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DARLENE M. ROXAS

NATIONAL INSTITUTE OF MOLECULAR BIOLOGY AND BIOTECHNOLOGY, COLLEGE OF SCIENCE

UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES

DATE SUBMITTED: 10 DECEMBER 2013

DATE PERFORMED: 23 NOVEMBER 2013

ABSTRACT

In a given chemical reaction, the reaction rates are expressed and explained through chemical kinetics. The iodine-clock reaction aims

to explain concepts of reaction rate and show the effects of major factors in the reaction rates including the concentration, temperature

and presence of catalyst between persulfate and iodide ion. Five different runs with different concentrations of S 2O82- and I- were

prepared to find the reaction order of each reactant using the initial rate methods and graphical methods. The rate law established

base from the experimental data was R=k[S2O82-][I-]. Other sets of run with constant concentration were prepared under different

temperature condition: cold (50C), room temperature (29oC), and hot (50oC) and the calculated activation energy (Ea) and Arrhenius

constant (A) was 5.043 x104 J/mol and 1.639 x1010, respectively, using the Arrhenius equation. A set with constant concentration and

constant temperature was prepared and treated with CuSO 4 to test the effect of catalyst to the reaction rate. The change in

concentration, temperature and presence of catalyst showed a significant change in the reaction rates of persulfate and iodide ion.

Faulty timer and disturbed nature of solutions due to physical factors are the possible reasons of errors in the data.

INTRODUCTION

Chemical kinetics is the study of reaction rates, the changes in

concentrations of reactants (or products) as a function of time

[1] and can be described using the formula (1) given in this

hypothetical reaction

aA bB.

rate =

[A] [B]

a t

b t

(1)

based from thermodynamics. But whether the rate of this

reaction is slow or fast is described by chemical kinetics. Take

for example an enzyme-catalyzed reaction C D, where C is

the substrate and D is the product. Kinetics relates the

concentration of the reactants to the rate of reactions. Hence,

the rate law (2) is given by using the formula

(2)

where k is the rate constant and [C] is the given molar

concentration of reactant C. The overall order of reaction can

also be obtained using the equation (X) which is the sum of the

exponents, m, of the reactants. These exponents, however,

are not related to the stoichiometric coefficients; rather it is

determined from the actual experiment. The order of the

reaction sets up the rate law that can calculate rate constants

given the molar concentrations of reactants and establish an

integrated law that can relate the change of concentrations in a

given period of time [2].

This experiment has been used as a visual representation

involving the investigation of rate expression in chemical

kinetics. The "Iodine Clock" refers to a group of reactions

which involve the mixing of two colorless solutions to produce

a solution which remains colorless for a precise amount of

time, then suddenly changes to a deep purple-blue color. The

time is controlled by the temperature and/or the concentrations

reaction mechanism of the iodine clock reaction and to

describe the rate of reaction through measuring the rate of

formation of I2 from the reaction of S2O82- and I-. The time when

all 2O82- are consumed, the rate of I2 formation can be

calculated.

To describe the kinetics of the iodine clock reaction, certain

factors that may affect the rates of reaction were observed

including the concentration of the reactions, temperature, and

the presence of catalyst. In the experiment, the reaction (3)

between persulfate, S2O8-2, and iodide, I- was studied.

S2 O8 2- + 2I - 2SO 4 2- + I 2

conditions: varying concentrations at constant temperature,

varying temperatures at constant molar concentration, and

presence of catalyst.

Table 1. Different runs for the effect of concentration to

reaction rates

Beaker A, mL

Beaker B (+ 3 drops of

starch solution), mL

Ru

0.2

0.2 M 0.1 M

0.1 M

4 mM

n

m KI

KCl

K2S2O8 K2SO4 Na2S2O3

1

10

0

5

5

5

2

5

5

5

5

5

3

2.5

7.5

5

5

5

4

5

5

7.5

2.5

5

5

5

5

10

0

5

rate

The

rate

of

reaction for the first condition is measured using the following

rate law (4,5) according to the rate of disappearance of S2O82-/Iand appearance of I2 / SO42-.

