CHEM 324

Individual Project Proposal

 1L 0.20M NaOH
 Ethyl Acetate
 100 ml 1M HCl
 Potassium Hydrogen Phthalate (KHP)
 Phenolphthalein

Procedure

 Put exactly 100 ml of 1M HCl into an Erlenmeyer flask, seal it with a stopper and
regulate its temperature to 30 °C.
 Add 5 ml of room temperature ethyl acetate and shake briefly.
 Every 10 minutes, take 5 ml of sample and add it to an Erlenmeyer that contains 100
ml of cold water to stop the reaction. Titrate the sample quickly with 0.20M NaOH
and phenolphthalein.
 After the fourth titration, raise the temperature to 45 °C and repeat the previous step.

Theory:
In acidic environments, ethyl acetate goes into hydrolysis reaction as the following:
C H 3 COO C2 H 5+ H 2 O ⇌ C H 3 COOH +C 2 H 5 OH

This reaction follows a pseudo-first order reaction rate, which means even though it
actually has other steps, due to the large concentration of CH3COOC2H5¸ it acts like a first
order reaction. By determining the acetic acid concentration at a given time, the concentration
of the ethyl acetate can also be determined. Under these experimental conditions, equilibrium
shifts to the products. The rate constant for this reaction is as follows:
d cE
r =− =k ∗ c E ∗ c W ∗ c K
dt
r: Rate
k: Rate Constant
cE: Concentration of Ethyl Acetate
cW: Concentration of Water
cK: Concentration of the Acid

1
 Since concentration of the acid and the water are practically stays the same, Equation
1 reduces to the following:
d cE
r =− =k ∗ c E
dt
Which makes the reaction a pseudo-first order reaction. When integrated, the
following formula emerges:

ln
( )
cE, o
cE
'
=k ∗ t

k’: Constant
t: Time
cE,0: Initial Concentration of Ethyl Acetate
The initial concentration of ethyl acetate can be written as the difference between the
required base for complete reaction (VNaOH,f) and required base for neutralization at the t0
(VNaOH,i), which is the start. The temporal concentration of the acetyl can be determined using
the difference between the required base for complete reaction (VNaOH,f) and required base for
neutralization at the given time t (VNaOH).

ln
( V NaOH , f −V NaOH ,i
V NaOH ,f − V NaOH )=lnQ=k ' t

VNaOH,f and VNaOH,i can be experimentally determined, or can be calculated from

c HCl ∗ V 1 100
V NaOH ,i= −
c NaOH 105

dEVEV1
V NaOH ,f = +V NaOH ,i
M E V S c NaOH

cHCl: Concentration of HCl

V1: Sample volumes (5 ml)

dE: Density of Ethyl Acetate (0.895 g/ml)

ME: Molar Mass of Ethyl Acetate (88.12 g/mol)

VE: Volume of the ethyl acetate contained in the volume of the total system VS=105 ml
at time t0 (5ml)

2
 The equation above shows linear dependence of ln ( V NaOH ,f − V NaOH)
V NaOH , f −V NaOH ,i
versus time

with positive slope, k’ which contains all the parameters in the reaction such as temperature,
molecular interactions and so on.

Since the colliding molecules have to have a sufficient energy to achieve a successful
bonding, activation energy of the reaction is one of the important physical quantities in the
reaction. The activation energy is the difference between the initial energetic state of reactants
from the transition state. The required energy to bring reactants into transition state, i.e.,
activation energy can be taken from the environment as a heat or from molecular energy
exchange during the collision. In some reactions, the light can act as way of providing
external assistance in the reactions where starting molecules get activated and could react
effectively. Hence the activation energy directly depends on the temperature and any increase
will result in increase in number of successful collision. This energy can be determined
through the equation below:

− Ea / RT
k '=k max e

R = 8.314 J/mol*K and kmax is a rate constant at infinite temperature

For kmax activation energy is zero, therefore, any collision leads to reaction. By applying
linearization using rate constants at two different temperatures the following is derived:

'
T 1T 2 k2
Ea=R ln '
T 2 −T 1 k 1

In this equation, 1/T versus lnk’ result in a linear slope, therefore, Ea can be calculated by just
measuring rate constant at two different temperatures.

Standartization of NaOH 1st measurement 2nd measurement

Initial volume

Final volume

Reacted volume

Table 1: Standartization of NaOH solution

3
 At 25oC At 45oC

Time, s V(NaOH), ml Time, s V(NaOH), ml

600 600

1200 1200

1800 1800

2400 2400

3000 3000

VNaOH,i VNaOH,f

Table 2: Experimental data sheet