Experiment 5: Chemical Kinetics - the Iodine Clock Reaction

Purpose To measure the rate of a reaction and determine the rate law, rate constant, and Ea Equipment Needed clock or timer, hot plate, thermometer Chemicals Needed 0.050 M KI, 0.050 M Na2S2O3, starch solution, pH 4.7 buffer, 0.30 M HC2H3O2, 0.80 M H2O2 Discussion In this experiment, you will investigate the rate of the reaction 3 I (aq) + H2O2(aq) + 2 H (aq) I3 (aq) + 2H2O(l) The rate law for this reaction is given by rate = k[I ] [H2O2] [H ]
-x y + z + -

where the exponents x, y, and z and the rate constant k are to be determined. The reaction rate will be monitored by a clock reaction. A fixed amount of thiosulfate ion will be added to each reaction. Thiosulfate reacts rapidly with I3 2 S2O3 (aq) + I3 (aq) 3 I (aq) + S4O6 (aq) When all the thiosulfate is consumed, the I3 formed is free to react with added starch indicator and the solution will turn dark blue. The reaction rate [I ] rate = 3t is determined by the stoichiometric relationship between S2O3 , I3 , and I mol I = mol S2O3 x
2222-

1 mol I3

2-

2 mol S2O3

3 mol I 1 mol I3
-

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Experiment 5

Chemical Kinetics: the Iodine Clock Reaction 22-

3 [S2O3 ] [S2O3 ] so rate = x = 2 3t 2t By measuring the rate for a series of reactions in which only one reactant concentration at a time is varied, the order of the reaction for each reactant can be determined. Consider the reaction 2NO + 2H2 N2 + 2H2O experiment 1 2 3 [NO] 0.10 0.10 0.20 [H2] 0.10 0.20 0.10 Initial Rate 1.23 x 10 2.46 x 10 4.92 x 10
-3 -3 -3

In experiments 1 and 2, doubling [H2] results in a doubling of the reaction rate; therefore the reaction must be first order in hydrogen. In experiments 1 and 3, doubling [NO] results in a quadrupling (double-squared) of the reaction rate, therefore the reaction is second order in NO. Now that the rate law is known to be rate = k [NO] [H2] the value of k can be determined by substituting known values for [NO], [H2] and rate into the rate equation. By measuring the reaction rate at varying temperature, we can determine the activation energy for the reaction. According to collision theory, the rate of a reaction is controlled by the rate at which reactants collide to form the activated complex, a temporary species formed by collision prior to formation of products. The activation energy (Ea) is the minimum amount of energy required to form the activated complex. A + B activated complex C + D The rate of formation of activated complex controls the rate of the reaction.
2

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Experiment 5
Activated Complex

Chemical Kinetics: the Iodine Clock Reaction

Activated Complex

E A+ B E C+D A+ B C+D

exothermic reaction

endothermic reaction

The Arrhenius Equation relates the reaction rate constant to the activation energy and the temperature. k = Ae
-Ea/RT

where

Ea = activation energy in kJ/mol R = gas law constant, 8.314 J/K mol T = temperature in K A = frequency factor

-Ea + ln A so a plot of ln k vs 1/T gives a straight line with slope = -Ea/R and intercept = ln RT A. If k is known at two different temperatures ln k = k1 Ea 1 1 ln k2 = R T 2 - T 1

Procedure (work in pairs) A. Determination of the rate law Obtain 4 clean 400 mL beakers. Label them 1 through 4. To each beaker, add the reactants as specified in Table 1. Measure the temperatures of each solution and record these on the data sheet. If the temperatures are not within 0.5 C of each other, place the beakers close to each other and gently stir until the temperatures are within 0.5 C. Use a pH meter to measure the pH of each solution and record this data on the data sheet. In a separate beaker, measure 10.0 mL of 0.80 M H2O2 solution for reactions 1, 2, and 4, and 20.0 mL for reaction 3. Table 1: Initial volumes of reactants in a separate beaker

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Experiment 5 exp volume of H2 O (mL) volume of 0.050 M KI (mL) volume of 0.050 M Na2 S 2 O3 (mL)

Chemical Kinetics: the Iodine Clock Reaction volume of starch (mL) volume of pH 4.7 buffer (mL) volume of 0.30 M HC2 H3 O2 (mL) volume of 0.80 M H2 O2 (mL)

1 2 3 4

125 100 115 100

25.0 50.0 25.0 25.0

5.0 5.0 5.0 5.0

5.0 5.0 5.0 5.0

30.0 30.0 30.0 30.0

0 0 0 25.0

10.0 10.0 20.0 10.0

Perform each reaction separately. Use a clock or timer. Quickly add the H2O2 solution to the beaker and note the time required for the appearance of the intense blue color. Record this time (in seconds) on the data sheet.

