CHEMICAL KINETICS: THE IODINE CLOCK REACTION FORMAL REPORT IN CHEM 26.1 SUBMITTED BY STUDENT CLARICE MAE B.

DACASIN
C. M. B. DACASIN
DEPARTMENT OF FOOD SCIENCE AND NUTRITION, COLLEGE OF HOME ECONOMICS UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES DATE SUBMITTED: 10 DECEMBER 2013 DATE PERFORMED: 3 DECEMBER 2013

ABSTRACT This experiment, the iodine clock reaction, aims to determine the relationship of reactant concentration, temperature and the presence of a catalyst on the reaction rate of a chemical reaction. The kinetics of the reaction between I - and S2O82- was studied with both reactants having varied concentrations for each run, having S2O32- with constant concentration throughout the experiment. One by one, the reactions were timed and the formation of a deep blue complex marked the end of the reaction. This deep blue complex was from the reaction of iodine and starch. The overall reaction was found to be of second order through the presentation of the rate law and the calculation of reactant order, and the rate constant. For determining the relationship of temperature, the reaction was exposed to different temperatures. Increasing the temperature and having a catalyst present were proven to speed up the reaction.

INTRODUCTION The Iodine clock reaction experiment aims to observe and determine the effect of reactant concentration, temperature and the presence of a catalyst on the reaction rate. This experiment focuses on the rates of different runs with the usage of I- and S2O82- reaction mixture. The rate law, or rate expression/equation, expresses the rate as a function of reactant concentrations, product concentrations, and temperature [1]. The rate law for a reaction is experimentally determined relationship between the rate of a reaction and the concentration of its reactants, products, and other species such as catalysts, inhibitors, and activators [4]. The rate of a chemical reaction is the change of concentration of a reactant or product per unit time. In this experiment, to determine the rate law of the reaction, the initial rate method should be used. The rate law also contains a proportionality constant, k, called the rate constant. The rate constant is specific for a given reaction at a given temperature; it does not change as the reaction proceeds [2]. Reaction orders are the exponents at the concentration of each species in a reaction. Reaction orders define how the rate is affected by reactant concentration [2]. A reaction order of zero means that rate is not affected by reactant concentration. A reaction order of one (1st order) means that the rate doubles when the concentration of the reactant doubles. This is the same with the second order, but the rate quadruples. In this experiment, the kinetics of the reaction between persulfate, S2O82-, and iodide, I- ions was studied, S2O82- + 2I- 2SO42- + I2 (1)

The iodide ion in this reaction was oxidized by the persulfate to form molecular iodine. This was supposed to be a slow reaction, but since there was

an addition of the thiosulfate ion, the reaction continued faster, 2S2O32- + I2 S4O62- + 2I(2)

With the addition of the thiosulfate ion, the I2 formed from the S2O82-/I- reaction is reduced back to I- by S2O32- ions. Once the limiting reagent, S2O32-, is used up, I2 is free to react with the starch solution to form a deep blue complex. The rate expression of the reaction is as follows,
[ ] [ ] [ ] [ ]

(3)

In the first part of the experiment, the following solutions were prepared: 500 mL 0.2 M KI, 500 mL 0.2 M KCl, 500 mL 0.1 M K2S2O8, 500 mL 0.1 M K2SO4, 500 mL 4.0 mM Na2S2O3 (from Na2S2O35H2O), 20 mL of 1% fresh starch solution, and the catalyst, 5 mL 1 M CuSO4. Beaker A contains the prepared KI solution and KCl solution while beaker B contains the prepared K2S2O8 solution, the K2SO4 solution, the Na2S2O3 solution, and the starch solution. The five different runs of the experiment were done by varying the concentration of the reactants added to the reaction mixture. Every reactants concentration was altered in generally all five runs except for Na2S2O3, which was kept constant through all the runs. Varying the concentrations of the reactants was done to determine the reaction order of each reactant.

Table 1. The different runs for the effect of persulfate and iodide concentrations on reaction rate. Runa Beaker A Beaker B (+3 drops starch soln.) 0.2 M KI, mL 0.2 M KCl, mL 0.1 M K2S2O8 0.1 M K2SO4 4 mM Na2S2O3 1 10 0 5 5 5 2b 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 a Condition: room temperature b will be referred to as set 1 of run 2 (two more sets will be prepared in the next part) Runs 1-5 were done one at a time. By pouring the solution in beaker A to beaker B, that marks the start of the reaction and the immediate start of timing the reaction. When a dark blue complex is formed in the reaction, it marks the end of the reaction; therefore, stopping the timer. In the second part of the experiment, the effect of temperature on reaction rate was observed. Two more sets of run 2 were prepared and referred as sets 2 and 3. Set 2 was heated in a water bath up to 50OC. The contents of beaker A of set 2 were, then, mixed with the contents of beaker B of the same set and the reaction was immediately timed until a deep blue complex was formed. Set 3 was cooled in an ice bath up to 5OC. The contents of beaker A of set 3 were mixed with the contents of beaker B of the same RESULTS AND DISCUSSION Table 2. Effect of Reactant Concentration on Reaction Rate. set. The reaction was, again, timed until a deep blue complex formed. The third part of the experiment showed the effect of the presence of a catalyst on the reaction rate. A catalyst is a substance that enters into a reaction in such a way that it speeds up the reaction without itself being consumed or changed by the reaction [3]. A fourth set of run 2 was prepared. Beaker As contents were mixed with beaker Bs contents. Immediately after that, four drops of the catalyst, CuSO4 was added. By the addition of the catalyst, the reaction was timed until it turned blue or had a deep blue complex. Results were recorded and with this, reaction orders were found and the rate constant and rate law were calculated.

