Sara Nicole Eleazar Kristian Leonard Orante Experiment 1: Factors Affecting Reaction Rates Theoretical Framework

April 17, 2012 Chem 18.1 EG1

Chemical kinetics is a branch of chemistry and the study of ratesthe changes in concentrations of reactants over timeat which a chemical reaction occurs (Silberberg, 2010). The major concerns of chemical kinetics is to determine the rate of a reaction and its reaction mechanism. Different chemical reactions occur at a variety of rates. It is important to know how fast certain reactions occur in order to apply them in industries, factories, laboratories, and many more. Furthermore, it is important to take note that certain factors, such as the nature, concentration, temperature, and surface area of reactants can affect the rates of reactions. Catalysts are also often used to speed up or slow down reactions without being consumed in the reaction. Aside from determining the effects of these factors on reaction rate, the other objectives of the experiment include determining the rate law expression. The method of initial rates was used, in which the reaction of interest is carried out at different reactant concentrations, and the rate of each trial is measured. From this method, the reaction orders of each reactant with respect to the other and also the overall reaction order can be determined. The reaction order dictates how a reactants concentration affects the reaction. Afterward, the rate constant, which relates the rate to the reactant concentrations, can be computed. The final objective of the experiment is evaluating the activation energy, the energy required to initiate a reaction. This was determined by using the Arrhenius equation (k = Ae-Ea/RT), which shows the relationship between temperature and the rate constant (Silberberg, 2010). Data and Results A. Nature of Reactants Visible Results Test tube A The reaction progressed slowly. At first, the Mg ribbon floated but after some time, it sank to the bottom of the test tube. It then produced bubbles around the Mg ribbon. It was clearer than the solution in test tube B. The reaction quickly progressed. By the time the Na metal was mixed with water, it released heat and fizzed, producing so much bubbles. The Na metal dissolved quickly in water, due to the fact that Na is explosive when exposed with water. The solution became slightly yellowish and translucent.

o Mg metal has higher activation energy since the reaction is slower.

B. Concentration of Reactants I. Constant [HCl] [Na2S2O3] 0.125 M 0.1 M 0.075 M 0.05 M 0.025 M [HCl] 0.5 M 0.5 M 0.5 M 0.5 M 0.5 M ln[Na2S2O3] -2.079 -2.303 -2.590 -2.996 -3.689 time 14.1 s 20.9 s 28.2 s 35.6 s 87.3 s Rate (1/time) 0.0709 s-1 0.0478 s-1 0.0355 s-1 0.0281 s-1 0.0115 s-1 lnRate -2.6462 -3.0397 -3.3393 -3.5723 -4.4694

ln rate vs. ln [Na2S2O3]

-2.5 -2.75 -3 -3.25 ln rate -3.5 -3.75 -4 -4.25 -4.5 -4 -3.5 -3 ln [Na2S2O3] -2.5 -2 -1.5

Based on the formula, M1V1 = M2V2 we calculated the different concentrations of sodium thiosulfate due to different volumes and the constant concentration of hydrochloric acid. [Na2S2O3] = (0.15 M) (5 mL) 6 mL = 0.125 M [Na2S2O3] = (0.15 M) (4 mL) 6 mL = 0.1 M [Na2S2O3] = (0.15 M) (3 mL) 6 mL = 0.075 M

[Na2S2O3] = (0.15 M) (2 mL) 6 mL = 0.05 M [Na2S2O3] = (0.15 M) (1 mL) 6 mL = 0.025 M [HCl] = (3 M) (1 mL) 6 mL = 0.5 M The order of reaction can be calculated using linear regression. rate = k[Na2S2O3]x[HCl]y ln rate = xln[Na2S2O3] + yln[HCl] + ln k y =m x + b 2 r = 0.988816923142 m = order with respect to [Na2S2O3] = 1.067 b = yln[HCl] + ln k = -0.499 II. Constant [Na2S2O3] [HCl] 1.0 M 0.8 M 0.6 M 0.4 M 0.2 M ln[HCl] 0 -0.223 -0.511 -0.916 -1.609 time 12.7 15.4 18.3 20.7 25.8 Rate (1/time) 0.0787 0.0649 0.0546 0.0483 0.0388 lnRate -2.5416 -2.7343 -2.9069 -3.0301 -3.2504

[Na2S2O3] 0.1 M 0.1 M 0.1 M 0.1 M 0.1 M

ln rate vs. ln [HCl]

-2.5

-2.75 ln rate

-3

-3.25

-3.5 -1.75

-1.25

-0.75 ln [HCl]

-0.25

Based on the formula, M1V1 = M2V2 we calculated the different concentrations of hydrochloric acid due to different volumes and the constant concentration of sodium thiosulfate. [HCl] = (3 M) (2.5 mL) 7.5 mL = 1.0 M [HCl] = (3 M) (2.0 mL) 7.5 mL = 0.8 M [HCl] = (3 M) (1.5 mL) 7.5 mL = 0.6 M [HCl] = (3 M) (1.0 mL) 7.5 mL = 0.4 M [HCl] = (3 M) (0.5 mL) 7.5 mL = 0.2 M [Na2S2O3] = (0.15 M) (5 mL) 7.5 mL = 0.1 M The order of reaction can be calculated using linear regression. rate = k[Na2S2O3]x[HCl]y ln rate = yln[HCl] + xln[Na2S2O3] + ln k y =m x + b 2 r = 0.9509768868 m = order with respect to [HCl] = 0.417 b = xln[Na2S2O3] + ln k = -2.621 Since the order of Na2S2O3 is 2 and the order of HCl is 0, the overall order of the reaction between Na2S2O3 and HCl is 1. Substituting all values, we can say that, Rate = k[Na2S2O3]1.067[HCl]0.417 In finding the value of k, we might also use linear regression because the y-intercept is related to k. Actual 1.067 0.417 1.484 Theoretical 2 0 2

