Introduction

In this module, we attempt to explain the area of physical chemistry known as ( chemical)
kinetics, which involves the concept of "how fast" a reaction occurs. Do note that calculus is
crucial for a field like kinetics, but we will still provide high-level math warnings when it does
show up from time to time.

As of right now, the world of chemical kinetics has not matured to a point where they are
built upon three simple laws (like classical thermodynamics), or any set of unifying
principles. There are many different theories proposed in terms of how chemical kinetics
functions, but each has their own pros and cons (kind of like real gases, like you saw earlier).

We will first look into chemical kinetics from a macroscopic perspective, in which we will
learn about reaction rates and rate laws. Then, we will attempt to make connections with
these concepts with the microscopic world, in which we will introduce elementary
reactions and reaction mechanisms.

Rate Laws
Reaction rates
In order to determine how fast an object is moving, we use velocity. Similarly, to determine
how fast a reaction occurs, we use reaction rate.

To qualitatively determine how fast an object is moving, we must first determine the extent
of how far an object traveled. The easiest (if not only) metric to measure this concept is
displacement, or the difference between the initial position and the final position.
Similarly, to determine how fast a reaction occurs, we must first determine the extent of
reaction. A common metric to measure this concept is the change in concentration of any
of the reactants or products (In gas phase reactions, pressure is often used as well).

Given the general reaction described by

𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷

An example of the rate of the reaction is expressed as below:

∆[𝐴]
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴 = − Δ𝑡

CMA #1: In kinetics, all rates should be positive values. As shown in the expression above, 𝛥[A]
should be a negative value because the reactant is being consumed. Therefore, a negative sign is added
to make the overall expression a positive value. If you end up with a negative reaction rate, you have
already failed as a chemist.

CMA #2: It is crucial that you illustrate both the chemical equation and what speices is being utilized
to measure the rate of the reaction, especially when reactants or products have different coefficients.

Why?: Given a reaction 2A + B → C, two molecules of A and one molecule of B are

consumed, so we expect the rate of consumption of A to be two times greater than the rate
of consumption of B.

As most people are lazy, (unique) reaction rates are utilized to avoid this annoyance. The unique
reaction rate can be calculated as shown below:

1 ∆[𝐽]
υ= 𝑣𝐽 Δ𝑡

Where 𝑣𝐽is the coefficient of the species, and ∆[𝐽]is the change in concentration of the species. Do note
that you still need to report the chemical equation if it is not already present in your exam.

Calculus Alert!

Often, the instantaneous reaction rate is much more valuable than the average reaction rate.
The instantaneous reaction rate is the rate of the reaction at a certain instant, which can be
calculated by taking the derivative of concentration with respect to time:

𝑑[𝐴]
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴 = − 𝑑𝑡
In competitive chemistry, you'll often see the former in terms of algebraic expressions or
differential equations, and you'll see the latter when the question wants you to calculate it.

Rate Laws
For most, if not all of the reactions we are considering in this module, the unique reaction
rate is related to the concentrations of the reactants and products present at a given
instant. This relationship is known as the rate law, and will be used extensively throughout
your chemistry career. A general expression for the rate law of reaction A + B → P is shown
below.

𝑛 𝑚
υ = 𝑘𝑟[𝐴] [𝐵]

Do not forget that they are experimentally determined; they cannot be derived from a
chemical equation alone. This becomes obviously clear with two very similar reactions yet
totally different rate laws:

Chemical Equation Rate law

1/2
H2 (g) + Br2 (g) → 2 HBr (g) 𝑘𝑎[𝐻2][𝐵𝑟2]
υ= [𝐵𝑟2]+𝑘𝑏[𝐻𝐵𝑟]

H2 (g) + I2 (g) → 2 HI (g) υ = 𝑘𝑟[𝐻2][𝐼2]

the value 𝑘𝑟 is known as the rate constant, which is dependent on temperature. The units of
the rate constant will depend on the order of the reaction, but it will always ensure the units
of the unique reaction rate is concentration over time.

which is dependent on the values n and m. If n is equal to 1, the general reaction A + B → P is

first order with respect to A, if m is equal to 2, it is second order with reaction to B, and if
both n = 1 and m = 2, the overall order of the reaction is third order. The values of n and m
do not have to be integers. They can be fractions, negative values, or even zero.

Tip #1: Throughout competitive chemistry, checking units can give you a lot of help in terms of
determining the overall order of the reaction, or checking errors. Make sure the unique reaction rate
always ends with concentration over time!

Rate laws are an extremely powerful tool, and most problems related to kinetics will involve
rate laws. If you know the rate law, you can predict the reaction rate at any composition and
any time.
Determining Rate Laws
There are two very common ways that rate laws are determined. The first method is one
that you may have already mastered in your general chemistry course, and is known as the
method of initial rates.

The method of initial rates takes the reaction rate at the beginning of the reaction at
different initial concentrations of reactants. When determining the rate order, all except one
of the species' concentration is held constant, and one is varied.