Runs [S2O82-] [I-] 1 0.02 0.08 2 0.02 0.04 3 0.02 0.02 4 0.03 0.04 5 0.04 0.04 Temperature: 298 K Total volume of each reaction mixture: 25 mL

[S2O32-] 8 x 10-4 8 x 10-4 8 x 10-4 8 x 10-4 8 x 10-4

Reaction Time, s 40.44 68.00 124.54 23.41 21.81

Rate, Ms-1 9.89 x 10-6 5.88 x 10-6 3.21 x 10-6 1.70 x 10-5 1.83 x 10-5

Initial concentration of the reactants were calculated using the dilution formula (See Appendix A), M1V1 = M2V2 (4)

the change of reaction rate. Both of the reactants are directly proportional to the rate of reaction; meaning, doubling the concentration of the reactants means doubling the reaction rate. Since the rate law was already stated and reaction order is already computed, the rate constant can now be computed from it by substituting the average of all given concentrations of the reactants present in the equation and the average rate. The value of the rate constant will then be k = 9.43 x 10-3. For the reaction in this experiment, the overall order of reaction is 2. Therefore the integrated rate equation for this chemical reaction is as follows [6],
[ ] [ ]

Reaction rate was then determined using the following equation (See Appendix B),
[ ] [ ]

(5)

The thiosulfate just consumes the molecular iodine. Because of this, and by looking at equation (2), the change of the concentration of iodine is half the concentration of thiosulfate, known at the beginning of the reaction. Once each reaction rate was determined, the reaction order and rate constant can now be computed and the rate law can now be stated given the following equation format, [ ] [ ] (6)

(10)

In the integrated rate law for the reaction tackled in the experiment, [A]o is the initial concentration of S2O82- and [A]t is its final. The following graph shows the relationship of the persulfate ion concentration and the rate of the reaction, Figure 1. Graph showing the relationship between persulfate ion concentration and reaction rate. ln(rate)
-10.5 -6 -4 -2 -11 -11.5 -12 -12.5 -13 0

In the given equation, k is the rate constant and [A] and [B] are the concentrations of the reactants. The exponents m and n give the reaction order of the reactant. For this experiment, the rate law used was the following, [ ] [ ] (7)

Reaction order was computed by dividing the rates in run 1 and run since both have the same [S2O82-]. This would lead to cancellation of like variables (See Appendix C). The rate law, with exponents rounded off to the nearest whole number, could be stated as follows, [ ][ ] (8)

ln(rate) Linear (ln(rate))

The overall order of the reaction is 2. Having this overall order means that both reactants participate in

y = 1.8674x - 4.7265 R = 0.6511

ln[S2O82-]

The relationship is also defined by the following equation, The graph was done using the graph maker of Microsoft Excel 2013. From the graph maker, the equation could be made, including the correlation, r2. The significance of the correlation is that when it is near 1, it gives out a straight line. A straight line indicates the correctness of the order of the reaction. The correlation value could be rounded off to 1, therefore it shows a straight line. And since r2=0.6511, there is room for 34.89% error.

y = 1.8674x 4.7265

(9)

The manual computation for the equation, by treating ln(rate) values as x-values and ln[S2O82-] values as yvalues, could be done by replacing the variables in the two-point form line equation, ( ) ( )( ) (10)

The reactant concentration-reaction rate relationship could also be graphed using [I-] instead of [S2O82-],

Figure 2. Graph showing the relationship between iodide ion concentration and reaction rate.

ln(rate)
-6 -4 -2 -10.6 -10.8 0 -11 -11.2 -11.4 -11.6 -11.8 -12 -12.2 -12.4 -12.6 -12.8

ln(rate)

The relationship is also defined by the following equation, y = 0.8117x 9.0089 (11)

The same methods and programs were used in forming this graph. In manually computing for the equation, ln(rate) values were treated as x-values while ln[I-] values were treated as y-values. The correlation of this graph is very low. This may be due to experimental errors in the experiment. This leaves 70.7% error. Table 3. Temperature and Catalyst on Reaction Rate. Run 2 Temperature, Reaction time, s Rate, Ms-1 K Set 1 301.15 68.00 5.88 x 10-5 Set 2 323.15 9.00 4.44 x 10-5 Set 3 278.15 211.51 1.89 x 10-6 Set 4 301.15 0.10 4.00 x 10-3 2[S2O8 ]: 0.02 M [I ]: 0.04 M Rate Constant 7.35 x 10-2 5.55 x 10-2 2.36 x 10-3 5.00 [S2O32-]: 8 x 10-4 M

