Department of Chemical & Biomolecular Engineering

Chem. Eng. Process Laboratory I

B.Tech CN 2116E


Experiment R3

Batch Reactor































Objectives:

To determine the stoichiometric, the heat of reaction, and the rate constant of the reaction
between sodium thiosulphate and hydrogen peroxide in an aqueous medium.

Apparatus:

Dewar flask, thermometer, thermocouple, and chart recorder

Theory:

The oxidation of sodium thiosulphate with hydrogen peroxide can be written as:
A Na
2
S
2
O
3
+ B H
2
O
2
C Na
2
SO
4
+ D H
2
O + E Na
2
S
3
O
6


1. Stoichiometry
The stoichiometric coefficient is defined as the moles of hydrogen peroxide reacted per mole
of sodium thiosulphate consumed. This can be determined from a series of runs in which the total
volume of reactant solution is held constant and the volume of hydrogen peroxide is varied. Only
the overall temperature rise (AT) had to be measured. When AT is plotted against the volume of
hydrogen peroxide used, the temperature rise will go through a maximum when the reactants are
mixed in their stoichiometric ratio.

2. Water Equivalent of Dewar flask

The water equivalent is the amount of water that will absorb the same amount of heat as the
container (flask). From heat balance equation (i.e. M
.
Cp
.
AT), the heat loss by hot water is equal to
the heat gain by cold water and flask.

3. Heat of Reaction

In a chemical reaction, the total heat released can be calculated from the overall temperature
rise (AT), and the system heat capacity. In a solution, since reactant not in excess will react
completely, the heat of reaction can be calculated if the stoichiometric coefficient is known. In this
work the hydrogen peroxide is normally used in excess in order to suppress possible side reaction
and, therefore, the heat of reaction (AH), is reported as calorie per mole of Na
2
S
2
O
3
.

4. Activation Energy
The activation energy, essentially a measure of the effect of temperature on reaction rate, can
be derived from data obtained in a series of runs in which the initial reactant concentrations are
held constant and the initial temperature is varied. The initial concentrations being constant, it
follows that the concentrations at a temperature midway between the initial and final temperatures
will be the same for all runs, since at this point exactly half of the reactant not in excess will have
reacted. This temperature is called the midpoint temperature (T
m
). At the midpoint temperature, the
reaction rate is directly proportional to the rate of temperature increase i.e., the slope of the
temperature - time curve. Thus, if the logarithm of the midpoint slope is plotted against the
reciprocal of the absolute temperature and a straight line results, the assumption of an activation-
energy-like temperature dependence is justified and the slope of the line is equal to -E/R.

5. Reaction Rate Constant
For any point on the temperature vs. time curve, and in particular the midpoint, the slope of the
curve is given by the expression:

SYS
RT E
SYS P
V C C e C M H A . . . . ) ( ) (
dt
dT
2 1
/
1

A =

From the stoichiometry and the initial reaction concentrations, C
1
[Na
2
S
2
O
3
] and C
2
[H
2
O
2
] at
the midpoint can be calculated. Since the activation energy, the heat of reaction and the system heat
capacity are known, the value of the reaction rate constant k can be determined by multiplying A
with e
-E/RT
.

Experimental Procedures:

(A) Determination of the Stoichiometry of the reaction

Mix 50 ml of H
2
O
2
and 250 ml of Na
2
S
2
O
3
in a Dewar flask. Take note of the initial and
highest final temperature readings. With the total volume of reactant solution held constant at 300
ml, the experiment is repeated with five different sets of H
2
O
2
and Na
2
S
2
O
3
volumes.

(B) Determination of the water equivalent of the Dewar flask

Pour 100 ml of cold water into the Dewar flask, and then record the temperature.
Immediately, pour another 100 ml of hot water of known temperature into the flask to mix with the
cold water. Take note of the highest temperature reached.

(C) Determination of the heat capacity of reaction mixture (M Cp)
sys


100 ml of Na
2
S
2
O
3
at room temperature is poured into the Dewar flask. Note the initial
temperature .Start the chart recorder using a chart speed of 200mm/M. Next, 200 ml of H
2
O
2
, also
at room temperature is added. Look out for the highest temperature reached from the temperature-
time curve plotted on the chart recorder. When this happens, immediately add 150ml cold water of
known temperature into the Dewar flask. Record the steady equilibrium temperature. Derive the
energy balance equations to calculate (MCp)
sys
and the heat of reaction (AH). Repeat the run with
different sets of initial reactant temperatures, say at 40
0
C; 48
0
C and 55
0
C (separate flasks of
Na
2
S
2
O
3
and H
2
O
2
heat up to 40
0
C before mixing).












