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Experiment # 1: Factors Affecting Reaction Rates BIOLENA, Francheska O. and Endaya, Grant Kimmuel R. Group 1, Chemistry 18.

1, CD1, Ms. Arlou Kristina J. Angeles April 25, 2012 I. Abstract In this experiment, chemical kinetics was tackled by observing, determining, and analyzing the effect of certain factors on reaction rates. Basically, the five factors tested revolved around two things: manipulation of the frequency of collisions and the ease of overcoming the energy of activation or activation energy, Ea. The five factors which affected the reaction rates, and were consequently analyzed, were the nature of the reactants, concentration of the reactants, temperature, surface area of the reactants, and the presence of a catalyst. Generally, there are combinations of reactants which are highly reactive based on the activation energy characteristic of that reaction. Those that are highly reactive have low activation energies, and vice-versa. Furthermore, by increasing the concentration of the reactants, the frequency of collision also increases, thereby increasing the rate of the reaction depending on their order, except for those who have zero order where any change in the concentration of the reactants does not affect the reaction rate in any way. Delving deeper, the expression which relates the concentration of the reactants and the reaction rate, and where the rate constant and rate order can be obtained, is called the Rate Law (r=k[A]x[B]y). The Arrhenius equation (k=Ae-Ea/RT), on the other hand, relates the temperature with the rate constant and activation energy, and supports the fact that as the temperature at which the reaction is carried out is increased, the amount of molecules with enough energy to overcome the activation energy is also increased, along with the frequency of collision. Moreover, by increasing the surface area of the reactants, the exposed area for collision also increases, thus increasing the frequency of collision and the rate of reaction. Lastly, by the presence of a catalyst, the reaction proceeds into an alternative, multistep pathway with lowered activation energies, hence speeding up the reaction, and increasing the reaction rate. This process is more specifically known as catalysis. Moving forward, the technique of linear regression, and the usage of various chemical kinetics equations was utilized in this experiment due to the large amount of data obtained. These were used for further analysis and understanding. II. Keywords: Chemical Kinetics, Energy of Activation, Collision, Rate Law, Arrhenius Equation, Catalysis III. Introduction Concerned with substances and the various changes that they can undergo, as expressed in numerous chemical equations, Chemistry has always dealt with transformation. Chemistry has always been around us; millions, and even billions, of reactions occur on a day-to-day basis. These reactions have been observed and studied for years by people, especially by scientists, engineers and other professionals, for the sake of generating useful, scientific knowledge. By understanding the rates at which these chemical reactions occur, they have generated various applications in the fields of environment, health, industry, and many more. The specific area of chemistry which is concerned with the study and discussion of chemical reactions with respect to reaction rates, effect of various variables, re-arrangement of atoms, formation of intermediates etc. is called Chemical Kinetics. Moreover, the rate of a chemical reaction is a measure of the amount of products formed per unit of time, or the quantity of reactants consumed per unit of time. Also, it is defined as the change in the concentration of reactants or products per unit of time. Hence, the units for reaction rate are usually molarity per second (M/s) meaning, the change in concentration (which is measured in molarity) divided by an interval of time (measured in seconds). Chemistry 18.1, Factors Affecting Reaction Rates Up to now, the most specific and intricate details as to how reactions basically occur cannot still be known completely. Because of this, scientists refer to two reaction rate theories to explain how it happens: the collision theory, and the transition state theory. In the collision theory, we go into the molecular level, and state that the rate of a chemical reaction is directly proportional to the number of collisions happening per unit time (frequency of collision). Furthermore, collisions between reacting molecules shall only be productive if the colliding molecules possess the minimum energy required (activation energy, Ea or the energy barrier) to initiate a chemical reaction. It must also be noted that the reactant molecules must be properly oriented with respect to each other (proper orbital overlap) for the collision to be effective. Moving on, the other reaction rate theory, the transition state theory, states that an intermediate or activated complex is formed before finally forming the desired product. Such transition state complex had never been isolated since it is short-lived. Its rate of formation is equal to its rate of decomposition, and the rate of a reaction is dependent on the energy requirement (Ea) for the said complex to form. The higher the energy requirement for the formation of the complex, the more difficult it is to carry out such reaction, and consequently, the resulting reaction is slower. Page1 of 8

