ABSTRACT

Most chemical engineering processes are dominated by the need to react species to form desired

products. The dominant choice of a method of handling these reactions that is in

reactor design, estimation of the energy required for the reaction to occur, etc is the

essence of experiments such as this. The need to understand the mechanism of the
reaction: what affects the reaction and how the reaction is affected, is a major
motivation of the process.
Pseudo-first order reactions are reactions which have a concentration of an excess
reactant being constant while the other reactant is depleted during the reaction. In
this experiment, it was discovered that the reaction rate constants decreased
steadily with an increase in temperature. Also, the activation energy of the reaction
was observed to be moderate, implying that little heat is required to convert the
reactant to product. Titration was used to estimate the concentration of the limiting
reactant K2S2O8 that was converted to product.
Moreover, in this experiment, considerations are also given to the theory of the
pseudo-first order reaction process, method and calculation of the reaction rate
constants, activation energy and frequency factor, discussion and analysis of the
results of the experiment.

1
 TABLE OF CONTENTS
Title page
Abstract i
Table of contents ii

CHAPTER ONE- INTRODUCTION 1

1.1 Title of Experiment 1
1.2 Aims of the Experiment 1
1.3 Justification of Experiment 1

CHAPTER TWO- THEORY 3

2.1. Definition of Keywords 3
2.2. Pseudo-First Order Reaction 4
2.3. Variables Affecting the Rate of Reaction 6
2.4. Temperature Dependence of the Reaction Rate Constant 7

CHAPTER THREE- EXPERIMENTATION AND RESULTS 9

3.1. Definition 9
3.2. Apparatuses Used 9
3.3. Reagents Used 10
3.4. Experiment Procedure 10
3.5. Precautions Taken 11
3.6. Results of the Experiment 13
3.7. Graphs 14

CHAPTER FOUR- DISCUSSION 22

4.1. Result Analysis 22
4.2. Result Interpretation 24

CHAPTER FIVE- CONCLUSION/RECOMMENDATION 25

5.1. Conclusion 25
5.2. Recommendation 26

REFERENCES 27
APPENDIX 28

2
 CHAPTER ONE

INTRODUCTION
1.1. TITLE OF EXPERIMENT: Pseudo-First Order Reaction

In this Pseudo-First Order Reaction experiment, it is necessary to monitor the rate of

the reaction between two reactants KI and K 2S2O8, with one reactant (KI) in excess.
To determine this rate, the concentration of the un-reacted KI at appropriate time
intervals is calculated from the concentration of the I2 product formed. The
concentration of the product can be obtained using a titration method.

1.2. AIMS OF THE EXPERIMENT

The aims of the experiment are as follows:

I. To determine the velocity constant/rate constant, k of the pseudo-first order

reaction of K2S2O8 in excess KI, at four different temperatures.
II. To calculate the activation energy of the entire reaction.
III. To calculate the frequency factor/Arrhenius constant, A, for the reaction.

1.3. JUSTIFICATION OF THE EXPERIMENT

Chemical reactions are usually accompanied by the absorption or evolution of energy

due a difference in the structures of the reactants and products. The rate at which
the reactants are converted to products in these chemical reactions is a very
important property of the reaction. This rate may vary from a very large value (for
instantaneous reactions) to essentially zero (when no reaction occurs).

3
However, through experimentation, the rates at which industrially important
reactions take place can be obtained. The energy transfer required for the
conversion of the reactants to products could then be calculated using the
experimentally obtained values of the rates of the reactions. Then, the design of a
reactor for the reaction(s) will be done to suit the nature and requirements of the
reactions.

