Professional Documents
Culture Documents
Group 1-A
Keith Tan JunJie, Wang Jiaxi, Pranav Chokhani
For an adiabatic exothermic liquid-based reaction between 1M Hydrogen Peroxide and 1M
Sodium Thiosulphate in an adiabatic reactor while varying 6 volumes of the reagents to alter
mixing ratios and observing the temperature rise during the reactions using a PC datalogger
software.
Main findings of the experiment were generated by examining the mixing ratio with the
greatest rise in temperature:
Experiment Overall Reaction Stoichiometry: Na2S2O3+ H2O2 Na2S2O4+ H20
Calculated
Experimental
Values
Literature Values [1]
vA/vB
Ave H
(J/mol)
Ave A
(cm3/s.mol)
Ave E
(J/mol)
-160,857.6
7.2881038
215,340
1.96
-596,600
71014
76,500
Experimental and literature results differ due to main sources of error of incorrect
assumptions that there were no heat loss from the reactor and that reactants were perfectly
mixed. It can be seen that the results vary largely from literature values also due to high
percentage errors in calculation of parameters shown below.
Parameters
H
E
A
Percentage Error
0.69%
6.94%
582.86%
Experimental trends observed are that the reaction between H2O2 and Na2S2O3 generates the
greatest rise in temperature with the stoichiometry ratio of vA/vB=1.00. The experiment
indicates that the stoichiometry ratio of 1.00 is the natural reaction between the reagents and
hence creates the largest exothermic reaction when both reactants act as limiting reagents.
Production Rate
Capital Cost
Labour cost
Scale of production
Reactant conversion
Temperature control
BR
Small
Small
High
Small
Small
Easy
CSTR
High
High
Small
Large
Small
Easy
PFR
High
High
Small
Large
High
Difficult
The activation energy relates to the Arrhenius Equation correlates chemical reaction rate
constants with temperature. It indicates the sensitivity of the reaction rate to temperature.
From the Arrhenius Equation, the activation energy can be expressed as the equation below:
[2]
k =A e
E
RT
Where A is the frequency factor for the reaction, R is the universal gas constant, T is the
temperature, k is the reaction rate coefficient and E is the activation energy.
An adiabatic reactions is one that occurs without transfer of heat or matter between a system
and its surroundings, energy is transferred only as work (i.e. Q=0). Adiabatic reactors are
well-insulated as they are usually made of most plastics and polymers. Adiabatic reactors
ensure that the energy is well-trapped into the reactor and therefore in this experiment the
temperature rise can be measured easily in order to achieve the objectives given below:
2.2 Objectives
The objectives of this experiment are to determine, and compare with literature data, the
following parameters for an adiabatic exothermic liquid-based reaction by observing the
temperature rise during reaction:
i)
Overall reaction stoichiometry
It is to use relationships between reactants and/or products in a chemical reaction to
determine desired quantitative data.
ii)
Reaction enthalpy H
Enthalpy change is the name given to the amount of heat evolved or absorbed in
a reaction carried out at constant pressure.
iii)
Arrhenius parameters: Pre-exponential factor A and activation energy E
A is a term which includes factors like the frequency of collisions and their orientation. It
varies slightly with temperature, although not much. It is often taken as constant across small
temperature ranges. Activation energy E is the minimum energy needed for the reaction to
occur. To fit this into the equation, it has to be expressed in joules per mole.[2]
Assuming the reaction is irreversible and first order with respect to each reactant and using
the Arrhenius equation
k = A'e
-E
)
RT
-E
)
RT
EQ 8
Where T is in Kelvin.
EQ 9
Where:
C B0 v A
CA0 v B
EQ 10
-A'v A v Bc P
H
EQ 11
All the equations mentioned above have been obtained from the UCL lab book for the
module CENG3008 p.11 and 12.
