CHEMICAL EQUILIBRIUM

Chemical equilibrium can be defined as a balanced condition within a system of chemical

reactions. When in chemical equilibrium, substances form and break down at the same rate, and
the number of molecules of each substance becomes definite and constant. The ordinary laws of
chemical equilibrium have been applied to the case of the dissociation of a substance into its
ions. It is now know that the mass of enzyme does not influence the chemical equilibrium but
only the velocity of the reaction. An attempt to consider this factor was made by Claude Louis
Berthollet, who introduced the conception of chemical equilibrium.

In a chemical reaction, chemical equilibrium is the state in which both reactants and
products are present in concentrations which have no further tendency to change with time.
Usually, this state results when the forward reaction proceeds at the same rate as the reverse
reaction. The reaction rates of the forward and backward reactions are generally not zero, but
equal. Thus, there are no net changes in the concentrations of the reactant(s) and product(s). Such
a state is known as dynamic equilibrium.
 Basic Concepts of chemical equilibria
Consider the following gas-phase chemical reaction: H2 + I2 2 HI

Imagine a small mixing chamber into which gaseous H2 and I2 (substrates) are rapidly
introduced. Initially there is no HI (product), H 2 is present at 0.20 M concentration, and I 2 is
present at 0.024 M concentration. As time goes by, however, the hydrogen and iodine react to
form HI.
 As the reaction progresses, the concentrations of iodine and hydrogen decrease as they
are consumed while the concentration of hydrogen iodide increases as it is formed. Eventually,
however, the concentrations of all three species reach constant values. This behavior is as a result
of the back reaction in which hydrogen iodide dissociates to form iodine and hydrogen. Initially
there is no hydrogen iodide, so the back reaction cannot occur. As hydrogen iodide accumulates,
the back reaction becomes significant.

Eventually the rate at which iodine is being consumed by the forward reaction is perfectly
balanced by the rate at which it is being produced by the back reaction. The same is true for
hydrogen and hydrogen iodide. When the rates of forward and reverse reactions are perfectly
balanced in this way, the reaction is said to be at equilibrium.

The Law of Mass Action

When a chemical reaction reaches equilibrium, the concentrations of the reactants and products
obey the Law of Mass Action.

For the generic chemical reaction: aA+bB cC+dD

The Law of Mass Action is:

[C]c [D]d
KC =
[A]a [B]b

The uppercase letters represent chemical species while the lowercase letters represent the
corresponding stoichiometric coefficients. The notation [A] represents the molar concentration of
species A.

In this expression, the numerator contains the concentration of each product raised to the power
of its stoichiometric coefficient. The denominator contains the corresponding expression for the
reactants.

If the species are gases, an entirely analogous expression

may be written using partial pressures instead of molar
concentrations.
PCcPDd
 PAa PBb

One can convert between KC and KP using the ideal gas law: P=RTC
The equilibrium constant characterizes the "position" of the equilibrium:
KP =
The larger the equilibrium constant, the more the equilibrium favors products;

The smaller the equilibrium constant, the more the equilibrium favors reactants.

In an ideal system, the equilibrium constant depends only upon the

temperature of the system. Note that only species that are gases or solutes
appear in the equilibrium expression. Pure solids and pure liquids do not appear
in the expression.

The equilibrium constant KC applies to an equilibrium expression written in terms of molar

concentrations, and the equilibrium constant KP applies to an equilibrium expression written in
terms of partial pressures (with units of atm).

The concept of chemical equilibrium was developed after Berthollet (1803), who found
that some chemical reactions are reversible. For any reaction mixture to exist at equilibrium, the
rates of the forward and backward (reverse) reactions are equal. In the following chemical
equation with arrows pointing both ways to indicate equilibrium, A and B are reactant chemical
species, S and T are product species, and α, β, σ, and τ are the stoichiometric coefficients of the
respective reactants and products:

αA ….. + β B σS + ƭT
The equilibrium concentration position of a reaction is said to lie "far to the right" if, at
equilibrium, nearly all the reactants are consumed. Conversely the equilibrium position is said to
be "far to the left" if hardly any product is formed from the reactants.

