MAPUA INSTITUTE OF TECHNOLOGY School of Chemical Engineering, Chemistry, Biological Engineering, and Material Science and Engineering rd Physical

Chemistry Laboratory 2 - 3 Quarter SY 2010-2011 rd Neil Patrick P. Tangara , 3 Year B.S. Chemical Engineering

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

Meynard Austria , Neil Patrick Tangara, Darlene Pudolin, Emily Rose Santos, Aeiocellis Tan, Creza Loraine Talingting
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Professor; Students, all from CHM171L/A31, School of Chemical Engineering, Chemistry, Biological Engineering & Material Science and Engineering, Mapua Institute of Technology

ABSTRACT This experiment intends to determine the order of reaction, rate law constant, and activation energy needed to initiate the reaction. Also, the effects of temperature, concentration, catalyst, and other parameters such as pressure on the rate of reaction have been investigated using chemical kinetics. The hydrolysis of Methyl Acetate was carried out with HCl as the catalyst. It was found to be a 2nd order reaction with respect to the acid and had an activation energy value of 375,254.0016 J/mole. It was found that increasing both the temperature and the amount of catalyst present hasten the rate of reaction by an appreciable value by providing it more energy and an optimal reaction condition, respectively. Chemistry theories such as the kinetic molecular and collision theories have been taken into consideration upon interpretation of the results gathered. This report will discuss why such a phenomenon occurs.
Keywords: rate law constant, order of reaction, activation energy, catalyst

INTRODUCTION Chemical kinetics is the study and discussion of chemical reactions with respect to reaction rates, effect of various variables, rearrangement of atoms, formation of intermediates etc. At the macroscopic level, we are interested in amounts reacted, formed, and the rates of their formation. At the molecular or microscopic level, the following considerations must also be made in the discusion of chemical reaction mechanism. Molecules or atoms of reactants must collide with each other in chemical reactions. The molecules must have sufficient energy (discussed in terms of activation energy) to initiate the reaction. In some cases, the orientation of the molecules during the collision must also be considered. Methyl acetate hydrolyzes to form acetic acid and methanol, according to the following reaction:

(1) 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 will be studied. HCl also suppresses the ionization of acetic acid so as not to change the concentration of hydronium ions present.

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MAPUA INSTITUTE OF TECHNOLOGY School of Chemical Engineering, Chemistry, Biological Engineering, and Material Science and Engineering rd Physical Chemistry Laboratory 2 - 3 Quarter SY 2010-2011 rd Neil Patrick P. Tangara , 3 Year B.S. Chemical Engineering

METHODOLOGY To determine the effect of concentration and temperature on the reaction mechanism, two runs of difference concentrations were made at 25oC (assuming room temperature) and one run was made at 35oC. The concentration of methyl acetate at a given time and temperature was determined through titration of samples with a standard sodium hydroxide solution since concentration varies with temperature (25 and 35 oC). A test tube containing about 12 ml methyl acetate was set into a thermostat at 25 C. Approximately 250 ml of standardized 1 N hydrochloric acid was placed in a flask clamped in the thermostat. After thermal equilibrium has been reached (10 or 15 min should suffice), two or three 5-ml aliquots of the acid were titrated with the standard sodium hydroxide solution to determine the exact molarity of the sodium hydroxide in terms of the standardized hydrochloric acid. Then 50 ml and 100ml of acid was transferred to each of two 250-ml flasks clamped in the thermostat and 5 min allowed for the reestablishment of thermal equilibrium. Precisely 5 ml of methyl acetate was next transferred to one of the flasks with a clean, dry pipette; the timing watch was started when the pipette is half emptied. The reaction mixture is shaken to provide thorough mixing. A 5-ml aliquot was withdrawn from the flask as soon as possible and run into 50 ml of distilled water. This dilution slows down the reaction considerably, but the solution should be titrated at once; the error can be further reduced by chilling the water in an ice bath. The time at which the pipette has been half emptied into the water in the titration flask is recorded, together with the titrant volume. Additional samples were taken at 10-min intervals for an hour; then at 20min intervals for the next hour and a half. The

average values were determined by processing samples for 1 hour and 3 hour intervals. In similar fashion, another run was made on a temperature of 35. Because of the higher rate of reaction, three samples are first taken at 5min intervals, then several at 10-min intervals, and a few at 20-min intervals. To get the average values, a 1 hour interval run was made.

