CHEMICAL KINETICS: THE IODINE CLOCK REACTION FORMAL REPORT IN CHEMISTRY 26.

1 SUBMITTED BY STUDENT GLADYS ERICKA GALANG

GLADYS ERICKA GALANG1 AND IRENE LOURDES LUMANG1
1INSTITUTE

OF BIOLOGY, COLLEGE OF SCIENCE UNIVERSITY OF THE PHILIPPINES, QUEZON CITY 1101, PHILIPPINES DATE PERFORMED: 6 DECEMBER 2012 DATE SUBMITTED: 8 JANUARY 2013

ABSTRACT This experiment aims to discuss the kinetics of the reaction of I- and S2O82- by performing different runs containing different concentrations of the reactants, with a constant concentration of S2O32-. A starch indicator was used to form a blue-black Iodine-starch complex as the basis of the end of the reaction. The different runs were timed for the calculation of individual rates of the reactions, the rate law, and the rate constant, using the initial rate method. The data are as follows, the rate law being rate=k[S2O82-][I-], second order of reaction, and the rate constant= 6.576x10-3 M-1s-1. The effect of temperature and addition of catalyst on the reaction rates were also observed. An increase of temperature and an addition of CuSO4 catalyst sped up the reaction. Values from the experiment were used to calculate the Activation energy (Ea) and the Arrhenius constant (A), respectively 2.02x10-4 kJ and 2.3x10-3 M-1s1.

INTRODUCTION The Iodine Clock reaction experiment aims to determine the effect of reactant concentration, temperature and catalyst on the rates of reaction. It focuses on the rates of different runs of the Iodine, I-, and persulfate, S2O82-, reaction mixture. The rate law is an equation that relates the rate of a reaction to the concentrations of reactants (and catalysts) raised to various powers and the rate constant (k) is a proportionality constant in the relationship between rate and concentrations [1]. The experiment includes preparation of different solutions: 0.2 M KI, 0.2 M KCL, 0.1 M KzS2O8, 0.1 M KzSO4, 40 mM Na2S2O8, the starch solution and the catalyst CuSO4. Beaker A contains the first two solutions while beaker B contains the rest except the catalyst. The different runs of the experiment were done by varying the concentration of the reactants added to the reaction mixture. This way, effect of different concentrations to the rate of reaction can be determined.

The pouring of solution in beaker A to beaker B marks the start of the reaction and the start of recording the time of the reaction. Beaker A included the starch indicator which mixes with Iodine to form the blueblack complex which marks the end of the reaction. The color forms only when Iodine is formed. To observe the effect of temperature, a different setup was made from the second run of the experiment. The solutions were bathed in different water temperatures before mixing, and were timed the same way as the previous runs for the computation of the Activation energy which is the certain minimum amount of energy needed by the reaction to occur [2]. This experiment also tackled the addition of a catalyst. Catalysts are substances that increase the rates of a wide variety of chemical reactions [3]. To observe the effect of the addition of a catalyst, the second run of the experiment in room temperature was mixed with an addition of 1 M catalyst, CuSO4. The time was recorded as soon as the catalyst was added to the mixture of the solutions of Beaker A and B.

Figure 1. Sample Activation Energy of a Reaction with and without a Catalyst [3]

This reaction includes oxidation of the iodide ion to molecular iodine by the persulfate. This is a slow reaction. But because of the addition of the thiosulfate, the reaction continues further and faster: I2 (aq) + 2S2O32- (aq) 2I- (aq) + S4O62- (aq) (Eq. 2)

The Iodine formed in Eq. 1 is immediately consumed by the thiosulfate to reduce Iodine back to Iodide to repeat the reaction. This cycle goes again and again until the thiosulfate, being the limiting reagent, is exhausted and the Iodine is free to react with the starch to form the blue-black complex. The rate is determined by the equation: The catalyst would cause a decrease of required activation energy, which means, the reaction is required to use lower than normal amount of energy to progress. Going further, the rate of reaction with a catalyst would be faster than the reaction without. For the experiment to go well, the reaction of the solution mixture from beaker A and B with the catalyst should have a faster reaction than the one without, at the same temperature. After tabulating the values taken from the experiment, the rates of each reaction, the rate constant and the rate law were calculated. For the 2nd run in different temperatures, besides for calculating the same values above, the Activation energy and the Arrhenius constant were computed from the Arrhenius equation. RESULTS AND DISCUSSION Table 1. Effect of Reactant Concentration on Reaction Rate Runs [S2O82-] [I-] [S2O32-] Time, s Rate, M/s 1 0.02 0.08 8x10-4 40.55 9.86x10-6 -4 2 0.02 0.04 8x10 61.62 6.49x10-6 -4 3 0.02 0.02 8x10 102.33 3.91x10-6 -4 4 0.03 0.04 8x10 39.93 1.00x10-5 5 0.04 0.04 8x10-4 26.39 1.5x10-5 The reactions favor higher concentrations of S2O82and I-: 2I- (aq) + S2O82- (aq) I2 (aq) + 2SO42- (aq) (Eq. 1) rate= (1)