4
 CHAPTER TWO

THEORY
2.1. DEFINITION OF KEYWORDS

Activation Energy, Rate Constant, Rate-Controlling Step, Rate Equation, Rate of

Reaction, Frequency factor

I. Activation Energy: A parameter associated with the Arrhenius equation and

considered by Arrhenius as the energy in excess of the average energy level of
reactants required to enable the reaction to proceed.
II. Rate Constant: A proportionality constant in the rate equation. The rate
constant is markedly influenced by temperature and, to lesser degree, by pressure
and the presence of catalysts.
The units and value of the rate constant depend on the specific chemical component
to which it refers, the units for concentration (or other quantity) of the component,
and the reaction order.
III. Rate-Controlling Step: The slow steps that tend to control the overall rate of
reaction. In a complex reaction consisting of several chemical reaction steps (and
physical process steps in heterogeneous reaction), the reaction rate (and physical
process rate) of one or more steps may be much slower than other steps.
IV. Rate Equation: A functional expression describing the relationship between
the rate of reaction and the amounts (e.g., concentrations) of selected chemical
components participating in the reaction at any time under isothermal condition.
V. Rate of Reaction: The amount of a chemical component of concern being
converted or produced per unit time per unit quantity of a reference variable.
Examples of the reference variable include the volume of reacting mixture, the
reactor volume, the mass of solid (solid-fluid reaction), and the surface area of solid.
VI. Frequency Factor: in the Arrhenius equation, a constant indicating how many
collisions have the correct orientation to lead to products. The pre-exponential factor
is a function of temperature. As we see in the above table, the factor for the collision
theory and the transition state theory are both responsive to temperature changes.

5
The factor for the collision theory is proportional to the square root of T, while that
of the transition state theory is proportional to T. The empirical factor is also
sensitive to temperature. Intuitively, as temperature increases, molecules will begin
to move faster and as molecules move faster they are more likely to collide and
therefore effect the collision frequency, A. The frequency factor, A, depends on how
often molecules collide when all concentrations are 1 mol/L and on whether the
molecules are properly oriented when they collide.

2.2. Pseudo-First Order Reaction

Measuring a second-order reaction rate with reactants A and B can be problematic:
The concentrations of the two reactants must be followed simultaneously, which is
more difficult; or measure one of them and calculate the other as a difference, which
is less precise. A common solution for that problem is the pseudo-first order
approximation.

A second order reaction for the above equation has the rate equation
[ ][ ] because it involves two reactants, A and B. However, in a
pseudo-first order reaction, it is possible to manipulate the initial concentrations of
the reactants. One of the reactants, B, for example, would have a significantly high
concentration, while the other reactant, A, would have a significantly low
concentration, that is, [B]>>[A]. Then, we assume that reactant B's concentration
remains constant during the reaction because its consumption is so small that the
change in its concentration becomes negligible. Because of this assumption, the
reaction rate, k’, is multiplied with the concentration of the reactant with assumed
constant concentration, B, to create a new rate constant, k, [ ] ). This new
rate constant, k, will be used in the new rate equation to give, [ ], as the new
rate constant so that the second order reaction can be treated as a first order
reaction.

6
Another way to create a pseudo-first order reaction is to manipulate the physical
amounts of the reactants. For example, dumping a litre of 5M HCl into a 55M ocean
does not change the concentration of the ocean. The concentration of the mixture
would be closer or equal to that of the ocean because there is so much water
physically compared to the HCl, and also because 55M is relatively larger compared
to 5M.
In theory, if we have an instance where there are more than two reactants involved
in a reaction, it is possible to make the reaction appear like it is first order. If there
were three reactants, for example, we can make two of the three reactants be in
excess (whether in amount or in concentration) and then monitor the dependency of
the third reactant.

The pseudo-first order reaction equation could also be written as:

[ ] [ ] [ ]
[ ] [ ]

Finding the natural log of both sides of the pseudo-first order equation we get:

[ ] [ ] [ ] [ ] [ ]

Also, it could be written into another form:

[ ]
) )

Where,

[A]o is the initial concentration of A,

[B]o is the initial concentration of B,

k is the pseudo-first order reaction rate constant,

k’ is the second order reaction rate constant,

x is the concentration of A that has been converted to product, and

7
[A] = a is the concentration of A at time, t

However, when calculating the true rate constant, k’, the apparent rate constant, k,
must be divided by the [B], which is present in excess.

The overall stoichiometry of the reaction describes the reactants and products of a
reaction and tells us the proportion in which they react. It doesn't tell us how the
reaction proceeds. But, the rate expression describes the step which determines the
overall rate of the reaction. The combination of these two allows us to propose a
reaction mechanism, a molecular description of the reaction occurring.

2.3. Variables Affecting the Rate of Reaction

Many variables may affect the rate of a chemical reaction. Some of these variables
are: temperature, pressure, and composition. This implies that a change in any of
these factors will have a consequent impact on the rate of the chemical reaction. In
addition, the rate of heat transfer may also become a factor.