Graph 5.1: Experiment Reactor Temperature (C) Change Against Time (s) for varying mixing ratios of H2O2 and Na2S2O3
45
40
Run 1 : 0.5
35
Run 2: 1.0
Run 3 : 1.33
Run 4: 1.67
Run 5 : 2.0
25
Run 6 : 4.0
20
Time (s)
Graph 5.1: Raw Data Analysis of Experiment Results Runs 1-6 in Graphical Format
20
18.6
16.5
15.6
13.3
15
Temperature Change
[Tf-T0](C)
10 8.5
5
0
20 30 40 50 60 70 80 90
Volume of Reactant B Na2S2O3 (cm3)
Graph 5.2: Data Analysis of Experiment Results of Temperature Change against Volume of Reactant
B
20
16
12
8
19.2
16.5
15.6
18.6
13.3
8.5
4
0
Graph 5.3: Data Analysis of Experiment Results of Temperature Change against Mixing Ratios
Based on the experimental results from Table 1 and the raw data analysis in Graphs 1, 2 and
3, it can be seen that run 2 has the greatest temperature change and hence greatest rise in
Temperature.
As reaction terminates with complete consumption of either reactant, maximum heat
generation, per mole of reactants provided, takes place when there is no excess of reactants.
Thus the overall stoichiometry can be investigated by finding the mixing ratio of reactants
that provides the greatest temperature increase at constant initial volume and molarity.
Overall Stoichiometric ratio =
VtotalVB
VB
Hence, the overall reaction stoichiometry vA/vB is 1.00 as seen in run 2 with a greatest
Temperature Change [Tf-T0](C) of 19.2C.
The reaction between
Stoichiometr
y
vA/vB
Literature Reaction
Enthalpy
H (J/mol Na2S2O3)
6
1.00
-173 300
( Tf-To )
(CpVA
H )
CAo=
EQ 6
Where
H refers to the specific enthalpy of the reaction with respect to each mol of limiting
reactant in
J
mol ReactantA
CpVA
)(Tf-To)
CAo
C Ao=Reactant A
mol
60 cm3
M60 cm 3
1 cm 3
mol
1
=
=0.0005
120 cm3
1000 120 cm3
cm 3
2.
C Bo=Reactant B
ConcentrationReactant BVolume
Total Volume
mol
60 cm3
M60 cm 3
1 cm 3
mol
1
=
=0.0005
120 cm3
1000 120 cm3
cm 3
3. For the case of the specific heat capacity, as the initial concentration of reactants are
extremely small, with bulk of the solution mainly in water, we make the assumption
that the specific heat capacity of reactants will be 4.187
J
cm3 K
to 4.187
4.
J
gK [3] which is equivalent
5. Note, for all equations, vA and vB are -1 as the reaction is exothermic and the chosen
overall reaction stoichiometry is 1 for each reactant based on the equation below:
Experiment Reaction
Na2S2O3+ H2O2 Na2S2O4+ H20
Stoichiometr
y
vA/vB
1.00
Literature Reaction
Enthalpy
H (J/mol Na2S2O3)
-173 300
J
1
cm3 K
J
19.2 K=160,780.8
mol
molH 2O 2
0.0005
cm3
4.187
HA=
J
1
cm 3 K
J
19.2 K=160,780.8
mol
molNa2S2o3
0.0005
cm3
4.187
HB=
8. In the case of Run 2, as both reactants are limiting reactants, the Enthalpy of both A and
B can be calculated in the same manner. However, for other runs, we can only find the
enthalpy of the limiting reactant based on the equation and then convert the other
8
enthalpy of the excess reactant from the enthalpy of the limiting reactant in the
following fashion.
In Run 1, as the limiting reactant is H2O2, we will be able to calculate HA .
J
1
cm3 K
J
HA=
18.6 K =233,634.6
mol
molH 2O 2
40 cm3
cm3
0.001
120 cm 3
4.187
And from HA
HB = HA * vB/vA =233,634.6
J
J
* 1/1 = 233,634.6
molH 2 O 2
molNa2S2o3
For runs 3-6, reactant B is the limiting reagent hence calculate HA from HB
Run
CAo(mol/c
m3)
CBo(mol/c
m3)
1
2
3
4
5
6
0.000333
0.000500
0.000571
0.000625
0.000667
0.000800
0.000667
0.000500
0.000429
0.000375
0.000333
0.000200
Temperature
HA(J/molH2
Change
O2)
[Tf-T0](K)
18.6
-233634.6
19.2
-160780.8
16.5
-161052.8
15.6
-174262.4
13.3
-167141.1
8.5
-178032.5
Ave reaction Enthalpy HB
(J/molNa2S2O3)
HB(J/molNa2S2
O3)
-233634.6
-160780.8
-161052.8
-174262.4
-167141.1
-178032.5
-179182.1
r=kCACB=CACB A exp(
E
)
RT
EQ 8
Let
EQ 9
dT
1
=z
dt ( Tf T ) [ ( Tf )( T ) ]
E / RT
z= e
ln
( Zy )=(ER )( T1 )
lnz=
( ER )( T1 )+ ln y
Which is similar to
y=mx+C
10
Hence plot lnz vs 1/T to find the Pre exponential factor A and activation energy E.