the change of Iodide concentration per second. Since the thiosulfate just consumes the I2, the change in Iodide concentration is just half the concentration of the thiosulfate, which is known at the beginning of the reaction. This is true to the stoichiometric ratio of the thiosulfate and Iodine as seen in Eq. 2. After the rate of each reaction is determined, we can now compute for the rate law and rate constant given by the equation: rate = k [A]m[B]n (2) where k is the rate constant, and A and B are the reactants. The exponents of the concentrations m and n determine the relationship of the concentrations of the reactants with the rate of reaction [1]. The initial concentrations of the reactants were calculated by the formula M1V1=M2V2. To calculate the exponents, a comparison between rates is made. The second rate is divided by the first rate because the concentrations of the persulfate ions in the two rates are the same. Cancellation of those concentrations and the rate constant, leaves the equation with just one variable to solve for, n. Using the rules of logarithm, the value of n can be calculated. The same process was used to calculate for m, only this time, using the rates of the second and fifth run. Because of this, we can determine the rate law as: rate=k[S2O82-]1.2[I-]0.7. Rounding both the exponent to

its nearest integer, which is one, gives a rate law of rate=k[S2O82-][I-], a reaction having an overall order of 2. [ Although exponents in the rate law are not necessarily integers, this is done for the graphing. ] This relationship means that both reactants are directly proportional to rate of reaction. Doubling the reactants means doubling the rate of reaction. Using the rate law, substitution of the values of the concentration, rates, and the exponents to the rate law equation will give the rate constant value. Since the rate constant is not defined by concentration, all values of k from all the runs are closely similar [1]. In this calculation, however, the rate law used is rate=k[S2O82-]1.2[I-]0.7 for better accuracy and precision. After getting the values of k from all the runs, the values are added together and divided by five to get the mean value of k=6.576x10-3 M-1sec-1. A graph of the line of the relationship of the reactant persulfate ion and the rate of reaction is defined by the equation: y= 0.90x + 6.5 (3) Figure 2. Graph of the line y= 0.016x + 0.21

where [Ao] is the initial concentration of S2O82- and [A] is its final concentration [5]. This integrated rate law gives the values of the final concentrations of S2O82from the different runs of the experiment. Afterwards, the natural logarithm of the final concentrations is calculated. After determining the ln [S2O82-] for all the runs, the rates of reaction are inputtted to natural logarithm to complete the plot of the line. The line has correlation, r2, of 0.6, a value than can be rounded to 1. An r2 value of 1 defines a straight line, and a straight line defines the correctness of the order of the reaction. Since the computed value can be rounded to 1, it is a close straight line. This value has a 40% error percentage. The equation of the line was determined by using the points of ln rate as the x values and the ln [S2O82-] as the y values of the line, and inputting them in the twopoint form of a line equation: (y-y1)=(x-x1)[(y1-y2)/(x1x2)]. Substituting two points, we can get the equation of a line, although this will give a straight line with an r2 value of 1. An alternate more precise method of getting the equation of the line is to use the stat mode of the calculator. The calculator will provide a table with columns for the x and y axis. It will automatically compute for the slope and y-intercept values that will complete the line equation. Values calculated are rounded to the second significant figure. Substituting the values to the slope intercept form y=mx+b, where m is the slope and b it the y-intercept [4], gives us (3). Another method is to use a readily downloadable application from the internet, such the one used here, Graph, that graphs the inputted values, and computes the equation of the line. Whichever method used must have the same output. A line can also be graphed to determine the order of reaction with respect to I-.

This is the equation of the line of the plot ln rate vs. ln [S2O82-]. Since the overall order of the reaction is 2, the integrated rate law for this is: 1/[A] = kt + 1/[Ao] (4)

y=0.98x+7.9 (5)

Figure 3. Graph of the line y=0.98x+7.9

k=A*e(-Ea/R*T) (6) 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 in Kelvin and A is the Arrhenius constant. To compute for the Activation energy, we can plot the line that defines the equation: ln k = - Ea/(R*T) + A (7) Plugging the values to Equation (7), we can solve for the equation of the line and for the values of the Activation energy and Arrhenius constant. Looking closer, ln k becomes the values of y and 1/T, with R being a constant, becomes the values of x. Figure 4. Graph of the line y = -2.02x10-4x + 2.3x10-3

