CHM3103 Chemical Kinetics

Name Matric no Programme Partner Name Matric no Programme Experiment Title Date Lab Demo

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WAN KEE PENG 109630 Bachelor Of Science (Hons) Chemistry LIEW CHEE CHOONG 110353 Bachelor Of Science (Hons) Chemistry 8 Kinetic reaction of ion hydroxide and ethyl acetate 18-8-2004 440 LIM BOON PENG

Title: Kinetic reaction of ion hydroxide and ethyl acetate Objective: To determine of rate constant of the hydrolysis of ethyl acetate by sodium hydroxide by measurement of the electrical conductivity.

Introduction: A carboxylic ester is hydrolyzed to the corresponding carboxylic acid and alcohol when heated with aqueous acid or base. Under alkaline conditions, the carboxylic acid is obtained as its salt, from which the acid can be liberated by addition of mineral acid:

The reaction can be followed by titration of the alkali remaining in solution, or, better, by measurement of the electrical conductivity. The net result of the reaction, as regards the conductivity, is that OH- ions are progressively replaced by R. COO- ions. The latter have a lower electrical mobility (about one-fifth of that of OH-; consequently the conductivity falls. The change of conductivity is approximately proportional to the amount of reaction that has taken place. The reaction rate constant for the alkaline hydrolysis of esters such as ethyl acetate may be determined conductometrically. As the reaction proceeds, hydroxyl ions are consumed and acetate ions are produced. Hydroxyl ion has a very much larger specific conductance than acetate ion. Hence, the alkaline hydrolysis of ethyl acetate may be monitored by following the change in the conductance of the reaction mixture with time. By determination of the conductivity as a function of time, the rate constant is found.

The mechanism is simply a nucleophilic acyl substition(either SN1 or SN2, depending on reactant):

Base promotes hydrolysis of esters by providing the strongly nucleophilic reagent OH-. This reaction is essentially irreversible, since a resonance-stabilized carboxylate anion shows little tendency to react with an alcohol. Thus, basic hydrolysis of esters has a large equilibrium constant and it is sufficient to use only one equivalent of water in order for the reaction to proceed to completion.

Methodology:

100cm3 of 0.05M NaOH and 0.20M ethyl acetate were prepared Add 70cm3 of 0.05M NaOH into 200cm3 beaker Add 70cm3 of H2O into the solution and stir Put in the conductivity cell to the solution and then add in 10cm3 of ethyl acetate Stir Record the conductivity reading for every: 0.5 minute in first 5 minute 1 minute in 5 minute 5 minute in 20 minute

Result and calculation:

Preparation of 0.05M solution of NaOH: Mole of NaOH = MV/1000 Mass of NaOH need dilute to 100cm3 of 0.05M solution = MV/1000 * Mw = 0.05 x 100 / 1000 x 40.0 = 0.2g

Preparation of 0.20M solution of ethyl acetate: Mw /gmol-1 /gcm-3 % Purity /% = 88.11 = 0.9 = 99

M1/ moldm-3 = 1000/Mw x %Purity/100 x =1000/88.11 x 99/100 x 0.9 =10.11 V2 = 100cm3 M2 = 0.02M V1 = M2 x V2 / M1 = 0.02M x 100 cm3 / 10.11M = 0.20 cm3 Volume of ethyl acetate need to dilute to 0.02M is 0.20 cm3

 0 = 4.33mS = 2.50mS t(mS ) 4.33 4.18 4.05 3.94 3.84 3.76 3.69 3.60 3.55 3.49 3.43 3.34 3.27 3.20 3.15 3.09 2.96 2.87 2.81 2.76 2.50

t (minute) 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 6.0 7.0 8.0 9.0 10.0 15.0 20.0 25.0 30.0

0- 0 0.15 0.28 0.39 0.49 0.57 0.64 0.73 0.78 0.84 0.9 0.99 1.06 1.13 1.18 1.24 1.37 1.46 1.52 1.57 1.83

t- 1.83 1.68 1.55 1.44 1.34 1.26 1.19 1.1 1.05 0.99 0.93 0.84 0.77 0.7 0.65 0.59 0.46 0.37 0.31 0.26 0

( 0- t )/( t- ) 0.0000 0.0893 0.1806 0.2708 0.3657 0.4524 0.5378 0.6636 0.7429 0.8485 0.9677 1.1786 1.3766 1.6143 1.8154 2.1017 2.9783 3.9459 4.9032 6.0385 -

From the equation of second order reaction: ( 0- t )/( t- ) = akt A graph of ( 0- t )/( t- ) vs t is plotted A straight line with zero intercept was obtained and the gradient obtained represents the value of ak.

From the graph we plotted, Gradient = 0.1989 minute-1 a is the concentration of NaOH = 0.05M From the equation, k = gradient / 0.05 = 0.1989 / 0.05 = 3.978 M-1minute-1 The rate constant, k is 3.978 M-1minute-1.

7. 0000

6. 0000

5. 0000 ( 0- t ) / ( t - )

4. 0000

3. 0000

2. 0000

Discussion: The reaction of ethyl acetate and hydroxide ions yields ethanol and acetate ions, as shown below. CH3COOC2H5 (aq) + OH (aq) CH3CH2OH (aq) + CH3COO (aq) The progress of this reaction can be observed by monitoring the conductivity of the reaction mixture. Although the reactants and products each contain an ion, the OH ion has a higher ionic mobility than the CH3COO ion. This results in a net decrease in the conductivity of the reaction mixture as the reaction proceeds. Based on the data of the result, the conductivity is decrease by the time. The concentration of ethyl acetate decreased as the reaction proceeds and nearly achieve zero as the reaction is said to go to completion. The decrease of the concentration of hydroxide ion from the beginning of the reaction to its end is equal to the decrease of the concentration of ethyl acetate, and both of these changes are equal to increase of the concentration of acetate ion and ethanol. The reaction rate constant for the alkaline hydrolysis of esters such as ethyl acetate may be determined conduct metrically. As the reaction proceeds, hydroxyl ions are consumed and acetate ions are produced. In this experiment, the kinetics of the reaction between ethyl acetate and hydroxide ion would be studied. This reaction is a second order reaction. From the experiment, the graph of ( 0- t )/( t- ) versus time was plotted and A straight line with zero intercept was obtained. Then from the graph we can know the gradient, so the rate constant, k is determined as 3.978 M-1minute-1.

Precaution steps:

Make sure all the apparatus is clean, well rinsed with distilled water before use to avoid any oddment inside the apparatus. Make sure the mixture in the volumetric flaks is well shaken occasionally to get homogenize solution. Make sure there is no parallax when reading the value of each solutions from graduated cylinder scale so that to get accurate result

Conclusion: I. The constant rate, k is 3.978 M-1minute-1. II. The graph ( 0- t )/( t- ) vs t is a straight line.

Reference: Asas kinetic kimia , Salihan Siais , pg. 93-99 http://wyk.edu.hk/~paulsiu/Chemistry/Basic Hydrolysis of Ester.htm http://www.chem.ucalgary.ca/courses/351/Carey5th/Ch20/ch20-3-3.html