SOLUTIONS OF

NON
ELECTROLYTES
What is a solution?
A solution is a homogeneous mixture
A solute is dissolved in a solvent.
Solute is the substance being dissolved
Solvent is the medium in which the solute
dissolves
An aqueous solution has water as solvent

SATURATED
contains the max. no. of
solute that dissolves at
that temperature
SUPERSATURATED
Contains more than is
possible and are
unstable
Unsaturated solution Saturated solution
Solution
Unsaturated Saturated
Supersaturated
Super saturated solution
Solvent holds more solute than is normally possible
at that temperature.
These solutions are unstable; crystallization can
often be stimulated by adding a seed crystal or
scratching the side of the flask.
How Does a Solution Form?
1. Solvent molecules attracted to surface ions.
2. Each ion is surrounded by solvent molecules.
3. Enthalpy (DH) changes with each interaction
broken or formed.

It is a 3 step process
1. Separation of Solute
Must overcome IMF or ion-ion attractions in solute
Requires energy, ENDOTHERMIC ( + DH)

2. Separation of Solvent
Must overcome IMF of solvent particles
Requires energy, ENDOTHERMIC (+ DH)

3. Interaction of Solute & Solvent
Attractive bonds form between solute particles and
solvent particles
Solvation or Hydration (where water = solvent)
Releases energy, EXOTHERMIC (- DH)


Ways of Expressing
Concentrations of
Solutions
Mass Percentage
100


) / %( x
solution of mass
solute of mass
w w
100

) / %( x
solution of volume
solute of mass
v w
100


) / %( x
solution of volume
solute of volume
v v
Parts per Million (ppm) and
Parts per Billion (ppb)
10
9
solution of mass Total
solution in A of
X
Mass
ppb
10
6
solution of mass Total
solution in A of
X
Mass
ppm
Mole Fraction (X)
moles of A
total moles in solution
X
A
=
Molarity (M)
Because volume is temperature
dependent, molarity can change with
temperature.

mol of solute
L of solution
M =
Molality (m)
Because neither moles nor mass
change with temperature, molality
(unlike molarity) is NOT temperature
dependent.
mol of solute
kg of solvent
m =
Avogadro Number
Avogadro hypothesized that there was a
specific number that would represent the
number of atoms or molecules in a mole
of that atom or molecule.

The weight of that unit known as a mole
would be equivalent to the molecular
weight of the atom or molecule in grams.
(Mole = Molecular weight in grams)
According to this theory, one mole of carbon-12
would have a mass of 12 grams because carbon-12
has an atomic weight of 12.

One mole of hydrogen would weigh one gram

It would contain the same number of atoms as one
mole of carbon.

The magical number was, in fact, discovered to be
6.023E
23
(6.023 X 10
23
)

Equivalent weight (g/Eq)
It is the mass of one equivalent, that is the
mass of a given substance which will:
Supply or react with one mole of
hydrogen cations H
+
in an acidbase
reaction; or
Supply or react with one mole of electrons
e

in a redox reaction.
It is that weight of any atom/molecule
which displaces 1.008 g of H, 19 g of F or 8
g of O.
/mole equivalent
weight molecular
weight Equivalent
Normality (N)
The normality of a solution is the gram
equivalent weight of a solute per litre of
solution.

Normality is the only concentration unit
that is reaction dependent.
solution of L
A of weight Equivalent
Normality
Solutions of liquid in liquid
Ideal and Real solutions
Raoults Law
Deviation from Raoults law
Solutions of liquid in liquid
Liquid pairs
Completely
miscible
Partially
miscible
Completely
immiscible
Real
solutions
Ideal
solutions
Ideal solutions
Cohesion
Adhesion
No heat is evolved or absorbed during
mixing

Final volume of sol.= sum of both.

The properties of solution such as vapour
pressure, surface tension, viscosity etc are
the average of the two pure liquids.

Escaping tendency
Quantitative measure:
Pure substance: Molar free energy
Constituent of a solution: Partial molar free energy or
chemical potential
Ideal mixtures and intermolecular
forces
In a pure liquid, some of
the more energetic
molecules have enough
energy to overcome the
intermolecular attractions
and escape from the
surface to form a vapour.
The smaller the
intermolecular forces, the
more molecules will be
able to escape at any
particular temperature
Liquid A
If you have a second liquid, the same thing is true.

