Experiment No.

3
CHEMICAL KINETICS

Adam Jo J. Elatico
Institute of Chemistry, University of the Philippines, Diliman, Quezon City, Philippines

RESULTS AND DISCUSSION
The determination of the free energy of the system (G) is vital for evaluating the spontaneity of
a reaction system. But this does not signify the rate (whether slow or fast) of the reaction. Thus, chemical
kinetics is used to assess the problem.
Chemical kinetics deals with how rates of chemical reactions are determined, how they can be
predicted and how to use data obtained to suggest probable reaction mechanisms (Petrucci, Herring,
Madura and Bissonnette, 2011). Different factors which affect the rate of the reaction were investigated,
namely: concentration, temperature and presence of a catalyst.
In the experiment to determine the rate law of the reaction between thiosulfate and hydronium
ion, the effect of changing the concentration was studied. The balanced chemical equation is
Na
2
S
2
O
3
(aq)

+ 2HCl (aq)

2NaCl (aq) + S (s)

+ SO
2
(g) + H
2
O (l) (1.0)
with net ionic equation of
S
2
O
3
2-
(aq) + 2H
+
(aq) S(s) + SO
2
(g) + H
2
O(l)
where the following data were obtained.
Table 1. Summary of Data for Determination of Effect of Change in Concentration
Run Time
(s)
1/Time
(s
-1
)
Volume of 0.15
M S
2
O
3
2-
(mL)
Volume of
water (mL)
Volume of 3M
HCl (mL)
[S
2
O
3
2-
]
initial
[H
+
]
initial
1 21.0 0.0476 10.0 3.0 2.0 0.1 0.4
2 43.2 0.0231 5.0 8.0 2.0 0.05 0.4
3 115.4 0.00867 2.5 10.5 2.0 0.025 0.4
4 22.82 0.0438 5.0 1.0 1.5 0.1 0.6
5 23.25 0.0430 5.0 1.5 1.0 0.1 0.4
6 25.66 0.0390 5.0 2.0 0.5 0.1 0.2

Given the balanced chemical equation, the rate is given by the change in the concentration of the products
or reactants with respect to time. For any hypothetical reaction
aA + bB cC + dD (1.1)
the International Union of Pure and Applied Chemistry recommends that a general rate of reaction be
given by
rate =

[]

[B]

[]

[]

(1.2)
where the negative sign in the rate of the reactants denote a disappearing or decreasing rate vis--vis the
positive rate of the products denote build up or appearance. Equation (1.2) could be used in determining
the rate of the reaction between thiosulfate and hydronium which is given by
rate =
[S

-
]

=
[S]

=
[S

=
[

In this reaction, sulfur deposit increases in the form of a white solid. The completion of the formation of
this element serves as the end of the reaction manifested by the slow accumulation of sulfur which
makes the x-mark on the paper, placed on the bottom part outside of the beaker, invisible.
After the experiment, the data for the time of completion of the reaction were recorded. The rates
of the different trials are approximated to be 1/t to simplify the comparison between two different trials. It
is just a quantitative value for evaluating the rate of the reaction: the slower the reaction, the lower the 1/t
and vice versa (i.e. If a reaction finishes in 0.5 seconds, the rate would be 2 whereas if the reaction
finishes in 4 seconds, the rate would be 0.25.). Since the rate of the reaction is directly proportional to the
reaction time, the 1/t for the rate is reasonable.
There are different factors which could account for difference in the recorded rate of the different
trials done. These include the diameter of the beaker, the timer used and the person judging the end of the
reaction.
The diameter of the beaker affects the surface area of the solution previously in the beaker.
Changing the beaker diameter will also change the probability of the collision of the particles of the
reactants. If beakers of different diameters are used in different trials, then the probability of particles
colliding would also change as such the decrease in the diameter would decrease the surface area of the
solution in the vessel thus decreasing the probability of particle collision, making the rate of reaction
lower as compared to a beaker of larger diameter.
The timer used for the reaction could also account for a discrepancy in the rate of the reaction.
Different timers have different precision and calibration due to hardware limitations. This could translate
to some delay from the moment the Stop button is pressed to the actual time the timer stopped or, for
touchscreen phone-based stopwatches, the screen could be very sensitive that slight contact on the screen
could stop the timer even before the desired point. If the stop is premature, then the t would be smaller
than the desired value making the 1/t larger due to a smaller denominator. If the stop is late, then the 1/t
would be smaller due to a larger denominator.
Multiple persons to judge the completion of the reaction is another factor which could change the
rate. Different persons have different reaction times to stimuli. One person (A) might judge the end of the
reaction after say x seconds while another person (B) might judge the same reaction as x+3 seconds. In
the case of the example scenario, the determined rate by A would be 1/x while the rate for B would be
1/(x+3) which makes the rate of A higher than the rate of B.
In runs 1-3, the same amount (2 mL) of 3.0 M HCl was used while varying amounts of water and
Na
2
S
2
O
3
were used. For the first three runs, the total volume for each run was constant at 13.0 mL. Thus
the concentration of HCl is also a constant,
[A]
init
=
(olar) x (of )

