Reactor Design (IQ2011B) – CSTR

CSTR-Performance, prediction, and evaluation

OBJECTIVE

To study the performance of a continuous stirred tank-type reactor CSTR assuming that the
kinetics was previously determined.
Compare and discuss, the possibility of determining the kinetics of saponification using the tests
of performance of a CSTR reactor and compare with the previous methodology of a batch
reactor.

Objectives
1. To obtain experimental conversion and compare with the theoretical one.
2. Discuss, if the kinetic constant of the reaction rate, can be estimated by performance
studies of a CSTR.
3. Verify the validity of the results; compare them with the values reported in the
literature.

INTRODUCTION

Chemical kinetics studies the rate and mechanism by which a reaction occurs. For example, for
reaction A + B → C + D, the reaction rate of A can be expressed as:

𝑟 = 𝑘𝐶 𝛼 𝐶 𝛽 (1)
𝐴 𝐴 𝐵

This equation can be converted into a linear equation if the natural logarithm of each side of
the equation is taken:

𝑙𝑛(− 𝑟𝐴) = 𝑙𝑛(𝑘) + 𝛼 𝑙𝑛(𝐶𝐴) + 𝛽 𝑙𝑛(𝐶𝐵) (2)

Where:
− 𝑟𝐴 : reaction rate of A.
𝐶𝐴 : concentration of reactant A, mol/L
𝐶𝐵 : concentration of reactant B, mol/L
𝛼 : order of reaction with respect to reactant A, dimensionless.
𝛽 : reaction order with respect to reactant B, dimensionless.
𝑘 : constant of the reaction rate, or specific reaction rate, its value depends on the
temperature. Units depend on α and β values, and the units of – rA .

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 Reactor Design (IQ2011B) – CSTR

In a continuously stirred tank reactor operating at steady state, as shown in Figure 1, the
molar balance on substance A is:
𝑛̇𝐴0 − 𝑛̇𝐴 − 𝑟𝐴𝑉 = 0 (3)

Figure 1. Sketch of the experimental arrangement.

Where n = moles of A feeding into the reactor, gmol/s

A0
= moles of A leaving the reactor, gmol/s
n A

V = reactor volume, L

The moles of A entering and leaving the reactor can be calculated as:

n A0  V (4)
0
C A0 (5)
n A  VC A

Where
V 0 : total injected flowrate, L/s

CA0 : equivalent concentration of A flowing into the reactor, gmol/L (see Figure 1)

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 Reactor Design (IQ2011B) – CSTR

V : total volumetric flow at reactor outlet, L/s

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 Reactor Design (IQ2011B) – CSTR

Combining equations (3) to (5) the reaction rate is recast:

 r AV  CA0 VC (6)

A
V A

By a proper design of experiments, enough data can be collected, with the help of equations (2)
and (6), to fit the parameters by multiple linear regression. In this experiment, the studied
reacting system is the saponification of ethyl acetate with sodium hydroxide to obtain sodium
acetate and ethanol. And the parameters to determine are
k, and 

CH3COOC2H5 + NaOH → CH3COONa + C2H5OH (7)

The design of experiments should include the following:

1. Maintain a homogeneous reactive mixture (perfect mixing) so that the concentration of

reactants and products is the same at any point within the reactor and the concentration in
the effluent coincides with the concentration of the homogeneous mixture.
2. Maintain a constant temperature over time so that the reaction specific rate is kept
constant.
3. To set different flow rates, and different molar ratios.
4. To determine reactant concentrations in the effluent or within the reactor which may
coincide under ideal mixing.

MATERIALS AND SUBSTANCES

 1 Stopwatch  1 glass measuring cylinder of 50 mL

 1 Large spatula  1 glass measuring cylinder of 100
 1 Ribbed spatula mL
 3 - 100 mL beakers  1 Pipette
 2 - 1 L beakers  1 wash bottle
 1 Watch glass

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 Reactor Design (IQ2011B) – CSTR

APPARATUS

Figure 2. Experimental system: Continuously stirred tank reactor.

