Kinetics study

of
Soapification
reaction in
tubular flow
The
determination
of the effect
of varying
residence time
and
temperature
on conversion
and the
reaction rate
1 BACKGROUND
Plug or tubular flow reactor (PFR) systems involve flowing reagents through a pipe or hollow tube
[1]. This allows for uniform radial mixing [2], high conversion per unit volume and easy maintenance
[1]. Particularly in comparison with other continuous flow reactors, such as continuously stirred tank
reactors (CSTRs), PFRs are much more volume efficient. For these reasons, they are ideal reactors for
processes involving fluids, such as hydrocarbon cracking or gasification of biomass to produce
hydrogen [3].
Saponification can also be carried out in a PFR, ensuring a higher conversion rate and more uniform
product [4]. A saponification reaction is a hydrolysis reaction involving a strong base and an ester to
produce a salt and an alcohol. Equation 1 shows the saponification reaction between sodium
hydroxide and ethyl acetate.
NaOH +C H 3 COOC H 2 C H 3 → NaC H 3 COO+C H 3 C H 2 OH
Equation 1: Saponification reaction between sodium hydroxide and ethyl acetate produces sodium acetate and ethanol.

It is assumed that the reaction is first order with respect to each reagent and second order overall [5].
Under these conditions, a quadratic decrease of the rate of reaction is expected over time as the
concentration of the reagents decreases. This experiment uses equal initial concentrations of sodium
hydroxide to ethyl acetate, so the rate equation can be written as in Equation 2.
2
r =−k [ NaOH ]
Equation 2: The reaction rate equation for second order kinetics. r is the reaction rate in mol/L/s, k is the reaction rate
constant in L/mol/s [NaOH] is the concentration of sodium hydroxide in mol/L.

2 AIM
This experiment aims to study the kinetics of a saponification reaction between sodium hydroxide and
ethyl acetate in a plug-flow reactor. To do so, a calibration curve was constructed to measure the
concentration of sodium hydroxide over time. Following this, the reaction was allowed to proceed at
different flow rates to assess the effect of residence time on the conversion and calculate the rate
constant. The reaction was also allowed to proceed at various temperature values to assess the effect
of a changing rate constant on the temperature.

3 METHODOLOGY
Before monitoring the saponification reaction, a calibration curve was constructed by the lab manager
using varying concentrations of sodium hydroxide (0.00 M to 0.05 M) in solution with sodium acetate
(0.05M to 0.00 M) and measuring the conductivity of each solution. This allows for comparison to
accurately determine the concentration of the sodium hydroxide in the plug flow reactor as measured
via conductivity.
Throughout the saponification reaction in the PFR, peristaltic pumps were used to accurately control
the flow rate of the reagents. The initial concentrations of sodium hydroxide and ethyl acetate were
both 0.1 M, meaning it can be assumed that they are consumed at the same rate. Thus, the rate of
production of sodium acetate was assumed to be second order with respect to sodium hydroxide only,
meaning the ongoing changes in the concentration of ethyl acetate did not need to be measured. More
specifically, the conversion factor was measured, which is calculated in Equation 3.

[ NaOH ]0
X =1−
[ NaOH ] outlet
Equation 3: Calculation of conversion factor. [NaOH] is the concentration of sodium hydroxide (initial or at the outlet) in
mol/L.

Firstly, the flowrate was varied between 0.10 L/min and 0.30 L/min at increments of 0.05 L/min to
change the residence time of the reagents in the PFR. For each trial, the reagents were initially
allowed to flow through the PFR until the residence time associated with the flow rate was reached.
However, to ensure the conversion was constant, the trials were repeated and the reagents were
allowed to flow through the reactor until twice the residence time for each trial was reached. The
conversion factor for each flow rate was calculated when the conductivity measures were constant and
this data was used to calculate the rate constant for each trial. Through linearising the data, the rate
constant was also calculated at a constant temperature of 22.6 oC.
Secondly, the temperature was varied between 22.6 oC and 50oC at increments of ~10oC at a constant
flow rate of 0.15 L/min to determine the temperature dependence of the rate constant and, by
extension, the conversion factor.