At any particular temperature a certain escaping
tendency
Liquid B
In an ideal mixture of these two liquids.

There will be equal evapouration and hence equal
vapour pressure
1:1
Solution of A + B
Vapour pressure
Vapour pressure or equilibrium vapour pressure is the
pressure of a vapour in thermodynamic equilibrium with its
condensed phases in a closed system.
3:2
Raoults Law (1887)
Partial vapour pressure of each volatile constituent is equal to
the vapour pressure of the pure constituent multiplied by its
mole fraction in the solution. Thus, for two constituents A and B,
PA = PA XA
PB = PB XB
PA and PB partial vapour pressure
XA and XB mole fraction concentration
PA and PB - vapour pressure of pure components

The total vapour pressure of the mixture is equal to
the sum of the individual partial pressures.

Total Vapour Pressure = P
A
+ P
B
E.g. if vapour pressure of ethylene chloride in the
pure state is 236 mm Hg at 50C, then in a solution
consisting of a mole fraction of 0.4 ethylene
chloride and 0.6 benzene, the partial vapour
pressure of ethylene chloride is 40% of 236 mm.

PA = PA XA
Pec = Pec Xec
Pec = 236 X 0.4
Pec = 94.4 mm
The presence of a non-volatile solute means that
fewer solvent particles are at the solutions
surface, so less solvent evapourates!

Escaping tendency decreases
Thus, in an ideal solution, when liquid A is
mixed with liquid B in a manner depending on
the mole fractions of A and B present in the
final solution.
This will diminish the escaping tendency of
each constituent, leading to a reduction in the
rate of escape of the molecules of A and B
from the surface of liquid.
The total pressure is the sum of the partial
pressures of all the constituents.
P = PA + PB

Real Solutions
Cohesion
Adhesion
Do not adhere
to Raoults law
Cohesion
Adhesion
OR
Deviation from Raoults Law
Positive Deviation
Negative deviation
Negative deviation
Cohesion
Adhesion
Vapour pressure of
solution less than
expected
These are cases where
the molecules break
away from the mixture
LESS easily than they do
from the pure liquids.
New STRONGER forces
must exist in the mixture
than in the original
liquids.
AB AA, or BB
Chloroform (A)
Acetone (B)
Solution of acetone in
chloroform


Dilution of chloroform (A) by the addition of acetone (B).

Addition of B to A tends to reduce the vapour pressure of A to
a greater extent than can be accounted for by the simple
dilution.

Chloroform and acetone manifest such attraction for one
another through the formation of a hydrogen bond further
reducing the escaping tendency of each constituent.





This pair forms weak compound, Cl
3
C-HO=C(CH
3
)
2

which can be isolated and identified.
H C
Cl
Cl
Cl
O C
CH
3
CH
3
Reaction between dipolar molecules, or between a dipolar
and a non polar molecule, may also lead to negative
deviations.
Positive deviation
Vapour pressure of
solution greater than
expected
These are cases where
the molecules break
away from the mixture
MORE easily than they
do from the pure liquids.
New WEAKER forces
must exist in the mixture
than in the original
liquids.
AB << AA, or BB
Cohesion
Adhesion
Ethyl alcohol (A)
Chloroform (B)
Solution of chloroform in
ethyl alcohol
Benzene +
Ethyl alcohol
Carbon
disulphide +
Acetone
Other
examples
Raoults law describes the behavior of either of the
component of a real liquid pair only when that
substance is present in high concentration and thus is
considered to be the solvent.
In such a situation Raoults law can be expressed as
Psolvent = Psolvent Xsolvent
It is valid only for the solvent of a nonideal solution
that is sufficiently dilute with respect to the solute. It
cannot hold for the component in low concentration,
that is, the solute in a dilute solution.
Lowering of vapour pressure
According to Raoults law, the vapour
pressure of a solvent over a dilute solution
is equal to the vapour pressure of pure
solvent multiplied by its mole fraction
=
1

