Saponification of Ethyl Acetate by

Sodium Hydroxide in a Continuous
Stirred Reactor (CSTR)
Kurt Spies
Trevor Carlisle
ChE 414 Winter 2005

Presentation Overview
 Requested information
 Project objectives
 Planning and execution
 Team member roles
 Background and experimental methods
 Procedure
 Data/results
 Conclusions
 Recommendations
Requested Information
 Information Contained
 The procedures and results of the saponification
experiment
 Audience
 Peers
 Supervisors
 Educational Leaders
Objectives
1. Develop calibration curves for conductivity
2. Determine rate constant using batch reactor
3. Evaluate the CSTR reaction rate as a function of
residence time

Project Planning and Execution
 Planning
 Developed initial project plan
 Only deviation included an additional lab session
 Execution Lessons/Thoughts
 Plan first lab session before entering the room
 Prepare to put in sufficient out of lab time into
project to make lab time efficient
Team member roles
 Trevor- Operations Manager
 Responsible for the operation of the CSTR
 accountable for data collection
 In charge of making sure experiment is accurate and follows
correct procedures
 Kurt- Team Leader/Safety Manager
 Identify safety issues
 Develop the safety plan
 Monitor safe lab behavior
 Develop project plan
 Ensure lab work moves forward
 Responsible for the operation of batch reactor
Background and Experimental
Methods
 The Irreversible Reaction
Ethanol Acetate Sodium
Hydroxide Sodium
Acetate Ethyl
OH H C Na H O C NaOH H COOC CH
5 2 3 2 2 5 2 3
+ ÷ +
Logical Experimental
Organization
 Calibration
 Batch Experiment
 CSTR Experiment
Conductivity Calibration
15.0
Sample Solution
Conductivity Probe
Digital Conductivity Meter
Calibration Procedure
 Prepared and standardized 0.1M NaOH
Solution
 Diluted solution to various concentrations
 Fine-tuned conductivity using calibration
probe
 Measured Conductivity of different solutions
Calibration Data/Results
y = 0.00440x
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0 2 4 6 8 10 12 14 16
Conductivity [mS]
C
o
n
c
e
n
t
r
a
t
i
o
n

N
a
O
H

M
Calibration Conclusions
1) Calibration curves for conductivity cells
match well with a linear approximation

 [concentration NaOH M] = 0.00440*[conductivity]
Batch Reactor
15.0
Sample Solution
Conductivity Probe
Digital Conductivity Meter
Hot Water Bath
Theoretical Batch Calculation
 Alkaline Hydrolysis of Ethyl Acetate is a
second order reaction


 To solve using graphical methods
B A
B A
A
C kC
dt
dC
dt
dC
r = ÷ = ÷ = ÷
( )
|
|
.
|

\
|
+ ÷ =
|
|
.
|

\
|
0
0
0 0
ln ln
A
B
A B
A
B
C
C
kt C C
C
C
Experimental Batch Design
 Three Experimental Types
 Equal molar concentrations
 Significant excess Sodium Hydroxide
 Significant excess Ethyl Acetate
 Erlenmeyer Flask
 ~100 mL solution
 Hot water bath ~50
O
C
 Mixed with conductivity probe
Equal Molar Concentrations
y = 0.1125x + 12.5
12.00
13.00
14.00
15.00
16.00
17.00
18.00
19.00
20.00
21.00
22.00
0 10 20 30 40 50 60
Time (sec)
1
/
C
a

[
L
/
m
o
l
]
Run 1
Run 2
Run 3
Run 4
Run 5
Run 6
Run 7
Run 8
Linear (Theorey)
Equal Molar Concentrations
Results
 Experimental Rate Constant from Data


 Theoretical Experimental Rate Constant from
Tsujikawa and Inoue


 Theoretical Experimental Rate Constant from
Mata-Segreda


(
¸
(

¸

·
± =
s mol
L
k 00163 . 0 119 . 0
exp
(
¸
(

¸

·
=
s mol
L
k
th
1125 . 0
(
¸
(

¸

·
=
s mol
L
k
th
122 . 0
High Concentration of Sodium
Hydroxide
y = 0.00680x + 1.39
1.000
1.200
1.400
1.600
1.800
2.000
2.200
2.400
2.600
0 10 20 30 40 50 60 70 80 90 100
Time (sec)
l
n
(
C
b
/
C
a
)
Run 1
Run 2
Linear (Theory)
High Concentration of Sodium
Hydroxide Results
 Slope of experimental line excluding bottom points

 m=k(C
B0
-C
A0
)=0.00760 (+/- 0.000129)




