Sei sulla pagina 1di 6

DETERMINATION OF SECOND ORDER KINETICS

Aim :To determine the reaction rate constant of ethyl acetate in sodium hydroxide at room
temperature ,when initial molar concentration of both the reactant are same.

Apparatus : Conical flask,burette and beaker.

Chemicals : Ethyl acetate and sodium hydroxide.

Principle :
In a second order reaction,the rate of reaction depends on concentration of both the
reactants,the alkali hydrolysis of ethyl acetate (saponification) follows second order kinetics at
25°c .

CH3COOC2H5+NaOH CH3COONa+C2H5OH

If the initial concentration of ethyl acetate and sodium hydroxide are equal i.e,
"a" and the amount hydrolysed in time "t" is "X",then the amount unhyrdolysed is (a-x).since the
reaction is equimolar .then the rate is,

𝑑𝑥
= 𝐾(𝑎 − 𝑥)2
𝑑𝑡

Integrating the equation,

1 𝑥
𝑘= ×
𝑡 𝑎(𝑎−𝑥)

The "K"value will give us the rate constant and it's unit is lit.mol-1.time-1.
By taking the ethyl acetate and NaOH of equal concentrations ,the rate of the reaction can be
followed by titrating NaOH left unreacted .the half life is given as

𝑡1/2 = 1⁄𝑎𝑘

Where ,

a=initial concentration

K= specific rate constant

Half life is inversely proportional to initial concentration,in this experiment equal


concentrations of NaOH and ethyl acetate will react and the order is determined by substitution
and graphical method.

Procedure :
Preparation of solution

i) 0.5N HCl solution :

Normality of concentrated HCl =11.5N

HCl =1000×0.05 = 4.34 ml of Concentration.HCl

= 11.5N

Measure 4.34 ml of Concentration. HCl add 100 ml of water in 1000 ml of volumetric flask.
Shake well and make up the volume with distilled water up to 1000ml.

ii) 0.05N NaOH solution :

Molecular weight of NaOH=40g

40 gm in 1000ml =1N

4gm in 1000ml=0.1N

2gm in 1000ml=0.05N
Weigh 2gm of NaOH in 1000ml volumetric flask. Add 100 ml of water, shake well and
make up the volume to 1000 ml with distilled water. Filter if necessary.

iii) 0.5 N ethyl acetate:

Molecular weight of ethyl acetate=88.11

88.11g in 1000 ml =1N

0.4405gm in 1000ml =0.05 N

0.9gm =1ml;0.4405=2

1×0.4405/0.9=0.4895ml

0.4895 ml of ethyl acetate was made upto 100 ml with water which gives 0.05N ethyl
acetate.

Determination of rate constant :

1) 50 ml of ethyl acetate and 0.5N NaOH were mixed.


2) 10 ml of the mixture was withdrawn immediately into a volumetric flask containing 10
ml of ice cold water. Add few drops of phenolphthalein as indicator and titrate against
0.05NHCl and note down the titrate value as "a".
3) Similarly 10 ml of the mixture was withdrawn at 5,10,15,20,25 and 30 min interval and
titrate the sample as done earlier.
4) The titrant value was"a-x".

Substitute this in 2nd order rate equation and the specific rate constant was calculated. A graph
𝑥
was plotted by taking Vs time.
𝑥(𝑎−𝑥)

5) The slope gives "k" value.


6) 𝑡1/2 was calculated by using equation.
Calculations :
S.no Time(min) Volume of Amount of a(a-x) 𝒙 𝟏 𝒙
𝒂(𝒂 − 𝒙) 𝑲= ×
HCl in (ml) hydrolysed 𝒕 𝒂(𝒂 − 𝒃)

x=a-b

1 0 4 ml

2 5 3.6ml 0.4 14.4 0.027 0.05

3 10 3.1ml 0.9 12.4 0.072 0.025

4 15 2.9ml 1.1 11.6 0.094 0.015

5 20 2.5ml 1.5 10 0.15 0.0125

6 25 2.3ml 1.7 9.2 0.184 0.01

7 30 1.8ml 2.2 8.8 0.25 0 .007

After addition of all above" k" value excluding( all 7)

0 mins we will get (X)

Specific rate constant =0.1145

=0.1145/7

=0.0163

Theoretical half life :

𝑡1/2 = 1⁄𝑎𝑘

= 1/0.05×0.01

=2000

Graphically :
x1= 5 x2=10

y1= 0.020 y2 =0.054


𝑦2 −𝑦1
Slope =
𝑥2 −𝑥1

0.054−0.020
=
10−5

=0.0068

Report : Theoretically the specific rate constant of second order reaction was found to be
0.0053 min- 1 and t1/2 was found to be 0.106min .

At constant of second order reaction was found to be 0.005 min-1 and t1/2 was found to be
4000min