METHODOLOGY

3 runs will be performed at a single temperature (it is recommended to use the highest one that
was used in batch reactor practice for comparative purposes in your discussion of results).
1. Check that the NaOH and EtAc feed tanks are empty and that the drain valves are closed.
2. Estimate the volume of the reactive mixture by filling the reactor with distilled water
with the help of a 250 ml graduated cylinder.
3. Turn on the agitator and adjust ca. 500 rpm.
4. Turn on the heating system and select the temperature set point.
5. Verify that the conductivity meter is calibrated.
6. Prepare three or four combinations of reactants flows and calculate the rpm of the feed
pumps (see Table 1 and the Previous Activity).

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 Reactor Design (IQ2011B) – CSTR

Table 1: Recommended volumetric flows and its corresponding RPMs. If you are
interested in study the orders of reaction ( and )

Run RPM
(mL/min) (mL/min)
RPM
1 150 162 50 61
2 50 52 150 160
3 130 140 70 81
4 70 74 130 140
5 120 129 80 90
6 80 85 120 130

If you are willing to determine the specific reaction rate, you must run the experiment under
different flow conditions.

Table 2: Recommended volumetric flows and its corresponding RPMs. If you are
interested in study the specific reaction rate.

Run RPM
(mL/min) (mL/min)
RPM
1 50 52 50 61
2 75 79 75 86
3 100 107 100 110
4 125 135 125 135
5 150 162 150 160
6 175 190 175 184

7. Prepare 18 L of NaOH solution with an approximate concentration of 0.05 mol/L.

8. Pour the contents of the bucket into the NaOH feed tank.
9. Prepare 12 L of ethyl acetate solution with a concentration of approximately 0.05 mol/L.
10. Pour the contents of the bucket into the EtAc feed tank.
11. Establish the revolutions required to achieve the flows determined for the run.

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 Reactor Design (IQ2011B) – CSTR

12. Turn on the feed pumps and write down the revolutions and equivalent flows of the
reagents.
13. Verify that the conductivity meter reports 2 decimal places (x.xx) and start the stopwatch.
14. Measure and record the conductivity and temperature of the reactive mixture
every minute. Graph the data on a computer (conductivity vs. time).
15. When you notice in the graph that the conductivity reaches a stable reading (in
approximately 40 minutes), turn off the feed pumps and proceed to repeat step 11, until
you complete all the runs of the experiment (three or four runs).
16. Turn off the agitator and pumps.
17. Drain the holding tanks and reactor.
18. Fill the reactor tank with distilled water.
19. Clean the material and deliver it to the stockroom.

Rate Constants Activation Energy Technique

Investigators k at 30◦C (L mol−1 s) EA (kJ mol−1) A (L mol−1 s)
Smith et al. [2] 0.11 61.4 4.178E+09
Jensen et al. [3] 0.15 - -
Tsujikawa et al. [4] 0.16 48.4 3.497E+07
Schneider and Stoessel [5] 0.19 46.1 1.667E+07
Warder [6] 0.14 - -
Das et al. [1] 0.16 41.4 2.176E+06
First Term 2022 0.14 57.02 9.354E+08
Batch
PFR

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 Reactor Design (IQ2011B) – CSTR

APPENDIX I
Pump calibration curves

NaOH solution pump calibration curve ml/min

180
160 Q [cm3/min]= 0.90600 RPM + 3.11400
140
120
100
80
60
40
20
Q

050 100 RPM 150 200

Ethyl-Acetate pump calibration curve ml/min

180
160
140
120
100
80
60
40
20Q [cm3/min] = 1.01400 RPM - 11.74200
Q

050100 RPM 150 200

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 Reactor Design (IQ2011B) – CSTR

APPENDIX II
(RELATIONSHIP BETWEEN CONCENTRATION AND CONDUCTIVITY) [4]

The concentration of some components in the mixture can be calculated by measuring electrical
conductivity, but you must keep in mind, that two chemical species contribute to the electrical
conductivity, Sodium Hydroxide (a reactant), and sodium acetate (a product). To relate the electrical
conductivity to concentration, stoichiometry must be considered, and the fact that the total conductivity is
the contribution of both NaOH and NaOAc (NaOAc , short for sodium acetate). The relationship between
Concentration and conductivity, and its dependence with temperature are specific for each chemical
species.

