TNHL2 - Bài 2

 Acquirement:
+ determine the 2nd order reaction through the ester hydrolysis reaction in alkaline solution.
+ understand the meaning of activation energy and the effect of temperature on the rate constant of
the reaction through the Arrhénius relation
+ Understand the method of measuring conductivity
 Theory:
The reaction of ester ethyl acetate and NaOH:
CH 3 COO C 2 H 5 + NaOH → C H 3 COONa+C 2 H 5 OH
Initial: t= 0 a b 0 0
At time t a-x b-x x x
With a, b: initial concentration of ethyl acetate and NaOH respectively
(a-x), (b-x) : the concentration at time t of ethyl acetate and NaOH respectively
Assume that the alkaline hydrolysis is forward reaction, therefore, concentration of OH- and ethyl
acetate decreases while the concentration of ( sodium acetate) C H 3 COONa∧C 2 H 5 OH ( etℎanol)
increases.
Ion C H 3 COO−due to its larger size compared with ion OH-, the velocity of C H 3 COO− is smaller
than that of ion OH-, hence the conductivity of the solution will also decrease.
The equation to calculate the conductivity:
X =∑ z i C i λ i
i
Where:
z i: electrical charge
C i :concentration of ion
λ i: equivalent conductivity
We can ignore the interference of H+ since the pH of the solution if 10 ([OH-] >> [H+])
At initial time: t= 0, no ester dissociates
X 0=C0 λ Na+¿+C λ 0 OH − ¿
At time t:
X t =¿ C 0 λ Na+¿+(C − C ) λ
0 t OH − +C i λC H COO − ¿
3
Or
With:
C t : concentration of C H 3 CO O−
( C 0 − Ct ) : concentration of OH- or Ethyl acetate remained

At the end point:
Or
Calculate the equivalent conductivity:
C: equivalent concentration (g/L)
 Experiment:
1. Equipment:
Erlene 500 ml: 3
Beaker 100 ml: 2

Beaker 250 ml: 1
Stirring bar: 1
Timer: 1
Thermometer: 1
Conductometer: 1
Burette 25 ml: 1
Pipette 25 ml:1
2. Chemicals:
Ester Ethyl acetate
NaOH 0.1M
Prepare ethyl acetate 0.1M: 500 ml
3. Procedure:
Prepare 500ml ethyl acetate 0.1M from pure ethyl acetate (given density):
Density of pure ester, solution: ρ1, ρ2
n
C M =0.1 M =
V
=> n=0.1 M ∗ 0.5 L=0.05 mol pure ester =¿ m=4.4 g
Given density of pure ester: => V pure ester
=> V water = V solution - V pure ester
Determine the conductivity:
At initial time mix 100 ml of ester and 100 ml of NaOH into the beaker and stir continuously by stirring
bar.
Obtain the conductivity at initial time. Operation temperature is room temperature at around 30o C
To survey the dependence of reaction constant on temperature, we conduct the experiment and record
o
the data at T 2=45 C
 Result:
Later we conclude the table below in two different temperatures:
Time X t × 106 (Ω− 1 /cm¿ X0 − X1 −1 −1 −1

( μ Ω . cm . min )
t
0
2
3
4
5
6
7
8
9
10
11
12
13
14
With the equation concluded:
X0 − X t
Xt= + X oo
C0 kt
In which:
y= X t
X0 − Xt
x=
t
1
we obtain the linear form y=ax + b, therefore a=
C0 k
Draw the graph and withdrawn the a value so we can calculate reaction constant at different
temperature:
1
k=
a .C 0
using the Arrhenius equation:
k =k 0 . e − E/ RT
k2 E 1 1
=> ln
k1
=−
(−
R T2 T 1 )
In which:
k 2 , k 1 :reactionconstant at 45 o C ,30 o C
R= 8.314 ( J . kmol− 1 . K −1 ¿
T 2=45 o C
T 1=30o C
Proving that the alkaline hydrolysis of ester is second order:
Theory:
The reaction rate is defined as the change of the concentration of one of the reactants or one of the
products per unit time. The change of the concentration of the reactants enters the calculation with a
negative sign and that of the products with a positive sign.
For the alkaline ester hydrolysis, the reaction rate with respect to the ester concentration equals that
with respect to the hydroxide concentration as the two substances react with each other in the ratio
1:1:
d ( OH − ) d ( CH 3 COOC 2 H 5 )
r OH − =r CH COOC H5 =− =−
3 2
dt dt
Each reactant is at first order.
If the reaction is of first order with respect to the hydroxide concentration and independent of the ester
concentration, the overall rate equation would be of first order:
d (OH −)
r OH −=− =k [ OH − ]
dt
The same rate equation would result if the reaction exhibited a first order dependence on the ester
concentration and independence of the hydroxide concentration because:
d ( OH − ) d ( CH 3 COO C2 H 5 )
=
dt dt
In order to check the validity of this rate equation, its integrated form is used:
ln [ OH − ] =− k × t+ ln [ OH − ] 0
If ln[OH-] is plotted against the time t, the result is a straight line with slope -k and cut off ln[OH -]0 in the
case of a first-order reaction. [OH-]0 is the initial concentration on hydroxide ions.
In the case of a first-order reaction with respect to both components, the result is a second-order rate
equation:
d ( OH − ) d ( CH 3 COOC 2 H 5 )
− =− =k [ OH − ] [ CH 3 COOC 2 H 5 ]
dt dt
The integrated form of the rate equation reads:
ln [ OH − ] 0 × ¿ ¿
If the initial concentrations of the two substances are equal, the rate equation takes the simpler form:
d ( OH − ) d ( CH 3 COOC 2 H 5 ) 2
− =− =k [OH −]
dt dt
We integrate it into:
1 1
=kt +
[OH −] [ OH −]0
Based on the data given in the lab, we can fit into these two graphs in order to find the most fitted
model.

TNHL2 - Bài 2

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 Acquirement:

+ Understand the method of measuring conductivity

The reaction of ester ethyl acetate and NaOH:

CH 3 COO C 2 H 5 + NaOH → C H 3 COONa+C 2 H 5 OH

At time t a-x b-x x x

With a, b: initial concentration of ethyl acetate and NaOH respectively

The equation to calculate the conductivity:

At initial time: t= 0, no ester dissociates

( C 0 − Ct ) : concentration of OH- or Ethyl acetate remained

Calculate the equivalent conductivity:

C: equivalent concentration (g/L)

Erlene 500 ml: 3

Beaker 100 ml: 2

Ester Ethyl acetate

Prepare ethyl acetate 0.1M: 500 ml

Determine the conductivity:

Later we conclude the table below in two different temperatures:

Time X t × 106 (Ω− 1 /cm¿ X0 − X1 −1 −1 −1

With the equation concluded:

using the Arrhenius equation:

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