EXPERIMENT 3:

CHEMICAL KINETICS: KINETICS OF THE REACTION BETWEEN S2O3 2- AND H+;

FACTORS AFFECTING THE RATES OF CHEMICAL REACTIONS; CATALYSIS

JOSE, ESTELLE DIANE D. AND VERGARA, ANGELICA R.

THWX1
BS CHEMICAL ENGINEERING

CHEMICAL KINETICS

Chemical Kinetics concerns how rates of chemical reactions are measured, how they can be predicted, and
how reaction-rate data are used to deduce probable reaction mechanisms. Because it is somehow necessary for us
to understand chemical changes, it is essential to consider three dynamics aspects of chemical reaction: a.) reactant
and products’ concentrations by the time the reaction is complete, b.) the reactions ability to push itself forward and
release or absorption of energy, and c.) the rate of the reaction in a given moment. With this, we are up to the
sequence by which the over-all change is accomplished.

RESULTS AND DISCUSSION Then, the time it takes the sulphur to diffuse
in the solution making the mark behind the test tube
not visible is tested.

To deal with the factors that affect the rate

of chemical reaction, that is what this experiment
showcases. And the ability of those factors are shown
in the four parts of this study. The tabulated result is here as follows:
The factors are the following: Time(s
Run 1/Time (s-1) [S2O42-]init [H+]init
1. Concentration )
2. Temperature 1
3. Nature of Reactants 2
4. Effect of Catalysts 3
4
5
A. CONCENTRATION 6

Here, 0.15 M sodium thiosulphate (Na 2S2O3)

is made to react with 3M hydrochloric acid (HCl)
forming colloidal sulphur.
S2O32-(aq) + 2H+(aq) → SO2(g) + S(s) + H2O(l)
And in order to test the effect of
concentration to the rate of reaction, the volume of
reactants per set varies, in other words varying the
concentration of the solutions.
As seen in the result, it can be concluded
that the concentration of the reactants is directly
proportional with the rate of reaction. Or, the
reaction’s rate somehow depends on the time the
sulphur is formed.
Given the initial rates of reactions from the
six trials, the order of the reactants and also the
order of reaction can now be calculated.
 It is now determined that the order of
reaction with respect to S2O42- is in second order (see
Calculations). Also, holding the concentration of
[H+] as constant, when the concentration of S2O42- is
doubled, the reaction rate was quadrupled.
On the other hand, the order of reaction with
respect to H+ is in first order (see Calculations)..
While [S2O42-] is held constant, the rate of reaction
doubles as the concentration of H+ is doubled.
Plotting ln k versus 1/T gives a linear
relationship where –Ea/R is the measure of the slope
and lnA is the y-intercept.
Since the reactant concentrations were held
constant in all temperatures, the rate constants, k, for
two different mixtures will have the same ratio as the
reaction rates themselves for the mixture. Hence, the
mixtures will have the same time ratio as well. This
means that ln k could be justifiably replaced with ln
(1/T).

The over-all order of the kinetic reaction is the For this particular experiment, the
sum of the order of the reactants. Therefore, the determination of the activation energy was done by
reaction is in third order. plotting ln (1/t) versus 1/T.

The integrated rate law for this reaction is:

R = k [S2O32-]2 [H+] 1/T vs ln(1/t)

where, -5.4

ln (1/t)
R = rate of reaction -5.6 28 03 32 34 36 38
f(x) = 299.189189189189
00 .0 00 x − 6.7042972972973
00 00 00
k = rate constant -5.8
0 . 0 0 . 0 . 0 . 0 .
[S2O32-]2 = concentration of S2O32- -6
in its 2nd order
[H ] = concentration of H+ in its 1st
+ 1/T
order
Graphical representation of the rate constant
B. TEMPERATURE
as a function of time.
0.025 M S2O32- is reacted with 0.4 M H+,
This plot results to an activation energy, Ea, of
where in, here, the concentration must remain
__________ J mol-1.
constant and the experimental variable will be the
temperature.