Guldberg and Waage (1865), building on Berthollet’s ideas, proposed the law of mass action:

where A, B, S and T are active masses and k+ and k− are rate constants. Since at equilibrium
forward and backward rates are equal: and the ratio of the rate constants is also a constant, now
known as an equilibrium constant.

(Equilibrium constant) K = kproduct/kreactants

By convention the products form the numerator. However, the law of mass action is valid only
for concerted one-step reactions that proceed through a single transition state and is not valid in
general because rate equations do not, in general, follow the stoichiometry of the reaction as
Guldberg and Waage had proposed ( for example, nucleophilic aliphatic substitution by SN1 or
reaction of hydrogen and bromine to form hydrogen bromide).

Equality of forward and backward reaction rates, however, is a necessary condition for chemical
equilibrium, though it is not sufficient to explain why equilibrium occurs. Despite the failure of
this derivation, the equilibrium constant for a reaction is indeed a constant, independent of the
activities of the various species involved, though it does depend on temperature as observed by
the van 't Hoff equation. Adding a catalyst will affect both the forward reaction and the reverse
reaction in the same way and will not have an effect on the equilibrium constant. The catalyst
will speed up both reactions thereby increasing the speed at which equilibrium is reached.

Although the macroscopic equilibrium concentrations are constant in time, reactions do occur at
the molecular level. For example, in the case of acetic acid dissolved in water and forming
acetate and hydronium ions,

CH3CO2H + H2O ⇌ CH3CO2− + H3O+

a proton may hop from one molecule of acetic acid on to a water molecule and then on to an
acetate anion to form another molecule of acetic acid and leaving the number of acetic acid
molecules unchanged. This is an example of dynamic equilibrium. Equilibria, like the rest of
thermodynamics, are statistical phenomena, averages of microscopic behavior.

Le Chatelier's principle (1884) gives an idea of the behavior of an equilibrium system when
changes to its reaction conditions occur. If a dynamic equilibrium is disturbed by changing the
conditions, the position of equilibrium moves to partially reverse the change. For example,
adding more subsrates from the outside will cause an excess of products, and the system will try
to counteract this by increasing the reverse reaction and pushing the equilibrium point backward
(though the equilibrium constant will stay the same).

If mineral acid is added to the acetic acid mixture, increasing the concentration of hydronium
ion, the amount of dissociation must decrease as the reaction is driven to the left in accordance
with this principle.

If {H3O+} increases {CH3CO2H} must increase and {CH3CO2−} must decrease. The H2O is left
out, as it is the solvent and its concentration remains high and nearly constant.

J. W. Gibbs suggested in 1873 that equilibrium is attained when the Gibbs free energy of the
system is at its minimum value (assuming the reaction is carried out at constant temperature and
pressure).

What this means is that the derivative of the Gibbs energy with respect to reaction coordinate (a
measure of the extent of reaction that has occurred, ranging from zero for all reactants to a
maximum for all products) vanishes, signalling a stationary point. This derivative is called the
reaction Gibbs energy (or energy change) and corresponds to the difference between the
chemical potentials of reactants and products at the composition of the reaction mixture. This
criterion is both necessary and sufficient. If a mixture is not at equilibrium, the liberation of the
excess Gibbs energy (or Helmholtz energy at constant volume reactions) is the “driving force”
for the composition of the mixture to change until equilibrium is reached.

In thermodynamics, at constant temperature and pressure, one must consider the Gibbs
free energy, G, while at constant temperature and volume, one must consider the Helmholtz
free energy: A, for the reaction; and at constant internal energy and volume, one must consider
the entropy for the reaction: S.

In order to meet the thermodynamic condition for equilibrium, the Gibbs energy must be
stationary, meaning that the derivative of G with respect to the extent of reaction: must be zero.
It can be shown that in this case, the sum of chemical potentials of the products is equal to the
sum of those corresponding to the reactants. Therefore, the sum of the Gibbs energies of the
reactants must be the equal to the sum of the Gibbs energies of the products.