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Experiment 5

Chemical Kinetics: the Iodine Clock Reaction

B. Determination of the activation energy Obtain a clean 400 mL beaker and label it 5. Add the reactants as specified in Table 2. Use a pH meter to measure the pH and record this data on the data sheet. Table 2: Initial volumes of reactants
exp volume of H2 O (mL) volume of 0.050 M KI (mL) volume of 0.050 M Na2 S 2 O3 (mL) volume of starch (mL) volume of pH 4.7 buffer (mL) volume of 0.30 M HC2 H3 O2 (mL)

in a separate beaker
volume of 0.80 M H2 O2 (mL)

125

25.0

5.0

5.0

30.0

10.0

Prepare a hot water bath by heating about 600 mL of water in an 800 mL beaker to a temperature of 40 -45 C. Remove the water bath from the hot plate and put beaker 5 in the water bath. When the temperature of solution 5 is the same as the water bath temperature, record it on the data sheet and add the 10.0 mL of H2O2 solution. Record the time (in seconds) required for the appearance of the intense blue color on the data sheet.

Calculations A. Determination of the reactant concentrations Use the dilution formula M1V1 = M2V2 to determine the initial concentration of each reactant after being diluted from the original concentration to the new final volume of 200 mL. Record these values in the calculations table. [H ] is determined from the pH value. [H ] = 10 B. Determination of the rate of the reaction The rate of the reaction is determined by the time required for the formation of the blue starch complex. This is set by the amount of S2O3 present 1 [S2O3 ] rate = 2 t Calculate the rate for each reaction and record these values in the calculations table. C. Determination of the order of the reaction For a reaction with a rate law in the form rate = k[A] [B] [C] , the order of the reaction for each reactant can be found by comparing two experiments in which the concentrations of only one
x y z 22+ + -pH

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Experiment 5

Chemical Kinetics: the Iodine Clock Reaction

reactant (say, A) changes. Then,

x y z [A1] x rate1 k[A1] [B] [C] = = rate2 k[A ]x [B]y[C]z [A2] 2

From this, x can be determined by taking the log of both sides; rate1 log rate2 x= [A1] log [A2]
-

rate1 = x log [A1] log rate2 [A2]

Calculate the reaction order of I from reactions 1 and 2. Calculate the reaction order of H2O2 from reactions 1 and 3. Calculate the reaction order of H from reactions 1 and 4. Calculate and record the order of the reaction for each reactant to 2 significant figures, then rounded to the nearest integer value. The overall order of the reaction is the sum of the orders in each reactant. D. Determination of the rate constant Once the orders of the reaction x, y, and z are determined, the experimental rate constant for each run is calculated by substituting known values for rate and concentration into the rate expression rate = k[I ] [H2O2] [H ]
-x y + z +

Calculate the experimental rate constant for each reaction and record these values in the calculations table. Calculate the average for reactions 1 - 4 E. Determination of the activation energy The activation energy is calculated from the Arrhenius equation once values of k are known at two different temperatures: k1 Ea 1 1 ln k2 = R T 2 - T 1 where R = gas law constant, 8.314 J/mol K T = temperature in K (= C + 273.15)

30

Experiment 5

Chemical Kinetics: the Iodine Clock Reaction

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Lab Report Experiment 5 Chemical Kinetics

Name Date Lab Partner

I. Data
exp H2 O (mL) 0.050 M KI (mL) 0.050 M Na2 S 2 O3 (mL) starch (mL) buffer (mL) H2 O2 (mL) 0.30 M HC2 H3 O2 (mL) total volume (mL) pH temp (C) time (sec)

1 2 3 4 5

125 100 115 100 125

25.0 50.0 25.0 25.0 25.0

5.0 5.0 5.0 5.0 5.0

5.0 5.0 5.0 5.0 5.0

30.0 30.0 30.0 30.0 30.0

10.0 10.0 20.0 10.0 10.0

0 0 0 25.0 0

200 200 200 200 200

II. Calculations exp 1 2 3 4 5 [KI] [Na2S 2O 3] [H2O 2] [H ]

+

Rate

Reaction order of I

Reaction order of H2O2

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Reaction order of H

Overall reaction order

33

Lab Report Experiment 5 Chemical Kinetics Calculation of Activation Energy Average k for reactions 1 - 4 k for reaction 5 Calculated value of Ea

Name

34