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CHEMICAL KINETICS

Determination of Rate of Chemical Reaction for an Iodine Clock Reaction

Datoya Brown CHEM 160: General Chemistry II 26 July 2012

Datoya Brown 1 Abstract The factors that affect the rate of a chemical reaction are important to understand due to the importance of many such reactions to our health, well-being and comfort. It would be advantageous to slow down some of these reactions such as food spoilage and rust formations, while in the cases of reactions such as the Tums-stomach acid reaction and the conversion of organic matter to fossil fuels, it would be beneficial to them speed up. The purpose of this lab is to measure the effect of concentration upon the rate of a reaction of peroxydisulfate ion with iodide ion: 2 S 2 O82 2 I I 2 2SO4 ; to determine the order of the reaction with respect to the reactant concentrations; and to obtain the rate law for the chemical reaction: [ S 2O82 ] k[ S 2O82 ]x [ I ] y t Introduction The full purpose of this experiment is to deal with the laws of chemical kinetics, and by doing the experiment, compare the experimental results with the theories and see if they were consequently followed. From the kinetics studies, it is obvious that the rate of a reaction increases as the temperature of the reaction increases and as the concentration of the reactants increases. Also, the catalyst increases the rate of the reaction and decreases the activation energy. So, this experiment is divided into three sections and the dependence of the reaction rate from different factors is observed in step by step fashion. The idea of the first part of this experiment is to find the reaction orders with respect to each reactant and the rate constant, k. The method of initial rates to calculate the order with respect to each reagent will be used. With different times, the concentrations will vary in each trial. In this experiment, the following type of reaction is considered: The peroxodisulfate ion, S2O82-, oxidizes iodide ion reasonably slowly at room temperature in 2 accord with the equation: S2O82 2 I I 2 2SO4 (Equation 1) The rate of reaction can be expressed simply in terms of the decrease of any one of the reactants with respect to time or the increase of one of the products with respect to time and is written as follows: Rate = - [S2O82-]/t = - [I-]/2t = / [I2] t = [SO42-]/2t (Equation 2) The first equality states that the reaction rate is equal to the decrease in peroxodisulfate ion concentration for a given time interval. Equation 1 indicates that two iodide ions are used for every peroxodisulfate ion that reacts, and the second equation involving the iodide ion also shows this fact. One of the main purposes of a kinetics experiment is to find the rate law for the reaction, the expression that relates rate to the concentration(s) of the reactant(s). In the above reaction the rate depends both on the concentration of I- and S2O82- ions and takes the general form: Rate = k [I-] m [S2O82-] n (Equation 3), where k is the rate constant and m and n are the reaction orders. In this experiment you will study the kinetics of the reaction of iodide ion with peroxodisulfate ion and determine the rate law. The method for measuring the rate of the reaction involves what is frequently called a clock reaction. This is a second reaction (or set of rapid consecutive reactions)

Datoya Brown 2 that gives a signal, such as a color change, when a particular quantity of one of the reactants has been consumed. Our clock will be based on the facts that thiosulfate ion, S2O32-, reacts rapidly and quantitatively with iodine, I2: I2 + 2S2O32- 2I- + S4O62- (Equation 4) and an intense blue-black coloration is formed almost instantly when exceedingly small traces of I2 are in the presence of starch and I- (hence, an indicator that detects iodine). Thus, the reaction of peroxodisulfate ion with iodide ion is started in the presence of a known trace amount of thiosulfate ion and the starch indicator. As the reaction progresses, the iodine, as it is formed, immediately reacts with the thiosulfate and the reaction mixture remains colorless. When the trace quantity of thiosulfate is used up, iodine produced by the oxidation of iodide ion now remains in solution and causes the starch indicator to turn blue-black in color. Therefore, at time t, the time after mixing when the solution turns blue-black, for every mole of thiosulfate originally present, 1/2 mole of iodine has been produced and used up, and 1/2 mole of peroxodisulfate also has been used up. At this point, the change in concentration of S2O82- must be equal to half the original S2O32concentration, and thus, where a rate has been expressed in terms of -[S2O82-]/ t, or Rate = [S2O82-]/t = 1[S2O32-]orig/2t (Equation 5) The calculation of the rate constant ( k) and the orders of the reaction (m and n) with respect to Iand S2O82- follow from the dependence of the reaction rate on reactant concentrations. (Compare equations 3 and 5.) The factors that affect rates of reaction are as follows: o Nature of Reactants -The reactants must come into direct contact with each other and must collide with sufficient energy to result in a reaction o Concentration - Changes the number of particles per unit volume o Temperature - Changes the kinetic energy of the particles (i.e. velocity) which changes the number of collisions in a period of time o Catalyst - Lowers the activation energy of the reaction while remaining chemically unchanged o The Order of Reaction is as follows: A B C D The rate of the reaction may be expressed by: x y rate k A B o [A] and [B] are the molar concentrations of A and B o x and y are the powers which the concentration must be raised to describe the rate o k is the specific rate constant for a reaction Independent of concentration and depends only on temperature Once the rate is known the value of k can be calculated o Suppose we found that x = 2 and y = 1 for the reaction o The rate law would then be: If [B] is doubled (keeping [A] the same)the rate will double o If [A] is doubled (keeping [B] the same)the rate will quadruple o The powers in the rate law are the order of the reaction o The reaction above would be: Second order in A First order in B The overall order is the sum of the exponents or third-order overall

