Experiment C5 Kinetics in Solution

Chemistry 114

Goals: To measure rate constants for the saponification of Ethyl acetate in sodium hydroxide solutions at several temperatures. From these rate constants the activation energy and entropy of activation can be calculated. Additional experiments will explore the order of the reaction and the saponification rate of other esters. Background The alkaline hydrolysis of acetate esters, also know as the saponification reaction can be written as: AcO-R + Na+ + OH- AcO- + Na+ + R-OH (1)

As the reaction proceeds, hydroxide ions are consumed and acetate ions are produced. Since the hydroxide ion has a much larger specific conductance than the acetate ion, the kinetics for this reaction can be monitored by following the change in conductivity of the reaction mixture with time. The conductivity of the reaction (1) is determined by the presence of different ions in solution [1]: = OH COH + A CA + Na CNa (2) where the limiting molar conductivities (i) have units of cm2 equivalent-1 ohm-1, and the concentrations (Ci) are expressed in equivalents cm-3. The concentrations of the hydroxide (COH) and acetate (CA) ions are the only variables in Eq. (2) and they are related by the stoichiometry of the reaction. It can be shown that CA can be expressed as:

C A = b1 0

or

C A = a 1 0

(3)

Where the initial concentration of hydroxide (b) or acetate (a) represent the limiting reagent for the reaction mixture. The ratio is the normalized conductivity (starts at 1 and decays to zero). 0 It has been found (and you will have to prove) that the saponification follows second order kinetics:

dC A = kCOH C E dt
Integration of Equation 4 yields:

or

dC A = k (b C A )(a C A ) dt

(4)

b( a C A ) ln = k (a b)t a(b C A )

for a b

or

CA = kat a CA

for a = b

(5)

Equations (3) and (5) can be combined to obtain the expression that relates and t.

Revised Winter 2007

Experimental Procedure Conductivity measurements will be performed with a commercial conductivity meter that is connected to a computer running Lab View software. To start a kinetic run immerse the conductivity probe in a stirred NaOH solution, turn the meter on and press the record button (so the instrument will not auto shut-off in 10 minutes), then press the Temp. button to check that temperature compensation is at 0% (if not, use the Factor Adj. button to adjust it to 0%). Start the Lab View software. Wait for a stable conductivity value ( 0.01 mS in the 20mS scale) and add the ester with a micropipette while the reaction mixture is under vigorous stirring. Collect data until the conductivity value has decayed to a constant value. Do not discard the products of the reactions right away, but cover them to prevent evaporation and measure at the end of the lab period, or at least one hour later. Prepare 1000 ml of an aqueous NaOH solution in D.I. water at a concentration of about 0.06 M (you will need to know this concentration accurately) (this solution should be freshly prepared from solid NaOH, not a dilution of a pre-existing solution) and calculate the approximate that you expect to measure for this solution from the table of o values included with this handout. I) Second order rate law: You will start this lab. by verifying the second order rate law for the saponification reaction by studying the kinetics of this reaction with the following three initial concentrations of reactants: i) a=b=0.06 ii) a=0.04, b=0.06 iii) a=0.06, b=0.04 Where a=initial conc. of NaOH, b=initial conc. of Ethyl Acetate

In a 150 ml beaker prepare 100.0 ml of the appropriate NaOH concentration; then calculate the volume of pure Ethyl Acetate that will give you the required number of equivalents (the density of the different esters are listed on the bottles). Check that 0 for experiments i) and iii) is the same within experimental uncertainty and that it is 50% higher than 0 for experiment ii) After each run rinse the probe in DI water. Never use acetone, this solvent dissolves the probe. You will notice a thin film on top of the reaction mixture: This is due to the ester dissolving the probe, which is harmless to the experiment. II) Temperature scans: Prepare another 100 ml of NaOH 0.06 M in a 150 ml beaker and put it in an ice bath. Wait for a stable temperature (probably 1-4 C in 30 min- 1 hour) and start a run after adding ~0.15 equiv. of Ethyl Acetate (Since the temperature is not stable a faster reaction minimizes the error, thus a higher concentration of acetate is used). You should continue adding ice to the bath to try to keep the temperature constant throughout the experiment (a 3 C range is acceptable) Then, for the high temperature run, set the hot plate to the minimum setting (low or 1) and monitor the conductivity and temperature of 100 ml of a NaOH 0.06 M solution. Once the temperature is stable (30 min-1 hour, with the temperature in the low forties) start a reaction with ~0.06 equivalents of Ethyl Acetate. Throughout the reaction, try to keep the temperature constant (3C, by turning the hot plate on and off as necessary). You should also keep track of the volume of NaOH solution that evaporates before starting the reaction, to correct for b the initial NaOH concentration.

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III) Acetate structure: Use Methyl acetate and Propyl acetate for kinetic runs at room temperature with a=0.06 and b=0.04. Sometime during these experiments, you should do one duplicate run to check for consistency: The experimental conditions should be identical, but they could be done on different days. Data Analysis: Fit all your data to the appropriate Equation 5 following the instructions below: Discard the first few seconds of data after injection of the ester, since this corresponds to the mixing of the sample components. Slightly adjust to obtain a better fit (or better yet, fit ). Ignore any intercept value, this corresponds to a t0 (injection time) different from zero. You can also adjust 0 slightly: Although you have measured an initial conductivity, this is not quite the correct value for 0 ; adding the ethyl acetate changes the volume of the solution slightly and, more importantly, alters the viscosity, which will change the values of . This adjusted 0 should differ from your initial measurement by no more than a few percent. Discussion Compare the normalized (

) conductivity decay traces i), ii), and iii) to argue that the reaction 0

has to be first order on both reactants (reaction orders higher than 3 are very rare) and report the reaction constant for all 3 runs. (You should compare the reaction rates, that depend on concentration, not the rate constants, that only depend on temperature) Calculate the activation energy for the reaction with Ethyl Acetate from the slope of an Arrhenius plot. To calculate the entropy of activation, S, you need to use Transition State Theory, which says that the rate constant can be written as, k1 = (kT) h-1 Exp(- G /kT) = (kT) h-1 exp(+S /k) exp(-H /kT) II

where k is the Boltzmann constant, and h is Planck's constant. For reactions in solution, the enthalpy of activation is related to the experimental activation energy, Ea, by the expression, H = Ea - RT III

Evaluate the entropy of activation from your best estimate of the rate constant at 25 C and your experimental activation energy. Note that the value for S will depend on the units used for the rate constant; i.e. S depends on the standard state that is being used (normally 1 mole per liter for reactions in solution). What does the value of S tell you about the mechanism of this reaction? Finally, compare the reaction constants at room temperature for the different acetates and discuss the trend in terms of the inductive effect.

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Table of o Values as a Function of Temperature Units are cm2 equivalent-1 ohm-1. Ion Na+ OHCH3CO20 C 26.5 105 20.1 15 C 39.77 165.93 25 C 50.10 199.18 40.90 35 C 61.54 233.04 45 C 73.73 267.23 -

Refs [1] Atkins, P.; De Paula, J. Physical Chemistry, 7th Ed. Freeman, N.Y. [2] The cell constant is 1 cm

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