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

To deal with the factors that affect the rate The tabulated result is here as follows:
of chemical reaction, that is what this experiment
Run Time(s) 1/Time (s-1) [S2O42-]init [H+]init
showcases. And the ability of those factors are shown 1
in the four parts of this study. 2
3
The factors are the following: 4
1. Concentration 5
2. Temperature 6
3. Nature of Reactants
4. Effect of Catalysts
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
A. CONCENTRATION reaction’s rate somehow depends on the time the
sulphur is formed.
Here, 0.15 M sodium thiosulphate (Na2S2O3)
is made to react with 3M hydrochloric acid (HCl) Given the initial rates of reactions from the
forming colloidal sulphur. six trials, the order of the reactants and also the order of reaction
can now be calculated.
S2O32-(aq) + 2H+(aq) → SO2(g) + S(s) + H2O(l)
It is now determined that the order of reaction
And in order to test the effect of with respect to S2O42- is in second order (see
concentration to the rate of reaction, the volume of Calculations). Also, holding the concentration of [H+]
reactants per set varies, in other words varying the as constant, when the concentration of S2O42- is
concentration of the solutions. doubled, the reaction rate was quadrupled.
Then, the time it takes the sulphur to diffuse
in the solution making the mark behind the test tube On the other hand, the order of reaction with
not visible is tested. respect to H+ is in first order (see Calculations).. While
[S2O42-] is held constant, the rate of reaction doubles as For this particular experiment, the
the concentration of H+ is doubled. determination of the activation energy was done by
plotting ln (1/t) versus 1/T.
The over-all order of the kinetic reaction is the sum of
the order of the reactants. Therefore, the reaction is in
third order.
1/T vs ln(1/t)
The integrated rate law for this reaction is: -5.4
0 0.001 0.002 0.003 0.004
R = k [S2O3 2-]2 [H+] -5.6

ln (1/t)
where, -5.8
y = 299.1x - 6.704
R = rate of reaction
-6
k = rate constant 1/T
[S2O32-]2 = concentration of S2O32-
in its 2nd order
[H+] = concentration of H+ in its 1st Graphical representation of the rate constant as a
order function of time.