(1.3)
From Equation (1.4), the [H
+
]
init
therefore =
(. )(. m)
. m
= 0.4 M HCl
while the concentration of S
2
O
3
2-
, using Equation (1.3), is varying for runs 1-3
Run 1: [S
2
O
3
2-
]
init
=
(olar) x (a

)

=
(. )( m)
. m
= 0.1 M S
2
O
3
2-

Run 2: [S
2
O
3
2-
]
init
=
(olar) x (a

)

=
(. )( m)
. m
= 0.05 M S
2
O
3
2-

Run 3: [S
2
O
3
2-
]
init
=
(olar) x (a

)

=
(. )(. m)
. m
= 0.025 M S
2
O
3
2-

From here, we could see that the concentrations for Na
2
S
2
O
3
were varying while the concentration
of HCl was constant for Runs 1-3. For these set-ups, the acid was added last to the solution to determine
if there is a change in rate if the concentration of thiosulfate changes where the acid acts as a control
variable for the set-up which will act as an initiator for the reaction.
Runs 4-6 follow the same logic but this time the Na
2
S
2
O
3
has the constant concentration (5.0 mL
of 0.15 M Na
2
S
2
O
3
) which is, from Equation (1.3),
[S
2
O
3
2-
]
init
=
(olar) x (S

-
)

=
(. )( m)
. m
= 0.1 M HCl
while the concentration of H
+
for the runs 4-6 are
Run 1: [H
+
]
init
=
(olar) x (l)

=
(. )(. m)
. m
= 0.6 M S
2
O
3
2-

Run 2: [H
+
]
init
=
(olar) x (l)

=
(. )(. m)
. m
= 0.4 M S
2
O
3
2-

Run 3: [H
+
]
init
=
(olar) x (l)

=
(. )(. m)
. m
= 0.2 M S
2
O
3
2-

Now that the initial concentrations are known, the rate order of the respective reactants could be
determined. We take the rate as 1/t (as previously explained) into the equation
= [A]
m
[B]
n
(1.4)
for any hypothetical reaction a bB c d
[1]
where k is for the rate costant; m and n stand for the
orders for the respective reactant;[A] and [B] are the respective concentrations of the reactants.
The rate law for the reaction is rate rate = k[S
2
O
3
2-
]
m
[H
+
]
n
. To solve for the exponents m and n of
S
2
O
3
2-
and H
+
respectively, the respective rates two different trials are considered. To solve for m, two
different concentrations of S
2
O
3
2-
and same concentrations of H
+
from two different trials are needed.
Knowing this, runs 1 and 2 are possible. Thus, we can form the ratio

=
[

-
]

-
]

(1.5)

1
Note: The stoichiometric coefficients of the reaction generally do not affect the equation.
where [H
+
]
1
and [S
2
O
3
2-
]
1
are the concentration of H
+
and S
2
O
3
2-
in the first trial respectively; and [H
+
]
2
and [S
2
O
3
2-
]
2
are the concentration of H
+
and S
2
O
3
2-
in the second trial respectively. Plugging-in the known
values to Equation (1.5), we get

.s

=
[. ]

[. ]

[. ]

[. ]

x*
.