However, if the energy requirement is lower, the resulting reaction rate is faster. As demonstrated by this experiment, five factors allow us to change the rates at which a particular reaction occurs: (1) nature of the reactants, (2) concentration of the reactants, (3) surface area exposed, (4) temperature at which the reaction occurs and (5) the presence of a catalyst. These factors manipulate the frequency of collision and/or the ease of overcoming the energy of activation. Speaking of the activation energy, it is dependent on the kind (nature) of reacting substances involved in a given reaction. Also, it must be known that the difference in activation energies results in different reaction rates (high Ea=slower reaction rate; lower Ea=faster reaction rate). On another topic, the Rate Law is an equation that shows us how the rate depends on the concentration of the reactants, while the Arrhenius equation, (k=AeEa/RT ), relates the temperature with the rate constant and activation energy. Finally, it should also be noted that catalysts are what we call substances which increase the rate of a chemical reaction by providing an alternative reaction pathway with much lower Eas without itself being consumed in the process. IV. Experimental The experiment was divided into five parts, namely 1) Nature of the reactant, 2) Concentration of the reactant, 3) Temperature, 4) Surface area, and 5) Addition of a Catalyst. In the first part, two test tubes, labeled A & B, were prepared with 3 ml of water each. Mg ribbon was added to the first while a small piece of Na was added to the second and the results were observed. For the second part, a 10-mL beaker was placed right above a piece of white paper with an X mark. Then, add indicated amount of 0.15 M Na2S2O3 (see table 1.1 and 1.2) and H2O. Check if the X mark is clearly seen through the solution. Immediately add 3 M HCl indicated. Time the reaction from the moment the mark is no longer visible. Do the procedure in the following format: (I.) constant HCl concentration and (II.) constant Na2S2O3 concentration.
Table 1.1: Schedule for constant HCl concentration.

5 5 5 5 5

0 0.5 1 1.5 2

2.5 2 1.5 1 0.5

In the third part, two test tubes were prepared. The first test tube contained 5 mL of 0.15 M Na2S203 while the other had 7.5 mL of H20 and 2 ml of 3 M HCl. Room temperature was recorded. Both test tubes were immersed in a water bath containing tap water for about five minutes. Then, the reagents were immediately mixed in a 50-ml beaker and were timed when will the X to disappear. The procedure was then repeated in two other temperatures with one approximately 10C lower than room temperature and one 10C higher In the fourth part, two identical strips of Mg ribbon were prepared. One of the strips was cut into very small pieces. The uncut Mg ribbon and the shredded Mg ribbon were placed in to two separate test tubes with 5 ml of 3 M HCl solution each and were observed for difference. In the fifth and last part, two test tubes were prepared, each with 5 mL of 3% of H 2O 2 and about one gram of Rochelle salt (sodium potassium tartrate). One of the two test tubes was added with a pinch of CoCl 2. The test tubes were then heated and were observed for any difference. V. Results Table 2.0 shows the observations that were seen on Part A, which varied the type of the reactants used in order to see its effect on rate.
Table 2.0: Observations for Nature of Reactants

Reactants 3 mL H2O + Mg 3 mL H2O + Na

Observation Almost no evolution of gas present; gentle bubbling Evolution of gas present; fast bubbling with exploding action with a loud, fizzing sound

0.15 M Na2S203 (mL) 5 4 3 2 1 0.15 M Na2S203 (mL)

H20 (mL) 0 1 2 3 4

3 M HCl (mL) 1 1 1 1 1

Table 1.2: Schedule for constant Na2S2O3 concentration.

