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OBJECTIVE

reaction, the saponification of ethyl acetate.

THEORY

The alkaline hydrolysis of fats is referred to as saponification (literally, "soap-making"). Over the

years the term has come to be used also in referring to the alkaline hydrolysis of any type of ester.

The saponification of ethyl acetate

CH3COOC2H5 + OH- CH3COO- + C2H5OH

rxn (3-1)

Rate = k[CH3COOC2H5][OH-]

eqn (3-1)

d cA

= k cA cB

dt

eqn (3-2)

cB = concentration of OH- at time 't'.

In this experiment, the initial concentration of hydroxide ion is adjusted to be the same as that of

ethyl acetate. Since their initial concentrations are the same and since the mole ratio of OH - :

CH3COOC2H5 is 1 : 1, then at any time t, the concentration of ethylacetate must be the same as

hydroxide ions. That is,

cA = cB

eqn (3-3)

d cA

2

= k cA

dt

eqn (3-4)

The concentration of ethylacetate (or OH-) remaining at any time can be determined by

integration.

cA d c

t

A

eqn (3-5)

co c 2 = - k 0 dt

A

3-1

or

1

1

=k t+

cA

co

eqn (3-6)

( y = mx + b )

where co = initial concentration of ethylacetate and

cA = concentration of ethylacetate at time t.

1

Thus, according to equation (3-6), a plot of "

versus time" should be a straight line. The rate

cA

constant k can be accurately determined by measuring the slope of the graph.

Conductivity and Conductivity Bridge

As reaction (3-1) progresses, the amount of OH- ions in solution diminishes as CH3COO- ions

are produced. It is known that the electrical conductivity of OH- ions is much greater than that of

CH3COO- ions. Equivalent ionic conductivity at infinite dilution, at 25oC, for OH- and

CH3COO- are 198.6 mhos and 40.9 mhos respectively. Therefore, the progress of reaction (3-1)

can be followed conductometrically.

Conductance L is a measure of the ability of a substance to conduct electricity and is defined to be

the reciprocal of resistance. Thus, Ohm's law may be expressed as

E

R

eqn (3-7)

i=EL

eqn (3-8)

i =

or

The conductance of a solution is measured by dipping a cell containing two platinum electrodes

into the solution. The electrodes are connected to one arm of a Wheatstone bridge and an

alternating voltage is applied to the bridge. The conductance is then obtained from the scale by

nulling the bridge. An alternating voltage is used to prevent polarization of the electrodes.

Accurate measurements are obtained only with properly prepared electrodes.

The equivalent ionic conductivity is unique for each ion and is a measure of the velocity or

mobility of the ions under the influence of an electric field. Conductance of a solution is directly

proportional to its ionic concentration, the surface area of the electrode and is inversely

proportional to the distance between electrodes. Expressed mathematically,

L =

CA

d

eqn (3-9)

3-2

d = distance between electrodes (cm),

A = area of electrode (cm2),

= equivalent ionic conductivity constant.

is unique for each solvent and is dependent on temperature.

3-3

PROCEDURE

1.

Pipet 0.49 mL of ethylacetate from the reagent bottle and make up to 50 mL in a

volumetric flask.

2.

(i) pipet in 10.00 mL of 0.100 M ethylacetate,

(ii) add 40.00 mL distilled water from a burette.

3.

(i) pipet in 10.00 mL of 0.100 M NaOH,

(ii) add 40.00 mL distilled water from a burette.

4.

pipetting in10.00 mL of 0.100 M NaOH and diluting with water to 100.0 mL.

5.

Using lead donuts to stabilize the flasks, place all three flasks in a water bath at

approximately 25oC to obtain thermal equilibrium. Record the temperature of the

water bath.

6.

Measure the conductance of flask #3, the 0.0100 M NaOH. This conductance value is

Lo, measured at time = 0 sec.

[Lo should be approximately 2500 to 3500 mhos, or

2.500 x 10-3 to 3.500 x 10-3 Siemens, or

2500 to 3500 Siemens.]

7.

Start the saponification reaction by mixing together the entire contents of flasks

#1 and #2 containing the ethylacetate and sodium hydroxide respectively. Stir

the mixture and start the timer. Measure the first conductance reading after 300

seconds and continue collecting data at 300 seconds intervals for one hour.

3-4

DATA SHEET

Conductance of 0.0100 M NaOH, Lo =

Time [sec]

L [S]

Lo - L [S]

Siemens

300

600

900

1200

1500

1800

2100

2400

2700

3000

3300

3600

INTERPRETATION OF DATA

3-5

1

1

=k t

cA co

eqn (3-6)

1

"

versus time" where cA is the concentration of ethylacetate or hydroxide ion, at any time t.

cA

Since 'cA' is proportional to L - L and co is proportional to Lo - L, it follows that

co - cA (Lo - L) - (L - L)

Lo - L

eqn (3-10)

co k t =

co - cA

cA

eqn (3-11)

co k t =

Lo - L

L - L

eqn (3-12)

1 Lo - L

+ L

cok

t

(y =

mx

+ b)

L=

Lo - L

eqn (3-13)

1

. If

cok

we measure the slope of the line, we can calculate k provided we know the initial concentration,

co.

3-6

TREATMENT OF DATA

1.

2.

L L

Plot a graph of "L versus o

".

t

3.

Measure the slope in the straight portion of the curve and calculate the rate

constant for the second-order reaction. Note that the initial concentration, co,

of ethylacetate is not 0.02 M.

4.

In your lab report, comment on the difference between the value of conductance

'L' measured at the so-called t = 0 and, the value that might have been obtained at

the exact moment of mixing.

3-7

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