(4)

n

k[S2 O8 ] [I ]

(5)

concentrations to the rate of reactions, several sets from run 2

shown in table 1 were prepared at different temperatures: at

50oC, 15oC, and 27oC. Svante Arrhenius demonstrated that the

rate constant of chemical reactions vary with temperature in

accordance with the equation (6) that yields to varying values

of slope so we take the natural logarithm of both sides and

resulted to a linear equation (7). Plotting ln k vs 1/T gives a

linear equation (8) wherein the slope of the line (m) is equal to

-Ea/R, and y-intercept (b) is equal to ln A.

k Ae Ea /RT

(6)

ln k

E a 1

ln A

R T

(7)

y m (x ) b

(8)

where k is the rate constant, Ea is the activation energy, R is

the universal gas constant (8.314 J/mol K), T is the

temperature (K), and A is the Arrhenius constant (the fraction

of molecules with successful collision).

On the other hand, another set of run 2 was treated with

CuSO4 to compare the effect of the catalyst on the rate of the

reactions to the controlled set of run 2.

t

2t

2t

t

2 m

where k is the rate constant, m and n are the orders of the two

reactants obtained from the experiment using the initial rate

method and graphing ln rate vs ln [S2O82-]/[I-] to determine the

slope of the line as the order of the reaction with respect to

reactants.

(e.g. medicine, industry, business). Knowing the rate of the

cement to solidify after a period of time can make an impact in

flow of your business. Knowing the rate of an antibiotic to react

with your body can make an impact to your health. Having said

these real life situations, chemists study the kinetics to have a

higher percentage yield of products and to avoid unwanted

reactions [4].

RESULTS AND DISCUSSION

rate of this reaction is to couple it with a much faster reaction

that consumes I2 by adding up Na2S2O3 that results to a new

chemical reaction (9).

I 2 + 2S2 O3 2 I 2 + 2S4O 6 2

(9)

The second chemical reaction consumes all I 2 immediately

after its first reaction with S2O32-. After using all S2O32-, the

starch will react with the accumulating I2 to form a greenishblue color. The time elapsed after the mixture turns blue was

used to calculate the reaction rate of persulfate and iodide ion

[5].

For a given chemical reaction, the rate of reaction can be

measured through change of concentration over time. Runs 1,

2, 3 were used to compare the rates with respect to the varying

concentration of I-. Experimentally, the reaction time (time

when the reaction turns blue) showed a significant increase as

the concentration I- decreases shown in table 2. The same is

true for the rates of Runs 2, 4, 5 where concentration of S 2O82varies. However, the obtained rates of reaction for the different

runs were not obtained using the rate law (4). Instead, the

reciprocal of the time elapsed when the mixture turns blue was

used since it will produce the same amount of I 2 over time and

is directly proportional to the rate of the reaction.

Table 2. Effect of Reactant Concentration on Reaction Rate

[S2O82-], [I-],

[S2O32-], Rxn

Rate,

M

M

M

time, s

1/s

1 0.02

0.08 0.0008

31.34

0.0319

2 0.02

0.04 0.0008

53.86

0.0186

3 0.02

0.02 0.0008

115.94

0.00863

4 0.03

0.04 0.0008

38.06

0.0263

5 0.04

0.04 0.0008

29.34

0.0341

In order to describe the reaction of the iodine clock reaction or

how does concentration of the reactants affects the reaction, a

rate law should be established. Initial rate method (see

Appendix C for Calculations) can be used to express this

equation which gives us the orders (m, n) of the reactants for

the iodine-clock rate law (5). These exponents are conformed

from experimental data obtained. The reaction order with

respect to S2O82- /I- calculated by comparing rates for different

initial concentration of the rate law of each run is m=1 and n=1,

respectively. With these values, we can establish the rate law

(10) expression for iodine-clock reactions as

R k[S2 O8 2 ][I ]

(10)

On the other hand, reaction orders can also be determined

graphically by plotting ln (rate) vs. ln (conc. of reactants).

Figure X shows the graph of ln (rate) vs. ln ([S2O82-]) with the

obtained equation y=1.145x + 0.635 and linearity value R 2

equal to 0.999. The determined value of slope is the reaction

order of S2O82- is 1.145.

Figure 1. Effect of [S2O82-] on the rate

0

-4.2 -4 -3.8 -3.6 -3.4-1-3.2

-2

ln [S2O82-]

-3

-4

-5

ln rate

its order. Figure 2 below shows the equation of the line

y=1.049x + 1.043 with linearity value R2 of 0.989. The obtained

slope of the equation, m= 1.049, is the reaction order of I-.