+x*
.
.
+

. =
m

In order for 2
m
= 2, m = 1.
To solve for n, we will use the same procedure but this time we will look at values where the
concentration of H
+
varies while the concentration of S
2
O
3
2-
is kept constant. Thus, runs 4 and 5 are
possible. Using Equation (1.5) we get

. s

. s

=
[. ]

[. ]

[. ]

[. ]

x*
.

+x *
.

+
. = .
n

For 1.5
n
= 1, n = 0.
The rate orders that were experimentally determined are m=1 for S
2
O
3
2-
and n=1 for H
+
. This
means that the molecularity of the reaction is unimolecular which means that the process involves the
dissociation of a single molecule which is Na
2
S
2
O
3
in this reaction. This also means that since the kinetic
order of H
+
is 0 (zero), changing the concentration of H
+
does not change the rate of the reaction.
In order to set-up the rate law of the reaction, the value of the rate constant, k, should be
determined. Equation (1.4) is used to set-up the rate law thus we will use the said equation. We will use
the previously determined values to be plugged in to Equation (1.4)
rate = k[A]
m
[B]
n
In evaluating the equation, the values of any trial may be used. In this case, we will use values of run 1.
Since n = 0, this makes the [B]
n
= 1, leaving
rate = k[A]
m
and thus k =

[]

k =

. s
[. ]

= 0.476 M
-1
s
-1

We can now set-up the rate law that k, m and n are known
rate = k[S
2
O
3
2-
]
1
[H
+
]
0
= k[S
2
O
3
2-
]
1
= (0.476 M
-1
s
-1
) [S
2
O
3
2
]
A mechanism for this reaction may be given by the following (theoretical) elementary steps:


(1) Slow: Na
2
S
2
O
3
(aq) Na
2
SO
3
(aq)

+ S(s) (1.6)
(2)

Fast: Na
2
SO
3
(aq) + 2HCl(aq) H
2
O(l) + 2NaCl(aq) + SO
2
(g) (1.7)
________________________________________________________________________________
Overall: Na
2
S
2
O
3
(aq)

+ 2HCl(aq)

S(s)

+ 2NaCl(aq) + SO
2
(g) + H
2
O(l)
The suggested mechanism proposes that the first step occurs slowly but the second step occurs
rapidly. Thus we can write
rate (1) = k
1
[Na
2
S
2
O
3
] and rate (2) = k
2
[Na
2
SO
3
]
m
[HCl]
n

We can see that as Na
2
S
2
O
3
decomposes in the first step, the Na
2
SO
3
product is instantly
consumed in the second step. Thus the rate determining step is the first step which has a rate of
rate (1) = k
1
[Na
2
S
2
O
3
] which is the rate of reaction for the overall reaction.
The second set-up of the reaction of thiosulfate and hydronium ion as expressed by Equation (1.0)
investigates the effect of the change of temperature to the rate of the reaction as concentration is held
constant. In general, an increase in temperature results in a higher rate of reaction. This phenomenon
could be explained by collision theory. The theory states that in order for a reaction to occur (a) the
frequency of collisions must be enough, (b) the energy of the particles must be enough to make a reaction,
and (c) the orientation of the molecules must be correct (Petrucci et. al., 2011). Increasing the temperature
results in a higher average kinetic energy in the molecules thus the particles are moving in a higher rate
which results to a higher probability of the particles colliding together. If they are to collide, the increase
in kinetic energy increases the average energy of the particles thus satisfying the second requirement. This
concept is similar to cooking food. If we want to hasten biochemical reactions (e.g. turning garlic brown),
then we heat our food and if we want to slow down biochemical reactions (e.g. spoilage of food), we
refrigerate our food.
The previous set-ups were used to determine the effect of a change of concentration on the rate of
the reaction. As for this set-up, the effect of changing the temperature to the rate of the reaction is to be
determined. The trials done follow the Arrhenius equation
=

