of error for this part are the conditions 299.00000000
299.10000000
299.20000000
299.30000000
299.40000000
T, K
or operation of the equipment, problems with
the equipment itself or the calibration of the Figure 9. Plot of T versus k (T = 30 oC).
equipment measurements.
If given the opportunity of good data, the
The previous figures were the results when results should at least abide the theoretical
the set reactor temperature is 40 oC. For the concepts that specific rate of reaction should
temperature of 30 oC, same trend of the data increase with the increase in temperature,
was observed. These are shown in Figure 8 activation energy should have a positive
and Figure 9. value and the value of Arrhenius constant
should be logical enough.

k = f(T)
-0.305 CONCLUSION
0.003340.003341
-0.31 0.003342
0.003343
0.003344
0.003345

-0.315 Continuous-Stirred Tank Reactor is widely


ln k

-0.32
used in industrial applications and in
-0.325
-0.33 wastewater treatment units. Stirring is an
-0.335
1/T important characteristic of a CSTR. It is
operated at steady state where the
Figure 8. Estimation of k as a function of
accumulation is equal to zero and is assumed
temperature (T = 30 oC).
to be perfectly mixed. The objectives of the
experiment were obtained; the results of the
experiment were computed using graphical be positive and the value of the Arrhenius
representation. From the Arrhenius principle, constant should be logical enough.
when the temperature increases then the rate
constant decreases. It was observed that the
reciprocal of temperature increases and the REFERENCES
value of the natural logarithm of k also
increase. The slope gives off a positive value 1] Denbigh, K. G., and Turner, J. C. R., Chemical
Reactor Theory: An Introduction
wherein the value should be negative based
[2] Stenstrom, M.K. & Rosso, D., Fundamentals of
on the Arrhenius principle. The calculated
Chemical Reactor Theory. 2003
results using the graph were indefinite
[3] Levenspiel O., Chemical Reaction Engineering,
because the computed activation energy is 3 ed., 1999.
negative and the value of the Arrhenius
[4] CEM MKII Manual Issue 14
constant was too small. In the graphical
analysis of the temperature dependence, it
follows the principle; however, in reality the
reaction rate constant should increase with
the increase in the temperature. This is due
because of the activities of the molecules,
which the increase in temperature refers to
the increase of the energy of the molecule.
Possible errors in this experiment are that the
conditions of the equipment might be not
well established and it causes problem in
terms of gathering data using the equipment.
The calibration of the equipment
measurements also can be a source of error
for this experiment. If the data obtained were
good enough then the results can abide the
theoretical concepts in which the specific rate
of reaction should increase with an increase
in temperature, the activation energy should
APPENDIX 0.003226 -1.164
0.003226 -1.15687
Sample Computations: 0.003227 -1.16283
0.003226 -1.15687
1. Calculation of E.
0.003226 -1.164
0.003224 -1.16634
1
ln 𝑘 = 1124.1 ( ) − 4.7883 0.003224 -1.16634
𝑇
0.003224 -1.17341
-E/R = 1124.1 0.003225 -1.16518
0.003223 -1.16751
R = 8.314 J/ mol-K 0.003222 -1.16867
0.003223 -1.16751
E = - 8.314 J/mol-K (1124.1) 0.003221 -1.16983
0.003222 -1.16159
E = -10177.2 J/mol 0.003221 -1.13417
0.003221 -1.16983
2. Calculation of A
0.00322 -1.17098
0.00322 -1.17098
ln A = -4.78883
0.00322 -1.16393
0.00322 -1.16393
A = exp (-4.78883)
0.00322 -1.17098
A = 0.008327
0.003221 -1.16277
0.003221 -1.16983
Treated Data: 0.003218 -1.17328
0.003219 -1.17213
1/T ln k 0.003218 -1.17328
0.003238 -1.14234 0.003218 -1.17328
0.003238 -1.14965 0.003218 -1.16626
0.003239 -1.14843 0.003218 -1.16626
0.003238 -1.14965 0.003216 -1.17556
0.003237 -1.15086 0.003217 -1.16741
0.003238 -1.14965 0.003217 -1.16741
0.003237 -1.15086 0.003217 -1.18139
0.003237 -1.14357 0.003217 -1.17442
0.003235 -1.14603 0.003216 -1.17556
0.003234 -1.14725 0.003215 -1.17669
0.003234 -1.14725 0.003217 -1.17442
0.003232 -1.15689 0.003216 -1.16857
0.003231 -1.16526 0.003216 -1.17556
0.00323 -1.16643 0.003215 -1.17669
0.003228 -1.16165 0.003215 -1.16972
0.003216 -1.18252 0.00321 -1.17541
0.003214 -1.18476 0.003211 -1.17428
0.003214 -1.17086 0.00321 -1.1892
0.003213 -1.17895 0.00321 -1.18232
0.003214 -1.17086
0.003214 -1.17783
0.003216 -1.16857
0.003214 -1.17783
0.003214 -1.17783
0.003214 -1.17783
0.003213 -1.17895
0.003213 -1.15095
0.003213 -1.172
0.003213 -1.17895
0.003214 -1.17086
0.003213 -1.172
0.003213 -1.172
0.003212 -1.16617
0.003212 -1.18008
0.003212 -1.17314
0.003212 -1.18698
0.003213 -1.17895
0.003212 -1.18008
0.00321 -1.18232
0.003212 -1.18698
0.003211 -1.1812
0.003213 -1.17895
0.003212 -1.18008
0.003212 -1.17314
0.003212 -1.17314
0.003211 -1.1812
0.003211 -1.1812
0.003212 -1.18008
0.003211 -1.17428
0.003211 -1.1812
0.003211 -1.18809
0.003212 -1.17314
0.003211 -1.1812
0.003209 -1.17654
0.00321 -1.17541
0.00321 -1.18232

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