1
---------------------- 1
Because the solute is non-volatile, the
vapour pressure of the solvent is identical
to the total vapour pressure of the solution
It is more convenient to express vapour
pressure of the solution in terms of the
concentration of the solute rather than
the mole fraction of the solvent, the
conversion maybe achieved as follows:

1
+
2
= 1

1
= 1
2
-------------------2
Where, X
1
= mole fraction of the solvent
X
2
= mole fraction of the solute
Substituting 2 in 1, we get
p =
1

(1
2
)

0
1
p =
1
0

1
=
2
=

1
+
2

1
=

In the above eq.
P = P1 P is the lowering of the
vapour pressure; and
P / P1 is the relative vapour
pressure lowering.
If the concentration of the solute is very
less, its number of moles in the
denominator can be ignored, thus the
equation would become:

1
=

1
=

2



AEROSOLS
Uses Raoults law.
It has a drug and a propellant.
Common propellants used:
Trichloromonofluoromethane (propellant
11)
Dichlorodifluoromethane (propellant 12)

Distillation of binary
mixtures
Distillation
Distillation is a widely used method for separating
mixtures based on differences in the conditions
required to change the phase of components of
the mixture.
To separate a mixture of liquids, the liquid can be
heated to force components, which have different
boiling points, into the gas phase.
The gas is then condensed back into liquid form
and collected.
vapourization of a liquid and
subsequent condensation of the resultant gas back
to liquid form Distillation

Boiling point
The boiling point of an element or a substance is the
temperature at which the vapour pressure of the
liquid equals the environmental pressure surrounding
the liquid (760 mm Hg)
Atmospheric
pressure
Vapour
pressure
Boiling
point
Volatile
Vapour
pressure
Boiling
point
Using BP to separate a mixture
of 2 liquids
Miscible liquids
In case of miscible liquids, it is more useful to plot
the boiling point of various mixtures determined at
atmospheric pressure against composition.

The process of distillation can be used to separate
more volatile solvent from less volatile solvent
because vapour of binary mixture is always richer
in the more volatile constituent.
Azeotrope / Azeotropic Mixture
Very large deviations from ideality lead to a special
class of mixtures known as azeotropes, azeotropic
mixtures, or constant-boiling mixtures.

Azeotrope is a special class of liquid mixture that
boils at a constant temperature at a certain
composition.

At this condition, it behaves as if it was one
component with one constant boiling point.
AZEOTROPES
Minimum
boiling
Maximum
boiling
Minimum-boiling azeotrope
The positive deviations from ideality are sufficiently
large
EXAMPLES
Ethanol-Water system which at 1 atm occurs at
89.4 mole percent ethanol and 78.2
o
C.
Carbon disulfide Acetone 61.0 mole% CS
2
,
39.25
o
C, 1 atm
Benzene - Water (29.6 mole% H
2
O, 69.25
o
C, 1 atm)
Maximum-boiling azeotrope
It occurs when the negative deviations are very
large
The total pressure curve in this case passes through
a minimum, giving rise to a maximum in
the temperature (i.e. boiling point)
EXAMPLES
Hydrochloric acid - Water (11.1 mole% HCl, 110
o
C,
1 atm)
Acetone - Chloroform (65.5 mole% chloroform,
64.5
o
C, 1 atm)
Nitric acid Water (68 mole% HNO
3
120
o
C, 1 atm)
Immiscible liquids
When 2 immiscible liquids are heated while being
agitated, each constituent independently exerts its
own vapour pressure as a function of temperature
as the other liquid does not exist
Boiling begins when the sum of the partial pressures
of the two liquids just exceeds the atmospheric
pressure
This principle is used in steam distillation
Steam Distillation
Organic substances
insoluble in water can
purified
Water insoluble substances
can separated at
temperature below their
degradation temperature
Water
1oo C
Bromo-
benzene
156.2 C
Mixture
95 C
Useful for separating volatile oils from plant tissue without
decomposing the oils
Solutions of gas in liquid
Henry's law
Distillation of binary mixtures
Henrys Law
The effect of partial pressure on solubility
of gases
At pressure of few atmosphere or less,
solubility of gas solute follows Henry Law
which states that the amount of solute
gas dissolved in solution is directly
proportional to the amount of pressure
above the solution
c = k P
c = solubility of the gas (M)
k = Henrys Law Constant
P = partial pressure of gas
Henrys Law & Soft Drinks
Soft drinks contain carbonated
water water with dissolved
carbon dioxide gas.
The drinks are bottled with a CO
2

