NAME: ______________________________ DATE: ______________________

Group Number: _____CO-WORKER’S NAMES: ________________________________________

Instructor’s Signature:__________ Laboratory Technician’s Signature: _________

ACTIVITY NO. ___: Determination of the Reaction Rate Constant in a Continuous Stirred
Tank Reactor

INTRODUCTION

The Armfield continuous stirred tank reactor is designed to demonstrate the mechanism of a
chemical reaction in this type of reactor as well as the effects of varying the process conditions such
as reaction temperature, reactor volume, stirring rate, feed rate etc.

The reactor volume can be varied by adjusting the height of the internal standpipe. The actual
volume must be checked by filling the reactor with water to the overflow then draining the reactor
contents into a measuring cylinder.

The conductivity of the reacting solution in the reactor changes with the degree of conversion and
this provides a convenient method for monitoring the progress of the reaction either manually or by
computer.

N.B. In the absence of a conductivity meter, aliquot samples can be analyzed using titration
with acid.

The reaction chosen is the saponification of ethyl acetate by sodium hydroxide as it can be carried
out under safe conditions of temperature and pressure and is well documented.
Nomenclature:

aµ = concentration of NaOH in feed vessel, mol/L

ao = concentration of NaOH in mixed feed, mol/L

at = concentration of NaOH in reactor at time t, mol/L

a∞ = concentration of NaOH in reactor after ∞ time, mol/L

b = ethyl acetate concentration (same subscripts as a for the same conditions), mol/L

c = sodium acetate concentration (same subscripts as a for the same conditions), mol/L

F = total volume feed rate, L/s

Fa = volumetric feed rate of NaOH, L/s

Fb = volumetric feed rate of ethyl acetate, L/s

k = specific reaction constant

r = reaction rate

tR = residence time, s

t = elapsed time, s

T = temperature, K

V = reactor volume, L

Xa = conversion of NaOH

Dilution of Ethyl Acetate

Armfield recommends the use of a 0.1M solution of Ethyl Acetate, which should be made by diluting
concentrated Ethyl Acetate as follows:

Therefore add 9.79ml of concentrated Ethyl Acetate to 900ml of deionised or distilled water.

Shake the mixture vigorously until the two liquids have mixed. Add further water to make up the final
volume to 1000ml.

Note: The practice of making a strong solution (e.g. 1M) then further diluting this to the required
concentration (e.g. 0.1M) cannot be applied when using Ethyl Acetate. The required dilution should
be made directly as stated above.

Dilution of Sodium Hydroxide

Theory
The reaction:

NaOH + H3COOC2H5 → CH3COONa + C2H5OH

can be considered equi-molar and first order with respect to both sodium hydroxide and ethyl
acetate, i.e. second order overall, within the limits of concentration (0 - 0.1M) and temperature (20 -
40°C) studied.

The reaction carried out in a Continuous Stirred Tank Reactor or Tubular Reactor eventually
reaches steady state when a certain amount of conversion of the starting reagents has taken place.

The steady state conditions will vary depending on concentration of reagents, flowrate, volume of
reactor and temperature of reaction.

Method
Make up 2.5 litre batches of 0.1M sodium hydroxide and 2.5 litres of 0.1M ethyl acetate.

IMPORTANT: It is essential when handling these chemicals to wear protective clothing, gloves and
safety spectacles.

Remove the lids of the reagent vessels and carefully fill with the reagents to a level approximately
50mm from the top. Refit the lids.
Start the software using the option of the experiment with heater

Set PID controller loop according to the settings for a continuous experiment described in operation
section.

Adjust the set point of the PID to 30°C.

Change PID ‘mode of operation’ to ‘Automatic’

Collection of data will be until a steady state condition is reached in the reactor and this takes
approximately 30 minutes. It is advisable to set the data collection period to, say, 45 minutes.

Set the pump speed controls to 40ml/min flowrate in the software.

Fill the concentration of both solutions in their respective boxes in the software.

Fill the volume of the reactor in the box on the software. Set the agitator speed controller to 50% in
the software.

Press ‘Power on’ button (or begin taking readings if no computer is being used) and pumps
and stirrer will start to work. After a few minutes the temperature sensor tip will be covered
(about 25mm of liquid in reactor) – then press ‘Hot Water Circulator’ button and water will
start to recirculate through the whole system including the reactor.

Now enter the following known values from the experiment using the following nomenclature:
Fa Fb aμ bμ cμ T V

Time, s 300 600 900 1200 1500 1800 2100 2400 2700

at

Using the spreadsheet, calculate the values of 𝑎0 , 𝑏0 , 𝑐∞ , 𝑎∞ from the following formula:
 𝐹𝑎
𝑎0 = 𝑎
𝐹𝑎 + 𝐹𝑏 𝜇

𝐹𝑏
𝑏0 = 𝑏
𝐹𝑎 + 𝐹𝑏

𝑐∞ = 𝑏0 𝑓𝑜𝑟 𝑏0 < 𝑎0

𝑐∞ = 𝑎0 𝑓𝑜𝑟 𝑏0 ≥ 𝑎0

𝑎∞ = 0 𝑓𝑜𝑟 𝑎0 < 𝑏0

𝑎∞ = (𝑎0 − 𝑏0 ) 𝑓𝑜𝑟 𝑎0 ≥ 𝑏0

For the values of each of the above, the spreadsheet can be used to calculate values of sodium
hydroxide concentration (a1) and sodium acetate concentration (c1) and the degree of conversion
(Xa) and (Xc) for each of the samples taken over the period of the experiment.

𝑎0 − 𝑎𝑡
𝑋𝑎 =
𝑎0
𝑐𝑡
𝑋𝑐 = 𝑓𝑜𝑟 𝑐0 = 0
𝑐∞

To calculate the specific rate constant, k, the overall mass balance at steady-state condition may be
written used:

Input – Output ± Reaction = 0

i.e. for a reactant a in a reactor of volume V

𝑑(𝑉𝑎𝑡 )
= 𝐹𝑎0 − 𝐹𝑎𝑡 − 𝑉𝑘𝑎𝑡2
𝑑𝑡

For the continuous reactor operating at steady state the volume may be assumed constant and

𝐹 𝑎0 − 𝑎𝑡 𝐹𝑎 + 𝐹𝑏 𝑎0 − 𝑎𝑡 𝑚𝑜𝑙
𝑘= ∙ = ∙ 𝑖𝑛
𝑉 𝑎𝑡2 𝑉 𝑎𝑡2 𝐿∙𝑠

The steady state concentration of NaOH in the reactor (a t) may be used to calculate the specific rate
constant (k).

Comment upon the results obtained. How did temperature affect the reaction rate? and the
conversion?

Notes:

1. It is recommended that this experiment should be repeated at various other temperatures to

2. It is further recommended that the experiment be repeated using dissimilar flow rates for the
caustic soda and ethyl acetate solutions to investigate the effect that this will have upon the
saponification process.