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# 2.

0 OBJECTIVES

## - To determine the order of saponification reaction

- To determine the reaction rate constant, k

## - To determine the effect of temperature on reaction rate constant, k for

batch reaction
- To determine the activation energy of saponification.
3.0 THEORY

## A stirred- tank reactor (STR) may be operated either as a batch reactor or as a

steady-state flow reactor (better known as Continuous Stirred-Tank Reactor
(CSTR)). The key or main feature of this reactor is that mixing is complete so that
properties such as temperature and concentration of the reaction mixture are
uniform in all parts of the vessel. Material balance of a general chemical reaction
is described below.
The conservation principle requires that the mass of species A in an element of
reactor volume ∆V obey the following statement (Perry, 2008):

## Rate of A Rate of A Rate of A Rate of A

Into _ out of + produced = accumulated
volume volume within volume within volume
(1)
element element element element
BATCH STIRRED-TANK REACTOR (BSTR)
The reaction studied in this is the saponification of ethyl acetate. This reaction is
elementary and second-order. The reaction equation is

## NaOH + EtOAc  NaOAc + EtOH

A + B --> C + D

In batch reactions, there are no feeds or exit streams and therefore equation (1)
can be simplified into:

Rate of A Rate of A
produced = accumulated
within volume within volume
element element (2)

For a constant volume isothermal batch reactor, the design equation is:
dC A
 rA
dt

-rA = k CACB

## The rate of reaction of component A is defined as:

moles  A  appear  by
1  dN A  reaction
rA    = (3)
V  dt by  reaction volume  time
By this definition, if A is a reaction product, the rate is positive; whereas if it is a
reactant, which is consumed, the rate is negative (Perry, 2008).

## Rearranging equation (3);

 rA  V  N AO
dX A
(4)
dt
Integrating equation (4);
dX A
t  N AO  (5)
 rA V
where t is the time required to achieve a conversion XA for either isothermal or
non-isothermal operation.

## Figure 1: Graphical representation of the performance equations for

batch reactor, isothermal or non-isothermal at constant density.

## STEADY STATE MIXED FLOW REACTOR

The general material balance for this reactor is as equation (1) except no
accumulation of the material A in rector. As shown in figure 2 below, if FAO =
vOCAO is the molar feed rate of the component A to the reactor, then considering
the reactor as a whole we have,
Input of A (moles/time) = FAO (1 – XAO) = FAO
Output of A (moles/time) = FA = FAO (1 – XAO)
Disappearance of A by reaction (moles/time) = (-rA) V

moles  A  reacting
= volume  of  reactor 
(time )( volume)

## Replacing equation (1) with mathematical formula above,

FAOXA = (-rA) V
Which on arranging, will form the performance equation for mixed flow reactors,

V  X A 1 V VC AO C AO X A
  or,      (7)
FAO C AO  rA s vO FAO  rA

## Figure 2: Components of Mixed Flow Reactor

In mixed flow reactors, XA = XAF and CA= CAF. In a constant density system,
XA = 1 – (CA/CAO)

## The performance equation can be rewritten in terms of concentration, or

V X C  CA V C X
 A  AO , or ,   AO A (8)
FAO  rA C AO (rA ) v (rA )

These expressions relate the four terms XA, -rA, V, FAO; thus, knowing any three
allows the fourth to be found directly. In design, the size of reactor needed for a
given duty or the extent of conversion in a reactor of given size is found directly.
Each steady-state point in a mixed flow reactor gives the reaction rate for the
conditions within the reactor (Green, 2008). The mixed flow reactor provides
easier interpretation of reaction rate data and makes it very attractive in kinetic
studies.

Graphical Representation of the Design Equations for Steady State Mixed Flow Reactor.

## Figure 3: Plot of 1 / (-rA) versus XA

Or in constant systems,
Figure 4: Plot of 1 / (-rA) versus CA

## Irreversible Second-order Reaction (Bimolecular Type)

Consider the reaction:
A+B Products
The rate equation can be written as:

dCA dC
 rA     A  kCACB (11)
dt dt
Plot of ln (CB/CA) versus t (time) will produce a straight line with slope equals
(CBO – CAO)k.

## Figure 5: Plot of ln (CB/CA) versus t, CAO CBO (for equation 11)

While for steady state mixed flow reactor, the plot of rA versus CACB will give a
straight line (pass through the origin) with the slope equal to k.
Figure 6: Plot of –rA versus CACB, CAO CBO (for equation 11)

For second order reaction with equal initial concentrations of A and B, the rate
equation can be written based on only one component:
dCA
 rA    kCA2  kCAO
2
(1  X A )2 (12)
dt

## A plot of 1 / CA versus t will produce a straight line with slope equals to k.

Figure 7: Plot of –rA versus CACB, CAO CBO (for equation 11)

In the case of steady state mixed flow reactor, the plot –rA versus CA2 will give
the value of k and a straight-line pass through the origin.
Figure 8: Plot of –rA versus CACB, CAO CBO (for equation 11)

## In any single homogenous reaction, temperature, composition, and reaction rate

are uniquely related. They can be represented graphically in one of three ways as
shown below:

r3
C3

r2 C2
r1
C1

## The effect of temperature on reaction rate constant can be demonstrated by

performing a batch reaction run at different temperatures.
4.0 PROCEDURES

## By studying the saponification reaction of ethyl acetate and sodium hydroxide to

form sodium acetate in a batch and in continuous stirred tank reactor, the
students can evaluate the rate data needed to design a production scale reactor.

A process flow diagram of the reactor is shown in Figure 9. This reactor has a
total volume of approximately 4 liters. A scale is provided to determine the
reactor volume.