pressure greater than 1 atm.
When the bottle is opened, the
pressure of CO
2
decreases and the
solubility of CO
2
also decreases,
according to Henrys Law.
Therefore, bubbles of CO
2
escape
from solution.
Henrys law applies to the
SOLUTE and
Raoults law applies to the
SOLVENT
in dilute solutions of real liquid
pairs.

Colligative properties of
solutions
Properties of solutions
Solutions have properties different from both solute
and solvent
4 types of properties
Additive Constitutive Colligative
Additive &
Constitutive
Additive properties
Additive Properties: Additive properties
are those properties which is the sum of
the corresponding properties of the atoms
constituting the molecule.
These properties only depend on the
types of the atom and their numbers
e.g., mass is a additive property, similarly
molar volume is also a good example of
additive properties.
Constitutive properties
Constitutive property of a molecule is the
property which depends upon the
constitution of the molecule
i.e., upon the arrangements of atoms
within the molecule e.g.,
Optical activity.
Additive and constitutive
properties
The physical property which depend
upon the number of atom in a molecule
as well as their constitution
e.g., atomic volume, parachor etc.
Colligative properties
Colligative properties are those properties,
which depends upon the number of
molecules present in a substance

e.g., vapour pressure of gas, elevation in
boiling point, depression of freezing point,
osmotic pressure of the solution, etc.
Lowering of
vapour pressure
Lowering of vapour pressure
Pressure is measured with a manometer
When a non volatile solute is combined with a
volatile solvent, the vapour above the solution
is provided by the solvent only.
Solute reduces the escaping tendency of
solvent.
Vapour pressure of a solution containing a
non volatile solute is lowered proportional to
the relative number of the solute molecules.
Therefore the vapour pressure of the solvent,
P1 is identical to the total pressure of the
solution, P.

The presence of a non-volatile solute means that
fewer solvent particles are at the solutions
surface, so less solvent evapourates!

Escaping tendency decreases
It is more convenient to express the vapour
pressure of the solution in terms of concentration of
solute rather than the mole fraction of solvent
The sum of the mole fractions of the constituents in
a solution is unity:
X1 + X2 = 1
X1 = 1 X2
Where,
X
1
is the mole fraction of the solvent; and
X
2
is the mole fraction of the solute.

Raoults eq.
In the above eq.
P = P1 P is the lowering of the
vapour pressure; and
P / P1 is the relative vapour
pressure lowering.
Determination of
vapour pressure of
solutions
1. Manometer - Isopiestic
method
2. Hill and Baldes Apparatus
3. Wescor Method

Manometer
vapour pressure lowering is obtained by
subtracting the vapour pressure of the solution
from the vapour pressure of the pure solvent.







Vapour
pressure of
solution
Vapour
pressure
lowering
Vapour
pressure of
solvent


Apparatus for the isopiestic method
The vapour pressure of KCl solution of
various concentrations have been
determined accurately and thus the
vapour pressure of the test solution that
is isopiestic is thus readily obtained.
Isopiestic method is used for precise determination of
vapour pressures.
Hill and Baldes Apparatus