For instance, if we consider an exothermic reaction taking place at the interior

surfaces of a porous catalyst pellet and the heat released by reaction is not removed
fast enough, a severe non-uniform temperature distribution can occur within the
pellet, which in turn will result in differing point rates of reaction. These heat and
mass transfer effects become increasingly important the faster the rate of reaction,
and in very fast reactions, such as burning flames, they become rate controlling.
Thus, heat and mass transfer may play important roles in determining the rates of
chemical reactions.

8
2.4. Temperature Dependence of the Reaction Rate Constant

The number of collisions between the molecules of gases and liquids under normal
conditions is so high that if any collision between reactant molecules led to the
formation of the reaction product, all reactions would proceed virtually
instantaneously. But, this does not happen in practice. For a reaction to occur, it
requires a definite amount of energy. If the colliding molecules do not possess this
energy, a collision between them does not result in the formation of a new molecule.
For many reactions, and particularly elementary reactions, the rate expression can
be written as a product of a temperature-dependent term and a composition
dependent term. For such reactions the temperature-dependent term, the reaction
rate constant, has been found in practically all cases to be well represented by
Arrhenius' law:

Where A, is called the frequency or pre-exponential factor and E is called the

activation energy of the reaction. The Boltzmann factor represents the fraction
of the collisions which are energetic enough to lead to a reaction.
This expression fits experiment well over wide temperature ranges and is strongly
suggested from various standpoints as being a very good approximation to the true
temperature dependency.

At the same concentration, but at two different temperatures, Arrhenius' law

indicates that provided that E stays constant,

( )

9
 CHAPTER THREE

EXPERIMENTATION AND RESULTS

3.1. DEFINITION: Pseudo-First Order Reaction

This experiment entails the evaluation of the activation energy and the frequency
factor for the reaction, when it occurs as a pseudo-first order reaction.

3.2. APPARATUSES USED

The apparatuses used in this experiment are:
Pipette, Burette, Conical Flasks, Thermometer, Retort Stand, Stirrer, Stove, Water
Bath, Measuring Cylinder Indicator Dropper

I. Pipette: a small glass tube that liquid is drawn into so that it can be
measured, often before it is delivered to another container.
II. Burette: a glass tube with measurements marked on the side and a
stopcock at the bottom. It is used in laboratories to release an accurately
measured quantity of liquid.
III. Conical Flasks: these are conical glass vessels used to collect the reagents
for heating and mixing.
IV. Thermometer: This is an instrument used to measure temperature. It was
used to measure the temperature of the reagents while they were heated
up in the water bath.
V. Retort Stand: this is the stand that was used to hold the burette upright
while the titration process took place.
VI. Stirrer: this was used to stir the reaction mixture during the experiment, to
ensure that the contents are properly mixed together.
VII. Stove: this is a heating device used to heat the water bath that was used in
the experiment.

10
 VIII. Water Bath: this consists of a basin containing water. The stove heats the
water and as the reagents are inserted into the water bath, they are
heated too.
IX. Measuring cylinder: a graduated glass vessel used to measure the KI and
K2S2O8 solutions to their required volumes
X. Indicator Dropper:

3.3. REAGENTS USED:

a) 600ml of 0.05M Potassium Iodide, KI
b) 300ml of 0.01M K2S2O8 solution
c) 0.001M of Na2S2O3 solution
d) Glacial CH3COOH indicator
e) Starch indicator
f) Water

3.4. EXPERIMENT PROCEDURE:

I. We measured 200ml of 0.05M potassium Iodide, KI, solution and put it in a

conical flask.
II. We measured 100ml of K2S2O8 and put in a separate flask.
III. Then, we measured 1ml of glacial CH3COOH and added it to the flask that had
the potassium iodide solution in it.
IV. The two flasks containing the KI and K2S2O8 solutions were heated separately
in a hot water bath, until they were brought to the required temperature of T1=30°C.
This temperature was measured using a mercury-in-glass thermometer.
V. Immediately after heating, we then poured the KI and K2S2O8 solutions
together into another flask. We stirred the solution continuously, so as to ensure the
complete mixing of the reagents.

