CHOICE OF REACTOR -

Reactor Conditions

REACTOR CONDITIONS
REACTION
EQUILIBRIUM
REACTOR
TEMPERATURE
REACTOR PRESSURE
REACTOR PHASE
REACTOR
CONCENTRATION

Reactor Conditions
In the previous discussion, the choice of reactor
type was made on the basis of the most
appropriate concentration profile as the reaction
progressed.
However, there are still important effects
regarding reaction conditions to be considered.
Before considering reaction conditions, some
basic principles of chemical equilibrium need to
be reviewed.

Reactor Conditions
Reactions can be considered to be
either reversible or essentially
irreversible.

Reactor Conditions
For reversible reactions:
For a given mixture of reactants at a given
temperature and pressure, there is a maximum
conversion (the equilibrium conversion) that
cannot be exceeded and is independent of the
reactor design.
The equilibrium conversion can be changed by
appropriate changes to the concentrations of
reactants, temperature and pressure.

Reactor Conditions
The key to understanding reaction equilibrium is the
Gibbs free energy, or free energy, defined as:
G = H TS
Like enthalpy, the absolute value of G for a substance
cannot be measured, and only changes in G are
meaningful.
For a process occurring at constant temperature, the
change in free energy is:
G = H T S

Reactor Conditions
A negative value of G implies a
spontaneous reaction of reactants to
products.
A positive value of G implies the
reverse reaction is spontaneous.
A system is in equilibrium when G = 0

Reactor Conditions

Reactor Conditions
The free energy can also be expressed
in differential form:
dG = SdT + VdP

where V is the system volume.

At constant temperature,dT = 0 and
dG = VdP

For N moles of an ideal gas PV = NRT;

V=NRT/P
where R is the universal gas constant.

Reactor Conditions

Values for free energy are usually

referred to the standard free energy GO.
The standard state is arbitrary and
designates the datum level.

Reactor Conditions
A gas is considered here to be at a
standard state if it is at a pressure of
1 atm or 1 bar for the designated
temperature of an isothermal
process.
In terms of std. conditions

Reactor Conditions
For a real system, rather than an
ideal gas, Equation is written as

Reactor Conditions
The concepts of fugacity and activity have no strict
physical significance but are introduced to transform
equations for ideal systems to real systems.
However, it does help to relate them to something
that does have physical significance.
Fugacity can be regarded as an effective pressure,
and activity can be regarded as an effective
concentration relative to a standard state.

Reactor Conditions

Reactor Conditions
Note that the partial molar free energy is
used to designate the molar free energy of
the individual component as it exists in the
mixture.
This is necessary because, except in ideal
systems, the properties of a mixture are not
additive properties of the pure components.
Therefore

Reactor Conditions
The free energy change for reactants
and products at standard conditions
is given by:

Reactor Conditions

Reactor Conditions
At equilibrium G = 0

Ka is known as the equilibrium constant.

It represents the equilibrium activities for a system under
standard conditions and is a constant at constant
temperature.

Homogeneous gaseous
reactions
a = f/f0

For homogeneous gaseous reactions, the standard state

fugacities can be considered to be unity, that is,
f Oi = 1.

Homogeneous gaseous
reactions
If the fugacity is expressed as the
product of partial pressure and
fugacity coefficient
fi = i pi
where fi = fugacity of Component i
i = fugacity coefficient of Component i
pi = partial pressure of Componenti
Therefore Ka is given as

Homogeneous gaseous
reactions
By definition

Homogeneous Liquid
Reactions

For homogeneous liquid reactions, the activity

can be expressed as,

For ideal solutions, the activity coefficients are

unity, giving

Heterogeneous Liquid
Reactions
The state of all components is not
uniform (eg. Reaction between a gas
and a liquid)
This requires standard states to be
defined for each component.
The activity of solid in the equilibrium
constant can be taken to be unity.

Le Chateliers Principle
A basic principle that allows the
quantitative prediction of the effect of
changing the reactor conditions on any
chemical system in equilibrium
If any change in the conditions of a
system in equilibrium causes the
equilibrium to be displaced, the
displacement will be in such a direction
as to oppose the effect of the change

REACTOR TEMPERATURE