It consists of combination of wires of different alloys
formed onto two loops and connected to a
galvanometer.
Used for determining the relative vapour pressure of
small amounts of liquids.
This thermoelectric method measure the change in
potential with respect to change in vapour
pressure.
The solution of known vapour pressure and an
unknown evapourate in a chamber maintained at
constant humidity.
Vapour pressure lowering of solution is then
obtained from a standard curve of vapour pressure
versus galvanometer readings of potential.
This method is used to study the colligative
properties of ophthalmic solutions.
Wescor vapour pressure osmometer.
It is the fastest and easiest method of determining
osmolality.
Therefore it is the method of choice for most of the
fluids in biology and medicine in which water is the
solvent.
The test solution is absorbed onto a filter paper disk
which is usually 2 to 10 L.
The disk is placed in a sealed chamber near the
thermocouple, which is cooled below the dew
point of the solution.
Thermocouple is then equilibrated to the dew point
of the solution whereupon its potential is recorded.
The potential determined is proportional to the
vapour pressure lowering.
Reference standard solutions are used to calibrate
the potential readings against known vapour
pressures at the ambient temperature.
This instrument has been applied to quantitating
sodium in isotonic solutions and studying the
colligative properties of parenteral solutions.

This instrument is also called as vapour pressure
differentiometers as it does not involve
membrane diffusion operation.

Elevation of
boiling point
Normal boiling point is the temperature at
which the vapour pressure of the liquid
becomes equal to an external pressure of 760
mm Hg.
A solution will boil at higher temperature than
will the pure solvent.
The more the solute will be dissolved the
greater will be the boiling point elevation.
The boiling point of a solution of a non
volatile solute is higher than that of the pure
solvent because the solute lowers the vapour
pressure of the solvent.


Greater solute
Greater
elevation
Colligative
property
The vapour pressure curve for
the solution is below that of
the pure solvent, and the
temperature of the solution
must be elevated to a value
above that of the solvent in
order to reach the normal
boiling point.
The elevation of the boiling
point is shown in the fig as T-
T
0
= T
b
.
The ratio of the elevation of
the boiling point, T
b,
to the
vapour pressure lowering, p
= p
0
- p at 100C is constant at
this temperature.
P
0
is constant the boiling point elevation may be considered
proportional to p/ p
0
the relative lowering of vapour pressure.
By Raoults law the relative vapour pressure lowering is equal
to the mole fraction of the solute therefore
T
b
= kX
2
Boiling point elevation depends only on the mole fraction of
the solute.
In dilute solutions X
2
= m/(1000/M
1
) can be written as
T
b
= kM
1
m or T
b
= K
b
m
1000
Where T
b
is known as the boiling point elevation and K
b
is
called the molal elevation constant or the ebullioscopic
constant.


K
b
has a characteristic value for each solvent.

It may considered as the boiling point
elevation for an ideal 1m solution.

K
b
is the ratio of the boiling point elevation to
the molal concentration in an extremely dilute
solution in which the system is approximately
ideal.




After applying Clapeyron equation it is written as


Where,
V
v
and V
1
are the molar volume of the
gas and the molar volume of the liquid,
T
b
is the boiling point of the solvent, and
H
v
is the molar heat of vapourization.
V
v
the volume of 1 mole of gas is replaced by RT
b
/P
V
1
is negligible compared to V
v
the equation becomes
OR
but p/ P
1
= X
2
and this equation can be written as
The above equation provides less exact expression
with which to calculate T
b
.
The proportionality between T
b
and the molality is
exact only at infinite dilution at which the
properties of real and ideal solutions coincide.
The ebullioscopic constant, K
b
, of a solvent can be
obtained experimentally by measuring T
b
at
various molal concentrations and extrapolating to
infinite dilution (m = 0)
In case of very dilute solutions,

Thus,
Determination of boiling point elevation
Boiling point elevation is
determined experimentally by
placing a weighed amount of
the solute and the solvent in a
glass vessel provided with a
thermometer and a reflux
condenser.
In Cottrell boiling point
apparatus the vapour and
the boiling solvent are
pumped by the force of
ebullition through a
glass tube and sprayed
over the thermometer
bulb to obtain an
invariant equilibrium
temperature.
Landsberger-Beckmann
boiling-point apparatus

Freezing point
depression
Freezing point/ melting point temperature at
which solid and liquid phases are in equilibrium
under a pressure of 1 atm.
When solute is added, FP < Normal FP
FP is depressed when solute inhibits solvent
from crystallizing.

When solution freezes the solid form is
almost always pure.