(2.0)
By taking the natural logarithm of both sides, the following expression is obtained
=

) (2.1)
The graph of ln k versus 1/T is a straight line in the form of y = mx + b. This denotes that an increase in
the temperature results to an increase in the rate of the reaction as predicted by collision theory.
Increasing the temperature also directly increases the rate constant. The increase in the rate constant also
increases the rate of the reaction. Using 1/t for the rate constant determines if the reaction speeds up or
slows down with respect to a change in temperature as the rate constant varies directly with the rate of the
reaction. In summary, an increase in temperature results to a lower reaction time thus increasing the rate
constant which varies directly with the rate of reaction.
The following data were obtained after the experiment trials done.

Table 2. Summary of Data for Determination of Effect of Temperature
Temperature (K) 1/Temperature (K
-1
) Time (s) 1/Time (s
-1
)
325.15 0.00308 39.993 0.0250
300.15 0.00333 138.693 0.00721
282.15 0.00354 428.42 0.00233

Based on the data obtained, the graph of ln (1/t) versus 1/T results in a linear graph with an
equation of
y = -5052.5x + 11.866 (2.2)
and a linearity coefficient (R
2
) of 0.9993.

The determined R
2
is very close to 1 (one) which means that the proportion of having fluctuations of one
variable which is predictable from the other variable. This suggests that the linear regression is able to
explain the variation of the scattered points and that there is a great strength in predicting other values
from the given graph.
The resulting equation from the graph is Equation (2.2) which is represented by Equation (2.1)
where the y corresponds to ln k, the x corresponds to 1/T and 11.866 corresponds to ln A as shown below:
=

)

y = -5052.5 x + 11.866
This gives us a value for

= - 5052.5 K
-1
where R is the gas constant with value of 8.314

mol-
.
To solve for the activation energy,
E
a
= 5052.5 K
-1
(R) = 5052.5 K
-1
(8.314

mol-
) = 42006

mol
or 42.0

mol

y = -5052.5x + 11.866
R = 0.9993
-7
-6
-5
-4
-3
-2
-1
0
0.003 0.0031 0.0032 0.0033 0.0034 0.0035 0.0036
l
n

(
1
/
t
)

1/T, K
-1

Note that the sign of the activation energy is positive. This is because the activation energy is the
minimum required energy for the reaction to proceed thus energy intake by the system is necessary
(Petrucci et. al., 2011).
(17)
The last phase of the experiment is the investigation of the effect of the presence of catalysts to
the rate of reaction and the introduction of the concept of autocatalysis.
Catalysts are substances which decrease the activation energy of the reaction and provide for an
alternative path to the reaction (Petrucci et. al., 2011). In the experiments done, the reaction of persulfate
with iodide is represented by the net ionic equation of
S
2
O
8
2-
(aq) + 2 I
-
(aq) 2 SO
4
2-
(aq) + I
2
(aq) (3.0)
In the reaction represented by Equation (3.0), Cu(NO)
3
(aq) was added to the persulfate and iodide
solution. The following data were obtained.
Table 3. Summary of Data for Determination of Effect of Presence of a Catalyst
Condition Observation Relative Reaction Time
Without Cu
2+
ion Very light blue Slower (< x)
With 4 drops 0.1M Cu
2+
Dark blue Faster (x)

In the experiment done, the Cu
2+
acted as the catalyst for the reaction which is observable by the
increase in the reaction rate in the presence of Cu(NO)
3
. Starch was used in this experiment as the
indicator of the end of the reaction by forming iodo-starch complex which is blue-black in color.
The following diagram serves as the energy diagram of Equation (3.0).