The reaction will be done with three Metal + HCl Relative Rate
C.
different temperatures. One in an ice bath, at ambient Zn + HCl 2nd
temperature and at elevated temperature. Mg + HCl 1st
Fe + HCl 3rd
The activation energy, Ea, of the reaction
can be acquired by measuring how the rate of NATURE OF REACTANTS
reaction varies with temperature. This is obtained
by using the Arrhenius Equation: With this part, the nature of the reactants,
particularly the reducing property of metals and
ln k= -
Ea
R ( 1T ) + ln A the strengths of acids, are tested as factors on the
rate of chemical reactions.

where, First thing is different metals that are reacted

with 3M HCl. Here is the table showing the relative
k = rate constant rate of reaction of Zinc, Magnesium, and Iron with
Ea = Activation Energy (in ) HCl.
R = gas constant (8. 314 J mol-1 K-1)
T = temperature (in K)
A = Arrhenius constant

Mg + Acid Relative Rate
Mg + HCl
As 1st
Mg + HOAc 2nd metal
Fe + NaHSO4 and HCl
results
to the fastest rate relative to the reaction of Zn + HCl
and Fe + HCl. Moreover, the reaction of Zn with HCl
is faster than that of Fe + HCl.
Therefore, the greater the reducing
property of a metal the faster the rate of reaction of
it with acids.
Next one is the the reverse to the prior, now,
what to be dealt is different acids that are reacted
with Magnesium ribbon. Hereunder is the table
stating the rate of reaction of HCl, HOAc, and
NaHSO4 with Mg.
It was found out that Mg reacts faster with
HCl than with HOAc. These observations are
accounted to the relative strengths of these acids.
HCl, being a strong acid, dissociates completely in an
aqueous solution. This dissociation increases the
number of ions available for reaction with Mg. Thus,
it reacts faster with Mg because of the large number
of ions present. On the contrary, HOAc, because it
does not dissociate completely in an aqueous
solution, takes a longer time for it to react with Mg.
Thus, we may say that the stonger the acid
reacted with a metal, the faster the reaction will be.
D. CATALYSIS
In here, the effect of the catalysis presence
in the rate of reaction is the one being tested.
For Part A, persulphate (K2S2O8) and iodide
are made to react with each other and are observed
for reaction rate differences when a catalyst is present
and when it is not.
S2O82- + 2I- → 2S2O42- + I2
A starch solution was added to the mixture
to show the formation of iodide. As the reaction
proceeds, the amount of iodine produced willinterpreted
be used
to react with the starch solution, forming an iodo-
starch complex. Then, now, the rate of formation of
iodine can be monitored, which is the measure of the
rate of reaction.
Two set-ups are formed in this part: a. one
containing Cu2+ as the catalyst, b. and another one
without Cu2+. The one without Cu2+ was observed to
be unchanged after very much time. On the other
hand, the set-up containing the catalyst Cu2+
produced a blue iodo-starch complex after ____
minutes.
Because of those observations, it can be
concluded that the addition of a catalyst increases
the rate of the reaction.
Then now, reaction between oxalate and
permanganate is observed to determine the effect of a
catalyst in the rate of reaction.
2MnO4- + 5C2O42- + 16H+ → 2Mn2+ + 8H2O + 10CO2
This is the process of autocatalysis between
oxalate and permanganate ions. Autocatalysis occurs
when the product formed acts as a catalyst.
In this part of the experiment, the reaction
between MnO4- and C2O42- proceeds slowly for
sometimes because of the reaction between two
negative ions. Collision between these ions is
difficult.
However, when a sufficient amount of Mn2+
is formed as a product, the reaction immediately
speeds up.
On the first drop of MnO 4- in the reaction
vessel, the reaction took ___ seconds for the
permanganate to decolorize. On the second drop of
MnO4-, the reaction took a relatively short time (___
seconds) because the addition of MnO4- produces
more Mn2+, thus more catalysts. In the second set-up,
MnSO4 was introduced to the reaction. The addition
of more Mn2+ greatly accelerates the decolorization of
the permanganate.
ANSWERS TO QUESTIONS
 1. In a “clock” reaction, a dramatic color = (moles S2O32-) / 2(volume solution) (Δt)
change occurs at a time determined by RATE = (vol S2O32- added)[S2O32-] /
concentration and temperature. An example 2(vol sol’n)(Δt)
of such reaction is the iodine clock reaction.
The over-all equation is:
Trial I:
2I- + S2O82- ↔I2 + 2SO42-
As I2 forms, it is immediately consumed by Rate = (vol S2O32- added)[ S2O32-] /2(vol sol’n)(Δt)
its reaction with a fixed amount S2O32-:
= (0.01 L)(0.005 M) / 2(0.05 L)(29 s)
I2 + 2S2O3 ↔2I + S4O6
- 2- - 2-
= 1.72 x 10-5 M s-1
Once the S2O32- is consumed, the excess I2-
forms a blue – black product with a starch Trial II:
solution in the mixture:
Rate = (vol S2O32- added)[ S2O32-] /2(vol sol’n)(Δt)
I2 + starch ↔ starch – I2 complex
-

