THE RATE LAW

The equation relating the rate of reaction to the concentration of

molecular bromine,
rate = k[Br2]
is an example of a rate law. The rate law is an equation that relates
the rate of reaction to the concentrations of reactants. The rate of
a reaction is defined as the change of reactant or product
concentration in unit time. If we were to define the rate of a
reaction in
terms of the reactants, we should define the rate as the rate of
disappearance of reactants. If we were to define the rate in terms of
the products formed, we should define it as the rate of appearance of
products.

For further exploration of this concept, let's look at a hypothetical

reaction. In the hypothetical representative reaction shown below,
the small letters denote the coefficients of the corresponding
capital letter reactants or products.

In this reaction, A and B are reactants, and a and b their

coefficients respectively. X and Y are the products, and x and y
their coefficients respectively
For the general reaction,
aA + bB cC + dD

the rate law is

rate = k[A]x[B]y (Equation 14.2)

where k is the rate constant, [A] and [B] are the concentrations of
reactants A and B and the exponents x and y are numbers that must be
determined experimentally and that, in general, they are not equal to
the coefficients from the chemical reactions . When we know the
values of k, x, and y, we can use Equation 14.2 to calculate the rate
of the reaction, given the concentrations of A and B.
In the case of the reaction of molecular bromine and formic acid, the
rate law is
rate = k[Br2]x [HCOOH]y
where x = 1 and y = 0.
The values of the exponents in the rate law indicate the order of the
reaction with respect to each reactant. In the reaction of bromine
and formic acid, for example, the exponent for the bromine
concentration, x = 1, means that the reaction is first order with
respect to bromine. The exponent of 0 for the formic acid
concentration indicates that the reaction is zeroth order with
respect to formic acid. The sum of x and y is called the overall
reaction order. Thus, the reaction of bromine and formic acid is
first order in bromine, zeroth order in formic acid, and first order
(1 + 0 = 1) overall.

REACTION MECHANISMS

A balanced chemical equation does not tell us much about how a

reaction actually takes place. In many cases, the balanced equation
is simply the sum of a series of steps. Consider the following
hypothetical example. In the first step of a reaction, a molecule of
reactant A combines with a molecule of reactant B to form a molecule
of C:
A + B C

In the second step, the molecule of C combines with another molecule

of B to produce D:
C + B D

The overall balanced equation is the sum of these two equations:

Step 1: A + B C
Step 2: C + B D
A + 2B D

The sequence of steps that sum to give the overall reaction is called
the reaction mechanism. A reaction mechanism is comparable to the
route traveled during a trip, whereas the overall balanced chemical
equation specifies only the origin and the destination.
For a specific example of a reaction mechanism, we consider the
reaction between nitric oxide and oxygen:
2NO(g) + O2(g) 2NO2(g)

We know that NO2 does not form as the result of a single collision
between two NO molecules and one O2 molecule because N2O2 is detected
during the course of the reaction. We can envision the reaction
taking place via the following two steps:

2NO(g) N2O2(g)

N2O2(g) + O2(g) 2NO2(g)

In the first step, two NO molecules collide to form an N2O2 molecule.
This is followed by the step in which N2O2 and O2 combine to give two
molecules of NO2. The net chemical equation, which represents the
overall change, is given by the sum of the first and second steps:

Step 1: NO + NO N2O2
Step 2: N2O2 + O2 2NO2
Overall reaction: 2NO(g) + O2(g) 2NO2(g)

Species such as N2O2 (and C in the hypothetical equation) are called

intermediates because they appear in the mechanism of the reaction
but not in the overall balanced equation. An intermediate is produced
in an early step in the reaction and consumed in a later step.

REFERENCES:
Chemistry: Julia Burdge,UNIVERSITY OF IDAHO;Jason Overby,COLLEGE OF CHARLESTON
https://courses.lumenlearning.com/chemistryformajors/
The MCAT Chemistry Book:A Comprehensive Review of General Chemistry and Organic Chemistry for the
Medical College Admission Test
Ajikumar Aryangat