This plot results to an activation energy, Ea, of

B. TEMPERATURE
__________ J mol-1.
0.025 M S2O32- is reacted with 0.4 M H+,
where in, here, the concentration must remain constant
and the experimental variable will be the temperature.
C. NATURE OF REACTANTS
The reaction will be done with three different
With this part, the nature of the reactants,
temperatures. One in an ice bath, at ambient
particularly the reducing property of metals and the
temperature and at elevated temperature.
strengths of acids, are tested as factors on the rate of
The activation energy, Ea, of the reaction chemical reactions.
can be acquired by measuring how the rate of
reaction varies with temperature. This is obtained by First thing is different metals that are reacted
using the Arrhenius Equation: with 3M HCl. Here is the table showing the relative rate of
reaction of Zinc, Magnesium, and Iron with HCl.
Ea 1
ln k= - ( ) + ln A
R T
Metal + HCl Relative Rate
where, Zn + HCl 2nd
Mg + HCl 1st
k = rate constant
Fe + HCl 3rd
Ea = Activation Energy (in )
R = gas constant (8. 314 J mol-1 K-1)
T = temperature (in K)
A = Arrhenius constant As interpreted from the data, the reaction of
Mg metal and HCl results to the fastest rate relative to
the reaction of Zn + HCl and Fe + HCl. Moreover, the
Plotting ln k versus 1/T gives a linear reaction of Zn with HCl is faster than that of Fe +
relationship where –Ea/R is the measure of the slope and HCl.
lnA is the y-intercept.
Therefore, the greater the reducing
Since the reactant concentrations were held property of a metal the faster the rate of reaction of
constant in all temperatures, the rate constants, k, for it with acids.
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 Next one is the the reverse to the prior, now,
means that ln k could be justifiably replaced with ln what to be dealt is different acids that are reacted with
(1/T). Magnesium ribbon. Hereunder is the table stating the rate of
reaction of HCl, HOAc, and NaHSO4 with Mg.
 Mg + Acid Relative Rate
Mg + HCl 1st
Mg + HOAc 2nd
Fe + NaHSO4
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 will 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 MnO4- 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 change occurs
at a time determined by concentration and
temperature. An example of such reaction is the iodine
clock reaction. The over-all equation is:
2I- + S2O82- ↔I2 + 2SO42-
As I2 forms, it is immediately consumed by its reaction
with a fixed amount S2O32-:
I2- + 2S2O32- ↔2I- + S4O62-
Once the S2O32- is consumed, the excess I2- forms a
blue – black product with a starch solution in the
mixture:
I2- + starch ↔ starch – I2 complex
The rate of the reaction is also influenced by the total
concentration of ions, so KCl and (NH4)2SO4 are added
to maintain a constant rate. Use the data in the lab
manual to determine the ff:
I. AVERAGE RATE OF EACH TRIAL II. ORDER REACTION WRT
REACTANTS
The rate of reaction as the rate of formation
of I2 over a period of time is as follows. Trial [S2O82-], [I-], M Rate of
M Rxn, M s-1
Rate = Δ[I2] / Δt 1 0.04 0.04 1.72 x 10-5
2 0.04 0.08 3.45 x 10-5
where, Δ[I2] is measured by [I2]final - [I2]initial. 3 0.02 0.08 3.47 x 10-5
There is no I2 formed in the beginning of The table stated that doubling the
reaction. Therefore, Δ[I2] = [I2]final concentration of S2O82- while holding [I-]
constant does not affect the reaction’s rate.
RATE:
By that, the reaction is zero order with
= Δ[I2] / Δt respect to S2O82-.
= [I2]final / Δt
On the other hand, doubling the
= (mol I2) / (vol sol’n)( Δt)
concentration of I- while holding [S2O82-]
constant doubles the rate of reaction.
The number of moles of I2 produced can be Therefore, the reaction is first order with
calculated from the amount of thiosulphate added to
respect to I-.
the reaction vessel.
III. RATE CONSTANT AT 25oC
2S2O32- + I2 → S4O62- + 2I-

mol S2O32- = (vol S2O32- added) x [S2O32-] Rate Law : Rate = k [I-]

Then, we now have, With the first trail as basis,

RATE: Rate = k [I-]

= (moles I2) / (vol sol’n)( Δt) K = Rate / [I-]
= (moles S2O32-) / 2(volume solution) (Δt) k = (1.72 x 10-5 M s-1) / (0.04 M)
RATE = (vol S2O32- added)[S2O32-] / k = 4.3 x 10-4 s-1
2(vol sol’n)(Δt)

Trial I: IV. THE RATE LAW FOR THE OVER-

ALL RXN
Rate = (vol S2O32- added)[ S2O32-] /2(vol sol’n)(Δt)
Rate = k [S2O82-]0 [I-]1
= (0.01 L)(0.005 M) / 2(0.05 L)(29 s) Rate = k [I-]

= 1.72 x 10-5 M s-1

Trial II: b. A solution of permanganate was added to an

acidified solution of oxalate and resulted in the decoloriztion of
Rate = (vol S2O32- added)[ S2O32-] /2(vol sol’n)(Δt) the permanganate. The rate of the reaction as well as its energy of
activation was determined. Given 50 ml of 0.1 M permanganate
= (0.01 L)(0.005 M) / 2(0.05 L)(14.5 s) and 10.0 ml of 0.005 of M C2O42-,

