Chemical Kinetics

Lecture 3
CY 1101

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Integrated rate laws: Second order reaction

Case (i): where one type of reactant is being converted into product

In terms of appearance of the product:

stoichiometry is not being considered

A → P
initial concentration
concentration at t = t

What’s the unit of

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Integrated rate laws: Second order reaction
Case (ii): where two types of reactants are being converted into product

A + B → P

Can you draw the plot of

vs time?
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Examples of second order reaction
i) H2 + I2 → 2HI
ii) CH3COOC2H5 + OH- → CH3COO- + C2H5OH (basic hydrolysis of ethyl acetate)

Third order reaction:

A + B +C → P (such examples are hardly known)

2A + B → P (A few such examples are known!)

[considering stoichiometry]

We are not studying third order in details, as it is less common in chemistry.

Examples:
i) 2NO (g) + O2 (g) → 2NO2 (g)
ii) 2NO (g) + Cl2 (g) → 2NOCl (g)

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 Pseudo first order reaction:
Hydrolysis of ester in water

CH3COOC2H5 + H2O → CH3COOH + C2H5OH

This is a truly second order reaction, but water is present at a large extent than ester!

For a second order reaction, we saw earlier that:

Please note, that water is there in such a large extent, its conc. remains unchanged
even after completion of the reaction

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Methods of determination of the order/rate law of a reaction

i) Method of integration (trial and error method/graphical method)

A→P

In terms of disappearance of reactants, we need to collect a series of

graph plot outcome order

linear zero
linear first
linear second

Disadvantage: Since best fit would give the order, accuracy is problem. For
fractional order or complex reaction, this method will fail.

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Methods of determination of the order/rate law of a reaction
ii) Differential method (van’t Hoff’s method)

For an unknown reaction: A→P

Now, we choose two different initial concentrations, i.e. c1 and c2

Thus, we can write:

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…….. continued

By taking logarithms of both the equation (1) & (2), we get:

By subtracting equation (4) from equation (3), we get:

& are the rates with initial concentration &

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 Typical concentration versus time plot for a non-zero order
reaction:

= slope 1 at t → 0 (initial rate)

= slope 2 at t → 0 (initial rate)

Ideally, c vs. t plot is considered to be linear when t → 0. But for practical purpose
we apply an approximation that c vs. t plot behaves linearly within first 10%
of the reaction!

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Methods of determination of the order/rate law of a reaction
iii) Isolation method (Ostwald’s method)

This method works best for the following type of reaction:

A + B → P

Hereafter, we can use either method (i) or method (ii) to find α

Caution: Excess of one reactant should not cause any chemical change or affect
the mechanism.
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Methods of determination of the order/rate law of a reaction
iv) Initial rate method

This method works best for the following type of reaction:

A + B → P

The same reaction is run twice by keeping [B] constant but doubling up [A]

The same strategy can be applied to obtain β also.

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Simultaneous reactions (only first order cases)

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Simultaneous reaction
i) Opposing reaction:
A B
Assumption:
1st order in both ways
and
achieves equilibrium

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Simultaneous reaction
i) Opposing reaction:

Q: How to know ?

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Simultaneous reaction
i) Opposing reaction: in terms of disappearance of reactant

A B

may be
zero, but we
don’t bother!

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Simultaneous reaction
i) Opposing reaction: in terms of disappearance of reactant

(cont.)
……….

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