Experiment No.

6 CHEMICAL KINETICS: THE HYDROLYSIS OF METHYL ACETATE

GROUP No. 5: ESPIRITU, Arthur G.

ENTROLIZO, Regina V. FERNANDEZ, Juneil A. CHM171L A1 JAVIER, Danica Alexis U. Prof. Meynard Austria ROMERO, Von Joby M.

ABSTRACT The study of the rates and mechanisms of chemical reactions is called chemical kinetics. Chemical reaction rates are
the rates of change in concentrations or amounts of either reactants or products. The experiment intends to evaluate the hydrolysis of methyl acetate by studying its chemical kinetics, to quantify the activation energy requirement of the reaction, and to determine the change in enthalpy and change in entropy of the reaction. The hydrolysis of methyl acetate is carried out with the use of HCl as the catalyst. Titration of the solution with NaOH determined the amounts/concentrations of acetic acid formed and methyl acetate left. Two factors are considered that affect the reaction rate, the concentration of catalyst and the temperature. It is found to be in second order reaction with respect to the acid. The computed activation energy is 52.95 kJ/mol and the change in enthalpy and change in entropy of the reaction are 52.95 kJ/mol and 177.58 J/mol-K, respectively. The experiment showed that the concentration of catalyst and the temperature affect and increase the rate of reaction. Keywords: Chemical kinetics, reaction rate, hydrolysis, catalyst

INTRODUCTION
Chemical kinetics is the study of the rates and mechanisms of chemical reactions. It includes investigations of how different experimental conditions can influence the speed of a chemical reaction and yield information about the reaction's mechanism and transition states, as well as the construction of mathematical models that can describe the characteristics of a chemical reaction. Chemical reaction rates are the rates of change in concentrations or amounts of either reactants or products. Many factors influence rates of chemical reactions, and these are: Nature of Reactants. Acid-base reactions, formation of salts, and exchange of ions are fast reactions. Reactions in which large molecules are formed or break apart are usually slow. Temperature. Usually, the higher the temperature, the faster the reaction. Concentration Effect. The dependences of reaction rates on concentrations are called rate laws. Rate laws are expressions of rates in terms of concentrations of reactants. Rate laws apply to homogeneous reactions in which all reactants and products are in one phase (solution). Heterogeneous reactions. Reactants are present in more than one phase. For heterogeneous reactions, the rates are affected by surface areas.

Catalysts. Substances used to facilitate reactions. By the nature of the term, catalysts play important roles in chemical reactions. Methyl acetate hydrolyzes to form acetic acid and methanol, according to the following reaction:

The reaction is extremely slow in pure water, but is catalyzed by both hydronium and hydroxide ions. In this experiment, the kinetics of the reaction catalyzed by HCl is studied. Hydrolysis reactions of this type are reversible; the back reaction is called esterification. For any equilibrium the overall rate is the difference in rates of the forward and reverse reactions:

The acid-independent rate calculated using the equation,

constant

can

be

where Ea is the activation energy of the reaction. According to the transition state theory, the rate constant of an elementary reaction is given by

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Experiment No. 6 CHEMICAL KINETICS: THE HYDROLYSIS OF METHYL ACETATE

K+ is similar to an equilibrium constant for the formation of the activated complex from the reactant molecules. The evaluation of the hydrolysis of methyl acetate by studying its chemical kinetics, the quantification of the activation energy requirement of the reaction, and the determination of the change in enthalpy and change in entropy of the reaction are the objectives of the experiment.

For the third setting, the procedures done for the first setting are followed but the reaction mixture is placed in an electronic water bath at 35C. Also, before the mixing, the reactants are allowed to equilibrate in the water bath at 35C.

