A first-order reaction is a reaction that proceeds at a rate that depends linearly on only one

reactant concentration.

The Differential Representation

Differential rate laws are generally used to describe what is occurring on a molecular level during
a reaction, whereas integrated rate laws are used for determining the reaction order and the value
of the rate constant from experimental measurements. The differential equation describing first-
order kinetics is given below:

Rate=−d[A]dt=k[A]1=k[A](1.1)

The "rate" is the reaction rate (in units of molar/time) and k

is the reaction rate coefficient (in units of 1/time). However, the units of k vary for non-first-
order reactions.
What is the first order rate constant?
k is the first-order rate constant, which has units of 1/s. The method of determining the order
of a reaction is known as the method of initial rates. The overall order of a reaction is the sum
of all the exponents of the concentration terms in the rate equation.

First-Order Reactions
A first-order reaction depends on the concentration of one reactant, and the rate law is:
r=−dAdt=k[A]

Key Points

 k is the first-order rate constant, which has units of 1/s.

 The method of determining the order of a reaction is known as the method of initial rates.
 The overall order of a reaction is the sum of all the exponents of the concentration terms
in the rate equation.

Key Terms

 first-order reaction: A reaction that depends on the concentration of only one reactant (a
unimolecular reaction). Other reactants can be present, but each will be zero-order.

Second-Order Reactions
A second-order reaction is second-order in only one reactant, or first-order in two
reactants.
Key Points

 A second-order reaction will depend on the concentration (s) of one second-order reactant
or two first-order reactants.
 To determine the order of a reaction with respect to each reactant, we use the method of
initial rates.
 When applying the method of initial rates to a reaction involving two reactants, A and B,
it is necessary to conduct two trials in which the concentration of A is held constant, and
B changes, as well as two trials in which the concentration of B is held constant, and A
changes.

Key Terms

 second-order reaction: A reaction that depends on the concentration(s) of one second-

order reactant or two first-order reactants.
 reaction mechanism: The step-by-step sequence of elementary transformations by which
overall chemical change occurs.

Zero-Order Reactions
A zero-order reaction has a constant rate that is independent of the concentration of the
reactant(s); the rate law is simply rate=k

. Key Points

 For a zero-order reaction, increasing the concentration of the reacting species will not
speed up the rate of the reaction.
 Zero-order reactions are typically found when a material that is required for the reaction
to proceed, such as a surface or a catalyst, is saturated by the reactants.
 A reaction is zero-order if concentration data is plotted versus time and the result is a
straight line.

Key Terms

 zero-order reaction: A reaction that has a rate that is independent of the concentration of
the reactant(s).

.
Zero order
For zero-order reactions, the reaction rate is independent of the concentration of a reactant, so
that changing its concentration has no effect on the speed of the reaction. Thus, the concentration
changes linearly with time. This may occur when there is a bottleneck which limits the number
of reactant molecules that can react at the same time, for example if the reaction requires contact
with an enzyme or a catalytic surface.[7]

Many enzyme-catalyzed reactions are zero order, provided that the reactant concentration is
much greater than the enzyme concentration which controls the rate, so that the enzyme is
saturated. For example, the biological oxidation of ethanol to acetaldehyde by the enzyme liver
alcohol dehydrogenase (LADH) is zero order in ethanol.[8]

Similarly reactions with heterogeneous catalysis can be zero order if the catalytic surface is
saturated. For example, the decomposition of phosphine (PH3) on a hot tungsten surface at high
pressure is zero order in phosphine which decomposes at a constant rate.[7]

First order
A first order reaction depends on the concentration of only one reactant (a unimolecular
reaction). Other reactants can be present, but each will be zero order. The rate law for such a
reaction is

The half-life is independent of the starting concentration and is given by .

Examples of such reactions are:

In organic chemistry, the class of SN1 (nucleophilic substitution unimolecular) reactions consists
of first-order reactions. For example, in the reaction of aryldiazonium ions with nucleophiles in
aqueous solution ArN2+ + X− → ArX + N2, the rate equation is r = k[ArN2+], where Ar indicates
an aryl group.[9]
Second order
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.[10]

For the single-component system, the time dependence of the concentration is given by

The time dependence for two components with 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:[9]

CH3COOC2H5 + OH− → CH3COO− + C2H5OH

This reaction is first-order in each reactant and second-order overall: r = k[CH3COOC2H5][OH−]

If the same hydrolysis reaction is catalyzed by imidazole, the rate equation becomes[9] r =
k[imidazole][CH3COOC2H5]. 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
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 r = k[A][B], if the concentration of
reactant B is constant then r = 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 in acid solution is often cited as a first-order reaction with rate r =
k[sucrose]. The true rate equation is third-order, r = k[sucrose][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.[11]

What is meant by pseudo first order reaction?

Pseudo First Order Reactions. There are circumstances where a second order reaction might
appear, in an experiment, to be first order. That is when one of the reactants in the rate equation
is present in great excess over the other in the reaction mixture.

The main difference between a First Order Reaction & a Pseudo First Order reaction is that the Pseudo
first order eaction is a reaction that should actually happen by some higher order(higher than 1) but
occurs by first order beacuse the concentration of one reactant used is very high & another reactant
used is very low ...

The concentration of the reactant which is very low can be negleted & thus the concentration of the
reactant which has higher concentration is alone taken !

This makes the reaction follow a first order kinetics rather than some higher order.This is Pseudo First
order reaction !

What does it mean to be a second order reaction?

Definition of second-order reaction. : a chemical reaction in which the rate of reaction is
proportional to the concentration of each of two reacting molecules — compare order of a
reaction.