Departemen Teknik Kimia

Fakultas Teknik
Universitas Indonesia

Complicated Rate Equations Andre Fahriz Perdana Harahap

From: Chemical Kinetics by Kenneth A Connors (1990) (1406605843)
Mata Kuliah Teknik Reaksi Kimia Lanjut 2019 Program Magister Teknik Kimia
Terms
Parallel reactions: a reactant undergoes two or more concurrent
reactions to give different products (also called as competitive
reaction).

Consecutive reactions: the product of one reaction is the

reactant in the next reaction (also called as series reactions).
Integration of The Rate Equations
Reversible reaction Initial conditions:
C A = CA 0
Differential rate equation: Cz = 0
Mass balance:
CA 0 = CA + CZ

At equilibrium:
dCA/dt = 0
Reversible reaction (Cont’d)

After variable separation

and integration:

Note:
Experimental k is equal to the sum k1+k-1 and
k1/k-1 = K
Reversible reaction (Cont’d)
Where:
If pseudo first order can be
established, by setting CB0 >> CA0

Scheme II is more easily described in terms of quantity ∆ defined as

the displacement of a concentration from its equilibrium value.
Reversible reaction (Cont’d)
Let:

Eq. constant:

Where:
After variable separation
and integration:
Parallel reaction
Consider product Y:

Or integration:

And for product Z:

For case :

The ratio of product concentrations is equal to the ratio of rate

constant, independently of time.
Parallel reaction (Cont’d)
Mass balance:

Combination gives:

Suppose:
Parallel reaction (Cont’d)
Parallel reaction (Cont’d)

Define:

After variable separation

and integration:
Consecutive reaction
Reactant A follows first order:

To find dependence of CB on time (by

integrating factor method):
Consecutive reaction (Cont’d)
Suppose :
Consecutive reaction (Cont’d)

The time when CB reaches it maximum value is at dCB/dt = 0

If F is the experimental measure of the extent of reaction, combining (3-27) and (3-29) gives:

Define r = k2/k1 and d = k2t, Eq (3-32) becomes:

According to Beer’s law:

Consecutive reaction (Cont’d)
Consecutive reaction (Cont’d)
Consecutive reaction (Cont’d)

Dehydration of prostaglandin to methyl ester:

From equation (3-27):

Combining eq (3-26) and (3-27):

Consecutive reaction (Cont’d)
Consecutive reaction (Cont’d)

The result for initial condition CC = 0 at t = 0 is:

CD is found from mass balance as follow:

Consecutive reaction (Cont’d)

Consider:

Elimination of CA and
integration
Other Methods of Analysis
Measurement of Rates

Rearrangement:
Simplification of The Experimental Kinetics

1. Use of the isolation or pseudo-order technique.

2. Study of reversible reactions close to equilibrium.
3. Neglect of the terminal stages of the reaction.
4. Neglect of the initial stages of the reaction.
5. Use of a intermediate as a starting reactant.
6. Mimicking the reactant with a derivative or analog
that cannot undergo the full complexity of reaction.
7. Change of reaction conditions to minimize kinetic
complications.
8. Choice of initial conditions.
9. Exploitation of analytical selectivity.
Elimination of The Time Variable

Dividing one of these equations by the other gives dCY/dCZ = k1/k2, the time variable
cancelling. Integration yields:

Dividing (3-50) by (3-51)

 Elimination of The Time Variable (Cont’d)

Integration gives:
 Replacement of Time with an Area Variable

Consider second order reaction of A and B:

define:
The variable 𝜃 is the area under the curve of
CB vs time from t = 0 to time t.
Replacement of Time with an Area Variable (Cont’d)
 MODEL BUILDING

In a general way a kinetic study of reaction mechanism includes these 4 components:

- Experimental kinetics
- Determination of the rate equation
- Writing the kinetic scheme
- Proposal of transition state structures,stereochemistries, and energetics.

A postulated kinetic scheme is a model or hypothesis. Occam’s razor  the model

should be no more complex than is required to account for the experimental
observations.