4 RESULTS

4.1 VARYING FLOWRATE AS INDEPENDENT VARIABLE

Using the pre-prepared calibration curve, a correlation was able to be constructed between the
conductivity of a given reading and the concentration of sodium hydroxide. The calibration curve is
shown in Figure 1.

Calibration curve for NaOH

0.06
0.05 f(x) = 0.00798721365147756 x − 0.0246325456302816
0.04 R² = 0.959743592361544
[NaOH] (M)

0.03
0.02
0.01
0
3 4 5 6 7 8 9 10 11
Conductivity (mS/cm)

Figure 1: Calibration curve for sodium hydroxide to estimate concentration levels according to the conductivity of the
solution.

The calibration curve allows for an approximation of a concentration value, and thus a conversion
factor, at the outlet of the PFR. Equation 4 is used for second-order kinetics reactions when designing
a PFR to achieve the desired conversion.

( )
ν0 X
V PFR=
k C A 0 1− X
Equation 4: Volume calculation when designing a PFR for second-order kinetics conditions. V PFR is the volume of the PFR
in L, nu0 is the initial flowrate of the reactants in L/s, k is the rate constant in L/mol/s, C A0 is the initial concentration of
NaOH in mol/L and X is the conversion faction between 0 and 1.

Given the PFR’s constant volume, Equation 4 was rearranged to reflect the conditions of this trial,
wherein the flow rate is the independent variable, and the conversion factor is the dependent variable.
Experimental data is expected to fit Equation 5.
 1 1
= ν +1
X k C A 0 V PFR 0
Equation 5: Equation 4 rearranged and linearised to show relationship between conversion factor and changing flow rate.

Figure 2 validates the assumption of this linear relationship.

Linearised relationship between the conversion factor and the flow rate in a
PFR
3.5
3
2.5 f(x) = 398.037164678978 x + 1
2
1/X

1.5
1
0.5
0
0.0015 0.002 0.0025 0.003 0.0035 0.004 0.0045 0.005 0.0055
ν0 (L/s)

Figure 2: Linear relationship as in Equation 3 displayed graphically. The flow rate is in L/s.

The intercept of the linear relationship was set to 1 as in Equation 5. The gradient of the line is used
and rearranged as in Equation 6 to produce a value for the rate constant.
1
k=
398.04∗[ NaOH ]0∗V PFR
Equation 6: The gradient of the linear relationship between the conversion and flow rate of a saponification reaction can be
rearranged to get the rate constant of the reaction. [NaOH] 0 is the initial concentration of sodium hydroxide, which is 0.1
mol/L, VPFR is the volume of the reactor, which is 0.4 L and k is the rate constant in L/mol/s.

The value of the rate constant using Equation 6 was found to be 0.0628 L/mol/s. This corresponds
well with the average of the rate constant values found for each flow rate using a rearranged Equation
4, which was 0.0672 L/mol/s with an uncertainty of 27%. The k value calculated from the gradient
differs from the average value by 7%. Both values sit well within the range of theoretical rate constant
values of 0.010 to 0.106 L/mol/s [6].

4.2 VARYING TEMPERATURE AS THE INDEPENDENT VARIABLE

Varying the temperature under which the reaction proceeds affects the rate constant (k) as per the
Arrhenius equation [7] in Equation 7. This means the temperature dependence of the rate constant is
determined by the activation energy and pre-exponential factor for a given reaction. Equation 7 can be
linearised as seen in Equation 8 for easier analysis and prediction of trends.
−E a
Ea 1
k=Ae RT ln ( k )=ln ( A )−
Equation 7: Arrhenius equation showing the rate constant's
R T
temperature dependence. A is the frequency of collisions Equation 8: Linearised version of Arrhenius equation. Ln(A)
required for reactions, Ea is the activation energy in J/mol, R would be the intercept and -Ea/R would be the gradient when
is the rate constant in J/mol/K and T is the temperature in K comparing 1/T and ln(k).

Theoretical values for the pre-exponential factor and the activation energy for the saponification
reaction can be seen in Figure 3 [6]. Clearly, there are a variety of values against which this
experiment’s data can be compared.
Figure 3: Source [6]. Various activation energies and pre-exponential factors are quoted by different studies to be
substituted into Equation 7.