This line is the plot of ln rate vs ln [I-]. The same equations and methods are used to determine the Equation (5). The natural logarithms of the rates of reaction are plotted against the integrated rate law, using the concentration of I- instead of S2O82 as defined by Equation (4). Equation (5) has an r2 value of 0.4. This value has a 60% percentage of error. Table 2. Effect of Temperature and Catalyst on Reaction Rate Run 2 Temp, K Time, s Rate, M/s k, M-1sec-1 -6 Set 1 299.15 61.62 6.49x10 6.75x10-3 Set 2 278.15 268.86 1.49x10-6 1.55x10-3 -5 Set 3 323.15 22.62 1.77x10 1.8x10-2 -5 Set 4 299.15 6.30 6.35x10 2.3x10-3 These different sets have different temperatures: Set 1 at room temperature, set 2 is subjected to an ice bath, and set 3 to a hot bath. The reactions favor higher temperatures. That is because at higher temperatures, the molecules get more excited and, collide faster into each other. The higher the temperature, the greater the molecular kinetic energy [1] and therefore increases the rate of each reaction. The rate constant is computed as above, substituting the values of concentration of the reactants and the exponents to the rate law equation. Since the rate constant, k, varies at different temperatures, we can see different values of k for the different sets. The value of the rate constant, k, increases as the temperature increases, as given by the Arrhenius equation:

This is the graph of the line of the plot of ln k vs. 1/T of the sets 1-3. This gives us the value of the activation energy, which is 2.02x10-4 kJ and the value of the Arrhenius constant, which is 2.3x10-3. This proves that as the temperature increases, the value of the rate constant also increases. The correlation of this graph is 0.988. The activation energy does not change with temperature, but rather it appears as the slope of the line. In connection, the rate constant increases exponentially when the activation energy decreases. The reaction would proceed faster with a smaller activation energy to conquer [6].

Set 4 in Table 2 is the set in which a catalyst, Copper (II) sulfate, was added to the reaction. The catalyst speeds up the reaction by providing the reaction with an alternative route of lower activation energy than the uncatalysed reactions [3]. Observation of the set tells that the reaction with a catalyst, set 4, was faster than reaction without a catalyst, set 2, with both of them at the same temperature. The computation of the rate constant of set 4 is different because of its different rate law: Rate = k[S2O82-][I-][CuSO4]x (8) To calculate the rate constant for this rate law, we use the Arrhenius equation, Equation (6). Plugging in the values of the pre-calculated Arrhenius constant and activation energy, the value of k is 2.3x10-3 M-1s-1. SUMMARY AND CONCLUSIONS The rates of reactions favor a lower concentration of both the reactants, a higher temperature and an addition of a catalyst. The rate law is in second order, overall, being first order to both reactants. The graph of the line of the plot ln rate vs. ln reactant gave an r2 value that is far from expected which was supposed to be a value very close to 1. Even though the calculated values give both the reactants a first order, the line wasnt straight, and the points were scattered. That error may have come from the approximate reaction time. Due to the low accuracy of using the human eye to determine full reaction consumption, we have less accurate results. However, the graph of the line of line plot ln k vs 1/temperature, the r2 value is 0.98, a value that is very close to 1. Systematic errors did not do much to affect this data too much as it is very close to the needed value which is 1, unlike the first data. Uncertainties of the equipment used cannot be avoided, so the concentrations could have been higher or lower than its actual value. The stopwatch could also have its uncertainties, making the values father than what they are. Also these errors are impossible to avoid, more trials could improve the certainty of the data gathered.

There is also uncertainty in the reaction time. The recording of the time was stopped when a certain shade blue-black was attained. Because of low accuracy of the human eye, as stated above, there is a high probability of differences between the time recorded and the actual time the reaction finished progressing. More trials could decrease the percentage of error. REFERENCES [1] Ebbing, D., Gammon, S., 2009, General Chemistry, Cengage Learning, 200-535 [2]Hill, G., Holman, J., 2001, Chemistry in Context: Laboratory Manual, Nelson Thornes, 18 [3] Clungston, M.J., Flemming, R., 2000, Advanced Chemistry, Oxford University Press, 270 [4] Larson, R., Nolting, K., 2009, Elementary Algebra, Cengage Learning, 232 [5] Rate Laws from Graphs of Concentration Versus Time (Integrated Rate Laws) nd, Integrated Rate Laws. Retrieved January 4, 2013. From http://www.chem.purdue.edu/gchelp/howtosolveit/Kin etics/IntegratedRateLaws.html [6] del Mundo, G., Kareem, M., etc., Arrhenius Equation. Chemwiki. Retrieved January 4, 2012, from http://chemwiki.ucdavis.edu/Physical_Chemistry/Kinet ics/Reaction_Rates/Temperature_Dependence_of_R eaction_Rates/Arrhenius_Equation