Datoya Brown 3 Materials Apparatus Burets (2) 1-mL pipet Stopwatch Pipet bulb Buret clamp Ring stand Chemicals 0.2 M KI 1% starch solution, boiled 0.2 M (NH4)2S2O8 (freshly prepared) Part A: Preliminary Experiments 25-mL pipet 50-mL pipet test tubes (8) 250-mL Erlenmeyer flasks (4) 100-mL beakers (4)

0.4 M Na2S2O3 (freshly prepared) 0.1 M solution of Na2H2EDTA 0.2 M KNO3 Procedures

1. Dilute 5-mL of 0.2 M KI solution with 10-mL of distilled water, add 3 drops of starch solution, mix thoroughly, and then add 5 mL of 0.2 M (NH4)2S2O8. Mix thoroughly, wait, and observe color change. 2. Repeat step one. When the solution changes color, add 4 drops of 0.4 M Na2S2O3, mix and note the effect on the color. Part B: Kinetics Experiment Solution preparation. Prepare the four reaction solutions assigned to: Solution 1 25-mL KI 1-mL starch solution 1-mL Na2S2O3 48-mL KNO3 1-drop EDTA Solution 2 25-mL KI 1-mL starch solution 1-mL Na2S2O3 23-mL KNO3 1 drop EDTA

Total volume = 75.0 mL Total volume = 50.0 mL Solution 3 Solution 4 50-mL KI 12.5-mL KI 1-mL starch solution 1-mL starch solution 1-mL Na2S2O3 1-mL Na2S2O3 23-mL KNO3 35.5-mL KNO3 1 drop EDTA 1 drop EDTA Total volume = 75.0 mL Total volume = 50.0 mL Rate measurements.

Datoya Brown 4 Prepare solution 1 in a 250-mL flask. Transfer 25-mL of (NH4)2S2O8 solution into the flask. Swirl the solution strongly. Be ready to begin timing the reaction when the solutions are mixed. The reaction starts the moment the solutions are mixed. Note the time you begin mixing to the nearest second. The instant the blue-black color appears, note the time and immediately add 1-mL aliquot of Na2S2O3 (aq), which should be measured in 1-mL increments in the test tubes, to the solution; the color will disappear. Repeat this process for a total of 7 trials. Solutions 2, 3, and 4 should be treated in the same manner, using the following volumes of (NH4)2S2O8: Solution 2 3 4 mL (NH4)2S2O8 50.0 mL 25.0 mL 50.0 mL Results A. Preliminary Experiments 1. What are the colors of the following ions? K+ colorless ; I- colorless 2. The color of the starch I2 complex is blue-black B. Kinetics Experiment Solution 1. Initial [S2O82-] = 0.05 M; initial [I-] = 0.05 M Aliquot no. 1 2 3 4 5 6 7 Tim (s) between appearances of color 188 190 200 215 235 255 274 Cumulative Time (s) 188 378 578 793 1028 1283 1557 Total moles of S2O82- consumed 2.0 x 10-4 4.0 x 10-4 6.0 x 10-4 8.0 x 10-4 10.0 x 10-4 12.0 x 10-4 14.0 x 10-4

Solution 2. Initial [S2O82-] = 0.10 M; initial [I-] = 0.05 M Aliquot no. 1 2 3 4 5 6 Tim (s) between appearances of color 91 95 97 99 100 100 Cumulative Time (s) 91 186 283 382 482 582 Total moles of S2O82- consumed 2.0 x 10-4 4.0 x 10-4 6.0 x 10-4 8.0 x 10-4 10.0 x 10-4 12.0 x 10-4

Datoya Brown 5 7 102 684 14.0 x 10-4

Solution 3. Initial [S2O82-] = 0.05 M; initial [I-] = 0.10 M Aliquot no. 1 2 3 4 5 6 7 Tim (s) between appearances of color 122 126 136 143 153 160 170 Cumulative Time (s) 122 248 384 527 680 840 1010 Total moles of S2O82- consumed 2.0 x 10-4 4.0 x 10-4 6.0 x 10-4 8.0 x 10-4 10.0 x 10-4 12.0 x 10-4 14.0 x 10-4

Solution 4. Initial [S2O82-] = 0.10 M; initial [I-] = 0.025 M Aliquot no. 1 2 3 4 5 6 7 Tim (s) between appearances of color 192 198 203 209 209 218 221 Cumulative Time (s) 192 390 593 802 1011 1229 1450 Total moles of S2O82- consumed 2.0 x 10-4 4.0 x 10-4 6.0 x 10-4 8.0 x 10-4 10.0 x 10-4 12.0 x 10-4 14.0 x 10-4

