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CHEMICAL KINETICS

ABSTRACT
This experiment was conducted to examine the influence of concentration,
temperature, and the presence of a catalyst to the reaction under study. Tests were
conducted for each factor affecting the reaction rate, and the application of the rate
law, linear regression and Arrhenius equation determined significant quantities in
the reactions performed. Qualitative analysis was also used to identify the rate of a
reaction.

RESULTS AND DISCUSSION


The
effect
of
varying
concentration and temperature, and
the presence of catalyst on the
reaction rate were observed in this
experiment.
The
effect
of
concentration on the rate of reaction
was examined in the first part of the
experiment by reacting thiosulfate ion
and hydronium ion:
S2O32-

(aq)

+ 2H+ (aq) SO2


H2O(l) (1)

(g)

+S

(s)

The rate of this reaction can be


expressed in terms of change in
reactants and products with respect to
time ( []/ t):
rate = - [S2O32-] = -1 [H+] = [SO2]
= [S] = [H2O] (2)
t
2 t
t
t
t
The completion of the reaction
is identified by the appearance of
cloudiness in the reaction mixture
which indicates that the reactants
were consumed. This turbidity is due
to the formation of sulfur (S)
precipitate. The reaction vessels that

are used throughout the experiment


should be consistent in diameter and
size, if not only one is used. The area
of the reaction vessel affects the
collision of molecules[1]. The molecules
are closer to each other in a smallsized container than in a mediumsized one, and more collisions will
proceed, resulting to a higher reaction
rate. Varying the diameter and size of
the reaction vessel is inconsistency
and a possible source of error. Another
possible source of error is human
error. The opacity of the mixture is
measured using a high-functioning
device called the spectrometer, but in
this experiment the turbidity of the
mixture depends on the judgment of
the person observing the reaction. To
avoid committing this error, there
should only be one observer in order
for there to be no variety of opinion.
Time elapsed from the point of contact
of the two reactants until they were
used up was recorded (refer to
Appendix for data). The initial reaction
rate is inversely proportional to the
time it takes for the reaction to

complete. The initial concentration of


the reactants were constant while the
time unit differed, making 1/t valid as
derived from []/t. In the first three
runs the volume of the acid added to
the dilute thioslufate was kept
constant, while for the last three runs
the volume of the thiosulfate added to
the dilute acid was held constant. This
is done to determine the order of the
reaction with respect to the reactant
with varied initial concentration[2]. The
initial concentrations of the two
reactants in each run were calculated
using the dilution formula:
M1V1 = M2V2 (3)
where the concentration of the
reactant (M2) is multiplied by the given
volume (V2) divided by the total
volume (V1) or summation of the
volumes of Na2S2O3, H2O and HCl. The
calculation of the order of the reaction
goes by this equation:
rate 1 = k [A]1x [B]1y
rate 2
k [A]2x [B]2y

(4)

The rates correspond to the


initial
reaction
rates
(1/t)
as
mentioned, and on the right side of
the equation are the ratio of
concentrations of A and B. The x and
the y determine the reaction rate and
either can be obtained by holding the
initial concentrations B (B1 and B2)
constant while A (A1 and A2) differ, or
vice versa. The order of reaction with
respect to H+ is zero, meaning the rate
is independent of H+ concentration,
while the order of the reaction with
respect to S2O32- is one making an
overall kinetic order of the reaction

equal to one (see solution


Appendix), with a rate law

in

rate = k [S2O32-] (5)


where k is the rate constant and
[S2O32-] is the concentration of
thiosulfate. Based on the rate law, the
rate of reaction is dependent on the
concentration of the thiosulfate ion
and thus is a slow step [3]. Since it is a
first order rate of reaction, the
reaction is unimolecular[3]. These
inferences suggest a mechanism for
the reaction which is:
S2O32- S(s) + SO32- (slow)
SO32- SO2 + 1/2 O2 (fast)
2H+ + 1/2O2 H2O (fast)
The effect of temperature on
the rate of reaction was observed in
the second part of the experiment. In
the experiment, the same reaction
mixture from the first part of the
experiment (Run 3) was subjected to
three environments with different
temperatures: one in ice bath, one at
room temperature, and one at
elevated temperature. Based on the
data obtained, the reaction at
elevated temperature proceeded fast
than in the other two. The rates of
most reaction increases as the
temperature rises[2]. According to
collision theory, the rate of a chemical
reaction is proportional to the number
of
collisions
between
reactant
molecules[4]. Raising the temperature
greatly increases the kinetic energy of
molecules[2]. This high amount of
kinetic energy favors collision which
leads to the frequent reaction between
the two molecules making the reaction
rate faster[4]. Only a small fraction of

