Chapter 7

Kinetics & Equilibrium

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Lecture 1
General Chemical Rates
Essential Vocabulary terms:

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The time over which a chemical reaction takes place is referred to as the reaction rate and is studied by a branch
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of chemistry called Kinetics.

Importantly, kinetics is a purely empirical branch of chemistry. The Kinetic Molecular Theory (K.M.T.) which as
been used to study most of our chemistry so far in many respects breaks down when we try to understand how it is
that chemical reactions occur.

How reactions can be physically modeled is by the reaction mechanism, and this is how reaction rates are
often justified.

Essentially, the first mathematical step is to understand that all reaction rates are defined as:

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Rate =

[ Reactant(s)]t

[ Reactant(s)]t

t2 t1
or
[ Reactant(s)]
Rate =
t

However, as reactant concentration is always decreasing with time:

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Rate = -

[ Reactant(s)]
t

General rate influencing factors can be placed in the following categories, each of which can be explained by
K.M.T.:

Nature of Reactants: While not widely understood, some substances simply react faster than others due to their
unique quantum mechanical identities.

Surface Area: As particles are more widely dispersed, it becomes more likely that particle collisions can take
place. This in turn helps to increase the reaction flux, by giving a greater chance for activated complexes to form.

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Temperature: As temperature increases, the kinetic energy of particles increases. This means that any particle
collisions have a greater chance of forming activated complexes by increasing the energy of particle collisions and
increasing electron cloud overlap. Temperature increases reaction flux.

However a good approximation (in almost all cases) is that reaction rates double every 10 K. This can be written
as such:

T
10

R R 2
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2

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Concentration: Most importantly after the nature of the reactants is the concentration of the reactants for the
study of kinetics. With higher concentrations come a greater number of possible collisions so rates increase.
However, while all other conditions can be held constant, by its very nature, the concentration of reactants and
products must change during the course of a chemical reaction.

See the following graphs:

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Catalysis: catalysts and inhibitors are chemicals that only influence the rates of chemical reactions by lowering
the energy of a possible activated complex. Catalysis is little more than Haitian Voodoo!

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Rate Laws

Very importantly the rate of consumption during a chemical reaction will most probably decrease at a decreasing
rate during a chemical reaction. This means that graphical analysis becomes a vital tool in understanding kinetics.

Also, graphical analysis has difficulties that present problems with infinite solutions! However, the most important
graphical relationship between two variables is a linear curve. This is because it can always be described by only
one general equation:

y = mx + c
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y y2 y1
Strength of Character, Depth ofdy
where the gradient
of the line Knowledge.
=
=m
=
dx x x2 x1

In terms of kinetics, the rate of reaction is equal to:

[ Reactant(s)]
d [A]
Rate = =t
dt

Therefore a plot of reactant concentration vs. time displays the rate of a chemical reaction!

However, due to the complicated nature of reverse reactions and interruptions of reaction pathways by the
appearance of product molecules it is only the initial rate (soon after t = 0) of a chemical reaction that is actually
measured. In this way the reverse reaction is neglected (see graph).

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Let us consider the decomposition of nitrogen dioxide to become nitrogen monoxide and oxygen gas:

In this case the forward rate of the reaction is proportional to the initial concentration of the reactant molecules
thus:

Rate [ NO2 ]

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However, we are able to suggest
a rate
law by incorporating
a proportionality constant and an exponent to the
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concentration taken directly from the balanced chemical equation:

Rate [ NO2 ]
or
Rate = k [ NO2 ] Where n is the molar coefficient of the reactant
n

Rate = k [ NO2 ]

This can then be equated to our former statement:

[ Reactant(s)]
d [A]
a
b
c
Rate = == k [ A ] [ B] [C] ...
t
dt
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An expression of this type, which links rates to initial concentration(s), is called a Differential Rate Law.

Differential Rate Law: Commonly called the Rate Law, links reaction rate to the initial concentration of only the
reactants.

