Physical Chemistry Chemical Equilibrium

CHEMICAL EQUILIBRIUM
EFFECTS OF PRESSURE/TEMPERATURE ON
HETEROGENEOUS EQUILIBRIUM
Heterogeneous Equilibria
A heterogeneous equilibrium is a system in which reactants and products are

found in two or more phases. The phases may be any combination of solid, liquid,
or gas phases, and solutions. When dealing with these equilibria, remember that
solids and pure liquids do not appear in equilibrium constant expressions.
For example, for the reaction:
Br2(l) ↔ Br2(g)
The equilibrium constant K is simply [Br2], with the concentration of the pure
liquid Br2 excluded.
Heterogeneous Equilibria Involving Chemical Reactions
For heterogeneous equilibria, the equilibrium constants, K, should be

expressed as a function of the concentrations of reactants and products of
solution or gases. For convenience, the activity of a solid or liquid is given as 1
(unity).
For example, when limestone or shell (of shell fish), CaCO3(s), is heated,
CO3 gas is released leaving the CaO as a solid. We write the reaction and
equilibrium constant in this form:
CaCO3(s)⇌CaO(s)+CO3(g), Kp=P(CO3)
since the activities of the solids are considered unity.

The Kp is used to mean that the equilibrium constant is expressed in terms of
partial pressures. In this example, Kp is the saturated partial pressure
of CO3 when CaCO3 and CaO solids are present, and no net change will take
place.
The Effect of Pressure
It follows that pressurization by the addition of an inert gas has no

effect on the equilibrium composition of the system (provided the gases
are perfect). Alternatively, the pressure of the system may be increased by
confining the gases to a smaller volume (that is, by compression).
The Effect Of Temperature
Le Chatelier’s principle predicts that a system at equilibrium will tend to

shift in the endothermic direction if the temperature is raised, for then energy
is absorbed as heat and the rise in temperature is opposed. Conversely, an
equilibrium can be expected to shift in the exothermic direction if the
temperature is lowered, for then energy is released and the reduction in
temperature is opposed. These conclusions can be summarized as follows:
a. Exothermic reactions: increased temperature favours the reactants.
b. Endothermic reactions: increased temperature favours the products.
DISTRIBUTION LAW
Definition of distribution law
Distribution law is the distribution of activity of the solute dissolved in two

solvents that do not dissolve each other. According to the distribution law stated
by Nernst in 1891, that a dissolved substance will divide itself between two
solvents that do not dissolve each other in such a way that the ratio of activity at
an equilibrium state and a certain temperature is constant.
Distribution law applies when:
1. Dilute solution
2. The solute has the same relative molecular mass for the two solvents
Distribution Coefficient
According to the Nernst distribution law, when two immiscible solvents are added
to a solute that can dissolve in the two solvents, there will be a distribution of
solubility. The two solvents are generally organic solvents and water. In practice the
solute will distribute itself into the two solvents after being shaken and allowed to
separate. The ratio of the solute concentration in the two solvents is fixed, and is a
constant at a constant temperature. The distribution coefficient is expressed by the
following formula:
Where :
KD = distribution coefficient
C2 = solvent concentration 2
C1 = solvent concentration 1
Co = concentration of organic solvent
Ca = Water solubility concentration
If the value for KD large, the quantitative solute will tend to be
distributed more into the organic solvent and vice versa.
The formula above only applies if:
a. The solute is not ionized in any of the solvents
b. The solute is not associated in any of the solvents
c. The solute cannot react with any of the solvents or there are other
reactions
Appeal Figures
The distribution comparison figure expresses the ratio of the total

solute concentration in an organic solvent (organic phase) and aqueous
solvent (aqueous phase). If the solute is compound X then the formula for
the distribution ratio can be written:
In ideal conditions and there is no association, dissociation or

polymerization, the value of KD equal to D. The value of D is not constant,
partly due to the pH of the water phase.
D's Relationship With KD
To see the relationship between the distribution ratio and the distribution
coefficient and the factors that influence it, we can study the extraction of
a weak acid based on one (HA) in aqueous and organic phases. It can be
formulated mathematically as follows:
Percent Extracted (% E)
The extracted percentage is the number of moles of the substance

extracted into the organic phase divided by the total number of moles in
the organic phase and the water phase times 100.This expression can be
written with the formula:
Can also be searched by this formula,

