Osmotic Pressure and Its Measurement

Osmotic Pressure and its measurement:
Definition:
The osmotic pressure of a solution at a particular temperature may be defined as
the excess hydrostatic pressure that builds up when the solution is separated
from the solvent by a semi-permeable membrane. It is denoted by p.
“or”
Osmotic pressure may be defined as the excess pressure which must be applied
to a solution in order to prevent flow of solvent into the solution through the
semi-permeable membrane.
Explanation:
Osmotic pressure is a colligative property of solutions that is observed using a
semipermeable membrane, a barrier with pores small enough to allow solvent
molecules to pass through but not solute molecules or ions. The net flow of
solvent through a semipermeable membrane is called osmosis. The direction of net
solvent flow is always from the side with the lower concentration of solute to the
side with the higher concentration.
Demonstration of Osmotic Pressure:

Osmosis can be demonstrated using a U-tube which contains pure water in
the left arm and a dilute aqueous solution of glucose in the right arm. A net flow of
water through the membrane occurs until the levels in the arms eventually stop
changing, which indicates that equilibrium has been reached.
The osmotic pressure (ΠΠ) of the glucose solution is the difference in the pressure
between the two sides, in this case the heights of the two columns. Although the
semipermeable membrane allows water molecules to flow through in either
direction, the rate of flow is not the same in both directions because the
concentration of water is not the same in the two arms. The net flow of water
through the membrane can be prevented by applying a pressure to the right arm
that is equal to the osmotic pressure of the glucose solution.
The osmotic pressure of a solution depends on the concentration of dissolved
solute particles. Osmotic pressure obeys a law that resembles the ideal gas
equation:
nRT
Π= V =MRT
Where;
 MM is the number of moles of solute per unit volume of solution (i.e., the
molarity of the solution),
 RR is the ideal gas constant, and
 TT is the absolute temperature.
Measurements of osmotic pressure :

Following methods are used for the measurement of osmotic pressure,
 Pfeffer’s method,
 Morse and Frazer’s method,
 Berkeley and Hartley’s method,
 Townsend’s negative pressure method,
 De Vries plasmolytic method.
Theory and Measurement:

Jacobus van 't Hoff found a quantitative relationship between osmotic pressure and
solute concentration, expressed in the following equation:
Π=icRT
where Π is osmotic pressure, i is the dimensionless van 't Hoff index, c is
the molar concentration of solute, R is the ideal gas constant, and T is the
temperature in kelvins. This formula applies when the solute concentration is
sufficiently low that the solution can be treated as an ideal solution. The
proportionality to concentration means that osmotic pressure is a colligative
property.
Harmon Northrop Morse and Frazer showed that the equation applied to more
concentrated solutions if the unit of concentration was molal rather than molar;
[3] so when the molality is used this equation has been called the Morse equation.
For more concentrated solutions the van 't Hoff equation can be extended as a
power series in solute concentration, c. To a first approximation,
Π= Πo+Ac²
where Π is the ideal pressure and A is an empirical parameter. The value of the
parameter A (and of parameters from higher-order approximations) can be used to
calculate Pitzer parameters.
Empirical parameters are used to quantify the behaviour of solutions of ionic and
non-ionic solutes which are not ideal solutions in the thermodynamic
sense.The Pfeffer cell was developed for the measurement of osmotic pressure.
Concept of Azeotropic Mixture:

Definition:
An azeotropic mixture is a mixture of substances that has the same
concentration of vapour and fluid phases. It is basically a mixture that contains
two or more liquids. A zeotropic mixture basically has constant or same boiling
points and the mixtures’ vapour will also have the same composition as the
liquid.
Normally, we use distillation to isolate materials as the ideal solutions with one
part normally more volatile than the other. However, in an azeotropic mixture,
since the vapour and fluid concentrations will be the same and this approach will
prevent their separation.If the mixture deviates from Raoult’s Law then azeotropes
are formed and for azeotropes bubble point and dew points is the same. Mixtures
of non-azeotropic liquids under any circumstances are referred to as azeotropic.
The term is derived by combining the prefix "a," meaning "no," and the Greek
words for boiling and turning. The word was first used in a publication by English
chemists John Wade (1864–1912) and Richard William Merriman in 1911.
In contrast, mixtures of liquids that do not form an azeotrope under any conditions
are called zeotropic.
Types of Azeotropes:
Azeotropes may be categorized according to their number of constituents,
miscibility, or boiling points:
 Number of Constituents:
If an azeotrope consists of two liquids, it is known as a binary azeotrope. An

azeotrope consisting of three liquids is a ternary azeotrope. There are also
azeotropes made of more than three constituents.
 Heterogeneous or Homogeneous:
Homogeneous azeotropes consist of liquids that are miscible. They form a solution.
Heterogeneous azeotropes are incompletely miscible and form two liquid phases.
 Positive or Negative:
A positive azeotrope or minimum-boiling azeotrope forms when the boiling point

of the mixture is lower than that of any of its constituents. A negative azeotrope or
maximum-boiling azeotrope forms when the boiling point of the mixture is higher
than that of any of its constituents.
Examples:
 Boiling a 95% ethanol solution in water will produce a vapor that is 95%
ethanol. Distillation cannot be used to obtain higher percentages of ethanol.
Alcohol and water are miscible, so any quantity of ethanol can be mixed
with any quantity to prepare a homogeneous solution that behaves like an
azeotrope.
 Chloroform and water, on the other hand, form a heteroazeotrope. A mixture
of these two liquids will separate, forming a top layer consisting mostly of
water with a small amount of dissolved chloroform and a bottom layer
consisting mostly of chloroform with a small amount of dissolved water. If
the two layers are boiled together, the liquid will boil at a
lower temperature than either the boiling point of water or chloroform. The
resulting vapor will consist of 97% chloroform and 3% water, regardless of
the ratio in the liquids. Condensing this vapor will result in layers that
exhibit a fixed composition. The top layer of the condensate will account for
4.4% of the volume, while the bottom layer will account for 95.6% of the
mixture.
Azeotrope Separation:
Since fractional distillation cannot be used to separate components of an azeotrope,
other methods must be employed:
 Pressure swing distillation applies pressure changes to change the
composition of a mixture to enrich the distillate with the desired component.
 Another technique involves the addition of an entrainer, a substance that
alters the volatility of one of the azeotrope components. In some cases, the
entrainer reacts with a component to form a nonvolatile compound.
Distillation using an entrainer is called azeotropic distillation.
 Pervaporation involves separating components using a membrane that is
more permeable to one constituent than the other. Vapor permeation is a
related technique, using a membrane more permeable to the vapor phase of
one component than another.

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Osmotic Pressure and Its Measurement

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Osmotic Pressure and its measurement:

Demonstration of Osmotic Pressure:

Measurements of osmotic pressure :

Theory and Measurement:

Concept of Azeotropic Mixture:

If an azeotrope consists of two liquids, it is known as a binary azeotrope. An

A positive azeotrope or minimum-boiling azeotrope forms when the boiling point

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