Tables 3.1 and 3.2 show the results following the reaction schedule from Table 1.1 and 1.2 of Part B. This table shows the concentrations of the reactants computed using the equation M1V1 = M2V2 where M and V are the molarity and volume of the reactants in their initial and final states. The time of reaction is also shown here and the rate of reaction, which is computed by getting the reciprocal of the time of reaction, can be seen. Also shown is the ln [Na2S2O3] and the ln Rate to be used later in finding the order of the reaction with respect to the reactant.
Table 3.1: Reactions with constant HCl concentration showing their time and rate of reaction [Na2S2O3] [HCl] ln[Na2S2 Time Rate lnRate

H20 (mL)

3 M HCl (mL)

Chemistry 18.1, Factors Affecting Reaction Rates

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(M) 0.125 0.1 0.075 0.05 0.025

(M) 0.5 0.5 0.5 0.5 0.5

O3] -2.07944 -2.30259 -2.59027 -2.99573 -3.68888

(s)

(s-1)

29.1 33.9 36.6 39.9 42.5

3.43 x 10 2.94 x 10 -2 2.73 x 10 -2 2.54 x 10 -2 2.35 x 10 -2

-2

-3.37 -3.52 -3.6 -3.67 -3.75

30 43

3.3 x 10 -3 3.16 x 10 -3

38.6 29.2

2.5 x 10 -2 3.4 x 10 -3

0.4835 0.657

-0.726 -0.42

From the 1/T and lnk values, the plot of lnk versus 1/T can be made as seen from Figure 2.0.
Figure 2.0: Plot of ln k vs. 1/T

Using the ln [Na2S2O3] and the ln Rate from Table 3.1 and 3.2, the plot of ln Rate vs ln [Na2S2O3] was produced as shown in Figure 1.1 and 1.2.
Figure 1.1: Plot of ln Rate vs. ln [Na2S2O3]

0 0.0031 0.00315.0032 0 0.00325.0033 0 0.00335.0034 0 -0.5

-3.3 -4 -3 -2 -1 -3.4 -3.5 0

k n l
-1 -1.5

lnK(1/T )

e t a R n l

-3.6 -3.7 -3.8 ln[Na 2O 2S 3] -3.9

Table 5.0 shows the observations that were seen in Part D. As seen in the table, the surface area is specified in the left column and its corresponding observation is shown opposite it.
Table 5.0: Observations for reactions with different surface area of reactants

Reactants HCl + Mg strip HCl + Mg pieces


Table 3.2: Reactions with constant Na2S2O3 concentration showing their time and rate of reaction [Na2S2O3] [HCl] Time Rate ln[Na2S2O3] lnRate (M) (M) (s) (s-1) 0.1 1 0 12.93 0.077 -2.563 0.1 0.8 -0.2231 13.01 0.0768 -2.566 0.1 0.6 -0.5108 13.99 0.0714 -2.639 0.1 0.4 -0.9163 15.01 0.066 -2.718 0.1 0.2 -1.6094

Observation Slower evolution of gas Faster evolution of gas

For the last part, Table 6.0 shows the observations that were obtained from the catalyzed and uncatalyzed reactions. The table shows the reactants in each reaction and the observation that was seen opposite them.
Table 6.0: Observations for reactions with a catalyst absent and present

15.94

0.062

-2.78

Figure 1.2: Plot of ln Rate vs. ln [HCl]

-2

-1.5

-1 ln[H Cl]

-0.5

From Part C, Table 4.0 shows the rates of reactions under different temperatures obtained from the reciprocal of the time of reaction. Also shown here is k, which is solved from isolating it from the Rate Law, given the concentration and rate.
Table 4.0: Reactions with varying temperatures and reaction [Na2S2O3] = 0.0517 M [HCl] = 0.4138 M Temp 1/T Time Rate (C) (K-1 x 103) (s) (s-1)

e t a R n l

-2.7 -2.8 0 -2.9

Reactants HCl + Rochelle Salt HCl + Rochelle Salt + CoCl2

Observation Light evolution of gas; from colorless solution to light green Faster and more violent evolution of gas; from violet to green then back to violet again