Because the differential d[A]/dt cannot be determined, the average reaction rate at the very
beginning of the reaction is taken. (In easier words, the average reaction rate from 𝑡 = 0 to
𝑡 = 𝐴 𝑛𝑢𝑚𝑏𝑒𝑟 𝑐𝑙𝑜𝑠𝑒 𝑡𝑜 𝑧𝑒𝑟𝑜. The smaller the ∆𝑡, the more accurate)

∆[𝐴] 𝑑[𝐴]
∆𝑡
= 𝑑𝑡

The rates of reaction for two sets of initial conditions (where, [A] is held constant and [B] is
varied) for a general reaction:

𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷

are given by:

𝑛 𝑚
υ1 = 𝑘𝑟[𝐴]0[𝐵]1

𝑛 𝑚
υ2 = 𝑘𝑟[𝐴]0[𝐵]2

If υ1is divided by υ2, and the logarithm is taken of both sides, and then it is solved for m, we
obtain:

υ1
ln𝑙𝑛 υ2
𝑚= [𝐵]1
ln𝑙𝑛 [𝐵]2

The order of [A] can also be determined in a similar way.

CMA #3: Data of initial rates are far more valuable than rates at any other instance as they ignore the
presence of products, which can affect the overall rate of the reaction. Make sure the data you are using
are indeed initial rates.

The second method is known as the method of isolation. This involves having some of the
species to be in a large excess in comparison to the others.

Using the general reaction above, for example, if [𝐴]≫[𝐵], then we could assume that [𝐴]
stays relatively constant throughout the reaction. Therefore, if the true rate law is:

𝑛 𝑚
υ = 𝑘𝑟[𝐴] [𝐵]

We could approximate that:

𝑚
υ = 𝑘'𝑟[𝐵]

𝑛
Where 𝑘'𝑟 = 𝑘𝑟[𝐴] . The order of [B] can also be determined in a similar way (by holding [B] in
a large excess in comparison to [A].)

In competitive chemistry, you will sometimes always come across one or the other, but you
may also have to utilize both. Check Challenge Problem 1 for an example.

Integrated Rate Laws

Calculus Alert!

Integrated rate laws are found by taking the integral of the rate law. Given the general
reaction:

𝐴 + 𝐵→𝑃

Just as a reminder, the chemical equation is independent of rate law.

First-order to A
𝑑[𝐴]
υ =− 𝑑𝑡
= 𝑘[𝐴]

Taking the integral of this equation gives:

 [𝐴] −𝑘𝑡
ln 𝑙𝑛 [𝐴]0
=− 𝑘𝑡 or [𝐴] = [𝐴]0𝑒 or ln 𝑙𝑛 [𝐴] = ln 𝑙𝑛 [𝐴]0 − 𝑘𝑡

The first-order reaction undergoes exponential decay. The larger the rate constant, the
faster the species decays.

The first-order integrated rate law has a constant half-life independent of the concentration
of reactants. This is only true for first-order reactions.

ln𝑙𝑛 2
𝑡1/2 = 𝑘

The plot of ln 𝑙𝑛 [𝐴] vs. 𝑡 is linear for first-order reactions.

Second order to A
𝑑[𝐴] 2
υ =− 𝑑𝑡
= 𝑘[𝐴]

Taking the integral of this equation gives:

1 1
[𝐴]
= [𝐴]0
+ 𝑘𝑡

The half-life of second-order reaction is:

ln𝑙𝑛 2
𝑡1/2 = 𝑘[𝐴]

The plot of 1/[𝐴] vs. 𝑡 is linear for second-order reactions. Decay of second-order reactions
tend to be much slower in comparison to first-order reactions. Many pollutants tend to be
second-order.

Zeroth-order to A
For zeroth-order reactions, the rate of the reaction is constant independent of the
concentration of the reactant.
𝑑[𝐴]
υ =− 𝑑𝑡
=𝑘
Taking the integral of this equation gives:

[𝐴] = [𝐴]0 + 𝑘𝑡

The plot of [𝐴] vs. 𝑡 is linear for zeroth-order reactions.

Integrated Rate Laws

Order Reaction type Rate law Integrated Rate Law Half-life

0 A→P 𝑣 = 𝑘𝑟 [𝐴]𝑡 = [𝐴]0 − 𝑘𝑟𝑡

1 A→P 𝑣 = 𝑘𝑟[𝐴] ln 𝑙𝑛 [𝐴]𝑡 = ln 𝑙𝑛 [𝐴]0 − 𝑘𝑟 𝑡1/2 =

ln𝑙𝑛 2
𝑘𝑟

2 A→P 𝑣 = 𝑘𝑟[𝐴]
2 1
−
1
=− 𝑘𝑟𝑡 𝑡1/2 =
1
[𝐴]0 [𝐴]𝑡 𝑘𝑟[𝐴]0