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Integrated Rate Law: Links how the concentration of a reactant depends on time.

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Do not confuse these two types of Rate Law! The type of rate law stated depends on the data given, and the
number of steps (mechanism) within the reaction. Also, the value of the rate constant is temperature dependant,
and the units of the rate constant can be rather confusing!

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Proposing Rate Laws

When proposing a rate law for a reaction, it is important to remember the concentration of the substance, and how
the rate graph will look.

-3

Firstly, solutions and gases both can have units of concentration (mol dm ) expressed for them, so reactants with
these phases always appear in the proposed rate law.

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However, both solids and Strength

liquids haveofnoCharacter,
ability to be
expressed
in terms of concentration. This is because the
Depth
of Knowledge.
rate at which the volume of substance changes as you add more of the substance is fixed. This is the density of
the substance!

When proposing a rate law, all pure solid and liquid reactants are ignored, and they do not appear in the rate law
e.g.:

The thermal decomposition of

potassium hydrogen sulphite is as follows:
KHSO3(s ) SO 2(g ) + KOH (s )

So a proposed rate law for the reaction is

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However, how do we plot a graph of this type of reaction to show a rate of consumption? The answer is to tweak
-3
the units of the graph. Instead of concentration (molreactant dm ) vs. time (t), we can use molreactant vs. time!

N.B. as pure solids and liquids have no concentration, their rates of consumption are constant. This means that
they obey zeroth order reaction kinetics. Also, watch out for the new units of the reaction rate!

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Proposed rate laws are seldom correct due to the complex nature of reactions and the concept of molecularity.

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Differential Rate Law & Order of Reaction

In many reactions, the rate of reaction changes as the reaction progresses. Initially the rate of reaction is relatively
large, while at very long times the rate of reaction decreases almost to zero (at which point the reaction is
complete). In order to characterize the kinetic behavior of a reaction, it is desirable to determine how the rate of
reaction varies as the reaction progresses.

A rate law is a mathematical equation that describes the progress of the reaction. There are two forms of a rate
law for chemical kinetics: the differential rate law and the integrated rate law. The differential rate law relates the
rate of reaction to the concentrations of the various species in the system.

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Differential Rate Laws can take on many different forms, especially for complicated chemical reactions. However,
most chemical reactions obey one of three differential rate laws. These rate Laws are characterized by their order
of reaction.

Each rate law contains a constant, k, called the rate constant. The units for the rate constant depend upon the
-3 -1
-3
rate law, because the rate always has units of mol dm s and the concentration always has units of mol dm .

The Order of the Reaction is the value of the exponent(s) to which the rate law raised. This can be confusing, as
orders can be specific to individual reactants or to whole chemical processes.

Zero-Order Reaction: For a zero-order reaction, the rate of reaction is a constant. When the limiting reactant is

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completely consumed, the reaction abruptly stops. This is the most bizarre of all chemical reactions and is not
easily supported by K.M.T. However, it is commonly seen in pure liquids and solids.

th

Differential Rate Law (0 Order):

[A]
R=
=k
t
A Graphical plot that is linear is of Concentration vs. Time e.g.

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However, if the reactant is pure solid or liquid a graphical plot that is linear is of Amount of reactant vs. Time e.g.

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The rate constant, k, has units of...

First-Order Reaction: For a first-order reaction, the rate of reaction is directly proportional to the concentration of
one of the reactants.

st

Differential Rate Law (1 Order):

R=

[A]
= k [A]
t

A Graphical plot that is linear is of ln Concentration vs. Time e.g.

The rate constant, k, has units of...

Second-Order Reaction: For a second-order reaction, the rate of reaction is directly proportional to the square of
the concentration of one of the reactants.

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Differential Rate Law (2

R=

nd

Order):

[A]
2
= k [A]
t

A Graphical plot that is linear is of the inverse of the Concentration vs. Time e.g.