22

3.38 x 10 -3

58.3

1.7 x 10 -2

VI. Discussion The two reactions are the following that was observed during the first part of the experiment: Mg(s) + H2O(l) MgO(aq) + H2(g) 2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g) From these equations and observations, hydrogen gas evolved from both reactions was their time and rate of observed. However, the Na reaction was faster than that of the one with Mg because the activation k ln k energy of that reaction is lower than the one where -1 -1 (M s ) 0.3288 -1.112Mg is the reactant. Also, in the reactivity series of Page3 of 8

Chemistry 18.1, Factors Affecting Reaction Rates

metals, we can notice that Sodium is in the higher position compared to Magnesium, making Sodium more reactive to Magnesium. The reaction profile of both reactions can be seen below (superimposed):

Figure 3.0: Superimposed Reaction profiles of the reactions of Na and Mg metals with water

According to the Collision and Transition State Theories, if the activation energy of the reactants is lower, then it is easier to create an effective collision and form the transition state. Therefore, there is a faster rate of reaction as the Ea is lower, and it is accurate with our experiment. In the second part, the reaction Na2S2O3(aq) + 2HCl(aq) SO2(aq) + S(s) + H2O(l) + 2NaCl(aq) results to a white colloidal sulfur precipitate, which we can measure the rate of reaction by the sudden change in the appearance of the mixture. The reaction was done in two sets. The first schedule is composed of reactions with constant HCl concentration and the second has constant Na2S2O3 concentration. The first schedule finds out the effect of varying concentrations of Na2S2O3 on the reaction rate. Table 3.1 shows the set of varying concentrations and their corresponding reaction rates. As the table shows, as the concentration of Na2S2O3 decreases, the rate also decreases. Through the data in Table 4, we can determine the order of reaction with respect to Na2S2O3 by plotting ln Rate versus ln [Na2S2O3]. Plotting the points, we can see the exponential relationship of the two values. Using linear regression, we can find the order of reaction by getting the slope and the value of ln k[HCl]n with n, being the order with respect to HCl, by getting the y-intercept of the line. Using Table 3.1 as basis, the reaction is second order with respect to Na2S2O3. . The second schedule shows the effect of varying concentrations of HCl on the reaction rate. Table 3.2 shows the set of concentrations and their corresponding reaction rates. From the table, we can Chemistry 18.1, Factors Affecting Reaction Rates

see that the concentration of HCl has almost no effect on the rate. As seen from Figure 1.2, the line of the graph is horizontal, meaning that it has a slope and order of zero with respect to HCl. The overall reaction is a second-order reaction overall based from the sum of both orders of reaction based from the reactants. Also, knowing the orders based from the reactants we can form the rate law equation which is Rate = k[Na2S2O3]2. From the two y-intercepts, we can now solve for the rate constant. By isolating it from ln k[Na2S2O3]2 and ln k[HCl]0, and knowing the constant concentrations in each of the schedules, we can find the value of k which is 0.5702 M-1s-1. In part C, the same procedure in part B was done only in three different temperatures. It was observed that the higher the temperature, the faster the reaction rate. This is because at higher temperatures, an increase the initial energy of the molecules is observed due to higher kinetic energy of the molecules, causing a larger fraction of molecules to have sufficient or more than sufficient energy to overcome the activation energy, increasing the frequency of effective collisions and the rate of formation of the transition state. The rate constant of a certain reaction, k, has a specific value for a given temperature. Itsdependence on temperature can be expressed by the Arrheniusequation. To find the activation energy, Ea, of the reaction, an equation called the Arrhenius Equation, which relates the temperature with the rate constant is used. This equation k = Ae-(Ea/RT) can be converted into the form ln k = -(Ea/R)(1/T) + ln A where you can find the activation energy and the pre-exponential factor, A, from the plot of lnk and 1/T, which has a negative slope as seen on Figure 2.0. Given a set of 1/T and their corresponding ln k, you can use linear regression to find the slope (Ea/R) or the yintercept, ln A.. In this reaction, the activation energy was found to be 26,417 Joules by isolating Ea and ln A in the equation. In the fourth part of the experiment, the reaction Mg(s) + HCl(aq) MgCl2(aq) + H2(g) was observed using a Mg strip and pieces of Mg, both with the same volume but different surface area. As the results would show, a faster evolution of hydrogen gas in the reaction was seen using pieces of Mg. The reactant that has a larger surface area occurred faster because of the larger space available for collision to occur. If there is a larger space for collision, then there will be a greater chance that an effective collision will occur, which heightens the frequency of collision, which according to the Collision Theory increases the rate of reaction. In the last part, the following equations were observed:

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For the uncatalyzed reaction: 5H2O2(aq) + C4H4O62-(aq) 4CO2(g) + 2OH-(aq) + 6H2O(l) For the catalyzed reaction: 5H2O2(aq) + C4H4O62-(aq) + Co2+(aq) 4CO2(g) + 2OH-(aq) + 6H2O(l) + Co2+(aq) The uncatalyzed reaction was observed to have a light evolution of CO2 gas while the catalyzed reaction was observed to have a more violent evolution of CO2. There was also a color change in the reaction. From the pink Co2+ catalyst, there was a color change from pink to green, caused by the formation of a cobalt(III)tartrate complex. From this intermediate, the green color changed back to pink, reverting it to the initial Co2+ catalyst, and therefore the Co 2+ ions were not consumed. In this part, the Co2+ cation from CoCl2 serves as a homogenous catalyst in this experiment. It hastened the reaction between H2O2 and Rochelle salt by lowering the activation energy and taking the initial one-step reaction into a reaction with two steps, each lower than the Ea of the uncatalyzed reaction. At the end of the reaction, CoCl2, being the catalyst, was not consumed. Catalysts effectively lower the activation energies of processes and as said earlier, according to the Collision and Transition State theories, reactions with lower activation energies are faster. VII. Conclusion and Recommendation The five factors involving reaction rates affect rate by changing the frequency of effective collisions, and the ease of forming the transition state, which according to both the Collision and Transition State theories, change the rate of reaction. As the frequency of effective collisions increases, the reaction rate increases and as the activation energy decreases or the ease of formation of the transition state increases, the rate also increases. Reactants that are by nature reactive make the rate of reaction faster. Different kinds of reactants have different activation energies, which determine the rate of reaction. An increase in concentration of reactants affects reaction rate since it increases the frequency of collisions between molecules, except for zeroorder reactions which do not affect the rate. The magnitude of how the concentration can affect rate is based on the order of its reaction. A method of finding the order is through finding the slope of the plot of natural logarithms of k and the natural logarithms of the concentration of the reactant varied. From which you can find the rate law. From the rate law, you can find the rate constant. Increase in temperature of the reactants increases the rate of the reaction since it increases Chemistry 18.1, Factors Affecting Reaction Rates

the frequency of collision between reactants due to higher kinetic energy of the molecules. The increase in temperature increases the rate constant. From the relationship between the temperature and the rate constant, we can find the activation energy of the reaction using the Arrhenius Equation. An increase in surface area increases reaction rate since there will be more reactant particles available for collision. A positive catalyst increases the rate of the reaction by cutting the reaction into steps with lower activation energy. It is recommended to use a pipette to accurately measure the volume of reactants, especially in part B, where it is important to have an accurate measure of the amount of reactant in order to have accurate results. It is also important to have a keen eye on the time appearance of the cloudy sol in part B since there will be some discrepancies on the results. VIII. References Brown, T.L., Le May, H.E., & Burtsten, B.E. (2009). Chemistry: The Central Science. 11th ed. Upper Saddle River, NJ: Pearson Education Inc. Chang, R. (2003). General Chemistry: The Essential Concepts. 3rd ed. Boston: McGraw-Hill Engle, H.L., Ilao, L.V. (2007) General Chemistry 2. Manila: Department of Physical Sciences and Mathematics, University of the Philippines Manila. The Royal Society of Chemistry. (n.d.). A visible activated complex. Classic Chemistry Demonstrations. I hereby certify that I have given substantial contribution to this report. _________________________________________ Biolena, Francheska O. _________________________________________ Endaya, Grant Kimmuel R.