In your experiment the chemical species that contribute to the electrical conductivity are A and C
The relationship between conductivity and concentration has the following form:

A+B→C+D
𝜦𝐴
= 𝜸 [1 + 𝑎 (𝑻 − 𝑇 )] = 𝒎
(A.I.1) 𝐴 𝑅𝐴 𝐴
𝐴
𝑪𝐴
A is the electrical conductivity of species A, A is the ratio between the electrical conductivity and the
corresponding concentration of A (CA), at the reference temperature for that component TRA,
A is the effect of the temperature relative to the reference temperature. A and A are specific for each
chemical species, and the particular conductometer. If for each experiment you measure the initial
conductivity and the initial concentration is known, the slope mA can be calculated with the ratio.

𝜦 𝜦𝐴0
𝐴 = 𝑪𝐴0 = 𝒎𝐴
(A.I.2) 𝑪
𝐴

The previous relationship is valid only for if the temperature is constant, the same approach can be used
with species C.
𝜦𝐶
= 𝜸 [1 + 𝑎 (𝑻 − 𝑇 )] = 𝒎
(A.I.3) 𝐶 𝑅𝐶 𝐶
𝐶
𝑪𝐶
If the limiting reactant is NaOH, and if the reaction went to completion, the mC value can be estimated
with the final reading of the electrical conductivity and the final concentration of sodium

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 Reactor Design (IQ2011B) – CSTR

acetate which must coincide with the initial concentration of the initial sodium hydroxide, if not different
analysis must be done to relate the final reading with the mC values.
Knowing these previous variables (  ) and parameters (mA, mC) the concentration of sodium hydroxide
(Component A), can be calculated as a function of the total conductivity as (  AC ):

𝑪 = 𝜦 − 𝒎𝐶𝑪𝐴0
𝐴
𝒎𝐴 − 𝒎𝐶
(A.I.4)
Warning: you need to calculate your own values for each conductometer and for every
temperature.

Typical values reported by students working with similar conductometers. (these values can be used as a
guide, but you must obtain your own numbers)

TABLE No.1 Typical parameters of conductivity vs concentration calibration curves

Parameter Value Units

A 195 mS-dm3 /cm-mol

A 0.0118 1/K

TRA 294 K

C 69.204 mS-dm3 /cm-mol

C 0.01217 1/K

TRC 294 K

If you have not enough data to estimate relationship A.I.1 and A-I.3, and if you did run the
experiment using an equimolar mixture, and waited enough to have 100% of conversion, for each
experiment you can obtain your mA and mC values as:

𝜦𝐶∞
𝒎 ≈ 𝑪𝜦0 𝜦
𝒎𝐶 ≈ 𝑪 = 𝑪
∞
𝐴0 𝐴0 𝐶∞
𝐴
(A.I.5)

CA0 = Initial concentration of sodium hydroxide

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 Reactor Design (IQ2011B) – CSTR

0 = Initial concentration of sodium hydroxide, knowing there is no interference by any other

component.
∞= Electrical conductivity of the sodium acetate after very long enough time in the aqueous mixture,
when there are no other components contributing with electrical conductivity.

C∞/ CC∞ = 0.816 (T - TRC ) + 69.656

R² = 0.9996
95
90
[=] mS-dm3/cm-

85
80
75
70
65
60
C∞/

55
50
0 5 10 15 20 25 30
T - TRC [=] K

Figure A.I.1 Calibration curve for sodium acetate, with reference temperature is 21°C. A similar curve
needs to be obtained for sodium hydroxide, and your own data for sodium acetate. In this plot the
intercept corresponds to mC, and the slope is the product of C mC.

BIBLIOGRAPHY
Das, K; Sahoo, P; Sai Baba, M ;Murali, N; Swaminathan, P Int J of Chemical Kinetics, 2011 648-656
1 https://doi.org/10.1002/kin.20597
2 Smith, H. A.; Levenson, H. S. J Am Chem Soc 1939, 61, 1172–1175.
3 Jensen, F.W.;Watson, G. M.;Beckham, J. B. Anal Chem, 1951, 23, 1770–1773
4 Tsujikawa, H.; Inoue, H. Bull Chem Soc Japan 1966, 39, 1837–1842.
5 Schneider, M. A.; Stoessel, F. Chem Eng J 2005, 115, 73–83.
6 Warder, R. B. J Am Chem Soc 1881, 3, 203.