Plotting the data obtained against each of the values shown in Figure 3 produces Figure 4. In this plot,
the published data values produce the data labelled [a], [b] and [c] respectively whilst our data is
labelled ‘collected’.

Linearised Arrhenius equation with published data against

aquired data
0
0.00305 0.0031 0.00315 0.0032 0.00325 0.0033 0.00335 0.0034
-1
-2 f(x) = − 3299.92522407227 x + 8.62757825625941
ln(k)

-3
-4
-5

1/T (1/K)

log k published [a] log k published [b] log k published [c]

log k collected Linear (log k collected)

Figure 4: Plot of the linearised Arrhenius equations predicted from the data in Figure 3 and of the data collected in this
trial. The pre-exponential factor can be determined from the intercept and the activation energy from the gradient of the
trendline.

Analysing the intercept and the gradient of the line for the data collected in this experiment produced
a pre-exponential factor of 5584 L/mol/s and an activation energy value of 27.4 kJ/mol. Both these
values are lower than all three published values tabulated in Figure 3: the pre-exponential factor by
17800% to 512000% and the activation energy by 51% to 75%. Nonetheless, the collected data
clearly follows the expected general trend, indicating the rate constant’s temperature dependence.
The rate constant’s temperature dependence means the conversion factor is also temperature
dependent. Combining Equations 5 and 7 gives the approximate relationship expected in Equation 9.

X ∝ exp ( −1T )
Equation 9: Approximate relationship between the conversion factor and the temperature in K, given X's linear dependence
on the rate constant.

This positive relationship in values is demonstrated in the data, with a strong correlation with
interpolated exponential trendlines hence indicating that the conversion factor is following an
exponential relationship, as seen in Figure 5.
 Conversion factor against -1/T
1
Conversion factor

0.8
f(x) = 23.132438024204 exp( 1106.89565136059 x )
0.6
R² = 0.9668008003752
0.4
0.2
0
-0.0034 -0.00335 -0.0033 -0.00325 -0.0032 -0.00315 -0.0031 -0.00305
-1/T (1/K)

Figure 5: Conversion factor vs the temperature inverted. As expected, the conversion factor increases with the temperature
exponentially.

5 DISCUSSION
In general, the trends of the results align well with theory and expectations. The calculated rate
constant in the flow-rate dependent trial sat well within the range of k values calculated from the
variety of data in [6]. However, there is great error in the pre-exponential factor and activation energy
values, indicating a high level of systematic error. There are several sources of potential error.
Firstly, conductivity and concentration of sodium hydroxide are expected to be related linearly. The
calibration curve developed before the laboratory shows this assumption to be true to a large extent,
with a maximum error of 17%. This means each concentration measure may be inaccurate to 17%.
This is a random error, so repeating the calibration curve development would have served to decrease
this uncertainty.
Another critical issue is that the mixing point of the two reagents is before the first conductivity
meter. Given the high rate of reaction, this means a consistently lower conductivity was measured
than true at the start of the reaction. This became particularly apparent upon heating the rig as the rate
of reaction was increased and the measure at the first conductivity meter was lower (see Appendix A).
This systematic issue was overcome by using stock solutions with a known initial concentrations of
sodium hydroxide and ethyl acetate. However, validating the concentration of these solutions, either
by constructing the calibration curves ourselves, creating the solutions or consulting a reliable source
(such as a company-produced bottle label) would have served to decrease any uncertainty further.
Throughout the flow-rate dependent trials, it was observed that the second conductivity meter was not
reading constant values over time until at least twice the calculated residence time. The magnitude of
this error in the original methodology indicates the friction of the tubing may be non-negligible and
decrease the flow rate over time. This can be accounted for by estimating a larger pseudo-volume for
the PFR, which would serve to lower the calculated rate constant value. This error would apply to all
data points collected, for both the flow-rate dependent and the temperature-dependent trials, meaning
it is a systematic error. However, as the correct pseudo-volume would be a constant value for the
flow-rate dependent trial, the trend would remain the same and congruent with expectations.
Furthermore, the calculated rate constant would change by no more than a factor of 0.5, which would
still fit in the range of calculated k values from various studies [6]. Studies into temperature
dependent variables, such as viscosity and density, could help to further understand discrepancies
present for the temperature-dependent trials but were not possible in the time provided.
Furthermore, non-ideal behaviour of the PFR in the form of axial mixing was evidently present as the
conductivity meters gradually changed with time, indicating the absence of pulse-like behaviour. This
would produce a residence time distribution, rather than a singular time value for all molecules
entering the system to exit. This distribution would not change the mean residence time, meaning such
behaviour cannot account for the consistently higher time requirements to achieve constant
conductivity.
Finally, the consistently lower values for the activation energy and pre-exponential factor indicate the
presence of a systematic error. Most notably, it is important to recognise that this saponification
reaction is exothermic [6], meaning it releases heat and raises the temperature of the system and
surroundings. The rig measures the temperature of the water jacket rather than the reagents and
products themselves and, given water’s high heat capacity [8], the heat released would not notably
change the temperature of the surrounding jacket. However, it would have a greater effect on the
system, meaning the temperature values used are lower than the true values. This contributes to a
lower estimation of the activation energy and pre-exponential factor.