the collisions are effective collisions,


and these effective collisions result in
a chemical reaction[4]. In order to
attain effective collision, the reactants
must a) collide with each other, b)
have a sufficient amount of energy to
initiate
the
reaction
(activation
energy),
and
c)
have
proper
orientation.
To define the relationship of
temperature
and
time
further,
Arrhenius equation is used:
ln k = lnA (Ea/R)(1/T) (6)
This equation is similar to the equation
of the line y = mx + b, where -Ea/R is
the slope of the line, x is equal to 1/T
and y is equal to lnk (k = 1/t). From
the data, a plot of lnk vs 1/T is
constructed:

is relatively close to 1. The linearity


coefficient denotes the correlation
between the two variables, and a
correlation of 1 means that if one of
the two variables increase or decrease
and the other variable would also
increase or decrease[5]. As translated
from the graph, lnk is dependent on
1/T, and that there is an existing
relationship between temperature and
time.
As mentioned, the slope is
equal to Ea/R, where R is a gas
constant (8.314 J/mol-K). To get the
activation energy, or the minimum
energy required to initiate the
reaction, the gas constant is multiplied
by the slope -5410.78 K. the activation
energy is equal to 44.99 kJ/mol. This
would mean that
H>0 and the
reaction is endothermic. The activation
energy is usually positive in order to
overcome the energy barrier for
reactions to proceed, and high
temperature is also a factor for that.
This energy profile for this reaction is
show below.

Figure 1. Graph of lnk vs 1/T


Based on the data recorded (see
Appendix) and using linear regression,
the equation of the line is y =
-5410.78x + 12.70. The linearity
coefficient, R2, is equal to 0.90 which

Figure 2. Energy Profile of the Reaction


The last part of the experiment
focused on the influence of the

presence of a catalyst to the reaction


rate. The first component in this part
of the experiment dealt with the effect
of the catalyst CoCl2 on the reaction
rate of sodium tartrate (C4H4Na2O6)
and hydrogen peroxide (H2O2). The
balanced chemical equation of this
reaction is as follows:

In the second component in this


part of the experiment, autocatalysis
is observed and how it affects the rate
of reaction between sodium oxalate
(Na2C2O4)
and
potassium
permanganate (KMnO4). The balanced
equation for the reaction in acidic
medium is stated below.

5H2O2(aq) + C4H4O62-(aq) 4CO2(g) + 2OH(aq) + 6H2O(l) (7)

2MnO4- (aq) + 5H2C2O4(aq) + 6H3O+(aq)


2Mn2+(aq) + 10 CO2(aq) + 14H2O(l)
(8)

Placed in a hot water bath, two


different test tubes contained a
mixture of sodium tartrate and
hydrogen peroxide but with 8 drops of
cobalt chloride (CoCl2) added on
another (Test Tube 2). Under five
minutes, no apparent change was
observed in the first test tube.
Meanwhile in Test Tube 2, the pinkcolored solution turned green at 56
seconds and went back to a paler
shade of pink at 90 seconds.
Effervescence was observed upon
change in color of the solution from
pink to green. The majority of the gas
evolved is comprised of carbon dioxide
(CO2), although oxygen (O2) will also
be produced from the decomposition
of H2O2[6]. The change in color of the
solution is due to the catalyst. The
pink cobalt (II) ion (Co 2+) catalyzes the
reaction and is oxidized by H2O2 to
cobalt (III) (Co3+) and complexes with
tartrate ion responsible for the green
coloration[6]. This bonding into complex
allows oxidation to take place and
then Co3+ ion is reduced back to
Co2+[6].

To acidify MnO4-, H2SO4 was


used since it is a strong acid and
would completely dissociate. The
permanganate ion was acidified in
order to produce manganese (II) ion
(Mn2+). The completion of reaction is
indicated by the disappearance of
purple MnO4- to colorless Mn2+. MnSO4
catalyzes the reduction by oxalic acid
of purple permanganate to colorless
manganese (II) ion. In the reaction
without the addition of MnSO 4, the
reaction proceeded slowly at the first
drop of KMnO4 but eventually went
fast after the second drop due to the
autocatalysis of Mn2+[7]. As defined,
Autocatalysis
occurs
when
the
product of a reaction serves as a
catalyst for the reaction[7]. Mn2+ is the
autocatalyst because the reaction
started to proceed quickly after the
second drop where Mn2+ was already
produced.