11
VI. As soon as we poured the reagents into the flask, we started timing the
process.
VII. After time, t1=3min, we collected a 10ml sample of the solution into another
clean flask, using a pipette. Still, the stirring of the solution continued. Two drops of
starch indicator were introduced into the 10ml sample.
VIII. A solution of 0.001M sodium thiosulphate, Na2SO3, was poured into a clean
and functional burette. The 10ml sample was titrated with the Na 2SO3 solution. The
initial and final volumes of the Na2SO3 solution, before and after the titration, were
recorded and the difference calculated as the titre value for that sample at that time
and temperature.
IX. While the timing continued, steps VII-VIII were repeated for time, t2=8, t3=15,
t4=20, t5=30 and t2=40 min. The different titre values were also recorded.
X. Also, we repeated steps I-IX for different reaction temperatures, T2=35, T3=40
and T4=45°C. The titre values at the different times and temperatures were
recorded.

3.5. PRECAUTIONS TAKEN:

I. We carefully measured out the required volumes of KI and K2S2O8 solutions

into clean flasks.
II. We stirred the mixture of KI and K2S2O8 thoroughly and continuously, to
ensure uniform distribution of the species within the entire solution.
III. By placing each of the reactants in separate flasks, heating them together in
the water bath and measuring the temperatures of each solution, we ensured that
the temperatures of the KI and K2S2O8 solutions were uniform and that they were as
close as possible to the same temperature.

12
IV. We ensured that the burette was functioning well before we poured the
Na2S2O3 solution into it. This was done so as to avoid any delay, as result of a faulty
burette, while 10ml samples of the mixture were being withdrawn for titration.
V. In order to ensure accuracy during the experiment, we made sure that
different team members monitored the stirring of the reaction mixture, the timing of
the reaction, the titration of Na2S2O3 over each 10ml sample, and the reading and
recording of the titre values, simultaneously.
VI. We ensured that the 10ml samples were pipetted and collected into a clean
flask immediately the time had elapsed.
VII. Throughout the experiment, we used two drops of starch indicator for each
10ml sample withdrawn from the reaction mixture. This was done to ensure that the
removal of the blue-black colour from the sample was uniform throughout the
experiment.

13
3.6. RESULTS OF THE EXPERIMENT

GIVEN:

Initial Concentration of KI, [KI] = 0.05mol/dm3

Initial Concentration of K2S2O8, a = 0.01 mol/dm3

Concentration of Na2SO3, [Na2SO3] = 0.001N = 0.001mol/dm3

TABLES

Table of the titre values obtained for each temperature, at the specified time

T=30°C T=35°C T=40°C T=45°C

Time, t (min) Titre Values (ml)
3 1.65 0.9 2 2.1
8 2.15 1.7 2 2.1
15 3.2 2.7 2.5 2.2
20 4.35 3.1 2.5 2.4
30 6.2 4.4 3 2.7
40 6.35 4.5 4 3.5

A.

T=30°C
Time, t(min) Titre Values (ml) x (mol/dm3) )
3 1.65 0.0000825 2.0036
8 2.15 0.0001075 2.0047
15 3.2 0.0001600 2.0070
20 4.35 0.0002175 2.0096
30 6.2 0.0003100 2.0137
40 6.35 0.0003175 2.0140

14
B.

T=35°C
Time, t(min) Titre Values (ml) x (mol/dm3) )
3 0.9 0.000045 2.0020
8 1.7 0.000085 2.0037
15 2.7 0.000135 2.0059
20 3.1 0.000155 2.0068
30 4.4 0.000220 2.0097
40 4.5 0.000225 2.0099

C.

T=40°C
Time, t(min) Titre Values (ml) x (mol/dm3) )
3 2 0.000100 2.0044
8 2 0.000100 2.0044
15 2.5 0.000125 2.0055
20 2.5 0.000125 2.0055
30 3 0.000150 2.0066
40 4 0.000200 2.0088

D.