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GUIDE QUESTIONS: Part A. Nature of the Reactants 1. Which reaction has higher activation energy? Why? Test tube A (Mg ribbon + water) has higher activation energy compared to test tube B (Na + water) because the activation energy of Na is lower than the one where Mg is the reactant. Also, in the reactivity series of metals, we can notice that Sodium is in the higher position compared to Magnesium, making Sodium more reactive to Magnesium. The activation energy is dependent on the nature of reacting substances. The reaction is slow when the Ea is higher because it is harder to overcome. Part B. Concentration of Reactants 2. How does change in concentration of Na2S2O3 affect the rate of the reaction? The rate of Na2S2O3 decreases as the concentration of Na2S2O3 decreases exponentially. Its relationship is exponential: [Na2S2O3]2 rate. So, as the concentration of [Na2S2O3] increases, rate increases exponentially the power of two.

Chemistry 18.1, Factors Affecting Reaction Rates

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3. What is the order of reaction with respect to Na2S2O3? Theoretically, the order of reaction with respect to Na2S2O3 of reaction is second. 4. How does change in concentration of HCl affect the rate of the reaction? As the concentration of HCl changes, the rate has only a very little proportional change in the rate of reaction. We could assume that there is no change with the rate at all even if the concentration of HCl is increased or decreased. 5. What is the order of reaction with respect to HCl? The order of reaction with respect to HCl is zero. The rate of reaction is independent with the concentration of the reactant HCl. 6. What is the overall order of the reaction between Na2S2O3 and HCl? The overall order of the reaction is 2 (second order reaction). 7. What is the rate law expression of the reaction? Rate= k [Na2S2O3]2 [HCl]0 8. Solve for k: Constant HCl ln k[HCl]0 = y-intercept ln k = -0.5616 k = 0.5702 M-1 s-1 Solve for k: Constant Na2S2O3 ln k[Na2S2O3]2 = y-intercept ln k[Na2S2O3]2 = -1.113509 k = 0.5702 M-1 s-1 Part C. Temperature 8. What is the effect of temperature on the rate of a reaction? An increase in temperature of the reaction increases the rate of reaction for the average kinetic energy also increases, thereby increasing the frequency of collisions. Based on molecular collision theory, this will increase the probability of producing effective collisions. In other terms, we can say that by increasing the temperature, more of the reacting molecules will attain energies equal to or even higher than the required minimum energy barrier and can cross over the energy barrier. 9. Calculate the value of Ea (in Joule units) using Arrhenius equation.

Part D. Surface Area 10. What is the effect of the surface of reactant on reaction rate? The larger the surface area, the faster the reaction rate because more reacting molecules will be available for collision or contact, hence a greater probability for the reaction to occur. Part E. Catalyst 11. What is the role of CoCl2 in the reaction between Rochelle salt and H2O2? CoCl2 acted as a catalyst in this reaction. It speeds up the reaction by having steps (intermediate) with lower Ea without itself being consumed. 12. Briefly summarize the effects of the different factors affecting the reaction rates. The nature of reactants dictates the magnitude of reaction: lower Ea, faster reaction rate; higher Ea, slower reaction rate. An increase in the concentration of reactants also increases the reaction rate since according to the Collision theory, the more reactant molecules, more chances of collision will occur hence faster reaction rate. An increase in temperature also increases the reaction rate since molecules will have a higher kinetic energy as the temperature increases, hence more collision will occur. An increase in the surface area also increases the reaction rate for more molecules are exposed for collision. Lastly, the presence of a catalyst speeds up the reaction by taking the whole Ea of the reaction and lowering it down into smaller steps with lower Ea without itself being consumed.

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