Where,
= CBovA/CAovB
EQ 10
= -AvAvB Cp / H
EQ 11
2.
dT T i+1Ti
=
dt
t i+1ti
dT ( 29.429.0 ) K
K
=
=0.4
dt
s
( 3938 ) s
3. At t=38s
( Tf T =43.5 ( C ) 29.0 ( C )=14.5 ( C )=14.5 K
4.
z=1.90210
6.
1
Ks
7. Plot lnz
1
Ks
vs (1/T) K
1
Ks
11
-2
0
-3
Linear (Run 1)
Run 2
Linear (Run 2)
-4
-5
-6
lnz (1/Ks)
Linear (Run 1)
Linear (Run 2)
Run 3
Linear (Run 3)
Run 4
Linear (Run 4)
Run 5
-7
Linear (Run 5)
Linear (Run 5)
-8
Run 6
Linear (Run 6)
-9
1/T (K^-1)
12
E
1
8. From plot, comparing the linear plot to the equation lnz= R T +lny
( )( )
( ER )=25901
lny=78. 929
9. Hence,
1
Ks
1
Ks
y=e78.929 =1.89810 34
10. Hence
cm3
mols
( ER )=25901 K
J
[ 4]
molK
Where R = 8.314
Rearrange for E,
E=25901 K8.314
Run
1.33
1.66
4
Average
J
J
=215340
molK
mol
A'
cm 3
mols
3.14267E+2
3
7.29055E+3
8
1.26276E+3
2
1.88571E+3
0
9.21266E+3
0
9.20444E+4
2
1.53419E+4
E
J
mol
127304
215340.
9
175915.
9
165224.
1
169148.
3
237082
181669.
13
Table 5.9 of Arrhenius Parameters: Pre exponential factor A and Activation energy E
Calculation from runs 1-6
From Runs 3-6, the limiting reactant is Na2S2O3 while in run 1, the limiting reactant is
H2O2 and in run 2, both reagents were limiting. The calculation for defers in which
reactant is limiting.
The Graphs of the runs are included in the appendix.
Hence, the Average Pre exponential factor A and activation energy E from runs 1-6
are as follows:
A = 1.53419E+42
E = 181669.2
cm 3
mols
J
mol
6) Error analysis
If y=f(xi) is a function of N independent variables and xi is the uncertainty of the ith
variable
Then the resulting combination is being calculated using the formula below:
y
x i xi
N
()2
i=1
y =
Variable
Uncertainty ( xi )
T = 0.05
Temperature
v = 0.5 ml
Volume
Dependent variables and partial derivatives are given in the table below,
Dependent variable
Partial derivatives
14
H =
c p A (T f T 0 )(V A +V B )
CAV A
H c p A ( V A +V B )
=
Tf
CA V A
H c p A ( V A +V B )
=
T 0
CA V A
H c p A V B ( T f T 0 )
=
V A
CA V A2
H c p A ( T f T 0 )
=
VB
CAV A
E=mR
E
=R
m
ln y
'
e H
A=
A B c p
'
ln
A
e H
=
ln A B c p
A'
e ln
=
H A B c p
6.1) Error of C A 0C B 0
Common sense method is used to calculate the errors of concentration for reactant A&B
Sample calculation is carried out below for Run 2:
3
C B 0,nominal =0.0005
cm
mol
C B 0,max =
1
60+0.5
cm
=0.000506
=1.2
1000 1200.5
mol
C B 0,min =
1
600.5
cm
=0.000494
=1.2
1000 120+0.5
mol
1.2 +1.2
=1.2
2
15
CA
CB
6.2) Error of H
Enthalpy change is calculated from the equation given below,
H =
c p A (T f T 0 )
C A0
When mixing ratio is smaller than 1, hydrogen peroxide is the limiting reactant, and when it
is larger than 1 then sodium thiosulphate is the limiting reactant.
