Chapter 3: Rate Laws and Stoichiometry

Objectives

• Write the relationship between the relative rates of reaction.

• Write a rate law and define reaction order and activation energy.
• Set up a stoichiometric table for both batch and flow systems and
express concentration as a function or conversion.
• Write -rA solely as a function of conversion given the rate law and
the entering concentration.
• Calculate the equilibrium conversion for both gas and liquid phase
reactions.
 Topics

Part 1: Rate Laws

• Relative Rates of Reaction

• Power Law Model
• Rate Constant, k
• Elementary Reactions
• Non-Elementary Rate Laws
• Reversible Reactions
 Topic 1: Rate law

• A rate law describes the behavior of a reaction. The rate

of a reaction is a function of temperature (rate constant)
and concentration.

• Given –rA = f(X) - can calculate reactor volume etc.

• But data –rA = f(X) is not given in table, unlike
thermodynamic data

• Derive from rate law equation using data from

experiment

• Homogeneous reaction - one phase

• Heterogeneous reaction -more than one phase

 Relative Rates of Reaction
• The relative rates of reaction - obtained from the ratio of stoichiometric
coefficients.

• For this reaction: aA + bB + cC + dD , the ratio of stoichiometric

coefficients, represented by the small letters a, b, c, d and the rate of
reaction are expressed as:

Example 1:

The Reaction:

is carried out in a reactor. If at a particular point, the rate of disappearance

of A is 10 mol/dm3/s, what are the rates of B and C?
 Solution Example 1
The rate of disappearance of A, -ra, is

Or or the rate of formation of species A is

The relative rates are:

Species B:

The rate of formation of species B is

The rate of disappearance of B, -rb,is

 Continue Solution Example 1

Species C:

The rate of formation of C, -rc, is

 Power Law Model

Power Law model:

 Rate Constant, k
• Rate constant(specific reaction rate) varies with the order of the reaction.

For a reaction order n, the units of k are:

k 
Concentrat ion  1n
Time

You can tell the overall reaction order by the units of k in the table below:

Reaction
CA -rA Order Rate Law k

(mol/dm3) (mol/dm3*s) zero -rA = k (mol/dm3*s)

(mol/dm3) (mol/dm3*s) 1st -rA = kCA s-1

(mol/dm3) (mol/dm3*s) 2nd -rA = kCA2 (dm3/mol*s)

 Rate constant, k
• Rate constant, k, is a function of temperature, T.

• k is given by the Arrhenius Equation:

Where:
E = activation energy (cal/mol , J/mol)
R = gas constant (cal/mol*K, J/mol*K)
T = temperature (K)
A = pre-exponential factor or frequency factor (units of A, and k, depend on
overall reaction order)
 Rate constant, k
Taking the natural logarithm,

Activation energy, get E the plot of ln k versus 1/T base on

the experimental data at different temperatures:

If k (T1) is known, then k at a certain temperature, T2 :

 Rate constant, k
Activation Energy, E

The activation energy - barrier to the reaction. For the reaction:

the reaction coordinate is:

Progress along reaction path

 Rate constant, k

For the reaction to occur, the reactants must overcome an energy

barrier EB. The energy barrier is related to the activation energy, E.

The barrier height is a result of:

(1) The molecules need energy to distort or stretch their bonds in

order to break them and thus form new bonds,

(2) The as reaction molecules come close together they must

overcome both steric and electron repulsion forces,

(3) The quantum effects that can in some cases produce a barrier.
 Elementary Reactions
• A reaction follows an elementary rate law if and only if the stoichiometric
coefficients are the same as the individual reaction order of each species.

• For the reaction in the previous example: , the rate law

would be:

Example 2

What is the reaction rate law for the reaction if the reaction
is elementary? What is rB? What is rC? Calculate the rates of A, B, and C in a
CSTR where the concentrations are CA = 1.5 mol/dm3, CB = 9 mol/dm3 and
kA = 2 (dm3/mol) (1/2) (1/s).
 Solution Example 2

-rA : -rB :

-rC :

Let's calculate the rate if,

 Continue Solution Example 2
Then:
 Non-Elementary Rate Laws

For the non-elementary reaction:

If the rate law is found to be:

then the reaction is said to be 2nd order in A, 1st order in B, and 3rd order

overall.

The rate law does not correspond to the stoichiometric coefficients. The
reaction order must be determined from the literature or from experiments.
 Reversible Reactions

• All the rate laws for reversible reactions must reduce to the thermodynamic
relationship relating the reacting species concentrations at equilibrium.

• The net rate of formation is equal to its rate of formation in the forward
reaction plus its rate of formation in the reverse reaction:

rate net = rate forward + rate reverse

• At equilibrium, rate net = 0, and the rate law must reduce to an equation that
is thermodynamically consistent with the equilibrium constant for the
reaction.
 Reversible Reactions
For example:
A gas phase reversible reaction of benzene to produce diphenyl and
hydrogen:

kB
2 C6 H 6  C12 H10  H 2
k B

kB
2B  D  H2
k B

  k B CB
2
rB, f
r B, r  k B CD C H2
 Reversible Reactions

continue
 rB, net  k B C B  k B C D C H 2
2

 2 k 
 rB, net  k B  C B  B C D C H 2 
 kB 

kB
Concentrat ion equilibriu m constant, K C 
k B

 2 CD CH2 
  rB, net  k B  CB  
 KC 

C D, e C H 2 , e
At equilibriu m,  rB, net  0; and K C  2
C B, e
 Reversible Reactions

• Example: Consider the exothermic, heterogeneous reaction

• At low temperature, the rate law for the disappearance of A is

At high temperature, the exothermic reaction is significantly reversible:

If the rate of formation of A for the forward reaction (A + B C) is

we assume the rate law for the reverse reaction (C A + B)

 Reversible Reactions

then:

and:

At equilibrium, rnet 0, so:

Solving for KP gives:

The conditions are satisfied.

 Example 3: Rate Law for Reversible Reactions

• Write the rate law for the elementary reaction

• Here kfA and krA are the forward and reverse specific reaction rates
both defined with respect to A.

Solution

At equilibrium
 Examples of Rate Laws

• First Order Reactions

Nonelementary Reactions