Chemical Kinetics

Abstract
The experiment aims to present the concepts of Chemical Kinetics through a series of
reactions. The first system involves the reaction of sodium thiosulfate and hydrochloric acid in
different concentrations. The next system involves the reaction of sodium thiosulfate and hydrochloric
acid is performed at three different temperatures: one in an ice bath, one at room temperature and
another at a hot water bath. The third and fourth system introduces the principles of catalysis in the
oxidation of tartrate by hydrogen peroxide and the reaction of oxalate with permanganate. Using the
initial rates method, it is found that the concentration of hydrochloric acid, a zeroth order reactant,
does not affect the rate of reaction. It is dependent on the concentration of sodium thiosulfate, which is
determined to be a first order reactant. Knowing the rate law helps in keeping the cost of a process
minimal by saving energy, effort and money. The activation energy of the reaction is then determined
by varying the temperature in which the reaction is happens. The activation energy is found to be
26,496 joules. The addition of Co
2+
in oxidation of tartrate speeds up the rate of reaction. Also, the
production of Mn
2+
in the reaction of oxalate with permanganate speeds up the reaction through
autocatalysis. A catalyst is important in many industrial processes. Sulfuric acid, which is used to
produce batteries, detergents, dyes, explosives, plastics, and many other produces, is commonly
produced using a catalyst called vanadium oxide. Ammonia, a primary component of many fertilizers,
could not be produced economically without the use of iron oxide which speeds up the reaction.


RESULTS AND DISCUSSIONS
The first and second parts of the experiment
studied the decomposition of sodium
thiosulfate in acidic medium. The balanced
chemical equation is as follows:
Na2S2O3(aq) + 2HCl(aq) SO2(g) + S(s) +
2NaCl(aq)
The average rates of the reactants and
products can be expressed through the
following equation:

[

[]

The decomposition of sodium thiosulfate in
acidic medium is performed in different
concentrations. The table below shows the
concentrations of S2O3
2-
and H
+
ions with their
corresponding reaction rates.
Table 1.1 Reaction Rates and
Concentrations
Run
No.
Time
(s)
1/Time*
(s
-1
)
[S2O3
2-
]initial
[H
+
]initial
1 21.96 0.04554 0.1 0.4
2 56.31 0.01776 0.05 0.4
3 109.61 9.123 x
10
-3

0.025 0.4
4 42.90 0.02331 0.05 0.3
5 47.54 0.02103 0.05 0.2
6 45.16 0.02214 0.05 0.1

Using the initial rates method, the rate orders
of S2O3
2-
and H
+
are determined. It is found
that the reaction is zeroth order with respect
to Hydrochloric acid. This means that the
concentration of Hydrochloric acid does not
affect the rate of reaction. It is also found that
the reaction is dependent on the
concentration of sodium thiosulfate, which is
a first order reactant. The proposed
mechanisms for the reaction are:
S2O3
2-
(aq) SO
2-
(aq) + S(s)
SO3
2
-(aq) + H
+
(aq) HSO3(aq)
HSO3-(aq) + H
+
(aq) SO2(g) + H2O (l)

Figure 1.1 Graph of Reaction Rate vs
[S2O3
2-
]initial

Figure 1.2 Graph of Reaction Rate vs
[S2O3
2-
]initial

Table 1.2 Part 1 Experimental Results
Order with Respect
to

Na2S2O3 1
HCl 0
Overall Order 1
Rate Expression Rate=[

]

In the second part of the experiment, the
decomposition of sodium thiosulfate in acidic
medium is observed in three different
temperatures. The effect of different
temperatures to the reaction rate is shown on
the table 1.3.
Table 1.3
Reaction rates at different Temperatures
Temperatu
re (K)
1/Temperat
ure (K
-1
)
Time
(s)
1/Time
** (s
-1
)
278.15 3.5952 x 10
-3
275.5
0
3.6298
x 10
-3

298.15 3.3540 x 10
-3
109.6
1
9.1232
x 10
-3
359.65 2.7805 x 10
-3
19.80
0
0.0505
05

0
0.01
0.02
0.03
0.04
0.05
0 0.05 0.1 0.15
R
e
a
c
t
i
o
n

T
i
m
e

(
s
)


[S
2
O
3
3-
]
initial

Effect of Concentration to
Reaction Time
0
0.02
0.04
0.06
0 0.05 0.1 0.15
R
e
a
c
t
i
o
n

R
a
t
e

(
1
/
s
)


[S2O33-]initial

Effect of Concentration to
Reaction Rate

In this part, the activation energy of the
reaction is computed using the Arrhenius
equation shown below.

)

By multiplying the negative of the slope of the
lnk vs 1/T graph by the gas constant, the
activation energy is computed. The graph of
the lnk vs 1/T graph is shown in figure 1.3.

Figure 1.3 Graph of lnk vs 1/T
The linearity coefficient (R
2
) suggests that the
graph of lnk vs 1/T is linear. The activation
energy is the minimum energy above the
average kinetic energy that molecules must
bring to their collisions for a chemical
reaction to occur.
Table 1.4 Part 2 Experimental Results
Theoretical H 65,900 J
Calculated Ea 26,496 J

In the third part of the experiment, the
oxidation of tartrate by hydrogen peroxide is
observed.

The observations and the relative reaction
time are stated below in table 1.5.

Table 1.5
Oxidation of Tartrate by Hydrogen
Peroxide
Test Tube Observations Relative
Reaction
Time
1 With
effervescence;
pale yellow
green
Slow
2 With
effervescence;
Pale pink to
green then
back to pale
pink
Fast


The bubbles formed in the reaction are the
Carbon dioxide produced in the reaction.
Cobalt(ll) ions are pink. The hydrogen
peroxide initially oxidises the cobalt(II), Co
2+
,
to cobalt(lll), Co
3+
, which is green. The
cobalt(III) bonds to the tartrate ion, allowing
the oxidation to take place. The CO
3+
is then
reduced back to CO
2+
and the pink color
returns. The reaction utilized a catalyst
(CoCl2) to take place because the oxidation of
tartrate by hydrogen peroxide is very slow
even at high temperatures. The cobalt
catalyst provides an alternative path for the
reaction to take place. This alternative path
y = -3186.8x + 5.9018
R = 0.9964
-6
-5
-4
-3
-2
-1
0
0 0.001 0.002 0.003 0.004
l
n
k

1/Temperature
lnk vs 1/Temperature
has lower activation energy and that is why
the reaction happens faster.
In the reaction of oxalate with permanganate,
oxalate is oxidized to carbon dioxide and
permanganate is reduced to Mn
2+
.

Autocatalysis is a reaction where a reaction
product itself is the catalyst for the reaction.
In the experiment, the manganese (II) ion is
the autocatalyst. The manganese (II) ion is
oxidized by permanganate ion to manganese
(III) ion and is reduced back to manganese
(II) ion. The manganese (II) ion provides an
alternative path for the reaction to take place.
This alternative path has lower activation
energy and that is why the reaction proceeds
faster.

References
[1] Petrucci, R., Herring, G., Madura, J.,
Bissonnette, C. General Chemistry, Principles
and Modern Application, 10
th
Ed. Prentice
Hall, New Jersey. 2010
[2] Silberberg, M. Chemistry: The Molecular
Nature of Matter and Change, 5
th
Ed. McGraw-
Hill, New York. 2010
[3] Masel, R. Chemical Kinetics and Catalysis,
John Wiley and Sons, New York. 2001