RESULTS AND DISCUSSIONS A. At Room Temperature and Low Concentration Reaction Time, minutes 0 10 20 30 40 50 60 80 100 120 180 360 Volume NaOH used, mL 2.7 2.9 3.0 4.0 4.2 4.3 4.5 4.6 4.9 5.1 5.4 6.2 Conc. Acetic Acid, M 0.2847 0.3058 0.3164 0.4218 0.4429 0.4535 0.4745 0.4851 0.5167 0.5378 0.5695 0.6538 Conc. Methyl Acetate left, M 0.8532 0.8321 0.8216 0.7161 0.6950 0.6845 0.6634 0.6529 0.6212 0.6001 0.5685 0.4841

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. 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. This part will give us the basis of comparison later on in the determination of the
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MAPUA INSTITUTE OF TECHNOLOGY School of Chemical Engineering, Chemistry, Biological Engineering, and Material Science and Engineering rd Physical Chemistry Laboratory 2 - 3 Quarter SY 2010-2011 rd Neil Patrick P. Tangara , 3 Year B.S. Chemical Engineering

effect of increasing the amount of catalyst (HCl) present and of increasing the temperature of the reaction vessel. Two theories (kinetic and collision) shall be the basis for comparison. B. At Room Temperature and High Concentration Reaction Time, minutes 0 10 20 30 40 50 60 80 100 120 180 360 Volume NaOH used, mL 2.8 3.1 3.3 3.5 3.6 3.9 4.2 4.5 4.7 4.8 5.0 5.1 Conc. Acetic Acid, M 0.4060 0.4495 0.4785 0.5075 0.5220 0.5655 0.6090 0.6525 0.6815 0.6960 0.7250 0.7395 Conc. Methyl Acetate left, M 0.3763 0.3328 0.3038 0.2748 0.2603 0.2168 0.1733 0.1298 0.1008 0.0863 0.0573 0.0428

This proves the capacity of the catalyst to initiate and hasten the rate of reaction by providing the best possible reaction conditions that require minimal activation energy. C. At High Temperature and Low Concentration Reaction Time, minutes 0 10 20 30 40 50 60 80 100 120 180 Volume NaOH used, mL 2.1 2.5 2.7 3.1 3.4 3.7 4.0 4.2 4.7 4.8 4.9 Conc. Acetic Acid, M 0.4779 0.5690 0.61445 0.7055 0.7738 0.8421 0.9104 0.9559 1.0697 1.0924 1.1152 Conc. Methyl Acetate left, M 0.6600 0.5690 0.5235 0.4324 0.3641 0.2959 0.2276 0.1821 0.0683 0.0455 0.0228

As compared to part A, part B, having a higher concentration of catalyst (100ml versus 50ml), have had a faster rate of reaction as evident on the higher concentration of acetic acid produced after initiating the reaction at time 0 until time equals 6 hours. The catalyst works by providing the optimal conditions for a reaction to occur. 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. However, adding too much catalyst on the system might not help hasten the reaction rate especially when it already dilutes the system from its optimal reaction conditions with useless catalyst sites.

