Second order[edit]

A reaction is said to be second order when the overall order is two. The rate of a second-order
reaction may be proportional to one concentration squared , or (more commonly) to the product of
two concentrations . As an example of the first type, the reaction NO2 + CO → NO + CO2 is second-
order in the reactant NO2 and zero order in the reactant CO. The observed rate is given by , and is
independent of the concentration of CO.[17]
For the rate proportional to a single concentration squared, the time dependence of the
concentration is given by
The time dependence for a rate proportional to two unequal concentrations is
;
if the concentrations are equal, they satisfy the previous equation.
The second type includes nucleophillic addition-elimination reactions, such as
the alkaline hydrolysis of ethyl acetate:[16]
CH3COOC2H5 + OH− → CH3COO− + C2H5OH
This reaction is first-order in each reactant and second-order
overall: 0 = k [CH3COOC2H5][OH−]
If the same hydrolysis reaction is catalyzed by imidazole, the rate equation
becomes v = k[imidazole][CH3COOC2H5].[16] The rate is first-order in one reactant (ethyl
acetate), and also first-order in imidazole which as a catalyst does not appear in the
overall chemical equation.
Another well-known class of second-order reactions are the SN2 (bimolecular
nucleophilic substitution) reactions, such as the reaction of n-butyl bromide with sodium
iodide in acetone:
CH3CH2CH2CH2Br + NaI → CH3CH2CH2CH2I + NaBr↓
This same compound can be made to undergo a bimolecular (E2) elimination
reaction, another common type of second-order reaction, if the sodium iodide and
acetone are replaced with sodium tert-butoxide as the salt and tert-butanol as the
solvent:
CH3CH2CH2CH2Br + NaOt-Bu → CH3CH2CH=CH2 + NaBr + HOt-Bu
Pseudo-first order[edit]
If the concentration of a reactant remains constant (because it is a catalyst, or
because it is in great excess with respect to the other reactants), its
concentration can be included in the rate constant, obtaining a pseudo–first-
order (or occasionally pseudo–second-order) rate equation. For a typical
second-order reaction with rate equation v = k[A][B], if the concentration of
reactant B is constant then 0 = k [A][B] = k'[A], where the pseudo–first-order rate
constant k' = k[B]. The second-order rate equation has been reduced to a
pseudo–first-order rate equation, which makes the treatment to obtain an
integrated rate equation much easier.
One way to obtain a pseudo-first order reaction is to use a large excess of one
reactant (say, [B]≫[A]) so that, as the reaction progresses, only a small fraction
of the reactant in excess (B) is consumed, and its concentration can be
considered to stay constant. For example, the hydrolysis of esters by dilute
 mineral acids follows pseudo-first order kinetics where the concentration of
water is present in large excess:
CH3COOCH3 + H2O → CH3COOH + CH3OH
The hydrolysis of sucrose (C12H22O11) in acid solution is often cited as a first-
order reaction with rate r = k[C12H22O11]. The true rate equation is third-order,
r = k[C12H22O11][H+][H2O]; however, the concentrations of both the catalyst
H+ and the solvent H2O are normally constant, so that the reaction is
pseudo–first-order.[18]

Summary for reaction orders 0, 1, 2, and n[edit]

Elementary reaction steps with order 3 (called ternary reactions) are rare
and unlikely to occur. However, overall reactions composed of several
elementary steps can, of course, be of any (including non-integer) order.

Zero First Second nth order (g = 1-

order order order n)

Rate Law [19]

Integrated Rate [19] [Except first order]

Law

Units of Rate
Constant (k)

Linear Plot to  vs. t

determine k
[A] vs. t  vs. t  vs. t
[Except first order]

[Limit is necessary
Half-life [19]
for first order]