The rate constant, k, has units of...

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These three behaviors are illustrated in the following plots. The graph at the left shows concentration-time plots for
zero-order (red line), first-order (green line), and second-order (blue line) reactions. The corresponding rateconcentration plots are shown at the right.

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This means that determining the order and character of a chemical reaction simply becomes a matter of graphical
and data analysis/manipulation. The key is to manipulate data until it becomes linear. This is called the method

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of graphical linearization.

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Elementary Reaction Kinetics

For many chemical reactions, an accurate rate law can be proposed from the balanced chemical equation itself.
This is achieved simply by stating the rate in terms of the reactants raised to the power of their molar coefficients
e.g.:

N2

(g )

+ 3H2

(g )

2NH3

(g)

R = k N2 H2

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This is possible due to the molecularity of the reaction. That means that the reaction moves in a fashion where
of Character,
Depth of Knowledge.
all molecules must collideStrength
to form one
activated complex.
Reactions can be unimolecular, bimolecular, and
termolecular etc.

Reactions that obey a proposed rate law are called Elementary. This means that the reactions occur in a single
step, directly from reactants, to activated complex, to products (in accordance with the molecularity of the
reaction). Elementary reaction kinetics is the simplest form of reaction kinetics to study.

For an elementary reaction we can express the Overall Order of the Reaction, or the Individual Order of a
single reactant e.g.:

R = k N2 H2
th

The overall order of this reaction is 4 order.

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The order of the reaction with respect to nitrogen is

The order of the reaction with respect to hydrogen is

In this manner, we can plot the linear graphs that confirm our rate law e.g.:

Considering nitrogen, to prove that it is __________ order, a plot of __________________ will be linear.

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Considering hydrogen, to prove that it is __________ order, a plot of __________________ will be linear.

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Considering the overall reaction, to prove that it is __________ order, a plot of __________________ will be
linear.

However, as the molecularity increases, it becomes increasingly less probable that the reaction takes place in this
manner (i.e. termolecular), and therefore the rate law is not valid in this form.

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Integrated Rate Law & Half Life

The differential rate law describes how the rate of reaction varies with the concentrations of various species,
usually reactants, in the system. Typically, the rate of reaction is proportional to the rates of change in
concentrations of the reactants and products; that is, the rate is proportional to a gradient (derivative) of a
concentration e.g.:

The rate of this reaction (R ) is given as:

[ A]
d [ A]
or R =
t
dt
Suppose this reaction obeys 1st order kinetics
R=

[ A]
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= k [ A]
t of Knowledge.
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Integrating this expression leads to...

Writing this in the linear form

This type of rate law is known as the Integrated Rate Law. This rate law is very useful for examining time
sensitive reaction issues, and is a common way of finding the reaction constant from experimental data.

Experimentally one almost always measures how the concentration of a reactant or product changes as the
reaction progresses. In previous notes, you saw how the gradient of the concentration-time curve is used to
determine the differential rate law for a reaction (method of graphical linearization).

In fact the integrated rate law enables chemists to find the half-life of a chemical reaction.

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For all chemical processes reversible reactions can occur while the products and reactants are mixed (i.e. during
the reaction), and because of this the amount of reactant and product will never meet their theoretical maximum
(theoretical yield) or minimum (run out of reactant). Because of these asymptotes, the idea of reaction completion
is very difficult to define.

At a basic level, reactions are complete when the rates of consumption and production are equal, opposite, and
unchanging. But at this time some reactant and product will still be present after an infinite period of time.

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Chemists use the conceptStrength

of a half-life
examine the
timeofit Knowledge.
takes for reactions to consume reactants. That is,
of toCharacter,
Depth
the amount of time it takes for the reaction to consume half of the original amount of reactant.

Do not be confused: Half-lives are equal through out the reaction, independent of their order, or where you start
the measuring the reaction.

