1.

Evaluation of Arrhenius parameters: Activation Energy and Frequency factor

Aim
To determine the Arrhenius parameters; Ea -activation energy and A-frequency factor.

Principle
The excess energy that the reactant molecules having (or) excess threshold energy must acquire
in order to react to yield product/s is known as activation energy, Ea. Arrhenius (parameter)
proposed the following empirical equation for the calculation of the Ea and the A for a reaction
with rate constant k at temperature T as,

k = A e-Ea/RT. eq (1)

Both A and Ea are characteristic of the reaction and both have definite values for the particular
reaction. On taking logarithm of the Arrhenius equation and differentiation, we can get

Log k1/k2 = Ea/(2.303×R). [ T2-T1/(T1×.T2)] eq (2)

Where k1 and k2 were rate constants for the same reaction at temperatures T1 and T2 respectively.
It is possible to evaluate Ea and then substituting this in the Arrhenius equation (eqn (1)) can
offer the A value.

Apparatus & chemicals required

SI.No Apparatus Chemicals

1 Thermostat
2 Conical flasks
3 Burette
4 Pipette (1mL)
5 Stop watch
6. Thermometer (100 oC)
2 N HCl (100 mL)
2 N NaOH (250 mL) 0.1 N NaOH (250mL)
Methyl acetate (5 mL each time)
Phenolphthalein indicator
Iced distilled water

Procedure
Rate constant of acid catalyzed hydrolysis of methyl acetate is followed at two different
temperatures namely room temperature and at a higher temperature with a thermostat. In both
cases 50 mL of N HCl and 50 mL of water were taken in the reaction bottle. Then 5 mL of the
methyl acetate is added to it through a pipette noting down the time started when half thepipette
is drained. During the course of reaction, 1 mL of aliquots were withdrawn, quenched and
titrated against the 0.1 N NaOH solution. Meanwhile, in order to find out the rate at infinite, ꝏ
time, 50 mL of the aliquot is heated on water both for 30 minutes and allowed to complete the
reaction and titrated against the NaOH. This gives value of Vꝏ1. Then concentration parameter:
Vꝏ1 – V0 is corresponds to the net reaction value, where V0 belongs to volume of NaOH at zero
time of the reaction. The parameter, Vꝏ1 – Vt gives the concentration of ester after time t,
therefore the rate constant for these reaction at T1 (room temperature) is given by:
k1 = 2.303/t(sec). log (Vꝏ1 – V0/ Vꝏ1 – Vt) eq (3)
Similarly at T2 (elevated temperature, ~40oC):
k2 = 2.303/t(sec). log (Vꝏ2 – V0/ Vꝏ2 – Vt) eq (4)
Where, k1 and k2 for two different temperatures, are calculated the substituted in the eqn (2) to
get the value of Ea. Then Ea is substituted in eqn (1) to get the value of “A”.

Analysis steps:
1. Reactant addition and start to analyzing the aliquots with NaOH at different timings at
Temperature T1 and T2 separately.
2. Enter the Vo, Vt (1,2,3,4 -- (ꝏ-1)) and Vꝏ1 in the Tabulator column for T1 and T2.
3. Calculate the rate constant rate constant (k1 and k2) both by calculation andgraphical
methods.

I) By Calculation method
Use the eqn (3) or eqn (4) by substituting the t = time in sec, Vꝏ – V0 & Vꝏ – Vt values
correspondingly for each reading then make average, k1, and similarly k2.

2) By graphical method
Make a plot log (Vꝏ – Vt) vs t (sec) for respectively temperature reading and calculate the k1 or
k2 for the overall reaction. Plot based on eqn (3) or eqn (4).
 log (Vꝏ – Vt)
Plot-1
Slope = -k1 (or) k2 /2.303

t (sec)
Calculation of Ea and A
Respective k1 and k2 values were substituted along with T1 and T2 in the eqn (2) for the Ea
calculation, and the Ea is then substituted in Arrhenius eqn (1) for the parameter, A calculation.

Table 1: Tabulator column for the k by calculation Method

Reaction at Reaction at Rate constant, k sec-1

S.No. Time T1 K, V, NaOH T2 oK, V
o

(sec)
Vt Vꝏ1-Vt Vt Vꝏ2-Vt At T1 oK At T2 oK
1 0 k11 k21
2 600 k12 k22
3 1200 k13 k23
4 1800 k14 k24
5 2400 k15 k25
6 7200 k16 k26
7 ꝏ1 or ꝏ2 --- ---
(30 min.)

Table 2: Tabulator column for the rate constant, k by graphical Method

Log (Vꝏ1-Vt)
S.No. Time (sec)
For k1 For k2
1 0
2 600
3 1200
4 1800
5 2400
6 7200
7 ꝏ1 or ꝏ2
(30 min.)

Average: k1 k2
Results
Arrhenius parameters Ea and A were calculated.
The values are:1A. Ea = K Cals
1B. Ea = ------ K Cals (by graphical method)
2A. A = --------- at temperature --- oK
2B. A = --------- at temperature --- oK