= (0.01 L)(0.005 M) / 2(0.05 L)(14.5 s)

The rate of the reaction is also influenced by
the total concentration of ions, so KCl and = 3.45 x 10-5 M s-1
(NH4)2SO4 are added to maintain a constant
rate. Use the data in the lab manual to Trial III:
determine the ff:
Rate = (vol S2O32- added)[S2O32-]/2(vol soln)(Δt)

= (0.01 L)(0.005 M) / 2(0.05 L)(14.4 s)

= 3.47 x 10-5 M s-1

I. AVERAGE RATE OF EACH TRIAL

II. ORDER REACTION WRT
The rate of reaction as the rate of formation REACTANTS
of I2 over a period of time is as follows.

Rate = Δ[I2] / Δt Trial [S2O82-], [I-], M Rate of

M Rxn, M s-
where, Δ[I2] is measured by [I2]final - [I2]initial. 1

1 0.04 0.04 1.72 x 10-

There is no I2 formed in the beginning of 5

reaction. Therefore, Δ[I2] = [I2]final 2 0.04 0.08 3.45 x 10-

5
RATE: 3 0.02 0.08 3.47 x 10-
= Δ[I2] / Δt 5
= [I2]final / Δt
= (mol I2) / (vol sol’n)( Δt)
The table stated that doubling the
concentration of S2O82- while holding [I-]
The number of moles of I2 produced can be
constant does not affect the reaction’s rate.
calculated from the amount of thiosulphate added to
By that, the reaction is zero order with
the reaction vessel.
respect to S2O82-.
2S2O32- + I2 → S4O62- + 2I- On the other hand, doubling the
concentration of I- while holding [S2O82-]
mol S2O32- = (vol S2O32- added) x [S2O32-] constant doubles the rate of reaction.
Therefore, the reaction is first order with
Then, we now have, respect to I-.

RATE: III. RATE CONSTANT AT 25oC

= (moles I2) / (vol sol’n)( Δt)
 Rate Law : Rate = k [I-] Test Tube 1:
Rate = Δ[MnO4-] / 2 (Δt)
With the first trail as basis, = (-8.33 x 10-2 M)/2(100.15 s)
= 4.16 x 10-4 M s-1
Rate = k [I-] Test Tube 2:
K = Rate / [I-] Rate = Δ[MnO4-] / 2 (Δt)
k = (1.72 x 10-5 M s-1) / (0.04 M) = (-8.33 x 10-2 M)/2(63.55 s)
k = 4.3 x 10-4 s-1 = -6.55 x 10-4 M s-1
Test Tube 3:
Rate = Δ[MnO4-] / 2 (Δt)
= (-8.33 x 10-2 M)/2(15.35 s)
IV. THE RATE LAW FOR THE OVER- = -2.71 x 10-3 M s-1
ALL RXN Test Tube 4:
Rate = Δ[MnO4-] / 2 (Δt)
Rate = k [S2O82-]0 [I-]1 = (-8.33 x 10-2 M)/2(5.87 s)
Rate = k [I-] = -7.10 x 10-3 M s-1