Set 1 was subjected to room temperature (28OC), set 2 was subjected to a hot both (50OC), and set 3 was subjected to an ice bath (5OC).

ln[I-]

Linear (ln(rate))

y = 0.8117x - 9.0089 R = 0.293

The activation energy, or the energy barrier for the reaction [5], can be computed by using the Arrhenius equation (12), (12) Figure 3. Graph showing the relationship between temperature and reaction rate. lnk
0 0.003 0.0032 0.0034 0.0036 0.0038 -1 -2

1/T

-3 -4 -5 -6 -7

lnk Linear (lnk) y = -6526.9x + 17.928 R = 0.7345

From the graph, the slope is known to be the activation energy of the reaction. It is noted that when activation energy decreases, there is an exponential increase on the rate constant. The activation energy is 6526.9 J while the Arrhenius constant is 17.928. The correlation is near one but still makes room for 26.55% error. The last set, set 4, in table 3 is the set in which there is the presence of a catalyst. The catalyst for this reaction is CuSO4. Comparing it with the control, set 2 in table 3, it was shown to have a faster reaction than that of the control. It should be noted that both sets were in room temperature. Therefore, there was no way temperature would interfere with the reaction. SUMMARY AND CONCLUSIONS The rate of the reaction is affected by concentration of its reactants, temperature, and the presence of a catalyst. The overall reaction order in this experiment is 2nd order, having a first reaction order for both reactants. The reaction favors a lower concentration of the reactants, a higher temperature and the presence of a catalyst to have small rates or a faster reaction. The experiment was a failure due to experimental errors so results for verification were from another group. The results in this paper are the results verified and proved to be correct. Experimental errors include the preparation of starch solution and/or the preparation of the other solutions, most probably the Na2S2O3. Other errors in the experiment include the error in timing the reaction. Some may have stopped the timer when a blue complex appeared, and others may have stopped the timer when the blue complex consume the solution. REFERENCES [1] Silberberg, M. Chemistry: The Molecular Nature of Matter and Change 5th ed. 2010. Avenue of the Americas, NY: McGraw-Hill. 691. [2] Silberberg, M. Chemistry: The Molecular Nature of Matter and Change 5th ed. 2010. Avenue of the Americas, NY: McGraw-Hill. 692.

[3] Petrucci, R.; Herring, F. G.; Madura, J.; Bissonnette, C. General Chemistry: Principles and Modern Applications 10th ed. 2011. Toronto, Canada: Pearson Prentice Hall. 116. [4] Skoog, D.; West, D.; Holler F.J.; Crouch, S.R. Fundamentals of Analytical Chemistry 8th ed. 2004. Belmont, CA: Brooks/Cole, Thomson Learning. 879. [5] Harris, D. Quantitative Chemical Analysis 8th ed. 2010. Madison Avenue, NY: W.H. Freeman and Company. 134. [6] Whitten, K.; Davis, R; Peck, M.; Stanley, G. Chemistry 8th ed. 2010. Belmont, CA: Brooks/Cole, Cengage Learning. 625. APPENDIX A Sample calculations: Concentration M1V1 = M2V2 Run 1 M1V1 = M2V2 [S2O82-]: ( [ ] [I-]: ( [ ] [S2O32-]: ( [ ] Run 2 [S2O82-]: ( [ ] [I-]: ( [ ] [S2O32-]: ( [ ] Run 3 [S2O82-]: ( [ ] [I-]: ( [ ] )( )( ) ) ( ( ) ) )( )( ) )( ) ( ) ( ) ( ) ) )( )( ) )( ) ( ) ( ( ) ) )

[S2O32-]: ( [ ] Run 4 [S2O82-]: ( [ ] [I-]: ( [ ] [S2O32-]: ( [ ] Run 5 [S2O82-]: ( [ ] [I-]: ( [ ] [S2O32-]: ( [ ] APPENDIX B Rate [ Note: )( )( )( )(

)(

) ) )( ( )

( ) (

) ) )( ( )

( ) (

Part 1 (Concentration vs. Rate) Part 2 Temperature + Catalysts vs. Rate)

Part 1, Run 1: [ ] Part 1, Run 2: [ ] Part 1, Run 3: [ ] Part 1, Run 4: [ ]

Part 1, Run 5: [ ] Part 2, Run 1: [ ] Part 2, Run 2: [ ] Part 2, Run 3: [ ] Part 2, Run 4: [ ] APPENDIX C Reaction order APPENDIX D Rate constant [ Part 1, Run 1: ( )( ) ][ ]

Part 1, Run 2: ( )( )

Part 1, Run 3: ( )( )

Part 1, Run 4: ( )( )

Part 1, Run 5: ( )( )

Average rate constant (k): ( k = 9.43 x 10-3 M-1s-1 (second order overall reaction) Part 2, Run 1: ( )( )

Part 2, Run 2: ( )( )

Part 2, Run 3: ( )( )

Part 2, Run 4: ( )( )