Solute particles does not fit into the crystal
lattice of the solvent because of the
differences in size.
The solute essentially remains in solution and
blocks other solvent from fitting into the
crystal lattice during the freezing process.
A situation exists similar to elevation of boiling point.
Freezing point depression is proportional to molal
concentration of the solute
T
f
= K
f
m
Where, T
f
freezing point depression
K
f
molal depression constant or cryoscopic constant
Determination of freezing
point depression
2 methods
1. Beckmann method
2. Equilibrium method
Beckmann method
Temperature is read on
the Beckmann
differential
thermometer at freezing
point of pure solvent
A known weight of
solute is introduced to
the solvent
Freezing point is then
recorded.
Equilibrium method
Most accurate method
The freezing point of
pure solvent is
determined by intimately
mixing the solid and
liquid solvent (eg. Water
and ice) in a jacketed
tube
Temperature is read with
a Beckmann
thermometer
Beckmann differential thermometer
K
b
and K
f
values of some solvents
Applications
Salting of snow
Antifreeze used in car batteries
Propylene glycol, glycerol, honey etc
Elevation of boiling point and
depression of freezing point can help
in determining molecular weights of
substances
Osmotic Pressure
Diffusion both the solute and solvent molecules
travel freely
Osmosis only solvent molecules pass through the
semi permeable membrane.
Passage of solvent molecules through a
semipermeable membrane, from an area of low
solute concentration to an area of high solute
concentration is called as osmosis.
This happens by equalization of escaping
tendency of the solvent on both the sides
of the membrane.
Escaping tendency can be measured as
osmotic pressure.

Osmotic Pressure - The Pressure that
must be applied to stop osmosis

Preparation
Addition of non-volatile solute to solvent
Lowering of vapour pressure
Setup
Pure solvent is placed adjacent to above solution but
separated by semipermeable membrane
Solvent molecule pass through membrane into the solution to
dilute out the solute and to raise the vapour pressure back to
original value
Measurement
Osmotic pressure is measured by:
Measuring the hydrostatic head appearing in the solution
Applying a known pressure which just balances the osmotic
pressure
Osmotic pressure lowering of vapour
pressure
Works on the principle of
thistle tube apparatus
Once equilibrium is
obtained, height on the
solution side of the
membrane is greater than
the height on the solvent
side
= hg
osmotic pressure
h difference in heights
solution density
g acceleration due to
gravity
Measurement of osmotic
pressure
Two methods:
Measuring the hydrostatic head
appearing in the solution NOT USED
Applying a known pressure which just
balances the osmotic pressure i.e. there is
no passage of solvent molecules through
the semipermeable membrane
Pressure can be measured by a
manometer or by more sensitive electric
techniques

vant Hoff equation
1886 Jacobus vant Hoff recognised a
relationship between osmotic pressure,
concentration and temperature
He concluded that,
op in a dilute
solution
pressure that the
solute would exert if it
were a gas
occupying the same
volume
Where,
osmotic pressure in atm
V volume of solution in liters
n number of moles of solute
R gas constant
T absolute temperature
V = nRT
V
nRT

Where,
c = concentration of solute in
moles/ liter (molarity)
Morse equation
He proved that if concentration when
expressed in terms of molality rather
molarity, the experimental results were
more accurate.

= RTm
A cell placed in an
isotonic solution. The
net movement of water
in and out of the cell is
zero because the
concentration of
solutes inside and
outside the cell is the
same.

If the solute
concentration
outside the cell is
greater than that
inside the cell, the
solution is
hypertonic.

Water will flow out of
the cell, and
crenation results.
Cells
shrink
If the solute
concentration outside
the cell is less than
that inside the cell,
the solution is
hypotonic.

Water will flow into
the cell, and
hemolysis results.
Cells
burst
Reverse osmosis
Osmotic pressure can be used in
determination of the molecular weight of
substances Choice of colligative
property for
determination of
molecular weight
Boiling point
elevation
Solute is non-
volatile
Doesnt
decompose
at bp
Freezing point
depression
Solute should
be volatile
High
accuracy for
solutions of
small
molecules
Osmotic
pressure
No difficulties
Widely used
for molecular
weight
determination
of polymers
Reference:
Physical Pharmacy by Martin