VA
C
=C
A
0
A
Given that
V A +V B
H =
c p A (T f T 0 )(V A +V B )
CAV A
H =
2
2
2
H
H
H
H
T f +
T0 +
V A +
VB
T f
T 0
V A
VB
)(
)(
) (
H 4.189 1 1 19.2
J
=
=1340.48
2
3
V A
0.001 60
mol c m
H 4.189 1 19.2
J
=
=1340.48
VB
0.001 60
mol c m3
H 4.189 1 120
J
=
=8378
Tf
0.001 60
mol K
H 4.189 1 120
J
=
=8378
T 0
0.001 60
mol K
c p A ( V A +V B )
CAV A
)(
Tf +
c p A ( V A +V B )
CA V A
)(
T0 +
c p A V B ( T f T 0 )
C A V A2
)(
V A +
c p A ( T f T 0 )
CA V A
J
= 1117.76 mol 0.69%
The combination errors for all runs are given in the table below:
The average percentage error for all six runs is 1.41% from the table above.
In order to calculate the errors of E and A, standard errors of the fitting line have to be
obtained, the formula for standard error is given as
s y .x
y yest 2 ,
N
sy .x 2
y 2 a y b xy
N
For our convenience, and also for higher accuracy, LINEST Function in Excel is used in our
calculation.
17
6.3) Error of E
E can be calculated from the gradient of the fitting line, therefore , we use the equation E=mR
J
Sample calculation for Run 2, when E= 215340.9 mol , m=1798.17
E=
2
E
J
m =8.314 1798.17= 14949.99
6.94
m
mol
Results for all other runs are given in the table below
The average percentage error for all six runs is 6.24% from the table above
6.4) Errors of A
Pre-exponential factor A is calculated from the equation
'
A=
eln y H
A B c p
In order to obtain the combination error for this dependent variable, we need the derivatives
with respect to the two independent variables in this formula, which are lny and H
A '=
2
A'
A'
lny +
H
lny
H
)(
18
78.93
A'
e
e
cm
=
=
=4.53 10 33
H A B c p 11 4.189
Js
The average percentage error for all six runs is 167.31% from the table above
19
For a liquid based adiabatic exothermic reaction between Sodium Thiosulphate and Hydrogen
Peroxide.
Based on our calculations obtained from the raw data of the experiment, we can say that the
highest temperature rise occurs when the Overall Reaction Stoichiometry is 1. This can
clearly be seen in Graph 5.1 of the report. The theoretical reason behind this maximum rise in
temperature to 43.5C in run 2 is that in this case both the reactants are in equimolar
quantities and are completely consumed by the end of the reaction leading to a release of
maximum heat. Talking about the trends of various mixing ratios in Graph 5.1 we see that the
temperature for all runs start increasing as soon as H2O2 is added in the adiabatic reactor and
as the reaction proceeds the curves starts becoming stable after reaching a maximum value. In
run 2 and run 5 the temperature decreases after reaching a maximum value but by a very
minor amount, which can be accounted as an experimental error due to loss of heat to the
surroundings. Once the maximum temperature has been attained the temperature then
remains constant as seen from the curves. This occurs when the reaction has been completed
where either one or both of the limiting reagents have been completely consumed and hence
there is no more heat released.
Talking about Graph 5.2 of the report which shows the temperature change in the reactor
against the volume of Na2S2O3 in the mixture we can see that the temperature change
increases as the volume of Na2S2O3 increases and reaches a maximum value of 19.2C when
the volume of Na2S2O3 is 60cm3. But then decreases as the volume of Na2S2O3 is further
increased. This is because at low volumes of Na2S2O3 it acts as the limiting reactant and the
reaction finishes when Na2S2O3 is completely consumed therefore releasing less heat.
