KINETICS OF REACTION BETWEEN THIOSULFATE AND

HYDROCHLORIC ACID

DEPARTMENT OF NATIONAL INSTITUTE OF GEOLOGY, COLLEGE OF SCIENCE UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES

ABSTRACT This experiment illustrates the basic concepts of Chemical Kinetics like the rate law and the Arrhenius Equation. These concepts are widely utilized by modern technology such as food storage and in the field of medicine. Indeed, chemical kinetics plays a vital role in the advancement of technology and survival of the human race. The significance of doing this experiment is for students to see and understand how molar concentrations of reactants and temperature affect the rate of a reaction. From observation, the researchers determined the rate law from initial rates and interpreted the reaction of thiosulfate and Hydrochloric acid. A total of 6 runs of different concentrations at the same temperature were tested for the time that was used as initial rate. Then, using one particular solution exposed to different temperatures, they were able to construct a line graph with a slope of line and were able to calculate an activation energy value. With this graph and data, they determined the relationship of temperature with the reaction rate. The rate law determined was rate k[ s 2o3] meaning that only the molar concentration of the solvent can affect the rate. The graph produced a negative slope of -4501.229869 while the activation energy produced was 37.423 kJ/mol. The value of r squared is -0.91600241 which describes the error. Based from these data, it can be said that as temperature increases, so does the rate of reaction.

INTRODUCTION This experiment focuses on Chemical Kinetics, the study of reaction rates. These rates are changes in the concentration of the reactants or products as time changes. For the most part of the experiment, these rates will be broken down to what they call a rate law (1).

In this equation, k is called the rate constant and m and n are called reaction orders. Rate constant does not change for a reaction while reaction orders states how the rate is affected by reactant concentration [2]. The rate law is important for any kinetic study for a reaction. This rate law is always based on experimental fact as it expresses the rate as a function of concentrations and temperature [2].

r k[ A]m [ B]n (1)

The rate constant however can be affected by the temperature. Their relationship can be found in the Arrhenius equation (2) in which k is the rate constant once more, A is the Arrhenius constant, Ea is the energy of activation, R is the universal gas constant and T is the temperature.

Run 1 2 3 4 5 6

k Ae Ea / RT (2)
Chemical Kinetics is very important because of various applications. How quickly a medicine acts or blood clots are fatal in saving a life. Products like milk are stored in refrigerators to slow down its spoiling process. Also, the relatively dangerous photochemical smog forms in particular rates [1]. Thus, it is quite important to study Chemical Kinetics for it gives mankind a much deeper understanding of the chemical processes around him [3]. One of the objectives of the experiment is to determine the rate law of the reaction between thiosulfate and Hydrochloric acid using initial rates. Then, the researchers are to interpret this rate law. The other is to construct a graph to illustrate the effect of temperature on reaction rate with a calculated slope of a line. METHODOLOGY The researchers prepared 250 ml of 0.15 M Na2S2O3 5 H2O. By calculation, they used 9.30 g of Na2S2O3 5 H2O to prepare this. 100 ml of 3M HCl was also prepared. Thiosulfate solution and water was placed in a 50 ml beaker with an X mark at its bottom. For greater visibility of the mark, this beaker was placed above a white paper. The researchers then added the required amount of acid rapidly and recorded the time the instant that the mark became invisible. A total of 6 runs were performed. The volume of each component (water, Na2S2O3, and HCl) is shown in table 1

0.15 M Na2S2O3 20 ml 10ml 5ml 10ml 10ml 10ml

water 6ml 16ml 21ml 2ml 3ml 4ml

3M HCl 4ml 4ml 4ml 3ml 2ml 1ml

With the data given in Table 1, the researchers computed for the concentrations of S2O3- and H+. These data are shown in table 2. Table 2: The New Concentrations of S2O3 and H+ Run 1 2 3 4 5 6 [S2O3] 0.1M 0.05M 0.025M 0.1M 0.1M 0.1M With the given data, determined by the reciprocal the initial rate. [H] 0.4M 0.4M 0.4M 0.6M 0.4M 0.2M the rate law can now be of the time recorded as

For the 2nd part, the researchers made 2 more solutions of run 3. Using the temperature in the first test as the room temperature (304.15 K), they increased the temperature by heating one of the solutions of run 3. They also decreased the temperature by placing the other solution in an ice bath. The heated solutions temperature was 323.15 K while the cooled solutions temperature was 289.15 K. Again, like in the first part, the heated and the cooled solutions of run 3 were timed at the moment the X mark disappeared when acid was added. When all data was gathered, the researchers solved for the graph of log (1/t) versus 1/Temperature. Encoding the data will yield the slope of the line of the graph and the energy of activation as well. RESULTS AND DISCUSSION For the first part of the experiment, it was important for the beakers containing each of the solutions to be of the same size. This was to ensure that only the concentrations of the S2O3 and H+ varies. This way, the researchers can easily monitor the

Table 1: The Components of the Runs Performed

disappearance of the mark the same way for all the other runs. After adding the specified volume of the HCl, the researchers recorded their data as shown in Table 3. Table 3: The Recorded Time when mark is no longer visible after adding 3M HCl Run 1 2 3 4 5 6 Time (s) 18.47 26.89 42.58 16.93 20.98 26.00 1/Time (initial rate) 0.0541 0.0271 0.0239 0.0591 0.0477 0.0385

S 2O 32 SO 32 S _________( slow) SO 32 H HSO 3 HSO 3 H SO 2 H 2O

Figure 1: The Multi Step Reaction Mechanism of the Reaction of Thiosulfate and HCl. Cancelling the intermediates yields to an overall reaction