RESULTS AND DISCUSSION

For the three different settings performed in the experiment, it was found out that the hydrolysis of methyl acetate is in the second order rate based on the values of the R2 of the graphs. The graph that had the value of R2 nearest to 1 is the order of the reaction rate (see Appendices). The slope of the line determined the acid-dependent rate constant for each setting. At room temperature and low concentration of HCl, the rate constant is 0.00002. For the higher concentration and higher temperature, the rate constants are 0.00004 for both. On Table 1 (see Appendices), results show that methyl acetate is being consumed as it is in the reactant side while acetic acid is being produced as it is in the product side. Product formation is favored since HCl is the catalyst used which suppresses the ionization of acetic acid. More NaOH was used as the reaction further took place since the concentration of acetic acid increases with time and thus, requiring more NaOH to reach its equivalence point during titration. On Table 2 (refer to Appendices), the concentration of HCl is increased from 50 mL to 100 mL. HCl served as the catalyst which favors the forward reaction as it suppresses the ionization of acetic acid. It can be seen that the formation of acetic acid is more than that of the hydrolysis with lower concentration of HCl. Thus, much more NaOH was used to reach the equilibrium point. Generally, the more catalyst there is, the more contact with the reactants there is, thus, increasing the rate of reaction until it reaches its maximum speed. On Table 3 (see Appendices), the effect of temperature is studied. The temperature is increased from 25C to 35C. It was found that increasing the temperature increases the reaction rate based on more production of acetic acid compared to the one with lower temperature. Increasing the temperature increases the kinetic energy of the molecules. The more energy there is, the more the molecules move, thus, increasing the number of collisions taking place. With this more collisions, the more the reactants react which lead to a faster rate of reaction. The effect of increasing the temperature is to increase the rate of reaction. By the application of activation energy equation, it can be seen that the rate is dependent on temperature at constant activation energy, Ea. Using the values of k, the activation energy is determined as well as the change in enthalpy and
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METHODOLOGY Materials
The reagents used are distilled water, methyl acetate, 1.0 M HCl solution, standard NaOH solution, and phenolphthalein. Electronic water bath, timer, Erlenmeyer flasks, graduated cylinders, burette, and pipettes are the instruments used in studying the chemical kinetics of the hydrolysis of methyl acetate.

Methods
To evaluate the hydrolysis of methyl acetate, the effect of concentration and temperature are to be considered. Three different settings are performed in the experiment: (1) at room temperature and lower concentration of HCl, (2) at room temperature and higher concentration of HCl, and (3) at high temperature and lower concentration of HCl. To start with, 30 150-mL Erlenmeyer flasks are filled with 50 mL of distilled water and are chilled in an ice bath (ten flasks are used for each setting). This will make sure that the hydrolysis is sufficiently slowed. For the first setting, 20 mL of methyl acetate, 50 mL of water, and 50 mL of 1.0M HCl are obtained and allowed to equilibrate at room temperature. After the equilibrium is reached, the water and the HCl are combined in a 250-mL Erlenmeyer flask. Then, 10 mL of methyl acetate is added to the flask using a pipette. The timer is started when the pipette is half emptied. The solution is mixed thoroughly. Immediately, a 5 mL aliquot of the reaction mixture is withdrawn and is transferred to one of the pre-chilled Erlenmeyer flask with water. The time at which the pipette is half emptied is noted. Then, the diluted aliquot is titrated with standard NaOH using phenolphthalein as the indicator. The change of color is from colorless to light pink. The volume of NaOH used in the titration is noted. The previous procedure is repeated at 10 minute intervals for one hour and at 20 minute intervals for another hour. For the second setting, same procedures are followed but the reaction mixture contained 50 mL of water, 100 mL of 1.0M HCl, and 10 mL of methyl acetate.

Experiment No. 6 CHEMICAL KINETICS: THE HYDROLYSIS OF METHYL ACETATE

change in entropy of the reaction (see Sample Computation). The computed activation energy is 52.95 kJ/mol and the change in enthalpy and change in entropy of the reaction are 52.95 kJ/mol and 177.58 J/mol-K, respectively. Overall, the effect of increasing the temperature and the concentration of HCl is the rate of reaction of the hydrolysis of methyl acetate increases. The experiment had shown clearly the effect of some factors affecting the reaction rate of a chemical reaction.

REFERENCES
[1] Atkins, P., & De Paula, J. (2006). Atkins' Physical Chemistry 8th Edition. W. H. Freeman and Company. [2] Williams, K. R. (1995). Laboratory Manual for Introductory Analytical Chemistry. Fall, pp 44-47. [3] Chemical Kinetics. Retrieved from Waterloo Science Website. [4] Discussion of Principles of Experiments 1-6. CHM171L Physical Chemistry Laboratory 2.