= 3.45 x 10-5 M s-1 I. BALANCED REACTION. Assuming that the rxn is in

first order wrt to the permanganate ion and first order over-all,
Trial III: calculate the rxn rate for each test tube.
Rate = (vol S2O32- added)[S2O32-]/2(vol soln)(Δt) a. Given:
Volume (MnO4-) = 0.05 L
= (0.01 L)(0.005 M) / 2(0.05 L)(14.4 s) Concentration (MnO4-) = 0.1 M
Volume (C2O42-) = 0.01 L
= 3.47 x 10-5 M s-1 Concentration (C2O42-) = 0.005 M
I. Balanced equation: Test Tube 3:
k = Rate / [MnO4-]
=(-2.71 x 10-3 M s-1)/(-8.33 x 10-2 M)
2MnO4- + 5C2O42- + 16H+ = 3.25 x 10-2 s-1
Test Tube 4:
→ 2Mn2+ + 8H2O + 10CO2 k = Rate / [MnO4-]
=(-7.10 x 10-3 M s-1)/(-8.33 x 10-2 M)
= 8.52 x 10-2 s-1
[MnO4-]init = (0.1 M)(0.05 L) / (0.06 L)
= 8.33 x 10-2 M Plot ln k versus 1/T to identify a best-fit line
and get the slope.
Based on the table given, [MnO4-]final = 0 M

Therefore, k ln k Temp (K) 1/T

values
Δ[MnO4-] = [MnO4-]final - [MnO4-]initial 0.00499 -5.30 293 0.00341
= 0 M - 8.33 x 10-2 M 0.00787 -4.84 303 0.00330
= -8.33 x 10-2 M 0.0326 -3.42 313 0.00319
0.852 -2.46 323 0.00310
Test Tube 1:
Rate = Δ[MnO4-] / 2 (Δt)
= (-8.33 x 10-2 M)/2(100.15 s) Graph of lnk vs. 1/T
= 4.16 x 10-4 M s-1
Test Tube 2: 0.00
0.00300 0.00310 0.00320 0.00330 0.00340 0.00350
Rate = Δ[MnO4-] / 2 (Δt)
= (-8.33 x 10-2 M)/2(63.55 s) -2.00
lnk

= -6.55 x 10-4 M s-1

Test Tube 3: -4.00
y = -9360.8x + 26.424
Rate = Δ[MnO4-] / 2 (Δt) R² = 0.9601
= (-8.33 x 10-2 M)/2(15.35 s) -6.00
= -2.71 x 10-3 M s-1 1/T
Test Tube 4:
Rate = Δ[MnO4-] / 2 (Δt) Using the slope above as the value for - Ea /
= (-8.33 x 10-2 M)/2(5.87 s) R, we get,
= -7.10 x 10-3 M s-1
- Ea / R = -9360
II. CALCULATE FOR Ea. Ea = -(R)(-9360)
Ea = -(8.314 J mol-1 K-1)(-9360 )
To calculate for the Ea, the rate Ea = 7.78 x 104 J mol-1
constant (k) for every test tube must first be
determined. Since it is assumed that the III. If MnSO4 was added to the solution, what will
reaction is first order with respect to MnO 4- happen to Ea?
and first order overall, we get a rate law of
Rate = k[MnO4-] If MnSO4 would be added to the
solution, the value of Ea would decrease.
Thus, MnSO4 will act as a catalyst that would
decrease the Ea of the reaction, allowing it to
k = Rate / [MnO4-] proceed faster than its normal rate.

Test Tube 1:
k = Rate / [MnO4-]
=(-4.16 x 10-4 M s-1)/(-8.33 x 10-2 M) REFERENCES
= 4.99 x 10-3 s-1
[1] Petrucci, R.H., Harwood, W.S., Herring, F.G.
Test tube 2:
k = Rate / [MnO4-] General Chemistry: Principles and Modern
=(-6.55 x 10-4 M s-1)/(-8.33 x 10-2 M) Applications (8th ed.). Prentice-Hall, Inc., USA.
= 7.86 x 10-3 s-1 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/
CCA3/MAIN/AUTOCAT/PAGE1.HTM>.

APPENDIX

1. Calculations