T=45°C
Time, t(min) Titre Values (ml) x (mol/dm3) )
3 2.1 0.000105 2.0046
8 2.1 0.000105 2.0046
15 2.2 0.00011 2.0048
20 2.4 0.00012 2.0052
30 2.7 0.000135 2.0059
40 3.5 0.000175 2.0077

15
 3.7. GRAPHS

A Graph of -Log (a-x) against time, t(min)

at 30°C
2.016

2.015

2.014

2.013

2.012
y = 0.0003x + 2.0027
2.011

2.01

2.009
-Log (a-x)

2.008

2.007

2.006

2.005

2.004

2.003

2.002

2.001

2
0 5 10 15 20 25 30 35 40 45
Time, t(min)

16
 A Graph of -Log (a-x) against time, t(min)
at 35°C
2.016

2.015

2.014

2.013

2.012

2.011 y = 0.0002x + 2.002

2.01

2.009
-Log (a-x)

2.008

2.007

2.006

2.005

2.004

2.003

2.002

2.001

2
0 5 10 15 20 25 30 35 40 45
Time, t(min)

17
 A Graph of -Log (a-x) against time, t(min)
at 40°C
2.016

2.015

2.014

2.013

2.012

2.011

2.01

2.009
-Log (a-x)

y = 0.0001x + 2.0036
2.008

2.007

2.006

2.005

2.004

2.003

2.002

2.001

2
0 5 10 15 20 25 30 35 40 45
Time, t(min)

18
 A Graph of -Log (a-x) against time, t(min)
at 45°C
2.016

2.015

2.014

2.013

2.012

2.011

2.01

2.009
-Log (a-x)

2.008

y = 8E-05x + 2.0039
2.007

2.006

2.005

2.004

2.003

2.002

2.001

2
0 5 10 15 20 25 30 35 40 45
Time, t(min)

19
 A Graph of -Log (a-x) against time, t(min)
at 30, 35, 40 and 45°C
2.016

2.015

2.014

2.013

2.012

2.011

2.01

2.009
-Log (a-x)

2.008

2.007

2.006

T=30C
2.005
T=35C

T=40C
2.004
T=45C

2.003 Linear (T=30C)

Linear (T=35C)
2.002 Linear (T=40C)

Linear (T=45C)
2.001

2
0 5 10 15 20 25 30 35 40 45
Time, t(min)
20
 A Graph of -ln k against 1/T
10

9.5

8.5
-ln k

7.5
y = -8986.8x + 36.937
7

6.5

6
0.00312 0.00314 0.00316 0.00318 0.0032 0.00322 0.00324 0.00326 0.00328 0.0033 0.00332
Temperature -1, 1/T(°C-1)

Determination of the Reaction Rate Constants, k

From the slopes of Graphs 1-4 plotted above, the reaction rate constant,

k = 2.302 x slope

Hence, the reaction rate constants for each temperature are:

At 30°C; k1 = 6.91 x 10-4 min-1

At 35°C; k2 = 4.62 x 10-4 min-1

At 40°C; k3 = 2.30 x 10-4 min-1

At 45°C; k4 = 1.84 x 10-4 min-1

21
The average reaction rate constant,

Determination of the Activation Energy, E, and Frequency Factor, A of the Reaction

From the above equations, the activation energy of the reaction, E, is from the slope
of the graph of –ln k against 1/T.

Also, the value of the frequency factor is the inverse natural log of the y-intercept of
the graph.

Hence,

Therefore, the activation energy, E for the reaction is 74716.25KJ/mol.

Also,

Therefore, the frequency factor, A for the reaction is 1.1 × 1016 min-1.

22
 CHAPTER FOUR

DISCUSSION
4.1. RESULT ANALYSIS

Reaction Equation:

According to the equation relating the reaction rate constant of the reaction to the
concentration of K2S2O8, the concentration of the reactant at each time, t, was
derived from the titration of a 10ml sample of the mixture with sodium thiosulphate
solution. As the reaction progressed, iodine was formed as product. Initially, the
concentration of iodine was zero, but with time, the concentration increased. A
particular volume of sodium thiosulphate reacted with the iodine (which had been
coloured blue-black by the starch indicator) in the sample to form products. As soon
as the iodine was depleted, the blue-black coloration disappeared.

Hence, according to the following relation, the concentration of the iodine product in
the 10ml sample which is equivalent to the concentration of the reactant converted
to products was calculated.

Titration Reaction:

From the stoichiometric titration equation above,

[ ]
[ ]

This is re-written as,

[ ]

Therefore, the volume of the NaS2O3 solution which was titrated over the 10ml
sample is a function of the concentration of the limiting reactant that had been
converted to product.