APPENDICES
Table 1. Determination of Hydrolysis Rate at Room Temperature and Lower Concentration of HCl
Estimated Reaction Time, min Time of Withdrawal of Aliquot Actual Reaction Time, min Volume of NaOH used, mL Moles of Acetic Acid in Aliquot Concentration of Acetic Acid, mol/L Concentration of Methyl Acetate Left, mol/L

0 10 20 30 40 50 60 80 100 120

30 sec 10 min 4 sec 20 min 3 sec 30 min 5 sec 40 min 4 sec 50 min 4 sec 60 min 1 sec 80 min 2 sec 100 min 2 sec 120 min 2 sec

0.5 10.06667 20.08333 30.08333 40.06667 50.06667 60.01667 80.03333 100.0333 120.0333

2.5 2.7 2.9 3.1 3.2 3.4 3.6 3.9 4.2 4.5

2.5 2.7 2.9 3.1 3.2 3.4 3.6 3.9 4.2 4.5

x x x x x x x x x x

10-3 10-3 10-3 10-3 10-3 10-3 10-3 10-3 10-3 10-3

0.5 0.54 0.58 0.62 0.64 0.68 0.72 0.78 0.84 0.90

1.1416 1.1413 1.1409 1.1405 1.1404 1.1400 1.1396 1.1391 1.1385 1.1380

Zero Order
1.142 1.141 ln Ya Ya 1.14 1.139 1.138 1.137 0 50 time 100 150 y = -3E-05x + 1.1415 R = 0.9968 0.133 0.132 0.131 0.13 0.129 0

1st Order
y = -3E-05x + 0.1324 R = 0.9968

50 time

100

150

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Experiment No. 6 CHEMICAL KINETICS: THE HYDROLYSIS OF METHYL ACETATE

2nd Order
0.879 0.8785 0.878 0.8775 0.877 0.8765 0.876 0.8755 0 50 time

1/Ya

y = 2E-05x + 0.876 R = 0.9969

100

150

Table 2. Determination of Hydrolysis Rate at Room Temperature and Higher Concentration of HCl
Estimated Reaction Time, min Time of Withdrawal of Aliquot Actual Reaction Time, min Volume of NaOH used, mL Moles of Acetic Acid in Aliquot Concentration of Acetic Acid, mol/L Concentration of Methyl Acetate Left, mol/L

0 10 20 30 40 50 60 80 100 120

23 sec 10 min 12 sec 20 min 5 sec 30 min 5 sec 40 min 8 sec 50 min 5 sec 60 min 4 sec 80 min 7 sec 100 min 4 sec 120 min 5 sec

0.3833 10.2000 20.0833 30.0833 40.1333 50.0833 60.0667 80.1167 100.0667 120.0833

3 3.2 3.5 3.8 4.1 4.3 4.5 4.7 5.0 5.3

3 x 10-3 3.2 x 10-3 3.5 x 10-3 3.8 x 10-3 4.1 x 10-3 4.3 x 10-3 4.5 x 10-3 4.7 x 10-3 5.0 x 10-3 5.3 x 10-3

0.6 0.64 0.70 0.76 0.82 0.86 0.90 0.94 1.00 1.06

0.7842 0.7840 0.7836 0.7832 0.7829 0.7826 0.7824 0.7821 0.7817 0.7814

Zero Order
0.7845 0.784 0.7835 0.783 0.7825 0.782 0.7815 0.781 0 -0.242 y = -2E-05x + 0.784 R = 0.9644 ln Yb -0.243 -0.244 -0.245 -0.246 -0.247 50 time 100 150 -0.248 0

1st Order
50 100 150

Yb

y = -3E-05x - 0.2433 R = 0.9645

time

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Experiment No. 6 CHEMICAL KINETICS: THE HYDROLYSIS OF METHYL ACETATE