The equations for half lives are generated as follows:

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Using the integrated form of the first order rate law we find that:
ln [R ]t = kt + ln [R ]0

( )

The half-life t 1 , is the time required for [R]

2

to drop from its initial value [R]0 (at t 0 ) to

[R]0
2

Substituting this gives...

Remember that half-lives are dependant on the rate constant and are unique to every reaction!

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Equilibrium

An important chemical concept is the reversibility of chemical processes. Many chemical reactions (if not all)
continually create products and reactants even when the chemical reaction is considered to be over. In fact, only
physical separation of the reactant/product mixture causes true chain termination in chemical reactions.

If we consider the Maxwell-Boltzman interpretation of matter, along with collision theory/chain theory, we see that
there are always some molecules with sufficient kinetic energy to produce small quantities of reactant or product
molecules.

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However, the logical conclusion is that such reactions are under kinetic control.

But what happens when the energy of an activated complex is very low with respect to the reactants and products,
and the enthalpy change of the reaction is also very low? This can produce a situation in which large amounts of
reactant and product are present when the reaction is over.

Again it must be stated that reactions are complete when reaction rates are equal opposite and unchanging.
Consider the following graphs:

However, we can now add to this that reactions are complete, when the rates and concentration of reactant &
product remain constant.

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These conditions produce a situation of dynamic equilibrium; this situation is very different to the static
equilibrium of the physical world.

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Law of Mass Action

In order to describe the nature of the equilibrium in terms of empirical evidence, two chemists proposed the Law of
Mass Action. This in itself has little inherent meaning, but rather provides a numerical value that describes the
position of the equilibrium (in terms of reactants and products).

The Law of Mass action is effectively a ratio of products and reactants:

[ PRODUCTS]

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[ REACTANTS
]
K eq =

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This means that the value of the equilibrium constant (Keq) is really a numerical ratio that discusses the amounts
(concentration) of reactants and products in an equilibrium mixture i.e.

K eq < 1
K eq = 1
K eq > 1

However, in this simplistic form we have not taken into account the molecularity of the reaction, so the law is
expressed as follows:

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K eq =

[ PRODUCTS]

[ REACTANTS]

For the following reaction:

aA + bB
c C + dD

[C ] [ D ]
K eq =
a
b
[A ] [ B]
c

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Again it must be stated that only solutions and gases can appear in the equilibrium expression. Also, the value of
the equilibrium expression Strength
is dimensionless
due to non-ideal
behavior.
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Depth of
Knowledge.

However, the value of the equilibrium constant is highly susceptible to changes in state.

Also, the value of the equilibrium constant can also be determined for the reverse reaction:

The Law of Mass Action can be widely applied, and it should be noted that all chemical reactions have Keq value,
it is simply that most chemical reactions have such extreme values that we state that the position of the equilibrium
is so far to the left or right of the reaction that we need not express it.

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If we consider the ammonia synthesis (Haber Process), we can determine the equilibrium constant from the
concentrations of system at equilibrium:

N 2(g ) + 3H 2(g )

[ N 2 ] = 2.59 mol dm-3

[ H 2 ] = 2.77 mol dm-3
[ NH 3 ] = 1.82 mol dm-3

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Le Chteliers Principle

Chemists and chemical engineers typically view reactions with a mind to increase the amounts of product
obtainable for any chemical process.

In 1888 French chemist Henri Louis Le Chtelier Developed a principle that predicted (with great accuracy) how
equilibrium positions (respectively the amounts of reactant and product in an equilibrium mixture) can be altered.
This has been said to be one of the boldest, simplest, most accurate statements in the history of science!

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Effectively stated the principle reads as follows:

Any system at equilibrium that is subjected to a chemical or physical stress (such as changes of state) will
accommodate that stress by moving the position of the equilibrium in such a manner that the stress is
relieved.