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 MODEL BUILDING
1. Background information on the reasonable and expected chemistry of the system.
Knowledge of the pertinent literature is valuable. In deciding whether to write an elementary
reaction as either a reversible or an irreversible reaction, we take the practical view that if the
reverse reaction is negligibly slow on the experimental time scale, the reaction is essentially
irreversible.
Rate equation of alkaline hydrolysis of an ester:

An abundance of mechanistic information suggest this scheme:

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 MODEL BUILDING
Scheme XXII
Alkaline solution of the carboxylic acid and alcohol does not generate
the ester and that the postulated tetrahedral intermediate can not be
detected. Thus, overall reaction is irreversible and the intermediate is
present at very low concentration. These considerations lead to Scheme
XXII.

2. Direct detection of an intermediate

When acetonitrile solutions of acetyl chloride and N-methylimidazole
are mixed, the absorbance of the resulting solution is much greater than
that calculated for the sum of reactants. On the other hand, when
acetonitrile solutions of acetic anhydride and N-methylimidazole are
mixed, no excess absorption is observed. This considerations lead to
Scheme XXIII.
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MODEL BUILDING

A general treatment of Scheme XXIII requires

specifications of the detailed nature of k’A and k’I is
too complicated to be practical use. However,
several important special cases may arise from
operation of the ratio k1/k-1, the behavior of
apparent rate constant k’A and k’I, the relative
magnitudes, and nature ROH. This case is outlined
in Scheme XXIV.

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 MODEL BUILDING

3. Indirect detection of an intermediate

Overall reaction of hydroxylamine with a carboxylic acid derivative yields a hydroxamic acid as
the product.

In this case the intermediate is O-acetylhydroxylamine, which subsequently reacts with

hydroxylamine to form the hydroxamic acid.

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 MODEL BUILDING

4. Kinetic evidence for a common

intermediate
Suppose a series of related reactants
each separately reacts with a common If kx = ky = kz, these rate constants all describe
reagent, and rates of product the same reaction, in this example of B- with
common intermediate A+:
formation are the same for each
reactant:

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 MODEL BUILDING

5. Concentration-time curves

Figure beside shows an induction period in the reaction

of carbon suboxide with triethylamine. The final product
concentration are all related to the triethylamine
concentration.

6. Dependence of apparent constant on

concentration

Continuing consideration of Scheme XXII by making

chemically reasonable tentative solection of form k’A
and k’I.
- First, consider the acetyl chloride-alcohol reaction.
The observed reaction:
Absorbance-time plots for reaction of carbon suboxide
and triethylamine in either solution in the presence of
acetic anhydride
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 MODEL BUILDING
• The hypotical rate equation is:
• Therefore the experimental rate equation is:
A plot of Kobs/[ROH] vs [N] will be linear. The conversion
to the intermediate is quantitative  [N] = [N]o – [AX]o
• Turning to the acetic anhydride-alcohol system, it is
inferred that k1/k-1 is close to zero (Scheme XXIV).
• Rate of equation for loss of anhydride:
• The assumption is made that all of the H+
produced in the acetylation is accepted by
X- (acetate), [X-] = 0, therefore:
• By hypothesis k’A = kA + kAN[N], the
experimental rate equations is –d[AX]/dt =
kobs =[AX]. If in a series of experiments the
catalyst concentration is held constant
while the alcohol concentration is varied,
whereas if [ROH] is kept constant and [N]
is varied, therefore:
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 MODEL BUILDING
• k1 and kA were not significantly different from zero. All of these rate equations can be
succinctly expressed in the form of Scheme XXVIII.

• This manner of impicity including the rate equations in the kinetic scheme is very convenient. It
is amplified with the statement that when AX is acetyl chloride, k1/k-1 is very large and reaction
occurs essentially only via the I+ route. When AX is acetic anhydride, k1/k-1 is 0, and the
reaction occurs entirely via the AX route.

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