EXPERIMENT NUMBER: 02

DATE: ------ / ------ / ----------

DIAGRAM/ IMAGE:

1
 ARRHENIUS PARAMETERS
Objective :- To study of non-catalytic homogeneous reaction in
Batch Reactor and verify Arrhenius equation.

Aim: To determine frequency factor (k0) and activation Energy (E) for
given Saponification reaction of ethyl acetate in aqueous NaOH
Solution.

Theory :-
Basic Equations to be used are:

For second order unidirectional & equimolar reactions:

2A Product
1 d
-1 V × dt NA¿ k CA2
1 1
=kt +
CA C AO

V
t= ׿ )
t

1 1 1
t= ×( − )
k C A C AO

# Saponification of ethyl acetate & NaOH,

NaOH + CH3COOC2H5 CH3COONa + C2H5OH
(A) + (B) (C) + (D)

2
Temperature dependency fro Arrhenius’ law:
The dependence of 𝑘 on 𝑇 is more clearly seen when we linearize the
equation by taking the natural logarithm on both sides; we get:
𝐥𝐧 𝒌 = − (𝑬𝒂 /𝑹) ( 𝟏/ 𝑻 ) + 𝐥𝐧 𝑨 …
𝑤ℎ𝑖𝑐ℎ 𝑙𝑜𝑜𝑘𝑠 𝑙𝑖𝑘𝑒 𝑦 = 𝑚𝑥 + c
𝑊ℎ𝑒𝑟𝑒: 𝑦 = lnk ; 𝑚 = − 𝐸𝑎/ 𝑅 𝑎𝑛𝑑 𝑥 = 1/ 𝑇 ; c = ln 𝐴.
This means we can use rates of reactions (rate constants) at different
temperatures to find the activation energy for a particular reaction using
Arrhenius equation.

And so, as seen above, the slope of the line obtained is: 𝑚 = − 𝐸𝑎/𝑅
Since 𝑅 is a constant and the slope is negative, this means reactions with
higher 𝐸𝑎 form steeper lines.
All molecules possess a given amount of energy (both potential and
kinetic). When molecules collide, the energy is used to stretch, bend, and
ultimately break atomic bonds, which in turn leads to a chemical
reaction. However, if molecules do not collide with enough energy, then

3
they simply bump on each other and go their separate ways. Therefore,
there is a minimum energy required so that a collision leads to breaking
bonds and to obtain products; this minimum energy (or energy barrier) is
what we call activation energy, 𝐸𝑎. We know the kinetic energy (K.E.)
of a gas increases with temperature, so, gas particles move faster as the
temperature increases; in turn, more molecules can have the minimum
energy for a productive collision (one that leads to breaking bonds) and
the reaction goes faster (the K.E. also increases with temperature for
liquids and solids, but the relation is harder to describe). Clearly then,
the higher the 𝑇, the faster the reaction. As mentioned before, Arrhenius
equation helps us to see the dependence of the reaction rate on the
activation energy as well.
𝒌 = 𝐴𝑒 – (𝑬𝒂 /𝑅𝑇)
It is evident 𝐸𝑎 is part of an exponential function; this means the rate
constant – and the rate of reaction – is highly sensitive to its value.
Furthermore, the negative sign implies a higher 𝐸𝑎 leads to slower
reactions; conversely, we can say the rate constant of a reaction
increases exponentially as the activation energy decreases. Additionally,
we also know a catalyst works by providing an alternate route for a
reaction – one with lower activation energy; since the Arrhenius
equation can be used to calculate 𝐸𝑎 (using constant rates at different
temperatures), this means we can also assess how good a particular
catalyst happens to be. In other words, we now see how 𝑘 also depends
on the use of a catalyst, which is another factor that affects rates of
reaction . If we look at the whole exponential part of Arrhenius equation:
𝑘 = 𝐴𝑒 –( 𝑬𝒂/ 𝑹𝑻)
𝐸𝑎 of an uncatalyzed reaction is higher than 𝐸𝑎 of its catalyzed
counterpart, from Arrhenius equation (the exponential part) we see 𝐸𝑎 of

4
the uncatalyzed reaction will have a larger impact on 𝑘; which also
means the uncatalyzed reaction is more affected by temperature changes.
− Ea
Also, k = k0× e RT

k= pre exponential factor or frequency factor.

E= activation energy of the reaction, J/mol or cal/mol
R= gas constant = 8.314 J/( mol.K) = 1.987 cal/(mol.K)
T= absolute temperature, K
This equation is known as Arrhenius’ equation/ Arrhenius’ law.

Utilities Required:
1. Water supply
2. Drain
3. Electricity supply: 1phase, 220V AC. 1.5 kW.
4. Instruments, laboratory glassware & chemicals reqd. for analysis
as per system adopted.

Chemicals :
1. NaOH 0.1N
2. HCl 0.1 N
3. Ethyl acetate 0.1 N
4. Indicator (Phenolphthalein)

Experimental Procedure:
1. Prepare a solution of 0.1 N ethyl acetate by mixing 8.8 gms of
ethyl acetate in 1L of solution.
2. Prepare a solution of 0.1 N NaOH by dissolving 4 gm/L of solution
5
 3. Prepare solutions of 0.1 N HCl and 0.1 N NaOH for the titration.
4. Use phenolphthalein as indicator.
5. Take 7 Number of 250 ml beakers & put 20 ml of 0.1 N HCl in
each beaker.
6. Take 0.1 N NaOH in burette.
7. Take 500ml each of 0.1 N CH3COOC2H5 & 0.1 N NaOH in two
separate flasks & transfer these solutions quickly in batch reactor.
Star immediately the mixer & the stop watch.
8. At regular intervals of 5 min withdrawn 10 ml of reaction mixture ,
three time at the interval of 5 minutes and put it in marked beakers
containing 0.1 N HCl.
9. Take at-least 3 samples at regular interval of 5 minutes, at each set
of temperature.
Transfer the solution from beaker to conical flask and titrate the
excess 0.1 N in each flask using 0.1 N NaOH from burette &
phenolphthalein indicator. Record the burette reading.

Formulae:
CA=0.2−(V ¿¿ NaOH × .01) ¿

C A −C AO
Degree of conversion, X A=[
C AO
]

Observations & calculations:

Reaction:
A + B C + D
Reaction temperature = ____0C

6
Concentration of NaOH (A) = 0.1 N
Concentration of ethyl acetate (B) = 0.1 N

Observation table:
Sr. Temperature Time, t (min) Titrated Average
no. (K) volume (ml) Burette
(VNaOH) Reading
1
2
3

4
5
6

7
8
9

10
11
12

Sample calculations:

For 1st reading:-

CA, CA=0.2−(V ¿¿ NaOH × .01) ¿
CA =______, gmol/L

7
 1 1 1
Rate constant = k = t [ C A − C AO ]

k =______
ln k =________
1/T=_______
CALCULATION TABLE:
Sr Temperature Time VNaOH CA k ln k 1
T
No.

1
2
3

4
5
6

7
8
9

10

8
11
12

By Graphically,
1
Tabulate the ln k and T data.
1
Plot a Graph between ln k and T , should give a straight line with slope
equal to –E/R.
E= Activation Energy of the Reaction, J/mol or cal/mol.
R= Gas constant =8.314 J/ (mol.K)=1.987 cal/(mol.K)
Determine the rate constant k by assuming the reaction to be of second
1
order and plotting ln k and T .

Slope= -E/R
ln k

1/T * 103

Result:
Activation Energy of the Reaction mixture: Ea= ___________________
Pre exponential factor / frequency factor : ko= ___________________

9
10