2nd Order
1.281 1.28 1.279 1.278 1.277 1.276 1.275 1.274 0

1/Yb

y = 4E-05x + 1.2754 R = 0.9647 50 time 100 150

Table 3. Determination of Hydrolysis Rate at High Temperature and Lower Concentration of HCl
Estimated Reaction Time, min Time of Withdrawal of Aliquot Actual Reaction Time, min Volume of NaOH used, mL Moles of Acetic Acid in Aliquot Concentration of Acetic Acid, mol/L Concentration of Methyl Acetate Left, mol/L

0 10 20 30 40 50 60 80 100 120

55 sec 10 min 50 sec 20 min 20 sec 30 min 25 sec 40 min 20 sec 50 min 16 sec 60 min 15 sec 80 min 13 sec 100 min 14 sec 120 min 14 sec

0.9167 10.8333 20.3333 30.4167 40.3333 50.2667 60.2500 80.2167 100.2333 120.2333

2.5 2.8 3.0 3.3 3.7 4.0 4.3 4.8 5.2 5.6

2.5 2.8 3.0 3.3 3.7 4.0 4.3 4.8 5.2 5.6

x x x x x x x x x x

10-3 10-3 10-3 10-3 10-3 10-3 10-3 10-3 10-3 10-3

0.5 0.56 0.60 0.66 0.74 0.80 0.86 0.96 1.04 1.12

1.1416 1.1411 1.1407 1.1402 1.1395 1.1389 1.1384 1.1375 1.1367 1.1360

Zero Order
1.142 1.141 1.14 1.139 1.138 1.137 1.136 1.135 0 0.133 0.132 0.131 0.13 0.129 0.128 0.127 0.126 0

1st Order
y = -4E-05x + 0.1324 R = 0.9906

50 time

100

150

ln Yc

Yc

y = -5E-05x + 1.1416 R = 0.9905

50 time

100

150

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Experiment No. 6 CHEMICAL KINETICS: THE HYDROLYSIS OF METHYL ACETATE

2nd Order
0.881 0.88 0.879 1/Yc 0.878 0.877 0.876 0.875 0 50 time 100 150 y = 4E-05x + 0.876 R = 0.9907

Sample Computation: A. Hydrolysis Rate at Room Temperature and Lower Concentration of HCl Volume: V [HCl] = 50 mL Volume of Aliquot = 5 mL : V [H2O] = 50 mL Actual Reaction Time = 0.9167 min : V [MeAc] = 10 mL Volume of NaOH used = 2.5 mL Concentration of HCl: [ ] Concentration of Methyl Acetate Left: [ [ [ ] ] ]

Moles of Acetic Acid in Aliquot (5 mL): [ ] ( )

Concentration of Acetic Acid: [ ]

B. Hydrolysis Rate at Room Temperature and Higher Concentration of HCl Volume: V [HCl] = 100 mL Volume of Aliquot = 5 mL : V [H2O] = 50 mL Actual Reaction Time = 0.383333 min : V [MeAc] = 10 mL Volume of NaOH used = 3 mL Concentration of HCl: [ ] Concentration of Methyl Acetate Left: [ [ [ ] ] ]

Moles of Acetic Acid in Aliquot (5 mL): [ ] ( )

Concentration of Acetic Acid: [ ]

C. Hydrolysis Rate at Higher Temperature and Lower Concentration of HCl Volume: V [HCl] = 50 mL Volume of Aliquot = 5 mL : V [H2O] = 50 mL Actual Reaction Time = 0.5 min : V [MeAc] = 10 mL Volume of NaOH used = 2.5 mL

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Experiment No. 6 CHEMICAL KINETICS: THE HYDROLYSIS OF METHYL ACETATE

Concentration of HCl: [ ]

Concentration of Methyl Acetate Left: [ [ [ ] ] ]

Moles of Acetic Acid in Aliquot (5 mL): [ ] ( )

Concentration of Acetic Acid: [ ]

Acid-dependent rate constant at low HCl concentration: K1 = 0.00002 Acid-dependent rate constant at high HCl concentration: K2 = 0.00004 Acid-dependent rate constant at high temperature: K3 = 0.00004 Ea (activation energy) of the reaction: Using K1 = 0.00002 @ T1 = 298.15 K K3 = 0.00004 @ T2 = 308.15 K [ ] [ ]

H of reaction: [ [ ] ]

S of reaction:

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