Rate of Rxn

The reaction rate is the rate at which a species loses its chemical identity per unit volume. The rate of a reaction can
be expressed as the rate of disappearance of a reactant or as the rate of appearance of a product. Consider species A:

A B

rA = the rate of formation of species A per unit volume
-rA = the rate of a disappearance of species A per unit volume
rB = the rate of formation of species B per unit volume

Example:

A B

If B is being created at a rate of 0.2 moles per decimeter cubed per second, ie, the rate of formation of B is,

rB = 0.2 mole/dm
3
/s

Then A is disappearing at the same rate:

-rA = 0.2 mole/dm
3
/s

the rate of formation of A is

rA = -0.2 mole/dm
3
/s

For a catalytic reaction, we refer to -rA
'
, which is the rate of disappearance of species A on a per mass of catalyst basis.

NOTE: dCA/dt is not the rate of reaction but it is simply mole balance that is ONLY valid for a constant volume batch
system.


The Convention for Rates of Reaction

Consider the reaction


in which the rate of disappearance of A is 5 moles of A per dm
3
per second at the start of the reaction.

At the start of the reaction

(a) What is -rA?
(b) What is the rate of formation of B?
(c) What is the rate of formation of C?
(d) What is the rate of disappearance of C?
(e) What is the rate of formation of A, rA?
(f) What is -rB?









Answers

(a) -rA is the rate of disappearance of A is


(b) For every one mole of A that disappears, two moles of B disappear. Reactant B is a is disappearing twice as fast
as reactant. i.e., A.
-rB = 2 x -rA = 10 moles/dm
3
/s

Multiplying by minus one (-1) we get the rate of formation of B


B is being used up therefore its rate of formation is a negative number.

(c) C is a product that is being formed three times as fast as A is disappearing

Because C is a product is being formed, its rate of formation is positive.

(d) The rate of disappearance of C is -rC. Therefore we multiply the rate of formation of C, rC, by minus one (-1) to
get


Because C is a product, its rate of disappearance, -rC, is a negative number.

(e) A is a reactant that is being used up therefore its rate of formation is negative


(f) -rB is the rate of disappearance of B



Summary

Rate of disappearance of A = -rA = 5 mole/dm
3
/s
Rate of disappearance of B = -rB = 10 mole/dm
3
/s
Rate of disappearance of C = -rC = -15 mole/dm
3
/s
Rate of formation of A = rA = -5 mole/dm
3
/s
Rate of formation of B = rB = -10 mole/dm
3
/s
Rate of formation of C = rC = 15 mole/dm
3
/s

For reactants the rate of disappearance is a positive (+) number.
For products the (-) rate of disappearance is a negative number because they are being formed and not disappearing.
For reactants the rate of formation is a negative (-) number because they are disappearing and not being formed.
For products the rate of formation is a positive (+) number.






Relative Rates of Reaction
The Reaction:


is carried out in a reactor. If at a particular point, the rate of disappearance of A is 10 mol/dm
3
/s, what are the rates of B and C?
Solution

The rate of disappearance of A, -ra, is


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

Species C
The rate of formation of C, -rc, is





Power Law Model































Rate Constant, k

k is the specific reaction rate (constant) and is given by the Arrhenius Equation:

Where:







Where:
E = activation energy (cal/mol)
R = gas constant (cal/mol*K)
T = temperature (K)
A = frequency factor (units of
A, and k, depend on overall
reaction order)



The larger the activation energy, the more temperature sensitive k and thus the reaction rate.

You can tell the overall reaction order by the units of k
C
A
-r
A
Reaction Order Rate Law k
(mol/dm
3
) (mol/dm
3
*s) zero -r
A
= k (mol/dm
3
*s)
(mol/dm
3
) (mol/dm
3
*s) 1st -r
A
= kC
A
s
-1

(mol/dm
3
) (mol/dm
3
*s) 2nd -r
A
= kC
A
2
(dm
3
/mol*s)






















Elementary Rate Laws
A reaction follows an elementary rate law if and only if the (iff) 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:
if 2NO+O
2
2NO
2
then -r
NO
= k
NO
(C
NO
)
2
C
O2
if elementary!

Self Test
Rate Laws
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/dm
3
, CB = 9
mol/dm
3
and kA = 2 (dm
3
/mol)
(1/2)
(1/s).

Solution




Let's calculate the rate if,

Then


Non-Elementary Rate Laws
Example: If the rate law for the non-elementary reaction
is found to be
then the reaction is said to be 2nd order in A, 1st order in B, and 3rd order overall.









Reversible Reactions

The net rate of formation of any species 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, ratenet 0 and the rate law must reduce to an equation that is thermodynamically
consistent with the equilibrium constant for the reaction.
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:
What is the corresponding rate law? Let's see.
If the rate of formation of A for the forward reaction (A + B C) is
then we need to assume a form of the rate law for the reverse reaction that satisfies the equilibrium
condition. If we assume the rate law for the reverse reaction (C A + B) is
then:

and:






Deriving -r
A
:
The forward rate is:

And the reverse rate law is:

The net rate for species A is the sum of the forward and reverse rate laws:

Substituting for rfor and rrev:


















Self Test

Rate Law for Reversible Reactions

Write the rate law for the elementary reaction

Here k
fA
and k
rA
are the forward and reverse specific reaction rates both defined with respect to A.

Hint
What is the net rate of reaction?
(1)
(2)


Solution
Write the rate law for the elementary reaction

Here k
fA
and k
rA
are the forward and reverse specific reaction rates both defined with respect to
A.
(1)
(2)





At equilibrium;






Examples of Rate Laws
First Order Reactions
(1)

(2)

(3)


(4)

While overall this reaction is first order, it is 1/3 order in ethylene and 2/3 order in oxygen.
(5)


(6)



(7)


Where and

Second Order Reactions
(1)


This reaction is first order in ONCB, first order in ammonia and overall second order.

(2)

This reaction is first order in CNBr, first order in CH3NH2 and overall second order.


(3)

with K
C
= 1.08 and


Nonelementary Reactions

(1)

Cumene Benzene Proplene
(C) (B) (P)



(2)