However as the volume of Na2S2O3 increases the reaction continues for a longer duration thus
releasing more heat leading to increase in temperature. But after a certain quantity (60 cm3 in
this case) the volume of Na2S2O3 exceeds that of H2O2 (to maintain total volume of 120 cm3)
and in that case H2O2 acts a limiting reactant causing the reaction to finish as it is completely
consumed giving off lower heat that than the previous result. Graph 5.3 of the report shows
that the lowest temperature change occurs when the mixing ratio is 4. This result is expected
because at this mixing ratio volume of sodium thiosulphate in the mixture is very low (24
cm3) causing the reaction to end very soon with the complete consumption of Na2S2O3 thus
releasing the least amount of heat.
Average values of all runs calculated in this report have been summarised in the following
table:
Parameter
Overall Reaction Enthalpy (H)
Pre-exponential Factor (A)
181669.2 J/mol
Table 7.1: Average Values of all runs
Table 7.2 compares our calculated values for run 2 with the literature values:
vA/vB
Calculated
Values
Literature
Values [1]
H
(J/mol)
A
(cm /s.mol)
E
(J/mol)
-160,857.6
7.2881038
215,340
1.96
-596,600
71014
76,500
From the Table above we can see that our calculated values are quite different from the
literatures values but lie in the same range. This can be explained by considering the errors
that might have occurred while performing the experiment. Some of the potential sources of
experimental errors in this experiment have been mentioned below:
The small hole on the top of the adiabatic reactor might cause some of the heat to
release to the surroundings thus varying the temperature rise
There might be unreacted liquid droplets on the walls of the adiabatic reactor
Parallax error while measuring liquid quantity in the measuring cylinder
Some liquid might be left on the funnel while transferring it into the reactor
Error could due to different pouring rates of H2O2
The magnetic stirrer inside the adiabatic reactor might generate some heat leading to
incorrect temperature measurements
Not all liquid might have transferred from the measuring cylinder to the reactor and
could have been left as droplets on the walls of the measuring cylinder
The equipment used in the experiment could have trace impurities from other
mixtures which would have not been removed completely even after washing
Some errors could have been introduced into our calculations due to the uncertainty of
measuring devices i.e. thermocouple and measuring cylinder. These errors have been
accounted for in the Error Analysis of the report using combination of errors technique and
the following percentage errors have been obtained for our calculated values of run 2:
Parameters
H
E
A
Percentage Error
0.69%
6.94%
582.86%
21
From the table above we can see that the percentage error in Reaction Enthalpy calculation is
almost negligible (<1%) and thus does not affect our final result much. However errors in
calculation of activation energy and pre exponential factor are significantly high compared to
reaction enthalpy. This is because in our calculations, we have assumed Graph 5.4 as a linear
graph for ease of calculation of E and A. Also this large percentage error in the calculation of
pre exponential factor justifies the large difference amongst the literature and our calculated
A values.
The other reason for the difference in our calculated and literature values are the assumptions
made during the experiment. We have assumed that there are no heat losses during the
experiment but this is almost never true as some heat is always lost to the environment due to
radiation. In this experiment we also might have lost some heat through the hole on the top on
the adiabatic reactor. The second assumption made was that all the components of the
reaction were perfectly mixed. However in many instances some of the reactant might have
stuck on the wall of the reactor and would have been left unreacted. Hence these assumptions
could have played a major role in the deviation of our calculated values from the literature
values.
Various improvements could be made to the experiment to get better and more accurate
results. Some of them are mentioned below:
Use of a more advanced adiabatic reactor that better insulates the heat evolved during
the exothermic reaction to give more accurate and precise temperature rises.
Use of a larger stirrer to ensure uniform mixing while avoiding generation of
additional heat.
Use of an automatic mechanism for addition of H2O2 rather than manual addition to
ensure uniformity while performing the experiment with different mixing ratios.
To summarize the findings of this experiment we can say that in the reaction between H2O2
and Na2S2O3 the maximum rise in temperature occurs when both the reactants act as limiting
agents. Our calculated values though not very similar to the literature values lie in the same
range. Error analysis shows that there is negligible error in enthalpy calculation but a
relatively larger error in activation energy and pre exponential factor calculation due to the
assumption made in calculations.
22