Calculations 1. Rate of reaction, [[S2O82-]/t, as calculated from graphs (that is, from slopes of lines): Solution 1 9.2 x 10-6 mol/L-s Solution 2 2.0 x 10-5 mol/L-s Solution 3 1.5 x 10-5 mol/L-s Solution 4 1.1 x 10-5 mol/L-s 2. What effect does doubling the concentration of I- have on the rate of this reaction? From one and three, rate increases by factor of 1.6 (should double) 3. What effect does changing the [S2O82-] have on the reaction? From one and two, rate increases by a factor of 2; doubling concentration doubles rate. 4. Write the law for this reaction that is consistent with your data. Rate law: rate = k[I-][S2O82-] 5. From your knowledge of x and y in the equation (as well as the rate in a given experiment from your graph), calculate k from your data. Rate = k[S2O82-]x[I-]y Solution (1) k = = 3.7 x 10-3 L/mol-s

Datoya Brown 6 Solution (2) k = Solution (3) k = Solution (4) k = = 4.0 x 10-3 L/mol-s = 3.0 x 10-3 L/mol-s = 4.0 x 10-3 L/mol-s

Initial [S2O82-] = 0.05 M; initial [I-] = 0.05 M

Solution 1

16.0 14.0 Moles S2O82- x 104 12.0 10.0 8.0 6.0 4.0 2.0 0.0 188 378 578 793 Time (s) 1028 1283 1400

Slope =

) )

= 9.2 x 10-7 mol/s = 3.7 x 10-3 L/mol-s

Rate = 9.2 x 10-6 mol/L-s Solution (1) k =

Datoya Brown 7

Initial [S2O8

2-]

Solution 2

= 0.10 M; initial [I-] = 0.05 M

16.0 14.0 Moles S2O82- x 104 12.0 10.0 8.0 6.0 4.0 2.0 0.0 91 186 283 382 Time (s) 482 582 684

Slope = 0.020 x 10-4 mol/s Rate = 0.20 x 10-4 mol/L-s Solution (2) k =
) )

= 4.0 x 10-3 L/mol-s

Initial [S2O82-] = 0.05 M; initial [I-] = 0.10 M

Solution 3

16.0 14.0 12.0 Moles S2O82- x 104 10.0 8.0 6.0 4.0 2.0 0.0 122 248 384 527 Time (s) 680 840 1010

Datoya Brown 8

Slope = 0.015 x 10-4 mol/s Rate = 0.15 x 10-4 mol/L-s Solution (3) k =
) )

= 3.0 x 10-3 L/mol-s

Initial [S2O82-] = 0.10 M; initial [I-] = 0.025 M

Solution 4

16.0 14.0 12.0 Moles S2O82- x 104 10.0 8.0 6.0 4.0 2.0 0.0 192 390 593 802 Time (s) 1011 1229 1450

Slope =

) )

= 1.0 x 10-6 mol/s = 4.0 x 10-3 L/mol-s Discussion

Rate = 1.0 x 10-5 mol/L-s Solution (4) k =


) )

According to the data the purpose was achieved. In the study of the effect of concentration on the rate of a reaction, it was found that when increasing the concentration of a reactant, the rate also increases. This was seen in the data. This result is expected when taking the collision theory into consideration. According to the collision theory, in order for reactants to form products there must be successful collisions between reactant molecules. Successful collisions are those that have enough energy to break and reform bonds and have the correct collision orientation or geometry. The

Datoya Brown 9 correct orientation is necessary to form the activation complex, a short-lived transition between reactants and products. When there are a greater number of reactant molecules available to react, there is a greater chance of a successful collision due to probability arguments. The more KIO3 that was present per unit volume, the greater opportunity there was for a successful collision to happen. There were more successful collisions as evidenced by more product being formed in a shorter period of time (color change faster). There were many possible sources of errors in the lab procedure. Reaction times when attempting to record the time it took for color to change are extremely variable. Since the procedure included the use of data from other lab groups, this would have a large affect on the results. Since the time it takes for the color change to first appear is used to calculate the rate values, this error will have a direct impact on the accuracy of the rate values. It is possible that the solutions that were provided were not exactly the same molarity. If the same solution was not used each time, the reaction times may be faster or slower than expected. Concentration will affect the reaction rate calculated. Also, the solutions may not be well mixed thereby changing their effective concentrations. Again, since the concentration values were used in order to calculate rate, this error will affect the results substantially. In the calculation of rate, the given molarity is used in the calculation. If the actual concentration was lower than the given one, the reaction time would be slower than expected. Conversely, if the actual concentration was higher than the one given, the reaction time would be larger than it should be. Conclusion According to the data, the purpose was reached. The rate of a reaction is seen to increase when concentration is increased considering experimental error. On can notice high concentration of certain reactants, high temperatures, and the presence of catalyst simply speeds up a reaction. The goal of the experiment was achieved through various trials of reactions. In the end the experiment could have been complete with more accuracy but do to haphazard human error in measuring for concentration purposes it was slightly off from other group that conducted the experiment as well. Acknowledgements Thanks to my professor/lab instructor, Dr. Shubo Han, and also lab partners. References Nelson, John H and Kenneth C Kemp. Laboratory Experiments to Accompany Chemistry The Central Science 11E. Upper Saddle River: Pearson Education, Inc., 2009