Figure 2. Effect of [I-] on the rate reaction

0

-5

-4.5

-4

-3.5

-1 -3

-2

ln [I-]

-3

-4

-5

ln rate

Based from the obtained values

of m and n from the plotted graph, another rate law (11) can

established as

(11)

Calculating the rate constants using different rate laws (10 and

12), table 3 shows the significance difference of constant, k in

different runs.

Table 3. Calculated

laws

Rate, 1/s

1

0.0319

2

0.0186

3

0.00863

4

0.0263

5

0.0341

k1*

1.994 x101

2.325 x101

2.158 x101

2.192 x101

2.131 x101

k2**

3.979 x101

4.800 x101

4.608 x101

4.267 x101

3.980 x101

the equation (12)

*

3

I ( aq ) S2O8 2 ( aq ) u

slow

uu

r [I...S2O8 ] ( aq )

*

Table 4. Effect

constants

Ru Temp,

n2

K

S 1 302.1

5

S2 323.1

5

S 3 278.1

5

k1*

k2**

Rxn

time, s

53.86

Rate,

1/s

0.0186

23.25

48.00

9.11

0.110

137.5

283.9

197.7

9

0.0050

6

6.325

13.06

**derived from rate law R=k[S2O82-]1.145[I-]1.049

the change of temperature wherein the time when mixture

turns blue increases as the temperature increases. The rate,

which was also obtained by reciprocating the time, and the rate

constants, which were calculated based from the established

rate laws (10 & 11) also matches the increasing trend of

temperature.

In order to calculate the Ea (activation energy) and the A

(Arrhenius constant), the graph of ln k vs 1/T should be

determined. Figure 3 shows us the straight line leaning to the

right giving us the negative slope of -6065.6, which is equal to

Ea/R, and a y-intercept of 23.52, which is equal to the ln A

given by the formula (7). The activation energy calculated

using the k obtained using the rate law (10) is 5.043 x10 4 J/mol

and the Arrhenius constant, A, is 1.639 x1010.

Figure 3. Effect of Temperature on Reaction Rate based from

R= k[S2O82-][I-]

[I...S2 O8 ]3( aq ) + I u

fast

uu

r I 2( aq ) 2SO 4

(12)

where I is a reactive, unstable species, so it has a higher

energy than the products or reactants. Since I 2 appears only in

the second fast reaction based from the experiment, the

mechanisms with slow initial step correlates the rate law given

wherein the overall rate law can include only reactants (or

products).

For the second condition, temperature often has a major effect

on reaction rates given by the Arrhenius equation (7).

Preparing the sets from Run 2 with varying temperature and

constant molar concentrations, the obtained rates and rate

constants are shown in table 4.

4

1/T 2

0

0

0

ln k

where k is obtained from the rate law (11). The graph gives us

a linear equation of y= -6065.6x + 24.24 with linearity R 2 of

0.971, where calculated Ea is equal to 5.043 x104 and the

Arrhenius constant equal to 3.367 x1010.

Figure 4. Effect of Temperature on Reaction Rate based from

R=k[S2O82-]1.145[I-]1.049

53.86 s. The catalyst decreases the activation energy without

being consumed during the reaction. In general principle,

causes a lower Ea, thus making the rate constant larger and

reaction rate higher [6]. This is very evident with the rate

constant obtained from the two rate laws and the rate

calculated shown in table 5.

and set w/ CuSO4 catalyst

Run 2

Temp, K

Rxn time, s

Rate, 1/s

S1

302.15

53.86

0.0186

S4

302.15

13.88

0.0720

*derived from rate law R= k[S2O82-][I-]

**derived from rate law R=k[S2O82-]1.145[I-]1.049

6

4

1/T 2

0

0

ln k

with each other to react [5]. To have a higher efficiency of

collision between molecules, the proper orientation of these

reacting species should be considered. Therefore the

evaluated Arrhenius constant, A, described as the number of

collisions that must occur for the reaction to proceed in a fast

or slow phase reflects the molecular structure or orientation of

the reacting species. Meanwhile, the activation energy Ea

calculated reflects the required energy of the molecules to

react as it is one of the requirements for a reaction to continue

based from collision theory.

The fourth set of run 2 which is prepared by adding CuSO 4 that

acts as a catalyst. The reaction time of set with catalyst has

compared to past studies. There may have a small amount of

difference but it can be accounted as errors in time and

temperature readings and other chemical or environmental

factor.

