Lecture 3

• Block 1: Mole Balances

• Block 2: Rate Laws
• Block 3: Stoichiometry
Stoichiometric Table: Batch
Stoichiometric Table: Flow
Batch system with variable volume
Flow system with variable volume
Calculate the Equilibirum Conversion Xe

Lecture 3 – Ojumu TV (PhD)

 Elementary Rate Laws
Recall:
An elementary reaction involves a single step in the
formation of product. The powers in the rate law is
identical to the stoichiometry of the reaction.
!
A reaction is say to follow an elementary rate law if the
stoichiometry of the reaction is identical to the
reaction orders in the rate law.

These reactions are not elementary

but follow the elementary rate law

Lecture 3 – Ojumu TV (PhD)

 Nonelementary Rate Laws
A large number of reactions do not follow elementary
rate laws. The overall order may not be an integer or
does the order be an integer w.r.t. an individual
component.

Gas phase synthesis of Phosgene

Rate expressions can be quite

complex , and may be difficult to
separate into temperature dependent
and concentration dependent parts.

Lecture 3 – Ojumu TV (PhD)

 Rate laws for reversible reactions
Thermodynamic relationship relating concentration of
species at equilibrium. i.e. equilibrium constant.
!
For a general reaction:

Consider the gas phase conversion of benzene to diphenyl benzene.

Assuming the reaction to be elementary and reversible, it can be

shown that the rate of disappearance of benzene is:

Lecture 3 – Ojumu TV (PhD)

 Two steps to get
!
Step 1: Rate Law

!
Step 2: Stoichiometry
!

Step 3: Combine to get

Lecture 3 – Ojumu TV (PhD)

 Stoichiometry
The objective is to express concentration as a function of
conversion.
!
If rate law depends on more than one species, then it is
important to relate the concentration of different species
to each other – Stoichiometric Table
!
Consider a general reaction:
!
In formulating stoichiometric table, the basis must be
established (i.e. limiting reactant).

Lecture 3 – Ojumu TV (PhD)

Stoichiometry Table – Batch System

Lecture 3 – Ojumu TV (PhD)

Constant-Volume Batch System

Lecture 3 – Ojumu TV (PhD)

Equilibrium conversion for gas phase reaction

Lecture 3 – Ojumu TV (PhD)

Stoichiometry Table – Flow System

Lecture 3 – Ojumu TV (PhD)

Stoichiometry Table – Flow System

Lecture 3 – Ojumu TV (PhD)

 Batch system with variable volume

For a variable volume or volumetric flow rate system, individual

species concentration can be expressed as a function of
conversion using equation of state
!
where V=volume and NT=total number of moles
T=temp, K; P=total pressure, atm
Z=compressibility factor
R=gas constant
At time t=0 (when the reaction is initiated

The task is to express V=V(X)

Recall total number of mole after rxn

Lecture 3 – Ojumu TV (PhD)

 Batch system with variable volume

Equation 1 becomes

Assuming that compressibility factor change is insignificant to the effects

of temperature and pressure such that:
!
then for batch system, the volume of gas at any time t is :

Lecture 3 – Ojumu TV (PhD)

 Flow system with variable volume

we obtain

The total molar flow rate is:

Substituting for FT gives

Lecture 3 – Ojumu TV (PhD)

 Flow system with variable volume

Consider a reaction:
!
!
The molar flow rate of species j is:
!
!
Where vj is the stoichiometric coefficient, -ve for reactants and +ve for
products.

Lecture 3 – Ojumu TV (PhD)

Equilibrium conversion for gas phase reaction
Contd.

Lecture 3 – Ojumu TV (PhD)

Equilibrium conversion for gas phase reaction
Contd.

Lecture 3 – Ojumu TV (PhD)

 Expressing concentration as a function of conversion

This schematic diagram

summarizes our discussion
upto this point. The
concentration of the key
reactant, A (the basis) is
expressed as a function of
conversion in both flow and
batch systems, for various
conditions of temperature,
pressure and volume

Lecture 3 – Ojumu TV (PhD)