Tabulation and Calculation:

Determination of the Stoichiometry of the reaction

Concentration of Na
2
S
2
O
3
C
A
= 1.0723M
Concentration of H
2
O
2
C
B
= 1.0937M

Volume of Na
2
S
2
O
3

V
A
(ml)
Volume of H
2
O
2

V
B
(ml)
Initial
T
i
(
o
C)
Final
T
f
(
o
C)

AT
(
o
C)
50 250 22.5

42.2 19.7
100 200 22.5 62 39.5
150 150 22.5 58.2 35.7
200 100 22.5 48.3 25.8
250 50 22.5 35.7 13.2


Plot AT vs. volume of H
2
O
2
used

Reading out from the graph plotted, the following volumes were obtained corresponding to
maximum T

Volume of H
2
O
2
occurred at maximum T 190ml
Volume of Na
2
S
2
O
3
occurred at maximum T 110ml
Maximum T 40
o
C

Therefore the stoichiometric coefficient can be determined by the following ratio:

7617 . 1
0723 . 1 110
0937 . 1 190
) (
) (
3 2 2
2 2
=

= =
A A
B B
C V
C V
reacted O S Na A of Moles
reacted O H B of Moles
A
B



0
5
10
15
20
25
30
35
40
45
0 50 100 150 200 250 300
A
T
Volume of H
2
O
2
Determination of the water equivalent of the Dewar flask

Mass of cold water m
c
= 100 g
Mass of hot water m
h
= 100 g
Temperature of cold water T
c
= 24.3
o
C
Temperature of hot water T
h
= 60.0
o
C
Equilibrium Temperature T
e
= 40.3
o
C

The water equivalent of the Dewar flask


( )
( )
( )
( )
g m
T T
T T m
m
c
c e
e h h
e
125 . 23
3 . 24 3 . 40
3 . 40 0 . 60 100
=

=

Determination of the heat capacity of reaction mixture (MCp)
SYS


Volume of Na
2
S
2
O
3
= 100 ml
Volume of H
2
O
2
= 200 ml
Volume of cold water = 150 ml

Initial
T
i
(
o
C)
Highest
T
h
(
o
C)
Equilibrium
T
e
(
o
C)
Cold water
T
c
(
o
C)
(MC
p
)
sys
*
(J/K)
-AH **
(kJ/mol Na
2
S
2
O
3
)
24 57.5 55 24.3 5037.582 1573.804
40 80 69 24.3 1602.321 597.714
48 85 70 24.3 1177.126 406.170
55 89 75 24.3 1417.434 449.433

Sample calculation:

* ( )
( )
( )
( )
( )
( ) water p e
e h
c e water p c
sys
p
C m
T T
T T C m
MC

=


( )
1810 . 4 125 . 23
55 5 . 57
3 . 24 55 1810 . 4

=

= 5037.582375 J/K

**
( ) ( )
3 2 2
O S Na of moles
T T MC
H
i h
sys
p

= A


( )
0723 . 1 1000 1 . 0
24 5 . 57 582 . 5037


=

=
3 2 2
804 . 1573 O S Na mol kJ

Average (MC
p
)
sys
= 2308.616(J/K)
Average -AH ** = 756.78(kJ/mol Na
2
S
2
O
3
)

Determination of the activation energy and rate constant

Midpoint
T
m
=0.5 (T
i
+T
h
)
(
o
C)
T
m

(k)
dT
m
/dt ln [dT
m
/dt] 1/T
m
A Rate
Constant
(k)
40.75 313.9 369.296 5.91159 0.003185728 1.3010
13


3201.97

60 333.15 951.857 6.85841 0.003001651 3.6310
12
3205.39
66.5 339.65 1358.6 7.21421 0.002944207 2.43310
12
3201.74
72 345.15 3451.5 8.14656 0.002897291 1.75710
12
3202.81


Plot ln [dT
m
/dt] vs. 1/T
m



Sample calculation

The slop of the curve = -E/R = -6945.4
Thus E = 57744.0556J/mol

Based on the intercept of the curve, the value of the frequency factor is determined:


SYS
RT E
SYS P
V C C e
C M
H A
. . .
) (
) (
dt
dT
2 1
/

A
=


y = -6945.4x + 27.919
R = 0.9032
0.00000
1.00000
2.00000
3.00000
4.00000
5.00000
6.00000
7.00000
8.00000
9.00000
0.00285 0.0029 0.00295 0.003 0.00305 0.0031 0.00315 0.0032 0.00325
l
n

[
d
T
m
/
d
t
]

1/T
m
Taking the natural logarithm on both sides of the equation yields:

( ) ( )
SYS
RT E
SYS P
V C C e C M H A . . . . ) ( ) ( ln ln
dt
dT
ln
2 1
/ 1
A + =
|
.
|

\
|


From experimental data, ln [dT
m
/dt] is evaluated to be:

91159 . 5
dt
dT
ln = |
.
|

\
|


It is also cautioned that the concentration of sodium thiosulphate and hydrogen peroxide is
evaluated with respect to initial concentration and stoichiometric ratio, thus the concentrations of
these two reactants are as follows:

C
1
(Concentration of Na2S2O3 at midpoint) = 1.0723 M
C
2
(Concentration of hydrogen peroxide at midpoint) = 1.0937 M

Thus, the frequency factor is calculated:

( )
|
|
.
|

\
|
+ =

3 . 0 0937 . 1 0723 . 1
616 . 2308
78 . 756
ln ln 91159 . 5
9 . 313 314 . 8
06 . 57744
e A

( )
11
10 836 . 2 ln 91159 . 5

+
= e A


13
10 302 . 1 =

The rate constant K = A.e
(-E/RT)
= 1.30210
13
e
(-6945.4/313.9)
= 3201.97


















Discussion:

Determination of the Stoichiometry of the reaction
From the experiment one has observed that the maximum temperature (40
o
C) occurred at
the mixture of H
2
O
2
and Na
2
S
2
O
3
reacting at a range of 190 to 110 ml. From this lab experiment,
one has also made a conclusion that the stoichiometric ratio is 1.761. This indicates that
approximately 2 moles of hydrogen peroxide is needed to react with 1 mole of sodium thiosulphate
to form products. Since the amount of reactant, H
2
O
2
in this experiment is found to be in excess, the
heat of reaction expressed in terms KJ/mol of Na
2
S
2
O
3
, and the value is 756.78KJ/mol.

Determination of the heat capacity of reaction mixture (MCp)
SYS
and Heat of Reaction
It was observed that the enthalpy relative to 1 mole of sodium thiosulphate decreases with
the increase in temperature T
h
. Reason being, the deviation of T
h
from equilibrium temperature of
the system causes the denominator of the expression to increase, thus the value of (MC
p
)
SYS

increases. As a result, the change in enthalpy of the system decreases.
It was also noted that, an average heat capacity and heat of reaction was taken instead of
individually. This is to ensure ease of calculation for the frequency factor.

Determination of the activation energy and rate constant
During the reaction, heat is liberated due to exothermic reaction and. This will cause the
temperature of the system to increase. If a desired temperature of the system is to be maintained so
as to meet the product specification, it is crucial that excess heat must be removed, in order to
maintain the reaction temperature. One solution is the addition of cooling coils to remove the
excess heat.
Based on the calculation of the activation energy, it is known that the activation energy of
this reaction is 57744.0556 J/mol. This indicates that this is the amount of energy needed for
product to be formed as sufficient energy is needed to overcome this energy barrier. From the
Arrhenius equation it is suggested that the value of rate constant depends on the temperature of the
system. This means that if the temperature of the system is high, the exponent term will become
bigger, hence result in a higher rate constant.
This is however not true, based on the calculations increasing the temperature of the system
does not have any effect on the rate constant. Reason being, the exponential constant, which is also
known as a frequency factor, is also proportionally inversed to the exponential term seen in the
Arrhenius equation. This indicates that when the temperature increases, the value of frequency
factor increases thus balancing the equation in the Arrhenius equation. Thus, the following
statement made in the literature does not coincide with this experimental findings that, Reactions
with high activation energies are very temperature-sensitive; reactions with low activation energies
are relatively temperature-insensitive.
Also, as one has noted, the order of the reaction of sodium thiosulphate and hydrogen
peroxide is second order. This indicates that the rate constant has a unit of mole/min.

Conclusion
Based on this lab experiment, one has calculated the mole ratio of the reactants to be 1.7617, which
is 2 moles of hydrogen peroxide is needed to react with 1 mole of sodium thiosulphate to form
product. Also, based on the calculation of heat capacity, it is known that the heat capacity of the
system tends to decrease in with the increase of the midpoint temperature. With the value of the
heat capacity and enthalpy change known, the activation of energy is evaluated to be 57744.066
J/mol. This means, at least 57744.066 J/mol of energy is needed in order for reactants to form
products. It was discovered later on that the temperature does not affect the rate constant as the
frequency factor is increased so that the Arrhenius equation is balanced. From this, one can
conclude that the frequency factor related to the exponential term as follows
RT E
e A

1 .



Reference:

Cohen, W. C. and Spence, J. C., Chem. Eng. Prog.,Vol 58, No.12 December,
pg 40-41, 1962.