## Reactants Preparation Procedure:

1. 0.05 M NaOH and 0.05 M Ethyl acetate solutions are prepared in two
separate 20-liter feed tanks.
2. The concentration of 0.1 M NaOH solution is confirmed by titrating a
small amount of it with standard 0.1 M HCl using phenolphthalein as
indicator. The concentration of ethyl acetate solution, on the other hand, is
evaluated in the following manner. First, 0.1 M NaOH solution is added to
a sample of feed solution such that the 0.1 M NaOH solution is in excess to
ensure all the ethyl acetate reacted. The mixture is reacted overnight. On
the following day, the amount of unreacted NaOH is determined by direct
titration with standard 0.1 M HCl. The ethyl acetate real concentration is
recorded.
3. 1 liter of quenching solution of 0.25 M HCl and 1 liter of 0.1 M NaOH is
prepared for back titration.
Batch Reaction Procedure:

## 1. To begin a batch reactor experiment, the overflow tube in the reactor is

adjusted to give a desired working volume, say 2.5 liters. The pump P1 is
switch on and start pumping 1.25 liters of the 0.1 M ethyl acetate from the
feed tank into the reactor. The pump P1 is stopped.
2. The pump P2 is switch on and starts pumping 1.25 liters of the 0.05 M
NaOH into the reactor. The pump P2 is stopped when 2.5 liters volume is
reached. The stirred is switched on and the speed is set in the mid range
(say 180 rpm). Timing the reaction is started immediately and the time is
recorded, tO.
3. 10 ml of the 0.25 M HCl is measured quickly in a flask.
4. After 1 minute of reaction, the sampling valve V7 is opened to collect a 50
ml sample and immediately the 10 ml of 0.25 M HCl prepared in step 3 is
added, and mixed. The HCl will quench the reaction between ethyl acetate
and sodium hydroxide.
5. The mixture is titrated with the 0.1 M NaOH to evaluate the amount of
unreacted HCl; this will provide the information that the amount of
NaOH in the feed solution, which has reacted, can be determined.
6. The steps 3 to 5 are repeated for reaction time of 5, 10, 15, 20 and 25
minutes.
Experiment B: Effect of Temperature on Rate Constant, k.

## The effect of temperature on reaction rate constant can be demonstrated by

performing a batch reaction run at different temperature.

## 1. To begin a batch reactor experiment, the overflow tube in the reactor is

adjusted to give a desired working volume, say 2.5 liters. The pump P1 is
switch on and start pumping 1.25 liters of the 0.1 M ethyl acetate from the
feed tank into the reactor. The pump P1 is stopped.
2. The pump P2 is switch on and start pumping 1.25 liters of the 0.05 M
NaOH into the reactor. The pump P2 is stopped when 2.5 liters volume is
reached. The stirred is switched on and the speed is set at the lower range.
Timing the reaction is started immediately and the time is recorded, tO.
3. 10 ml of the 0.25 M HCl is quickly measured in the flask.
4. After 1 minute of reaction, the sampling valve V7 is opened to collect a 50
ml sample and immediately the 10 ml of 0.25 M HCl prepared in step 3 is
added, and mixed. The HCl will quench the reaction between ethyl acetate
and sodium hydroxide.
5. The mixture is titrated with the 0.1 M NaOH to evaluate the amount of
unreacted HCl; this will provide the information that the amount of
NaOH in the feed solution, which has reacted, can be determined.
6. Steps 4 to 6 are repeated for reaction times 5, 10, 15, 20 and 25 minutes.
7. The experiment is repeated for reaction temperatures of 35, 40, and 45 oC
8. ln(CB/CA) versus t, lnK versus 1/T are plotted.
9. Activation energy is get from lnK versus 1/T plotted
10. All switches are switch off when the experiment is finished.
5.0 APPARATUS

EQUIPMENT DESCRIPTION

Before operating the unit, we have to be familiar with the unit. Figure at the
appendices is using as reference.

a) Reactor: The reactor consists of a glass vessel with top and bottom plate
made of stainless steel. The reactor comes with a cooling coil, a 1.0 kW
heater, a temperature sensor, stirrer system, an overflow tube and a gas
sparging unit.

b) Feed Inlet System (Liquid Reaction): For each liquid reactant, a 20-liter feed
tank, a pump, a needle valve and a flow meter are provided. Each
reactant is pumped from the feed tank to the appropriate inlet port at the
top plate.

c) Gas Inlet System (Gas-Liquid Reactions: Optional): Gas from gas cylinder
(not provided) flows through a needle valve, a flow meter and a gas
sparger before reacting with the liquid inside the reactor.

## d) Product/Waste Tank: A 50-liter rectangular tank made of stainless steel is

provided for collecting lar tank made of stainless steel is provided for
collecting lar tank made of stainless steel is provided for collecting the
product or waste before being discharged.
e) Control Panel: The control panel consists of all the necessary electrical
components for controlling the operations of the unit. Components mounted
on the panel door are all labeled for convenience. The control panel also
houses the necessary for data acquisition system.

## f) Data Acquisition System (Optional): The data Acquisition System consists of a

personal computer, ADC modules and instrumentations for measuring the
process parameters. A flow meter with 4 to 20 mA output signal is provided
for monitoring the changes in pH while the reaction is taking place. The ADC
modules into digital signal convert all analog signals from the sensors before
being sent to the personal computer for display and manipulation.

REFERENCES
1. Green, P. W. (2008). Continuous Stirred Tank Reactors (CSTRs). Chemical and
Biological Reaction Engineering, 5-6.
2. Perry, R. G. (2008). Perry Chemical Engineer's Handbook. New York: McGraw Hill.