Determination of Kinetic Parameters of a Homogeneous Reaction

In a Tubular Reactor

Introduction

Chemical kinetics is the study of the rate and mechanism by which one or more chemical
species are converted into one or more desired products. The rate is the mass, in moles,
of a product produced or reactant consumed per unit time. The mechanism is the
sequence of individual chemical events whose overall produce the observed reaction.

It is not necessary to know the mechanism of a reaction in order to design a reactor.

What is necessary is a satisfactory rate equation. However, knowledge of the mechanism
is of great value in extending the rate data beyond original experiments and in
generalizing the kinetics of the reactions. The rate of a chemical reaction can vary from
infinity to essentially zero. High temperature combustion reaction or that occur in a
photographic films are extremely fast. On the other hand, oxidation of a metal exposed
to atmospheric oxygen is very slow. Industrially important reactions occur at rates
between these two extremes.

The designer of a chemical reactor will depend on the reaction rate data to size the
reactor. Considerations should also be given to the heat and mass transfer aspects of the
overall process. It is particularly important to know how the rate and the product quality
change with the operating parameters, the most important of which are temperature,
pressure, the composition of the reaction mixture, residence time etc.

It is important to note that the design of a heterogenous reactor or a gas-solid reactor is

more complicated than a homogeneous reactor. In addition to chemical reactions, heat
and mass transfer play major roles in the overall rate of heterogenous and gas-solid
reactions.

Objectives:

An overall second order (first order with respect to each reactant) homogeneous liquid-
liquid reaction will be carried out in a tubular reactor. The reaction is the saponification
of ethyl acetate by sodium hydroxide. The products of this equimolar reaction are
sodium acetate and ethyl alcohol. Primary objective of this experimental exercise is to
determine the reaction rate and conversion and their dependency on other process
variables.

1. Determine the reaction rate and order of the reaction

2. Effect of temperature on the reaction rate
3. Effect of reactant concentration on the product
4. Effect of average residence time.
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Apparatus

Tubular Reactor

The experimental set up consists of a tubular reactor submerged in a temperature-

controlled water bath, two reactant holding tanks, two peristatic pumps to feed the
reactant to the reactor and a conductivity meter to monitor the final concentration at the
outlet of the reactor. Feed rate, temperature, conductivity measurements can be
monitored and controlled by a data acquisition system.

The tubular reactor is made up of polyethylene tubes, with total of length 26.67 m (87.5’)
with an i.d and o.d 4.32 and 6.35 mm respectively. The capacity of each feed pump is 0 -
95 ml per min. The temperature in the water bath can be controlled from 5 – 50 C.

The feed streams enter the water bath at the top and are preheated separately before both
reactants are mixed at the ‘T’ at the bottom of the reactor.

Procedure:

Draw up a schedule of experiments to meet the objectives. Assume that each experiment
can take up to 45 minutes.

Fill the both reactant holding tanks with 5L of each reactant. The concentration of the
reactant should be varied from 0 to 0.1 mols per litre.

Set the temperature of the water bath. Wait until temperature of the bath is steady.

Start feeding the reactant. Monitor the temperature and the conductivity. Take the
readings when the system reaches steady state.

Change the variables and repeat the procedure.

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Calculations:

The saponification reaction can be written as:

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

The reaction rate is:

r = k [CH 3 COOC 2 H 5 ] ⋅ [NaOH ]

Initial concentrations: (t = o )

Fa
ao = ⋅ aF
Fa + Fb

Fb
bo = ⋅ bF
Fa + Fb

a = NaOH

b = CH 3COOC 2 H 5

c = CH 3 COONa

a F and bF are respective concentrations in feed tanks, mol / l

At infinite time
c ∞ = b0 if b0 < a0
or
c∞ = a 0 if b0 ≥ a 0

if a 0 ≥ b0 , a ∞ = a 0 − b0

The conductivity of the reacting solution in the reactor changes with the conversion, and
this provides a convenient method to monitor the progress of the reaction.

Relations between conductivities and concentrations; for T ≥ 294 ° K

λc = 70[1 + 0.0248(T − 294)] ⋅ c (1)

and
λ a = 195[1 + 0.0184(T − 294 )] ⋅ a (2)

λ∞ = λc∞ + λ a∞ (3)

λ0 = λa 0 , assuming c0 = 0 , no products
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At time t , λ = λt (conductivity reading at time t ), at t = 0, λ = λ0 and at t = ∞, λ = λ∞ .

The same applies for concentrations a and c.

⎡ λ − λt ⎤
at = (a ∞ − a 0 )⎢ 0 ⎥ + a0 (4)
⎣ λ0 − λ ∞ ⎦

⎡ λ − λt ⎤
ct = c ∞ ⎢ 0 ⎥ for c0 = 0 (5)
⎣ λ0 − λ∞ ⎦

Symbols used in questions (1) – (5)

λ = conductivity in mS

a, b and c are concentrations in mol / l

F = flow rate, l / s

Other symbols
r = reaction rate, mol / ls

V = volume of reactor, l

Dr. Mladen Eić January 20, 2006

Course Instructor