(
¸
(

¸

·
=
s mol
L
k 127 . 0
exp
High Concentration Ethyl
Acetate
y = 0.0338x + 2.77
2
2.5
3
3.5
4
4.5
5
5.5
0 10 20 30 40 50 60 70 80
Time (sec)
l
n
(
C
b
/
C
a
)
Run 1
Run 2
Run 3
Linear (Theory)
High Concentration of Ethyl
Acetate Results
 Slope of experimental line only including reaction
region of first few points

 m=k(C
B0
-C
A0
)=0.0374 (+/- 0.0044)




(
¸
(

¸

·
=
s mol
L
k 125 . 0
exp
What accounts for theoretical and
empirical differences?
 Overall rate constant consistent with
theoretical data
 Initial concentration different then planned
Equal Molar Concentrations
y = 0.1125x + 12.5
12.00
13.00
14.00
15.00
16.00
17.00
18.00
19.00
20.00
21.00
22.00
0 10 20 30 40 50 60
Time (sec)
1
/
C
a

[
L
/
m
o
l
]
Run 1
Run 2
Run 3
Run 4
Run 5
Run 6
Run 7
Run 8
Linear (Theorey)
The Continuous Stirred Tank Reactor
Theoretical CSTR Calculation
 Second order mixed
flow reactor



 Graphical Solution


( )
( )
2
0
2
0
1
A A
A
A
A A
X C
X
C
C C
k
÷
=
÷
= t
| | ) log( ) log( ) log( k C order reaction r
A A
+ · = ÷
Experimental Design for CSTR
 Filled chemical reservoirs with equal
concentration sodium hydroxide and ethyl
acetate

 Preformed experiment with different flow
rates with different concentrations
CSTR Data
y = 2x - 0.949
0.4
0.5
0.6
0.7
0.8
0.9
1
1.1
0.7 0.75 0.8 0.85 0.9 0.95 1
Log(Ca) [log(mol/L)]
L
o
g
(
-
r
a
)

[
l
o
g
(
m
o
l
/
L
-
H
r
)
]
Linear (Theory)
CSTR Results
 The theoretical information for the CSTR should
be the same rate constant



 Our experimental data contains considerable
noise and does not conform to any experimental
trend for determining the order of reaction

2 1125 . 0 =
(
¸
(

¸

·
= order l theoretica
s mol
L
k
th
CSTR Data
y = 27.9x
-0.977
0
2
4
6
8
10
12
0 1 2 3 4 5 6 7 8 9 10
tau (resonance time) [sec]
r
e
a
c
t
i
o
n

r
a
t
e

[
m
m
o
l
/
L
-
H
r
]
CSTR Data
Power (CSTR Data)
CSTR Results
 Our experimental data can be approximated by a
inverse relationship



 This makes sense because as the resonance
time increases the rate should approach that of
the batch reactor

| | | |
977 . 0
Re 9 . 27 Re
÷
· = Time sonance Rate action al Experiment
What accounts for theoretical and
empirical differences?
 The CSTR reaction has significant noise in
the reaction and the order is difficult to
experimentally confirm
 The flow rates for the CSTR feeds may not
be correctly calibrated


Experimental Conclusions
2) Batch reaction information suggests the reaction
rate constant is



3) Experimental data suggests the correlation
between resonance time and reaction rate is
(
¸
(

¸

·
± =
s mol
L
k 00163 . 0 119 . 0
exp
| | | |
977 . 0
Re 9 . 27 Re
÷
· = Time sonance Rate action al Experiment
Recommendations
 Leave more time for CSTR data collection
 Flow rate calibrations
 Solution prep
 Temperature adjustment
 Use volumetric glassware as much as
possible
 Gather sufficient technical information about
experiment
Questions?...
References
“Density of Water: Vapor Pressure of Water”. Retrieved February 15, 2005 from the World Wide Web:
http://www.ncsu.edu/chemistry/resource/
H2Odensity_vp.html

“Kinetics: Alkaline Hydrolysis of Ethyl Acetate”. Retrieved January 29, 2005 from the World Wide
Web: Http://www.uni-regensburg.de/fakultaeten/nat_fak_IV/
organische_chemie/didaktik/keusch/chembox_etae_e.htm

Levenspiel, Octave. 1999. Chemical Reaction Engineering (3
rd
Ed). United States of America: John
Wiley & Sons Inc.

Segreda-Mata, Julio F., “Hydroxide as General Base in the Saponification of Ethyl Acetate”. Journal of
American Chemical Society, 124: 10: 2259-2262

Traceable Expanded Range Digital Conductivity Meter Instructions. Model VWR 23226-523. 2000
Control Company.

Tsujikawa, Hiroo, and Inoue, Hakuai. “The Reaction Rate of Alkaline Hydrolysis of Ethyl Acetate”.
Bulletin of the Chemical Society of Japan, 39: 1837-1842