The effect of increasing the temperature was studied in this part. It was found that it made the rate of reaction faster as evident on the higher concentrations of acetic acid produced as compared to part A (35 versus 25 oC). Increasing the temperature increases the kinetic energy of the molecules (kinetic theory). The more energy there is, the more the molecules move, thus, increasing the number of collisions taking place in the reaction vessel. The more collisions there is, the more the reactants react, thus, leading to a faster rate of reaction compared to non-excited molecules (collision theory). CONCLUSION In summary, the rate of reaction was found to be dependent on several factors such as the

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MAPUA INSTITUTE OF TECHNOLOGY School of Chemical Engineering, Chemistry, Biological Engineering, and Material Science and Engineering rd Physical Chemistry Laboratory 2 - 3 Quarter SY 2010-2011 rd Neil Patrick P. Tangara , 3 Year B.S. Chemical Engineering

concentration, catalyst, temperature and other parameters such as pressure and surface area which were kept constant throughout the experiment. It was found that increasing the amount of catalyst hastens the rate of reaction by providing the optimum reaction conditions, that is, by lowering the activation energy needed for the reaction to initiate. It was also found that increasing the temperature hastens the rate of reaction as well by providing the molecules more kinetic energy which leads to more collisions within the system which initiates reactions faster as based on kinetic and collision theories of chemistry. APPENDICES Preliminary Data Sheet *Please refer to the attached document for the preliminary data sheet. Kinetics Graphs *Please refer to the attached document for the graphs. Sample Computations Given: Hydrolysis of Methyl Acetate Vol. of 1.16 M HCl = 50 ml Vol. of water = 50 ml Vol. of MeAc = 10 ml Required: concentration of HCl in mixture Solution: [ ] = 0.527272727 M
( )

K1 (low conc.) = 0.0041 K2 (high conc.) = 0.00004 K3 (high temp.) = 0.00003 Required: activation energy Solution: Arrhenius Equation [ ]

Substituting the values, [ ]

REFERENCES Knight, S.B, Crockford, H.B., Fundamentals of Physical Chemistry 2nd ed., Wiley International, 1964, {Accessed: 02-26-11} Atkins, Physical Chemistry 5th edition, chapter 24, page 841, W.H. Freeman & Company, {Accessed: 02-26-11}

Given: Hydrolysis of Methyl Acetate Part A: Hydrolysis Rate at Room Temperature and Lower Concentration of HCl

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MAPUA INSTITUTE OF TECHNOLOGY School of Chemical Engineering, Chemistry, Biological Engineering, and Material Science and Engineering rd Physical Chemistry Laboratory 2 - 3 Quarter SY 2010-2011 rd Neil Patrick P. Tangara , 3 Year B.S. Chemical Engineering

1 0.8 0.6 0.4 0.2 0 0 y = -0.002x + 0.8144 R = 0.8665 50 100 time,min 150

0 -0.1 0 -0.2 -0.3 -0.4 -0.5 -0.6

ln Yb

Zero Order

1st Order
2 50 100 150 1.5 1/yb 1 y = -0.0029x - 0.2019 R = 0.8925

2nd order

0.5 0 0 time, min

y = 0.0041x + 1.218 R = 0.9163 50 100 time,min 150

Part B: Hydrolysis Rate at Room Temperature and Higher Concentration of HCl

Zero Order
moles acetic acid, Yb
1 0.8 0.6 0.4 0.2 0 0 50 100 time,min 150 y = -0.0051x + 11.634 R = 0.7638

0 -0.1 0 -0.2 -0.3 -0.4 -0.5 -0.6

ln Yb

1st Order
2 50 100 150 1.5 1/yb 1

2nd order

y = -0.0004x - 2.4539 R = 0.7709

y = 0.0042x + 1.2056 R = 0.9122

0.5 0 0 time, min 50 100 time,min 150

Part C: Hydrolysis of Rate at High Temperature and Lower Concentration of HCl

zero order
0.8 0.6 0.4 0.2 0 -0.2 0 50 100 150 200 y = -0.0037x + 11.754 R = 0.8378 0 0 -1 -2 -3 -4 -5 50

1st order
50 100 150 200 40 30 20 10 y = -0.0003x + 2.4643 R = 0.8412 0 -10 0 50

2nd order
y = 3E-05x + 0.0851 R = 0.8446

100

150

200

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