This statement is made possible by the very nature of the dynamic equilibrium within the equilibrium mixture.
However, it cannot be explained without a mind to examining the thermodynamic and kinetic nature of the reaction.

PRESSURE

Pressure changes effect only gases within the equilibrium mix.

Increasing pressure in effect increases the concentration of the gas. This in turn increases the

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rate at which the gas is consumed, so the system moves in a direction that consumes the gas.

The reverse is true for deceases in pressure.

After a brief period of initial instability, the position of the equilibrium will shift, but the value of
the equilibrium constant (Keq) will not be affected.

In order to increase the pressure, it is necessary to decrease to volume of the reaction

chamber. If another inert gas is introduced, no effect will take place.

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CONCENTRATION

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Concentration is effectively the state of amount, and as such affect the reaction rates.

Increasing concentration increases the rate at which the reagent is consumed, so the system
moves in a direction that consumes the reagent.

The reverse is true for deceases in concentration.

After a brief period of initial instability, the position of the equilibrium will shift, but the value of
the equilibrium constant (Keq) will not be affected.

As pure solids and liquids are not present in the equilibrium expression (and because they can
react with zeroth order kinetics) they have no impact on the equilibrium constant.

TEMPERATURE

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Because all Keq values are temperature dependant, both position and magnitude of the
equilibrium are effected.

Temperature changes affect reactions based upon their thermodynamic properties (endo, or
exo-thermic). It is best to view energy or temperature as a reactant or product, as such the
principle clearly states that increasing the temperature for exothermic reactions, shifts the
equilibrium position toward the reactants; and increasing the temperature for an endothermic
reaction, shifts the equilibrium toward the products.

The reverse is true for deceases in temperature.

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After a brief period of initial instability, the position of the equilibrium will shift, and the value of
the equilibrium constant (Keq) will be affected.

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Because the temperature change affects the value of the equilibrium constant, we state only
whether the magnitude of the constant is increased or decreased. This is because the ratio of
reactant and product has been upset.

CATALYSTS & INHIBITORS

Because catalysis only affects the rates of a reaction, as a forward rate increases (catalyst),
so must a reverse rate to compensate.

The reverse is true for inhibitors in temperature.

This means that neither the position nor the value of the equilibrium constant (Keq) is
effected.

Catalysis only affects the time it takes for a reaction to reach equilibrium.

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N.B: If reactions form heterogeneous products, there is a very good chance that the resulting products will not
form an equilibrium mixture. This means that the value of the equilibrium constant will be very high, and the
completed form of the reaction will contain very little of the original reactant molecules.

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Common Ion Effect & KSP

The shift in an equilibrium mixture can also be achieved through solubility rules.

Solubility is another state of equilibrium, and unsaturated, saturated, and super-saturated are all terms used to
express the position of the solubility equilibrium e.g.:

Unsaturated

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+1
1
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NaCl (sStrength
+
H
O
Na
+
Cl
2
)
(l)
(aq )
( aq )

Saturated

NaCl (s ) + H 2O (l)

Na +1

+ Cl (1aq )

Na +1

+ Cl (1aq )

( aq )

Super-saturated

NaCl (s ) + H 2O (l)

( aq )

Because of this, it is possible to shift the equilibrium by addition of more solute (obviously) or in a saturated
solution, by adding simply an ion that is common to the new solute and the existing one.

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This is called the common ion effect. It is used strongly in pH chemistry in what chemists call buffering solutions.

Another solubility equilibrium expression is the Solubility Product. This number is a mathematical expression that
relates the solubilitys of insoluble substances to the equilibrium constant of the dissolution process i.e.:

The solubility of calcium fluoride is extremely low at 1.7 mg100g H2O

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CaF + H O
Ca
+ 2F

+2
2 (s )
2 (l)
( aq )
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(aq )

If we write an equilibrium expression for this we can also determine the value of the equilibrium constant:

N.B: The clue to KSP calculations is in the name, it is only the product ions that count!

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