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CHEMICAL EQUILIBRIUM

K.C. DURON1 AND C.B. GARCIA2 1DEPARTMENT OF SCIENCE EDUCATION, COLLEGE OF EDUCATION 2DEPARTMENT OF MECHANICAL ENGINEERING, COLLEGE OF ENGINEERING UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES
INSTRUCTOR: IRINA DIANE CASTAOS

Chemical Kinetics, according to Brown and Lemay, is the area of chemistry that is concerned with the speeds, or rates, of reactions. There are four factors affecting the rates at which reactions occur:(1)the physical state of reactants,(2)the concentration of the reactants,(3)the temperature at which the reaction occurs, and(4)the presence of a catalyst. This experiment aims to study the last 3 factors and determine how they affect the rate of reaction in different systems. Effect of Concentration on Reaction Rate The balanced chemical equation for the reaction under study is: Na2S2O3(aq) + 2HCl(aq) 2NaCl(aq) + S(s) + SO2(g) + H2O(l) with the net ionic equation: S2O32-(aq) + 2H+(aq) S(s) + SO2(g) + H2O(l) We could say that observations coincide with the balanced equation since the end of the reaction was signaled by the solution getting cloudy causing the X-mark to be unseen. It actually is the formation of sulfur. According to Petrucci, rate of reaction = -[product] x 1 . t number of moles of product or the rate of formation of the products and = [reactant] x 1 . 1

t number of moles of reactant or the rate of disappearance of the products. For the reaction above, Rate = -[S2O32-] = -[H+] = [SO2] = [S] t*1 t *2 t*1 t*1 To be able to study the concentration on reaction rate, 6 runs were t be done, each with volumes and molarity of Na2S2O3, water. effect of different different HCl, and

To compute for the initial concentrations, we take the original molarity and multiply it with the given volume. For example, using date in run 1, 0.15 M x 10mL x 1L/1000mL = 0.0015 mol S203 Then divide it by the total volume of the thiosulfate + water + HCl, 0.0015 mol S203 15 mLsoln = 0.1 M S203 Upon computation, we could see that the concentration of HCl was the same for the first 3 runs while the concentration of the thiosulfate was the same for the last 3 runs. We also need to compute for the initial rates for each run, Recall that rate = [S2O32-]/t. But since we keep the change in concentration the same for each run, we could say that the rate is approximately equal to 1/t. Using the data collected (refer to Table A of datasheet) and the initial rates

method, we could now compute for the order of reaction with respect to the reactants. For thiosulfate, we use run 1 and run 2 since they have the same concentration for HCl but different for thiosulfate. Rate 1 = k[S2O32-]1m [H+]1n Rate 2 = k[S2O32-]2m [H+]2n Substituting values, 0.04347826 = k[0.1]m [0.4]n 0.026315789 = k[0.05]m [0.4]n 1.65217391 = [2]m m = log21.65217391 m = 0.724366 1 Meanwhile, using run 4 and run 5 to compute for the order of reaction with respect to H+ Rate 4 = k[S2O32-]4m [H+]4n Rate 5 = k[S2O32-]5m [H+]5n Substituting values, 0.037037037 = k[0.1]m [0.6]n 0.032258064 = k[0.1]m [0.4]n 1.148148165370371 = [1.5]n n = log1.51.148148165370371 n = 0.340721 0 The overall kinetic order of the reaction is m + n = 1 + 0 = 1. Therefore, the rate law is rate = k[S2O32-]1 [H+]0 rate = k[S2O32-] We can imply from the rate law that the rate of the reaction relies on thiosulfate alone. A possible mechanism is: (Fast) 1: S2O32- + 2H+ H2S2O3 (Slow) 2: H2S2O3 S + SO2 + H2 S2O32- + 2H+ S + SO2 + H2O

Effect of Temperature on Reaction Rate The second part of the experiment studies the effect of temperature on the reaction rate. There were three set-ups, all with the same concentration of thiosulfate and same concentration of Hcl but with different temperatures. It has been observed that as the temperature of the set-up increases, the faster a reaction will end. This can be explained through the Arrhenius equation: k = A e-Ea/RT which implies that rate of reaction is directly proportional with temperature. Since the reaction is first order, we assume 1/T to be the rate constant because initial concentrations are constant while the temperatures are varied.. By manipulating the Arrhenius equation, we get lnk = + lnA Recall that in high school algebra, the equation of a straight line is y = m x + b. lnk = + lnA Applying it to the Arrhenius equation, the graph of lnk vs. 1/T gives us a straight line with the slope of -Ea/R.

0 0 -1 -2 ln K -3 -4 -5 -6 -7 1/T ln K vs. 1/T 0.0005 0.001 0.0015 0.002 0.0025 0.003 0.0035 0.004

Using this and the data from Table B (refer to datasheet), we could now solve for the activation energy by multiply the slope by the constant R. (m = -Ea/R) Ea = m x R. Ea = -4841 x 8.314 J x 1 kJ = 40.25 kJ/mol K mol K 1000J Catalysis The third part of the experiment is further divided into two parts to study the effects of the presence of a catalyst. For the first part, our balanced equation is: S2O82- + 2I- I2 + 2 SO4 with Cu as the catalyst. For the second part, our balanced equation is: 5C2O42- + 2MnO4- + 16H+ 10CO2 + 8H2O + 2Mn+ with Mn as the catalyst. A strong acid is needed in part 2 so that MnO4 could be converted to Mn. It involves autocatalysis which means that the reaction produces the compound that is used as a catalyst for the second reaction.

The reaction in part 1 has ended if we see the solution turning blue due to the reaction of I with starch. In part 2, the signal is the decolorization of the solution. The presence of a catalyst, either by manual addition or by the production of the reactants themselves lowers the activation energy of the reaction. By the Arrhenius equation, we know that a lower activation energy means a faster reaction rate.

REFERENCES [1] Brown, Theodore E., Lemay, H. Eugene, et.al., 11th edition. Chemistry: The Central Science. Pearson Education Inc., 2009. [2] Petrucci, Ralph H.,William S. Harwood, and Geoffrey F. Herring, 8th edition. General Chemistry.Prentice-Hall, 2002. [3] Whitten, Kenneth W., et.al., 8th edition. Chemistry. USA: Thomson Brooks/Cole, 2007.