23
The equation,

gives the relationship between the concentration of the reactant converted to

product, x, and the time, t, taken for the conversion. Graphs 1-4 were plotted based
on this equation. Their slopes were gotten and used to calculate k for each reaction
temperature. The positive slope of the graphs reflects that as time increased, the log
of the concentration of the unreacted K2S2O8 reduced. This is because the reactant
was being converted to product.

Also, on Graph 5, the relationship among the graphs at different temperatures was
revealed. As the reaction temperature increased, from 30-45°C, the sloppiness of
each graph reduced, meaning that k also reduced.

From the Arrhenius equation,

and from Graph 6, the slope of the graph was negative which indicates that as
temperature increased, the natural log of k decreased. The intercept on the vertical
axis of the graph was the natural log of the frequency factor.

24
4.2. RESULT INTERPRETATION

In this experiment, we have considered a reaction whose rate depends on

temperature alone. From the results above and the analysis given, the following
interpretation is made. An increase in temperature for this reaction will inhibit the
conversion of reactants to products. This also means that a more steady temperature
distribution will likely favour the reaction even more.
Furthermore, the reaction has a moderate activation energy which implies that little
heat or no heat is required for the reaction.

25
 CHAPTER FIVE

CONCLUSION/RECOMMENDATION
5.1. CONCLUSION

In this experiment, we have reacted KI which is in excess together with K 2S2O8 to

produce products at different temperatures and also to monitor the rate of the
reaction with change in temperature. The reaction was carried out as a pseudo-first
order reaction rather than a second order reaction, since KI was in excess. The
reaction rate constants for each temperature were evaluated from the graphs
plotted. And, the activation energy for the reaction, as well as the frequency factor,
was obtained.

In an ideal situation, the rate of most reactions increases rather than decrease with
an increase in temperature. However, as obtained from this experiment, the reaction
rate constants decreased. This anomaly could be traced to an arbitrary
approximation of the volume of the iodine product in the 10ml sample of the
reaction mixture, at each specified time and temperature.

26
5.2. RECOMMENDATION

For future experimentation on pseudo-first order reactions, a relation for obtaining

the volume of the iodine constituent of the 10ml sample of the reaction mixture with
respect to change in time should be used.

Also, a means of maintaining the temperature of the reaction mixture could be

employed, such as an insulation of the vessel containing the mixture, so as to ensure
a steady temperature for the whole period, while the samples are collected.

Aside from the above, the report gives an acceptable description of the experiment
and thus can be adopted for further analysis.

27
 REFERENCES
Obibuenyi J. I., “Laboratory Manual on CHE 310: Chemical Engineering
Lab 2- Pseudo-First Order Reaction”, FUT Owerri.

Octave L., “Chemical Reaction Engineering: Homogenous Reactions in

Ideal Reactors”, 3rd Edition, Wiley, pp. 7-29.
Ronald W. M., Charles A. M., “Introduction to Chemical Reaction Engineering and
Kinetics”, pp. 42-57

Salil K. G., Shyamal K. S., “Introduction to Chemical Engineering: Chemical Kinetics”,

Tata McGraw Hill Education Private Limited, pp. 304-320.

28
 APPENDIX

Reaction Equation:

Titration Reaction:

Calculation of the Concentration of the Product (Iodine), x

[ ]

Where [NaS2O3] = 0.0001M

At 30°C,
t=3 min;
t=8 min;
t=15 min;
t=20 min;
t=30 min;
t=40 min;
At 35°C,
t=3 min;
t=8 min;
t=15 min;
t=20 min;
t=30 min;
t=40 min; M

At 40°C,
t=3 min;
t=8 min;
t=15 min;
t=20 min;

29
 t=30 min;
t=40 min;
At 45°C,
t=3 min;
t=8 min;
t=15 min;
t=20 min;
t=30 min;
t=40 min;

Calculation of –log (a-x)

At 30°C,
t=3min; ) )
t=8min; ) )
t=15min; ) )
t=20min; ) )
t=30min; ) )
t=40min; ) )

At 35°C,
t=3min; ) )
t=8min; ) )
t=15min; ) )
t=20min; ) )
t=30min; ) )
t=40min; ) )

At 40°C,
t=3min; ) )
t=8min; ) )
t=15min; ) )
t=20min; ) )
t=30min; ) )
t=40min; ) )

30
At 45°C,
t=3min; ) )
t=8min; ) )
t=15min; ) )
t=20min; ) )
t=30min; ) )
t=40min; ) )

31