CHAPTER 3 Determination of a Theoretical Rate Equation

3.1 Determination of the empirical rate equation

The empirical rate equation is experimentally determined by

measuring the reaction rate and/or rate constant of a reaction as
function of the concentrations of all possible reagents and products.
The following example reaction is considered:

2A + B + C  products

Firstly one must decide which reactant (or product) can most easily be
monitored by an available technique. Assume the choice is A. [A] is
then monitored under conditions where [A] << [B] and [C] to
determine whether more than 95% of A was used during the reaction.
If this is not the case, the possibility of reversible reactions should be
considered.
Determine the reaction order with regard to [A]. The value of [A],
ln[A], of [A]-1 will change linearly with time for zero-, first-, or second-
order reactions, respectively. (The concentrations of all the other
reagents are kept constant during the determinations).
Now determine the reaction orders with regard to each of the
reagents. Assume that it could be determined that the reaction is
second order with regard to A. To determine the rate equations, the
second-order rate constant, k, is measured as function of [B] and [C].
Assume the following results are obtained:

A and C constant
A and B constant
At constants [A] and [C]:

kobs1 = k0 + k1[B]

and at constants [A] and [B] is:

k obs2 = k2[C]-1

Therefore: k obs1 X k obs2 = kT = k'[C]-1 + k"[B][C]-1

with k' = k0k2 and k" = k1k2

so that: r = -d[A]/dt = k T[A]2 = k'[C]-1 [A]2 + k"[B][C]-1 [ A]2

Any suggested theoretical mechanism must now be in accordance

with this rate equation.
Additional notes
3.2 Deduction of the theoretical rate equation
For each empirical reaction mechanism a theoretical rate equation
can be deduced. A few general examples will now be discussed.

3.2.1 First-order reactions

Observe the simple process:

At t = 0 only A is present and the rate equation:

r = -d[A]/dt = d[P]/dt = k1[At]

A graph of -d[A]/dt against [A]t can therefore be drawn to determine

k1. The above-mentioned equation can alternatively be integrated:

ln [At] = ln [Ao] - k1t

from which follows that k1 can also be determined from a graph of

ln [A]t against t.
The advantage of a first-order rate equation is that any physical
parameter, f, that is proportional to the concentration of a reagent or
product, e.g. absorbance, volume, pressure, conductivity, etc. can be
used to calculate the first-order rate constant. For example:
3.2.2 Reversible first-order reactions

Consider the simple reaction:

The reaction starts from A, but does not run its course completely.
Thus, equilibrium is reached.

At t = 0 only A is present and the rate

equation is:

r = -d[A]/dt = k1[At] - k-1[P] (1)

because [Ao] - [At] = [P]

-d[A]/dt = k1[At] - k-1([Ao] - [At]) (2)

At equilibrium, at t = , it is valid that:

[Pe]/[Ae] = ([Ao] - [Ae])/[Ae] = k1/k-1

so that: [Ao] = {(k1 + k-1)/k-1}.[Ae] ( = (k1/k-1).[Ae] + 1.[Ae])

Substitution of this equation in the first equation produces:

-d[A]/dt = k1[At] - k-1.{{(k1 + k-1)/k-1}.[Ae] - [At]}

= k1[At] - (k1 + k-1).[Ae] + k-1[At]

= (k1 + k-1).([At] - [Ae]) (3)

Integration of this equation, therefore:

 {1/([A ] - [A ])}.d[A] = (k + k )dt produces:

 (4)

(Standard integral: (1/x)dx = ln (x2/x1)

A graph of ln ([A] - [Ae]) against t therefore produces a straight line

with slope -{k1 + k-1). From this follows that kobs = k1 + k-1. The relation
k1/k-1 = Kc can be calculated from the equilibrium concentrations after
which the calculation of k1 and k-1 is possible.
Additional notes
3.2.6 Reversible Second-order reactions
Consider the generalised reaction

The reaction starts with A and B but does not run its full course and
equilibrium is reached after a certain amount of time. The forward
reaction is a second-order reaction, but the backwards reaction is
first order. The process therefore leads to a mixed reaction-order
behaviour. The problem is overcome by executing the forward
reaction step under pseudo-first-order conditions. The processing
therefore corresponds to that of first-order reactions:
d
 [ A] k 2 [ At ][ B0 ]  k  2 [ Pt ] (1)
dt
because [A]0 – [A]t = [P]t

k 2 [ At ][ B0 ]  k  2 [ A0 ]  [ A]t  (2)
At equilibrium, that is t = , it is valid that:

K
[ P ]

[ A0 ]  [ A ] k 2

[ A ][ B ]0 [ B0 ][ A ] k 2

 k 2 [B0 ]  k  2 
from which: [A 0 ]  .[A  ]
 k 2 
Substitution of this equation in the first equation produces:
d  k 2 [ B 0 ]  k  2  
 [A] k 2 [A t ][B0 ]  k  2  .[A  ]  [A t ]
dt  k 2  
k 2 [A t ][B0 ]  k 2 [B0 ]   k 2 .[A  ]  k  2 [A]t
k 2 [B0 ]  k  2 [A t ]  [A  ] (3)
Integration of this equation produces:
 [A  ]  [A] 
ln   k 2 [B0 ]  k  2 t  k obs t (4)
 [A]0  [A] 

with: k obs k 2 [B0 ]  k  2 

A graph of kobs against [B]o will therefore produce a straight line of

which the slope = k2 and the intercept = k-2.
The relation k2/k-2 represents the equilibrium constant, K, for the
process and can also be verified thermodynamically. Several
processes present a two-term rate law as in this instance. Such a rate
law can be due to an equilibrium reaction, as in this case, but can
also be due to two parallel reaction courses, of which one of the
reaction courses is independent of [B], e.g.:
Additional notes
3.2.7 Reactions where a pre-equilibrium is present
Many second-order reactions take place via a fast pre-equilibrium,
e.g.: ion-pair formation or complex formation, followed by a rate-
determining product-formation step:

Rate determining step

For which the rate equation:

d[P]  d[A]  [AB]
 k[A][B]
is valid dt dt

From the law of mass balance, it is also valid that:

[A]  [AB]
[AB] K[B] k[A][B]
1  K[B]
because: [AB] k[A ][B] , it implies that [A ]  [AB] [A ]  k[A ][B]
so that we can write

[A]  [AB] 1  k[B]k and therefore [A] 

[A]  [AB]
1  K[B]
So that
d[A]  [AB] kK[B]
  [A]  [AB]
dt 1  K[B]

where kobs = kK[B]/{1 + K[B]} and {[A] + [AB]} are the total amount [AB]
that can react
At low [Bo], {1 + K[Bo]}  1 and therefore kobs = kK[Bo] under these
conditions.
At high [Bo], {1 + K[Bo]}  K[Bo] and therefore kobs = k under these
conditions.
Additional notes
3.2.10 The flow-equilibrium approach (stationary state
approximation)
Observe the case where the formation of the intermediate AB is
slow and competes with the rate-determining reaction step:

For the reaction scheme it is valid that:

d d
 [A]  [B] k1[A][B]  k  1[AB]
dt dt
If, according to the stationary state approximation, it is accepted that
[AB] is small and constant during the reaction course, it is valid that:
 d
[AB] 0 k1[A][B]  k  1[AB]  k 2 [AB]
dt
From which follows that: k1[A][B]
[AB] 
k1  k2

Substitution of [AB] in the first equation produces:

d k1k 2 [A][B] k1k 2 [B]
 [A]  k obs [A] , with k obs 
dt k1  k2 k1  k2

If the rate-determining reaction step also reaches equilibrium

it can, as in the above instance, by making use of the stationary state
approximation approach, be indicated that:

d  k1k 2 [A]  k  1k  2 
 [A]  [A t ]  [A  ] , with
dt  k1  k2 

k1k 2 [B]  k  1k  2
k obs 
k1  k2
The deduction of this takes places as follows:
d
 [A] k1[A][B]  k  1[AB] (1) and
dt
d
[AB]  k  1[AB]  k1[A][B]  k 2 [AB]  k 2 [P] 0 , from which
dt
k1[A][B]  k  2 [P]
[AB]  (2)
k  1  k 2 
Substitution of (2) in (1) and the substitution of [Pt] with [Ao] - [At]
produce:

d  k1k 2 [A t ][B])  k  1k  2 ([A 0 ]  [A]t  (3)

 [A]  
dt  k1  k2 
At equilibrium (3) = 0 and [At] = [A] and [P] = [Ao] - [A] so that:

 k1k 2 [A  ][B])  k  1k  2 ([A 0 ]  [A] 

0   (4)
 k1  k2 
(3) - (4) produces:

d  k1k 2 [A t ]  [A  ][B]  k  1k  2  [A t ]  [A]  

 [A]  
dt  k 1  k 2 
Additional notes