II. CALCULATE FOR Ea.

b. A solution of permanganate was added to
To calculate for the Ea, the rate
an acidified solution of oxalate and resulted in the
constant (k) for every test tube must first be
decoloriztion of the permanganate. The rate of the
determined. Since it is assumed that the
reaction as well as its energy of activation was
reaction is first order with respect to MnO 4-
determined. Given 50 ml of 0.1 M permanganate and
and first order overall, we get a rate law of
10.0 ml of 0.005 of M C2O42-,
Rate = k[MnO4-]
I. BALANCED REACTION. Assuming that the rxn is
in first order wrt to the permanganate ion and first Thus,
order over-all, calculate the rxn rate for each test
tube. k = Rate / [MnO4-]

a. Given: Test Tube 1:

Volume (MnO4-) = 0.05 L k = Rate / [MnO4-]
Concentration (MnO4-) = 0.1 M =(-4.16 x 10-4 M s-1)/(-8.33 x 10-2
Volume (C2O42-) = 0.01 L M)
Concentration (C2O42-) = 0.005 M = 4.99 x 10-3 s-1
Test tube 2:
k = Rate / [MnO4-]
I. Balanced equation: =(-6.55 x 10-4 M s-1)/(-8.33 x 10-2
M)
= 7.86 x 10-3 s-1
2MnO4- + 5C2O42- + 16H+ Test Tube 3:
k = Rate / [MnO4-]
→ 2Mn2+ + 8H2O + 10CO2 =(-2.71 x 10-3 M s-1)/(-8.33 x 10-2
M)
= 3.25 x 10-2 s-1
[MnO4-]init = (0.1 M)(0.05 L) / (0.06 L) Test Tube 4:
= 8.33 x 10-2 M k = Rate / [MnO4-]
=(-7.10 x 10-3 M s-1)/(-8.33 x 10-2
Based on the table given, [MnO4-]final = 0 M M)
= 8.52 x 10-2 s-1
Therefore,
Plot ln k versus 1/T to identify a best-fit line
Δ[MnO4-] = [MnO4-]final - [MnO4-]initial and get the slope.
= 0 M - 8.33 x 10-2 M
= -8.33 x 10-2 M
k ln k Temp (K) 1/T
 values
0.0049 -5.30 293 0.00341
9 APPENDIX
0.0078 -4.84 303 0.00330
7 1. Calculations
0.0326 -3.42 313 0.00319
0.852 -2.46 323 0.00310

Graph of lnk vs. 1/T

0.00
0 0 0 0 0 0
-2.000 3 0 0 31 0 32 0 33 0 34 0 35
.0 .0 .0 .0 .0 .0
lnk

0 0 f(x)0= − 9360.82622171227
0 0 0 x
-4.00
+ 26.4244131400302
-6.00 R² = 0.960107240888826
1/T

Using the slope above as the value for -

Ea / R, we get,

- Ea / R = -9360
Ea = -(R)(-9360)
Ea = -(8.314 J mol-1 K-1)(-9360 )
Ea = 7.78 x 104 J mol-1

III. If MnSO4 was added to the solution, what

will happen to Ea?

If MnSO4 would be added to the

solution, the value of Ea would decrease.
MnSO4 will act as a catalyst that would
decrease the Ea of the reaction, allowing it
to proceed faster than its normal rate.

REFERENCES

[1] Petrucci, R.H., Harwood, W.S., Herring, F.G.

General Chemistry: Principles and Modern
Applications (8th ed.). Prentice-Hall, Inc., USA.
2002.

[2] Silberberg, M.S. Principles of General Chemistry

(2nd ed.). McGraw Hill., USA. 2010.

[3] “Autocatalysis: Reaction of Permanganate with

Oxalic Acid.” Division of Chemical Education,
Inc., American Chemical Society. 1999. 05
December 2010
<http://jchemed.chem.wisc.edu/JCESoft/CCA/C
CA3/MAIN/AUTOCAT/PAGE1.HTM>.