6 CONCLUSION
Overall, the results of this study demonstrated good congruence with expectations and theory in a
number of ways: the conversion factor was shown to be inversely proportional to the flowrate of the
reactants, with the linearised data fitting with Equation 3 well; the rate constant calculated at different
flow rates and averaged had a difference of only 7%; and the temperature dependence of the rate
constant and conversion factor followed the general trend as prescribed by the Arrhenius equation [7].
However, there is a significant difference between the temperature dependence of the rate constant in
published data compared to the data values collected in this experiment, which may be partially
attributed to the exothermic nature of the reaction or non-ideal behaviour of the PFR.
Repeating all trials would have served to decrease random errors and to develop a better
understanding of errors present. Doing so would also have clarified the validity of these trials. Further
studies to investigate the changes in viscosity and density values with changing flow rates and
temperature would be highly beneficial to develop a better picture of the plug flow profile, thus
making it easier to understand potential errors associated with the rig or the flow.

7 REFERENCES

[1] “Plug Flow (PFR) - Visual Encyclopedia of Chemical Engineering Equipment,” Michigan
University, 2023. [Online]. Available: https://encyclopedia.che.engin.umich.edu/pfr/. [Accessed
21 October 2023].

[2] UNSW CEIC2005, “Plug Flow Reactors (Tubular Reactors),” UNSW, Sydney, 2022.

[3] M. Shamsi, A. A. Obaid, S. Farokhi and A. Bayat, “A novel process simulation model for
hydrogen production via reforming of biomass gasification tar,” International Journal of
Hydrogen Energy, vol. 47, no. 2, pp. 772-781, 2022.

[4] M. Danish and M. K. Al Mesfer, “A Comparative Study of Saponification Reaction in a PFR and
CSTR,” Research Journal of Chemical Sciences, vol. 5, no. 11, pp. 13-17, 2015.

[5] UNSW CEIC2007, “Tubular flow reactor unit: Pre-lab Preparation Module,” UNSW, Sydney,
2023.

[6] E. Borovinskaya, V. Khaydarov, N. Strehle, A. Musaev and W. Reschetilowski, “Experimental

Studies of Ethyl Acetate Saponification Using Different Reactor Systems: The Effect of Volume
Flow Rate on Reactor Performance and Pressure Drop,” Applied Science, vol. 9, no. 3, p. 532,
 2019.

[7] UNSW CHEM2011, “Lecture 1: Kinetics Recap,” UNSW, Sydney, 2023.

[8] D. R. Lide, CRC Handbook of Chemistry and Physics, 86 ed., Boca Raton: CRC Press LLC 2,
2005.

[9] M. D. N. &. G. C. Micha Peleg, “The Arrhenius Equation Revisited,” Critical Reviews in Food
Science and Nutrition, vol. 52, no. 9, pp. 830-851, 2012.

8 APPENDICES

8.1 APPENDIX A: LOWER MEASURES AT FIRST CONDUCTIVITY METERS UPON

TEMPERATURE INCREASE

Decreasing conductivity at QT01 with increasing temperature

12

10
Conductivity (mS/cm)

0
20 25 30 35 40 45 50 55

Temperature (oC)