Order with respect to Na2S2O3 Order with respect to HCl Overall Order

Solving for the rate constant (k): (a) b = yln[HCl] + ln k = -0.499 ln k = -0.499 (0.417) ln(0.5 M) = -0.20995 k = e-0.20995 = 0.8106

(b) b = xln[Na2S2O3] + ln k = -2.621 ln k = -2.621 (1.067) ln(0.1 M) = -0.16414 k = e-0.16414 = 0.8486 C. Temperature [Na2S2O3] = 0.0517 M Temp. (C) 12 30 43 1/T(K) 3.507 x 10-3 3.299 x 10-3 3.163 x 10-3 time 74.1 34.0 19.0 Rate (1/time) 0.0135 0.0294 0.0526 [HCl] = 0.4138 M k 0.4601 1.0020 1.7926 lnk -0.7763 1.9602 x 10-3 0.5837

1/T vs. ln k
0.75 0.5 0.25 ln k 0 -0.25 -0.5 -0.75 -1 0.0031 0.00315 0.0032 0.00325 0.0033 0.00335 0.0034 0.00345 0.0035 0.00355 1/T (in K)

Based on the formula, M1V1 = M2V2 we calculated the concentrations of hydrochloric acid and sodium thiosulfate in the reaction. [Na2S2O3] = (0.15 M) (5 mL) 14.5 mL = 0.0517 M [HCl] = (3 M) (2 mL) 14.5 mL = 0.4138 M

In solving for the rate constant (k), the equation used is, k = rate [Na2S2O3]1.067[HCl]0.417. In finding the activation energy (Ea) in Joules, we used the Arrhenius equation, lnk = (-Ea/R) (1/T) + lnA. Using linear regression, we substituted the values of xs and ys and find the slope of the line because m = -Ea/R. After finding the slope, we multiplied it with the gas constant. It was found that Ea = 32,722.84 J.

D. Surface Area Reactants Strip of Mg Pieces of Mg Visible Results The reaction occured quickly. As the Mg strip was put into the test tube, it reacted, producing few bubbles around it. The reaction occurred faster than the solution with the strip of Mg. Same results were exhibited compared to the reaction of HCl with the strip of Mg, but this time, more bubbles were produced because the Mg pieces were completely dissolved at a faster rate.

E. Catalyst Reactants H2O2 + Rochelle Salt H2O2 + Rochelle Salt + CoCl2 Visible Results After the reactants were mixed, the solution turned yellowish, producing bubbles. After heating, the white precipitate at the bottom was slowly dissolved in the solution. After the reactants were mixed, the solution turned yellowish but because of the addition of the catalyst, it instead turned violet. There was also formation of bubbles. After heating, the white precipitate at the bottom was quickly and completely dissolved in the solution. As the precipitate dissolved in the solution, the solution changed its color from bright violet to brownish black.

Answers to Questions 1. What is the significance of activation energy? The activation energy (Ea) is the energy with which molecules must collide in order to reach a state of activation from which they can be transformed from reactant to product. Reactant molecules must not only have frequent collisions to react, but they must also meet the minimum amount of energy required by the activation energy in order to lead to a reaction (Chang, 2010). Thus, the activation energy is significant because it is the barrier that dictates whether a reaction can occur or not. Knowledge of the activation energy of reactions can be applied in order to speed up certain desired reactions or delay spontaneous and possibly dangerous ones. 2. What is the overall order of the reaction between hydrochloric acid and sodium thiosulfate based from your experiment? What is the theoretical value? [answer] 3. Solve for the rate constant. [answer] 4. How is rate related to temperature? In general, rate is directly proportional to temperature, e.g., reaction rates increase when temperature is increased. This is because at higher temperatures, more collisions between reactant molecules occur. However, most collisions end up as molecules simply bouncing off of each other and not reacting. Thus, the significance of temperature with respect to the rate is that increasing the temperature of a reaction also increases the kinetic energy of the molecules, as well as the energy of their collisions. Because of this, a greater number of collisions with sufficient energy occur, which is needed for molecules to successfully react with each other. Therefore, raising the temperature results in a faster reaction rate by increasing the number and energy of collisions (Silberberg, 2010). 5. Solve for the Arrhenius constant. [answer] 6. What is the effect of particle size to the rate of reaction? Particle size is inversely related to the rate of reaction. Large particles have limited surface area because other reactants can only come in contact with the outer layer of each particle. Smaller reactant particles, however, are more accessible, therefore increasing the number of collisions between particles and subsequently, the rate of reaction. 7. Explain the process of catalysis.

Catalysts are often employed in chemical reactions because they increase the rate without being consumed in the reaction (Silberberg, 2010). In general, an accelerating or positive catalyst increases the reaction rate by lowering the activation energy. According to the Arrhenius equation, the rate constant k and the rate itself of is affected by the Arrhenius constant A which has the activation energy Ea as its exponentthe lower the value of Ea (and hence the larger the value of A), the greater the rate. A catalyst provides an alternate mechanism for the reaction with a set of elementary steps which is more favorable than those without a catalyst (Chang, 2010). Thus, the catalyzed reaction has a lower energy pathway than the uncatalyzed one. A catalyst may interact with a reactant molecule to form an intermediate, and is subsequently regenerated in a next step (as in most homogeneous or same-phase catalysts), or it may provide a reaction site by adsorbing reactant molecules (as in most heterogeneous or different-phase catalysts).

References Chang, R. (2010). Chemistry (10th ed.). New York, NY: McGraw-Hill. Silberberg, M. S. (2010). Principles of General Chemistry (2nd ed.). New York, NY: McGraw-Hill.