SUMMARY AND CONCLUSIONS

The reaction rates of persulfate and iodide under different

conditions: a) varying concentration, b) temperature, and c)

presence of catalyst were obtained. Effects of varying reactant

concentration affected the average reaction time affecting also

the rates of the reaction. From the given initial rates, the

reaction orders of 1 for both reactants were obtained using the

initial rate method. Graphing ln (rate) vs ln [S2O82-] gave a

linear equation of y=1.145x + 0.653 with linearity of R 2 equal to

0.999. The slope of the line determined the reaction order of

S2O82- which is 1.145. Plotting the graph of ln (rate) vs ln [I-]

showed a straight line with a linear equation of y= 1.049x +

1.043 with linearity of R2 equal to 0.989. The reaction order of Igiven by the slope of the equation is 1.049. The calculated

order of each reactant has a significant difference with the

orders obtained from the graph. Using the order obtained from

the experimental data, the rate law of the iodine clock

reactions is R= k[S2O82-][I-], while the rate law established from

the graph (x) is R= k[S2O82-]1.145[I-]1.049. The rate constant from

rate law (11) are doubled values of rate constant from rate law

(12).

On the second part where solutions are observed under

different temperature conditions, the rates of different set-ups

have varying values of rate. Following the reaction order

obtained from initial rates method, set-up under cold

temperature (at 5oC) has computed rate of 0.00506 s-1 and a

has a calculated rate of 0.0186 s-1 and a rate constant of 23.25

M-2s-1; and under high temperature (at 50oC) has a calculated

rate of 0.0110 s-1 and a rate constant of 137.5 M-2s-1. As

temperature increases, the rate of reaction of persulfate and

iodide ion increases along with the rate constant. Using the

Arrhenius equation (X), the computed activation energy Ea is

5.043 X104 J/mol and the Arrhenius constant computed is

1.639 x1010.

The following values may vary as many factors can affect the

chemical reaction of persulfate and iodide ion. Inaccurate timer

can be accounted as one major sources of errors as it can

have a different settings from the other types of error so a

primary and uniform timer should be used to lessen this errors.

Other factors such as thermometers can influence any great

changes especially in the temperature obtained. Proper

reading of the temperature should also be considered.

constant after using the reaction order of the two reactants

obtained from the graph. Set-up under 5oC has a calculated

rate constant equal to 13.06 M-2s-1, while set-up under room

conditions has a calculated k of 48.00 M-2s-1. Set-up under high

temperature (at 50oC) has a computed rate constant equal to

283.9 M-2s-1. The Ea is also equal to 5.043 x104, while the

Arrhenius constant has increased to 3.367 x1010 after using the

reaction orders obtained from the plotted graph (X). The

Arrhenius constant and the Ea reflects the efficiency of the

orientation of the molecules during the collision and the energy

required in order the two reactants to react.

REFERENCES

1.86 x10-2 to 7.20 x10-2 and in the rate constant from 23.25 M2 1

s to 90.00 M-2s-1 upon addition of CuSO4 as catalyst. The

calculated rate is based from the reaction order obtained from

initial rates method. Using the reaction order from the plotted

graph of ln (rate) vs. ln [S2O82-]/[I-], the computed rate constant

significantly increased from 48.00 M-2s-1 to 185.8 M-2s-1. The

results reflect the great influence of catalyst in the fast rates of

the reaction.

Principles and Modern Applications. 2011. Ontario: Pearson

Canada Inc.

Chemistry. 2007. New York: McGraw-Hill.

[3] Bertrand, Gary L. Iodine Clock Reaction: A Simulated

Experiment.

http://web.mst.edu/~gbert/IClock/IClock.html.

Web. 07 December 2013

[5]

Chemistry

102

http://www.csun.edu/chem/documents/Kinetics.pdf.

December 2013.

Manual.

Web. 09

Table 1. Different runs for the effect of

Table 2. Effect of Reactant Concentration on Reaction Rate

Table 3. Calculated rate and rate constants of different rate laws

Table 4. Effect of temperature to the reaction rate and rate constants

Table 5. Calculated rate and rate constants of set w/o catalyst and set w/ CuSO4 catalyst

APPENDIX B List of Figures

Figure 1. Effect of [S2O82-] on the rate

Figure 2. Effect of [I-] on the rate reaction

Figure 3. Effect of Temperature on Reaction Rate based from R= k[S2O82-][I-]

Figure 4. Effect of Temperature on Reaction Rate based from R=k[S2O82-]1.145[I-]1.049

APPENDIX C Calculations

A. Effect of Reactant Concentration on Reaction Rate

I.

a. Reaction order with respect to S2O82-

R 5 0.0341 s 1

[0.04]m x[I ]n

1

R 4 0.0263 s 1

[0.03]m x[I ]n

1 1.33m

m 1

[0.08]n x[S2O8 2 ]m

R 2 0.0319 s 1

2

R1 0.0186 s 1

[0.04]n x[S2 O8 2 ]m

2 = 2n

n 1

Reaction order with respect to I-

b.