Extraction Selectivity
Often it is found that it is not possible to extract one solute without

following another. The ability to separate the two solutes depends on the
magnitude of comparative figures relative distribution of the solute.
Extraction Classification
1. Based on the Extracted Mixed Form
a. Solid-liquid extraction : The extracted substance is present in the

mixture in the form of a solid. This extraction is mostly carried out in
an effort to isolate the efficacious substances contained in natural
ingredients such as steroids, hormones, antibiotics, lipids in seeds.
b. Liquid-liquid extraction (solvent extraction) : The extracted substance
is present in a liquid mixture. Example: separation of iodine or metals
in water.
Extraction Classification
2. Based on the Implementation Process
a. Gradual extraction : Several ways can classify extraction systems. The

classic way is to classify according to the nature of the substance to be
extracted, as a chelate or associated ion system. However, the current
classification is on a more scientific basis, namely the extraction process.
b. Continuous Extraction (until exhausted) : Extraction to completion
allows the separation of the components in the mixture which have a
less favorable distribution comparison value. A special apparatus is used,
in which the organic solvent is automatically distilled, cooled and flowed
continuously through the water layer. The extraction yield is equivalent
to several hundred times extraction using pure organic solvents, can be
obtained in approximately one hour using equipment that does not
require too much attention.
c. Extraction in the opposite direction according to Craig : This extraction
method is known as the Craig extraction method. This method is one
of the various ways to separate two or more substances, if the
distribution ratio (D) of these substances is very small. The "counter
current Craig" process is a gradual fractionation using special
equipment. The tool used in principle consists of a large number (can
be 100 or more) identical extracting tubes, which serve as a separation
funnel. In the next process, after matching to achieve distribution
equilibrium, the upper phase which is lighter than the lower phase is
transferred to the next number tube, which already contains the new
lower phase. This matching and moving was done repeatedly
Application of Distribution Law in
Everyday Life
Apart from being in the pharmaceutical sector. The law of distribution is

widely used in the solvent extraction process in analysis, including:
1. Giving out bromine and iodine in aqueous solution when the iodine
solution in water is shaken with carbon disulfide. The ion concentration
in disulfide can be separated by a separating funnel and done repeatedly.
In this way, the iodine concentration in the aqueous solution is small.
2. Test in quantitative analysis : Chromium pentaoxide is more soluble in
alcoholamyl than water by shaking a dilute solution in water in the
presence of chromate or H2O2.
3. Hydrolysis study : In the hydrolysis of a salt from a weak base with a
strong acid or a weak acid with a strong base there is an equilibrium
between the salt, base, or free acid.
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CHEMICAL EQUILIBRIUM

A heterogeneous equilibrium is a system in which reactants and products are

For heterogeneous equilibria, the equilibrium constants, K, should be

since the activities of the solids are considered unity.

It follows that pressurization by the addition of an inert gas has no

Le Chatelier’s principle predicts that a system at equilibrium will tend to

Distribution law is the distribution of activity of the solute dissolved in two

The distribution comparison figure expresses the ratio of the total

In ideal conditions and there is no association, dissociation or

The extracted percentage is the number of moles of the substance

Can also be searched by this formula,

Often it is found that it is not possible to extract one solute without

1. Based on the Extracted Mixed Form

a. Solid-liquid extraction : The extracted substance is present in the

2. Based on the Implementation Process

a. Gradual extraction : Several ways can classify extraction systems. The

Apart from being in the pharmaceutical sector. The law of distribution is

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