The demonstration of an autocatalytic reaction is given by the reaction of permanganate and
oxalate in the net ionic equation
16H
+
(aq) + 2MnO
4
-
(aq) + 5C
2
O
4
2-
(aq) 10CO
2
(g) + 2Mn
2+
(aq) + 8H
2
O(l) (3.1)
The following data were obtained in the autocatalysis.
Table 4. Summary of Data of Autocatalysis
Condition Observation Relative Reaction Time
1
st
drop 0.01M KMnO
4
Fast, discolored almost at contact Fast (x)
2
nd
drop 0.01M KMnO
4
Very fast, discolored at contact Faster (> x)
With 1 mL of 1% MnSO
4
Fast, but slower than the 1
st
drop Slow (< x)

The acid was added to the solution to reduce the permanganate by providing necessary
hydronium (H
+
) ions which act as the electron acceptors from MnO
4
2-
thus reducing the oxidation number
of manganese in permanganate from +6 to +2 in Mn
2+
. In this experiment, sulfuric acid (H
2
SO
4
), which is
a strong acid, was added to acidify the permanganate. Other acids could be substituted for sulfuric acid as
long as the acid is strong acids that dissociate completely which includes HCl, HNO
3
, HIO
4
, among
others.
The end of the reaction was manifested by the discoloration of the permanganate due to its
reduction to Mn
2+
. This reaction could also act as a titration reaction where the titrant is the permanganate
solution and the analyte is the heated oxalate solution. The titration is done until a faint pink color is
achieved.
Since this is an autocatalysis, the species which serves as the catalyst is the Mn
2+
. Autocatalysis is
a type of catalysis wherein a resulting product acts as the catalyst. The larger the amount of the product,
the more of the catalyst is produced and thus a faster reaction as the reaction goes on.
Answer to Questions
(I) Solve the following completely.
(1) Iodine clock reaction
This reaction is similar to the case of the first set of trials where the concentrations of the
reactants are being changed. The reaction will form a blue-black iodo-starch complex as in
Equation (3.0). Thus, the reaction time needed for the reactants to disappear is directly
proportional to the reaction time for the products to form. Thus the rate is considered to be 1/t (as
previously explained).
(A) Average rate for each trial
a. Trial 1: rate(1) = 1/t
1
= 1/29.0 = 0.0345 s
-1

b. Trial 2: rate(2) = 1/t
2
= 1/14.5 = 0.0690 s
-1

c. Trial 3: rate(3) = 1/t
3
= 1/14.4 = 0.0694 s
-1

(B) The order of reaction using initial rates method
Compute for [KI]
initial
and [Na
2
S
2
O
8
]
initial

Trial 1: [KI]
init
=
(. )( m)
m
= 0.04 M ; [Na
2
S
2
O
8
]
init
=
(. )( m)
m
= 0.04 M
Trial 2: [KI]
init
=
(. )( m)
m
= 0.08 M ; [Na
2
S
2
O
8
]
init
=
(. )( m)
m
= 0.04 M

Trial 2: [KI]
init
=
(. )( m)
m
= 0.08 M ; [Na
2
S
2
O
8
]
init
=
(. )( m)
m
= 0.02 M

=
[]

m
[a

n
[]

m
[a

.
=
[.]
m
[.]
m
. = .
m
m = 1

=
[]

m
[a

n
[]

m
[a

.
=
[.]
m
[.]
m
=
m
m = 0
The order with respect to I
-
is 1 while the order with respect to S
2
O
8
2-
is 0. This
means that the change in concentration of S
2
O
8
2-
does not contribute to any change in the
rate of reaction. The rate of reaction depends only on the dissociation of one moluecule,
KI.
(C) Rate constant at 25
o
C

1
= [KI]
1
m
[a

]
1
n
k =
rate

m
a

n

k =
rate

m
a

n
=

= 0.862 M
-1
s
-1
(D) The rate law for overall reaction
= [KI]
1
m
[a

]
1
n
=

d. rate = (0.862)[S
2
O
8
2-
]
REFERENCES
https://onlinecourses.science.psu.edu/stat501/node/29
http://www.lahc.edu/classes/chemistry/arias/Exp%208%20-%20Redox.pdf