S 2O32 ( aq ) 2H ( aq ) SO 2( g ) S ( s ) H 2O
This is the ideal overall reaction and thus the 1st multi step process is the correct mechanism [1]. The results of the 2nd part of the experiment, the effect of the temperature on the reaction rate, are found on Table 4. Table 4: Data of 2nd Part of .025M [S2O3] and 0.4M HCl at different temperatures Run Time 32.77s 42.58s 173s 1/time 0.031 0.0235 0.006 Temp(K) 323.15K 304.15K 289.15K 1/T 0.00329 0.00309 0.00346

The rate law can be calculated by the method of initial rates [3]. The initial rate is defined as the rate when time is 0 and occurs when reactants are just mixed before any product accumulates.

rate

1 time

Using the equation of the rate law where r is the initial rate, [A] is the [S2O3] and the [B] as the [H+], they were able to calculate for the rate law of the reaction. THE RATE LAW FOR THE REACTION

From the given data, it can be seen that as temperature decreases, so does the rate of reaction. The units of the rate constant can be determined by the overall order p of the reaction according to a relation, which when rearranged becomes

rate k[ s 2o3]
As stated here, the order of reaction with respect to thiosulfate is 1 while the order of the reaction with respect to Hydrogen ion is 0. The overall kinetic order of the reaction would be 1. In each of the 6 runs, the Na2S2O3 served as the solvent. As its concentration decreases, so does the initial rate of the reaction. This further solidifies the rate law stated. Out of the given choices, the 1st multi-step process has the desired overall reaction of the reaction.

units _ k (concentration)1 p (time) 1

Where p = m+n [3]. Since the rate law determined in the first part was first-order, the unit for the rate constant would be 1/seconds(time). Thus, 1/time would be their rate constant to be encoded in ln k as the y-values of the graph. 1/Temperature would be the x-values. All of these are in accordance of the modified Arrhenius Equation [2]

ln k ln A

y b mx

Ea 1 ( ) R T which can be seen as:

since the rate law could still be obtained with highly precise initial rates. Inaccuracy on this part can decrease, increase or mostly have no effect on the rate law. Another possible source of error is the time of addition of the acid in each of the runs. Sometimes the flow is not continuous and this increases the time for the initial rates thus affecting the values for estimation of the rate law. Also, since this is used in the graph, an increased time can decrease the accurate xvalue [3].

Through encoding and calculations, the value of the slope of the line is -4501.229869 and the energy of activation is 37.423 kJ/mol. The graph of the values can be seen in Figure 2. 0 0.003 ln (1/t) -2 -4 -6

0.0032

0.0034

0.0036

SUMMARY AND CONCLUSIONS In summary, the calculated rate law of the 1/T experiment rate k[ s 2o 3] means that only the concentration of the thiosulfate can have an effect in the rate of the reaction. This also means that the reaction between thiosulfate and HCl is a first order reaction based from the method of initial rates. No matter how much the concentration of the HCl, it will have no effect on the rate. This fulfils the first objective of the experiment. The 2nd parts results yielded a good graph of log (1/t) vs. 1/T with a slope of -4501.229869. From this graph, it was concluded that as temperature increases, so does the rate of the reaction. This is further supported by the Collision Theory since more collisions occur and thus react. Therefore, the 2 nd objective of the experiment was accomplished. With these data and the calculations done, the basic concepts of chemical kinetics were covered and presented to the researchers. The researchers suggest that the method of getting the time for initial rates be improved. If able to, they suggest that some lab instruments be used in measuring the exact time before a product forms in a reaction. Also, the experiment only covered the basic concepts of kinetics. It would be much more knowledgeable for students be given the opportunity to tamper with a reaction to get a desired rate of reaction. In conclusion, the experiment was successful in presenting the basics of chemical kinetics. The students were able to calculate for the centrepiece of the study, the rate law and the graph of a reaction(Figure 2). Albeit prone to error, the results

Figure 2: Effect of temperature on reaction rate by the Arrhenius Equation Ea, the activation energy, is the minimum energy the molecules must have to react. It was calculate by the formula

Ea . Knowing this R

value is useful because according to the collision theory, collisions must exceed the Ea to lead to a reaction. This is related to the temperature rise by the statement: As temperature rises, it enlarges the fraction of collisions with enough energy to exceed the activation energy. The smaller the Ea, the higher the temperature and that will increase the value of k, making the reaction faster. [2]. From the Arrhenius Equation (2), the term A contains the effect of molecular orientation. It is sometimes called the frequency factor, and is the product of orientation probability factor (p) and collision frequency (z). It is also a key factor in determining the y-intercept of the graph [2]. There are many possible errors in this experiment for it yielded an r squared value of 0.91600241. For instance, the method on how the initial rates were recorded. Notice that the time recording stops upon the perception of the researcher observing the visibility of the mark at the bottom of the beaker. This is a very inaccurate way in recording values. However, precision is given more importance

were supported by theories in the study of General Chemistry. In here, one can conclude that concentrations may or may not affect the rate of the reaction. Increasing the temperature to exceed the activation energy more can also speed up a reaction. The reaction between thiosulfate and HCl was a good illustration on how kinetics work and can be manipulated for greater purposes.

REFERENCES: [1]Petrucci, Herring and Madura, General Chemistry, 10th edition. Pearson, 2011. p. 602-632 [2]Silbeberg, Martin S. Principles of General Chemistry, 2010, 2nd edition. McGraw-Hill, 2010 [3]Skoog, West and Holler, Fundamentals of Analytical Chemistry, 10th edition. Thomson, 2004.pp. 880-893