Department of Chemical & Biomolecular Engineering

THE NATIONAL UNIVERSITY

of SINGAPORE

Chemical Engineering Process Lab

Experiment R2

Tubular Flow Reactor

Name :

Matric No. :

Group :

Date of Expt. :

GRADE :
Objective :

♦ To determine the rate equation for the alkaline hydrolysis of ethyl acetate using a tubular
flow reactor.

Apparatus :

Tubular flow reactor set-up and Autotitrator

Theory

The following equations shows the alkaline hydrolysis of ethyl acetate (EtAc) with sodium
hydroxide :

NaOH + CH 3 COO C 2 H 5 → CH 3 COO Na + C 2 H 5 OH

(A) (B)

The reaction is assumed to be irreversible with the following rate expression:

-r A = k Ca A .C b B (1)

The complete rate equation can be determined in two steps. Firstly, the method of excess is
used to find the order of the reaction with respect to NaOH. This method involves feeding
the reactants at different flow rates while maintaining a constant and high EtAc to NAOH
concentration ratio for each run. Therefore equation (1) becomes

-r A = k/ Ca A

where
k/ = k Cb B ≅ k Cb Bo (2)

The overall order of reaction is determined by using the same reactant concentrations and
equal flow rates of NAOH and EtAc solution. Since one mole of NaOH reacts with one mole
of EtAc, the final concentration will be the same and the rate equation reduces to

-r A = k Cn A

where n= a+b

The progress of reaction can be determined by adding HCl solution to the reaction mixture to
"freeze" the reaction and then by back titration using a standard NaOH solution; steady state
condition is achieved when subsequent back titration results are the same.
Data Analysis
Differential Method of Rate Analysis

Considering the following rate equation and taking logarithm

-r A = - dC A /dt = k Cn A

ln (- dC A /dt) = ln k + n ln C A

From the experimental C A vs t curve, the slopes of the curve dC A /dt at suitably selected
concentration values can be determined. The graph of In(- dC A /dt) against ln C A Will yield
the reaction order n and the y - intercept give the value of ln k.

Integral Method of Rate Analysis

This method consists of trial-and-error procedures. The reaction order is first assumed and
the rate expression is integrated. If the assumed order is correct, the appropriate plot should
be linear.

For a first order reaction

-r A = kC A

the integrated form is

ln C A = kt + ln C AO

Hence a first order reaction can be expected to give a linear plot of ln C A vs. t. with slope (-k)
and intercept (ln C AO ). Alternately, one can plot ln(C AO / C A ) against t and the slope will
give the value of k.

Experimental Procedure

Switch on power supply to the unit. Make sure enough water is present in the water
circulation system. Set the switch of the temperature controller to “0” position and note down
the room temperature indicated. Prepare equal concentration of NaOH (C AT ) and EtAc(C BT )
(0.05M) and fill the feed containers. Adjust the speed of both pumps to give flow rate of 30
ml/min (F A =F B ).

Get ready a number of beakers of 5.0 ml 0.10M HCl standard solution.

On the computer, access the reactor program and set the sample rate as 1 min. When 3
consecutive conductivity readings are consistent, collect 20 ml of product and immediately
add this to a beaker of HCl prepared earlier. Bring the beaker of mixture to the Autotitrator to
titrate (learn the procedure from the demonstrator). Collect two more samples at time
intervals of 2 minutes and analyse.

Repeat the above procedure with 3 different flow rates.

For the 2nd part of the experiment, run the system with 0.05 M NaOH and 0.2 M EtAc and
with the flow rate of EtAc double that of the NaOH.

Assignment:

1. Determine the order of the reaction with respect to NaOH and ethyl acetate.

2. Determine the rate constant of the reaction.

3. Compare and discuss the results obtained from differential and integral methods of
analysis.

4. Comment on the effect of changes in flow rate on conversion.

References:
rd
1. Fogler, S. H.; “Elements of Chemical Reaction Engineering,” Prentice Hall, 3 Edition
(1999), pages 15 – 55.

2. McKetta, John; “Encyclopedia of Chemical Processing and Design,” Volume 46

(1994), pages 245 – 261.

3. Levenspiel O., ` Chemical Reaction Engineering', John Wiley and Sons, Inc. 1962

4. Hill, C.G. Jr., 'An Introduction to Chemical Engineering Kinetics and Reactor Design',
John Wiley and Sons, Inc. 1977

5. Levine, Ira N. Physical Chemistry, Second Edition. McGraw-Hill book Company, New
York, 1983