Irreversible Reactions with Two or Three Components 117

3.1.1.3 Method of a Reactant in Excess

When the feed molar ratio of a reactant with respect to another is much
higher than the ratio of stoichiometric coefficients of the reaction, the feed
composition is considered to be with a reactant in excess. For instance,
in Eq. (3.1):

aA + bB Products
If MBA>>b/a, the reactant B is in excess.
Being in excess, the concentration of this reactant does not change
considerably as reaction proceeds, as illustrated in Figure 3.1 (i.e.
CBo≈CB≈constant).
With this consideration, Eq. (3.2) is:

− rA = kCAα CBβ = kCAα CBo

β β
= kCBo CAα
− rA = kex CAα (3.26)

where:
β
kex = kCBo 3 27
118 Chemical Reaction Kinetics

CBo
CB ~ CB0

CAo

Time

Figure 3.1 Profile of concentrations during a reaction with a reactant in excess.

The solution of this equation is similar to that of the equations of

Section 2.1, changing only kex with k, and n with α:

Constant Density
1 CAo 1 1
For α = 1 kex = ln = ln 3 28
t CA t 1 − xA
1
For α≠1 kex = C 1−α −CAo
1−α
α−1 t A

1 1 (3.29)
= α −1 α −1 −1
α − 1 CAo t 1 −xA

Variable Density
1 CAo + εA CA 1 1
For α = 1 kex = ln = ln 3 30
t CA + εA CA t 1 −xA
xA
α−1
1 1 + εA xA
For α 1 1 kex = α−1 α dxA 3 31
CAo t 1 − xA
0

With this method, the individual reaction order with respect to the lim-
iting reactant (α) and the reaction rate coefficient (k) is calculated. The
reaction order β can be calculated if the global reaction order (n) has been
determined by means of another method.