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Chemistry 1

Lab 5

Rates of Chemical Reactions

Students name: Azamat Amzebek (201493886)

Lab partners name: Nurdaulet Altynbekov (201374364)

Tutors name: Jorge Oa Ruales

Date: 17.10.16
Abstract

1. Introduction
One of the main branches of chemical thermodynamics
which deals with time and rate of chemical reaction is kinetics.
Chemical kinetics involves investigations of how different physical
and chemical conditions can influence the reaction rate or speed
and tries to determine the reaction mechanism. This experiment
consists of two parts. First part investigates the dependence of
rate of reaction on concentration and determination of reaction
order. Second part involves kinetic analysis of reaction at different
temperatures. The reaction that will be analysed in this work is
called Iodine Clock Reaction. First introduced by Hans Heinrich
Landolt in 1886, it remains as one of the most important reactions
to understand chemical kinetics. There are some variations of this
process and most famous involves reactions of bromate and
iodine, with subsequent reduction with persulfate.

2. Theory
The main aim of the experiment is to analyse the kinetics of
the following reaction:

6 I-(aq) + BrO3-(aq) + 6 H+(aq) 3 I2 (aq) + Br-(aq) + 3 H2O

To identify the completion or point, when known amount of


reagent have been reacted, should be known. At this point, a so
called clock reaction have been implemented.

I2(aq) + 2 S2O32-(aq) 2 I-(aq) + S4O62-(aq)

Amount of iodine, I2, produced in first reaction, will react with


thiosulfate until it is present. Once there is no S 2O32-, iodine will
accumulate in the solution, which is easily identifiable in presence
of starch indicator. By using above method, the exact amount of
bromate reacted can be found and measuring the time rate is
calculated.

There are various factors that can affect the rate of proceeding
reaction. The most significant deviation occurs due to change of
temperature, concentration, from nature of reactants and
presence of catalyst. Reacting particles should come in direct
contact and should have sufficient energy to collide. This factor is
affected by surface area of reacting substances. Changing the
concentration of reagent will increase probability of colliding
those increasing the rate of reaction. By increasing the
temperature of system one increases the kinetic energy of
particles. This results in increased velocity of molecules and
greater proportion of collisions. Also, adding catalyst can greatly
enhance the reaction rate. Depending on different types of
catalyst mechanism of actions can vary.

In this experiment alteration of temperature and concentration


has been conducted. The taken data can be used to calculated
the reaction rate and order of reaction. From the rate law:

I


Br O 3

+
H




rate=k

Where k is the specific rate constant, m, n and p are orders of the



I
+
reaction and , H are concentration of reagents. Here
Br O3

specific rate constant, k, has definite value independent of


concentration. The characteristic is unique to each reaction and
depends only on temperature. Due to small amount of thiosulfate
reacting with iodine ions the concentrations of reacting agents in
first equation are assumed to be constant. The rate of reaction
can be mathematically expressed as:

Rate of disappearance of Br O3 =


Br O3


Br O3
changeconcetration of =
changetime

Minus sign indicates that concentration of bromate is decreasing.

For qualitative explanation of chemical kinetics due to effect of


temperature equations of Vant Hoff and Arrhenius can be used.
But application of first equation is restricted to small range of
temperature. Arrhenius equation:
Ea
k ( T )=A exp [ ]
RT

Where R is gas constant, Ea is activation energy, A is


preexponential multiplier. Activation energy can be explained as a
barrier, that should be overcome to procession of reaction.

3. Method

Part A.

This part investigates the rate of reaction due to change in


concentration. To control the amount of each reagent added to
mixture, different of volumes will be added. For convenience one
pipette for each reagent have been appointed. Two separate
reaction mixture should be prepared to avoid reaction initiation
before recording. First flask contains potassium iodide, sodium
thiosulfate and water. Second flask contains potassium bromate
and hydrochloric acid. Volumes of each reagent have chosen
according to concentration in Table 1. Also starch indicator have
been added to second flask. Depending on the concentration of
indicator number of drops can vary, but to have distinct color
change starch have been added in excess. The initiation of
reaction starts right after mixing to flasks and time have been
recorded until blue color appears, indicating presence of excess of
iodine.

Part B.

The same procedure has been repeated in this part, but at


different temperature. First part has been conducted at room
conditions. To analyze parametric change in rate constant two
temperatures has been chosen. By dropping temperature to
approximately to 278K, rate slowdown has been conducted.
Dropping until freezing point of water is time consuming, so can
be eliminated. Second observation is done at 313K, using heating
mantle.

4. Materials
5. Results and Discussion

Part A.

The rate of reaction is calculated as:



Br O3


Br O3
Changeconcentrationof =
timerequired for change
Rate=

Br O3
Here , amount of bromate reacted during this time, can be

found from moles of thiosulfate, which reacts until completion.


Unlike in the manual the absolute rates have been calculated.
Using relative rates, it is easy to determine order of reaction, but
absolute rate gives real understanding about nature of proceeding
reaction.


Br O3

So, rate of reaction for reaction mixture 1 becomes:



Br O3


r 1=

Rates for all 5 reactions are tabulate in Table 1.

From the rate law equation of this reaction is:



I


Br O 3

+
H




rate=k

To evaluate the reaction orders, rates of two reactions with


different concentrations of reagents should be divided.