II.

a) Run 1

b)

R

[S2 O8 2 ][I ]

Run 2

R

2

[S2 O8 ][I ]

R

[S2 O82 ][I ]

0.0319 s 1

=

[0.02 M][0.08 M]

0.0263 s 1

=

[0.03 M][0.04 M]

0.0186 s 1

=

[0.02 M][0.04 M]

= 1.994 x101 M 2s 1

= 2.192 x101 M 2s 1

= 2.325 x101 M 2s 1

c) Run 3

d)

Run 4

R

[S2O8 2 ][I ]

0.00863 s 1

=

[0.02 M][0.02 M]

= 2.158 x101 M 2s 1

e)

Run 5

R

[S2 O8 2 ][I ]

0.0341 s 1

=

[0.04 M][0.04 M]

= 2.131 x101 M 2s 1

III.

b)

2 1.145

[S2 O8 ]

1.049

[I ]

R

[S2 O8 ]

[I ]1.049

0.0341 s 1

=

[0.02 M]1.145 [0.08 M]1.049

0.0186 s 1

=

[0.02 M]1.145 [0.04 M]1.049

b)

Run 2

c) Run 3

2 1.145

d)

R

2 1.145

[S2 O8 ]

1.049

[I ]

Run 4

R

2 1.145

[S2O8 ]

[I ]1.049

0.0263 s 1

=

[0.03 M]1.145 [0.04 M]1.049

0.00863 s 1

=

[0.02 M]1.145 [0.02 M]1.049

d) Run 5

R

[S2 O8 2 ]1.145 [I ]1.049

0.0341 s 1

=

[0.04 M]1.145 [0.04 M]1.049

= 3.980 x101 M 2.194s 1

Run 1

I.

a) Run 2: Set 1

b) Run 2: Set 2

R

[S2 O8 2 ][I ]

0.0186 s 1

=

[0.02 M][0.04 M]

= 23.25 M 2s 1

k

R

[S2 O8 2 ][I ]

0.110 s 1

=

[0.02 M][0.04 M]

= 137.5 M 2s 1

R

[S2 O82 ][I ]

0.00506 s 1

=

[0.02 M][0.04 M]

= 6.325 M 2 s 1

c)

Run 2: Set 3

II.

d) Run 2: Set 1

b) Run 2: Set 2

R

[S2O8 2 ]1.145[I ]1.049

R

[S2 O8 2 ]1.145 [I ]1.049

0.0186 s 1

=

[0.02 M]1.145[0.04 M]1.049

0.110 s 1

=

[0.02 M]1.145 [0.04 M]1.049

= 48.00 M 2.194s 1

= 283.9 M 2.194s1

R

2 1.145

[S2 O8 ]

[I ]1.049

0.00506 s 1

=

[0.02 M]1.145 [0.04 M]1.049

c)

= 13.06 M 2.194s 1

Run 2: Set 3

III.

ln k

E a 1

ln A

R T

Ea

R

Ea (6065.6)(8.3145 J/mol K)

m 6065.6

from both rate laws (10 & 11) are equal.

b ln A 24.24

a)

b ln A 24.24

I.

R

[S2 O8 2 ][I ]

0.0186 s 1

[0.02 M][0.04 M]

=

a)

= 23.25 M 2s 1

w/o catalyst

R

[S2 O8 2 ][I ]

0.0720 s 1

=

[0.02 M][0.04 M]

b)

= 90.00 M 2s 1

w/ catalyst

R

[S2 O8 2 ]1.145 [I ]1.049

0.0186 s 1

=

[0.02 M]1.145[0.04 M]1.049

a)

= 48.00 M 2.194s 1

w/o catalyst

R

[S2O8 2 ]1.145 [I ]1.049

0.0720 s 1

=

[0.02 M]1.145 [0.04 M]1.049

b)

= 185.8 M 2.194s 1

w/ catalyst

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