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Kinetic and Thermodynamic Studies in

Batch Reactor
Saddawi
Fall 2013

The Goal of the Experiment


The goal of this experiment is to determine kinetic and
thermodynamic parameters for the alkaline fading of
phenolphthalein (Organic Dye) in aqueous solution.
The reaction is carried out in an isothermal stirred batch reactor,
at various temperatures and concentrations.

Reaction
In this experiment, phenolphthalein reacts with
Sodium hydroxyl in an isothermal continuous
stirred batch reactor.

The fading of phenolphthalein in basic


solution is an excellent example of second
order reversible reaction kinetics

Where the structure of phenolphthalein at pH 8


or lower is colorless and at pH range 8-10 gives
a pink color.

Experimental Setup

1. Prepare aqueous solutions of 0.1, and 0.2 molar NaOH.


2. Prepare a 0.0002 molar solution of phenolphthalein in
a mixture of ethanol and water (2:98 by volume 0.0002
M).
3. Approximately 50 ml of the NaOH solution is mixed
with about 25 ml of the phenolphthalein solution
mixed in a 2:1 ratio. The solution absorbance is
monitored with an immersed colorimeter probe until
equilibrium is attained.
4. The experiment is repeated at several temperatures
(50, 40, and 30C).

Material Balance on perfect mix Batch Reactor


Input rate Output rate Disappearance rate = Accumulation rate

A batch reactor has neither inflow nor outflow of reactants or


products while the reaction is being carried out.

F = F =0 .
j0
j
2-

Assume the batch reactor is perfectly mixed, there are no


concentration gradients in the reactor volume

3-

the reactor volume is constant and equal to the reactants volume

dC
r VR =
VR
dt

dC
r =
dt

For Reversible Second order Reaction like in Phenolphthalein fading color

The kinetics of the reaction obey the rate law:

-r = k1[P][OH ]- k2 [POH]
d[P]
= r = -k1[P][OH -1 ]- k2 [POH ]
dt
where: k1 is the rate coefficient for the reaction that consumes P and OH-,
and k2 is the rate coefficient for the backwards reaction, which consumes
the product POH and produces P and OH-

At Equilibrium the forward reaction rate will equal backward reaction rat

d[P]
=0
dt
0 = k1[P]e [OH - ]e - k2 [POH]e

[POH ]
k1
Ke =
=
[P][OH ] k2

Pseudo-first-order
Measuring a second-order reaction rate with reactants P and OH- can be
problematic: The concentrations of the two reactants must be followed
simultaneously, which is more difficult; or measure one of them and calculate the
other as a difference, which is less precise. A common solution for that problem is
the pseudo-first-order

Therefore you should keep the concentration of one of a reactants e.g. NaOH
constant by supplying it in great excess, its concentration can be absorbed within
the rate constant, obtaining a pseudo first-order reaction constant.

-r = k1[P][OH ]- k2 [POH]
-

k = k1[OH ]
'

d[P]
= r = k2 [POH ]- k ' [P]
dt

At time =0
[P] = [P]0
[POH] = 0
At t=t
[P]=[P]t
[POH]=[POH]t
At t=

The system reach to Equilibrium


[P]= [P]e
[POH] = [POH]e
And the rate of forward reaction will equal to rate of
backward reaction

d[ p]
=0
dt

pseu
e

[POH ]e k
=
=
[P]e
k2
'

[POH] = [P]0 -[P]

[POH ]e = [P]0 -[P]e


k'
[POH ]e = [P]e
k2
k'
[POH ]e =
[P]0
'
k2 + k
k2
[P]e =
[P]0
'
k2 + k

By simplifying the rate equation you will end to the following equation

[P]-[P]e
[P]-[P]e
[P]0 -[P]e
= -(k2 + k ' )
dt
[P]0 -[P]e

Where

[P]-[P]e
= x (mole fraction of Phenolphthalien)
[P]0 -[P]e

dx
'
= -(k2 + k )x
dt
ln x = -(k ' + k2 )t

Diluted concentrations less than 0.01are obeying Beers Law,


the absorbance (A) can be related to the concentration of the
Phenolphthalein

To find k&k2

A - Ae
'
ln
= -(k + k2 )t
A0 - Ae

Let (k+k2)= kc
And knowing that Ke=k1/k2

k'
kc - k2 kc - k1 / K e
k1 =
=
=
[OH ] [OH ]
[OH - ]

From thermodynamic we know that

[P]e
DG
Ln
= ln K e = [POH ]e
RT

DG
Ke (T ) = exp(
)
RT

The standard enthalpy of the reaction H, can be found from the


following relation

DG
-d(
)
pseudo
DH
d(ln
K
)
d(ln
K
)
e
e
RT =
=
=
dT
RT 2
dT
dT
By plotting natural log of Kepseudo versus T temperature, H can be found.

And S the entropy can be find from

H - G
S=
T

From Arrhenious law, the activation energy (E) and the preexponential factor k0 can be found for the reaction

E
k = k0 exp()
RT

Vant Hoff Equation

DS DH
LnK e =
T RT