I

1


Br O3

+
H

p


I

2


Br O3

+
H

p


I

1

m


I

2









k
r2
=
r1
4.0 10
2.0 10
m 4.0 103 m m
(3) =( ) =2
2.0 103
(3) m

r2
=1.84=
r1

log ( 1.84)
m= =0.880 1
log ( 2)

The reaction order by Iodine is equal to one. The same


calculations have been for bromate and hydrogen ions:

Br O3

1.6 10
8.0 10
(3)n =2n
(2)n

r3
=2.21=
r1

log ( 2.21)
n= =1.14 1
log ( 2)

H

+

r4 (0.04)n n
=3.77= =2
r1 (0.02)n

log ( 3.77)
p= =1.92 2
log ( 2)
Rate of each reaction has been calculated and reaction orders are
known. Using data above rate constant of clock reaction can be
calculated:

I


Br O3

+
H

2




r
k 1= 1

The rate constant of each reaction has been calculated in the


same manner and tabulated in Table 1. The value for k should be
same for every reaction and similar data has been observed. The
average of these values is:
22.64 +20.83+25.04+21.34 +22.52
k= =22.47
5

Table 1. Part A data

Reacti Tempe- [I-], M [BrO3-], [H+], Tim Absolute Rate


on rature, M M e, s Rate, M/s constant,
mixtur K k
e
2.010 8.010- 1.4491
1 293.65 0.02 230 22.64
-3 3
0-7
4.010 8.010- 2.6671
2 293.95 0.02 125 20.83
-3 3
0-7
2.010 1.610- 3.2051
3 294.15 0.02 104 25.04
-3 2
0-7
4 293.15 2.010 8.010- 0.04 61 5.4641 21.34
-3 3
0-7
1.610 4.010- 1.2971
5 294.15 0.03 257 22.52
-3 3
0-7

Part B.

In this part of the experiment the kinetics of clock reaction have


been analyzed at different temperatures. To determine the
activation energy Ea of this reaction Arrhenius reaction has been
implemented:
Ea
ln k = +constant
RT

By plotting ln k against 1/T, a linear slope has been obtained,


which is equal to -Ea/R

lnk vs 1/T
5

4 f(x) = - 4997.27x + 20.37


R = 0.97
3

ln(rate constant)
2

0
0 0 0 0 0 0 0 0 0 0 0

1/Temperature

From the equation of linear relation, the activation energy has


been calculated:
J
Ea =m R=(4997.3 ) 8.314=41548 =41.55 kJ /mol
mol
Table 2. Part B data

Rate constant,
Temperature, K Time, s Rate, M/s
k
278.15 425 7.84310-8 12.25
293.65 230 1.44910-7 22.64
313.15 58 5.74710-7 85.53

Using the calculated value for activation energy preexponential


multiplier A can be calculated.

A=k exp [ ]
Ea
RT
=22.64 exp[ 41548
]
8.314 293.65
=556.8 106

Other method of finding A is using constant from line equation.


ln A=20.37

20.37 6
A=e =702.4 10

Second value considers two other temperatures, so A has been


taken as an average.

Part A consist five measurements with different concentration of


reagent. The time recorded from reaction initiation until
thiosulfate depletion have been observed from color change due
to presence of indicator. Starch used in experiment has been
prepared by dissolution and to avoid undissolved particles
solution has been heated. Due to small concentration of indicator
it is difficult to identify exactly the color change. Instead of blue
light solution with bluish shade appears, which can be confused
with original color. To obtain distinct color high amount of
indicator have been added with risk of increasing the temperature
with heated solution of starch. This alteration in time identification
result in deviation in rate constant and non-integer reaction order.
Also in calculation of reaction rate and rate constant,
concentration of thiosulfate has been considered as negligible
relative to reactant and they remain constant.

Second part of experiment consist procedures where heating and


cooling processes involved. To drop the temperature of solution to
278K ice bath has been used and to keep the mixture at this
constant temperature is burdensome. Heating of solution has
been made on heating mantle and adjusting two flasks with
mixtures to same temperature is difficult. During reaction, there is
always deviation in temperature. This results in change rate
constant and reaction rate.
6. Conclusion

References
Post lab Questions

1. Explain how and why a decrease in reactant concentration will


affect the rate of a chemical reaction? (2marks)
Changing the concentration of reactant in a system will
change the number of particles or molecules per unit volume.
More molecules present in a given volume, the greater chance
of their colliding and vice versa. Hence, decreasing the
concentration of a solution decreases number of collisions and
therefore the rate of reaction.

2. Looking at your results from Part B, explain the relationship


between the temperature and rate of a reaction. Give a
physical explanation for this. What is occurring at the molecular
level? (2 marks)
From part B It has been observed that increasing the
temperature of system results in increased rate of reaction.
Inversely, by decreasing the temperature reaction proceed
slowly.
Temperature is a measure of the average kinetic energy,
those increased energy causes particles to move with higher
velocity. Therefore, number of collisions in a given period of
time will increase.

3. In Part A, even though the concentrations of the reactants are


changing in each trial, the experimental values of the rate
constant (k) for each trial should be similar. Do your results
from Part A support this? (1 mark)
K is specific rate constant independent of concentration of
reactants. In part A calculated values for k has been around
22.5, which proves initial statement.

4. From the Ea and A you determined in this experiment, calculate


the rate constant at 85oC. Would your observed reaction rates
for the experiment have changed if you had doubled the
volume of each solution used in the experiment? Explain (3
marks)
From Arrhenius equation:

[ ]
Ea
RT
=702.4 106
[ 41548
8.314 (273.15+85)]= 612.0

k= A exp

It should be noted that k is an absolute rate constant, unlike


relative k given in manual. Dramatic change in constant can be
observed proving that increasing temperature causes the rate to
increase.

By doubling the volume of each solution added into mixture,


concentration of reactant stays constant. Those there is no
change in reaction rate.