10

Solutions
Solution is a homogeneous mixture of two or more substances in same
or different physical phases. The substances forming the solution are
called components of the solution. On the basis of number of
components a solution of two components is called binary solution.
Solute and Solvent
In a binary solution, solvent is the component which is present in large
quantity while the other component present in small quantity is
known as solute.

Classification of Solutions
(A) Following types of solutions are seen on the basis of physical state
of solute and solvent.
S.No. Solute Solvent Examples
Solid solutions
1. Solid Solid Alloys (Copper dissolved in gold)
2 Liquid Solid Hydrated salts, Amalgam of Hg with Na
3 Gas Solid Solution of hydrogen in palladium
Liquid solutions
4 Solid Liquid Salt/sugar solution in water
5. Liquid Liquid Alcohol in water
6 Gas Liquid Aerated drinks, O, in water
Gaseous solutions
7 Solid Gas lodine vapour in air
8 Liquid Gas Water vapour in air
9. Gas Gas Air (0, + N,)

If water is used as a solvent, the solution is called aqueous solution

and if not, the solution is called non-aqueous solution.
122 Handbook of Chemistry

(B) Depending upon the amount of solute dissolved in a solvent we

have the following types of solutions:
(i) Unsaturated solution A solution in which more solute
can be dissolved without raising temperature is called an
unsaturated solution.
(ii) Saturated solution A solution in which no more solute can
be dissolved further at a given temperature is called a saturated
solution.
(iüi) Supersaturated solution A solution which contains more
solute than that would be necessary to saturate it at a given
temperature is called a supersaturated solution.

Concentration of Solutions
The concentration of a solution is defined as the relative amount of
solute present in a solution. On the basis of concentration of solution,
there are two types of solutions:
(i) Dilute solution Solution containing relatively very small
quantity of solute.
(ii) Concentrated solution Solution containing relatively very
large quantity of solute.
Methods of Expressing Concentration of Solutions
Various expression for the concentrations of solutions can be
summarised as
(i) Percentage by weight (w/w %) It is defined as the amount
of solute present in 100 g of solution.
weight of solute
Wo = weight × 100
of solution
(ii) Percentage by volume (u/V%) It is defined as the volume of
solute present in 100 mL of solution,
volume of solute X 100
%=
volume of solution
(iii) Percentage of mass by volume (w/V%) It is defined as the
weight of solute present in 100 mL of solution.
%=
weight of solute x 100
V volume of solution
 Solutions 123

(iii) Mole fraction () It is defined as the ratio of the number of

moles of a component to the total number of moles of all the
components in solution. For a binary solution, if the number of
moles of Aand Bare n and ng respectively, the mole fraction of
A
will be
XA =
n nB
Similarly, XB= nB
n t nB

(iv) Parts per million (ppm) It is defined as the parts of a

component per million parts (10®) of the solution. It is widely used
when a solute is present in trace quantities.
number of parts of the component -x 106
ppm =
total number of parts of all the components
of the solution
(v) Molarity (M) It is the number of moles of solute present in 1L
(dm°) of the solution.
number of moles of solute
M=
volume of solution (L)
M=
mass of solute (in gram) x 1000
mol. wt. of solute x volume of solution (in mL)
Molarity varies with temperature due to change in volume of
solution. Its unit is g-molL.
IWhen molarity of a solution is 1M, it is called a molar solution.
0.1 M solution is called a decimolar solution while 0.5 M solution is
known as semimolar solution.
per cent by mass x density x 10
Molarity=
molecular weight
. Dilution law, M,V = M,V, (for dilution from volume V, to V,)
. For reaction between two reactants, MV_ M,V,
n
where, n, and n, are stoichiometric coefficients of reactants in
balanced equation.
" If two solutions of the same solute are mixed ten molarity of
the existing solution.
M= MV + MV
V + V2
124 Handbook of Chemistry
. Volume of water to be added to set a solution of molarity M,
from V, mL of molarity M, is
V,-V,=| M
- M2
M
(vi) Molality (m) Itis the number of moles of soluteper kilogram of
the solvent.
mass of solute in gram x 1000
Molality =
mol. wt. of solute x mass of solvent (in g)
Molality is independent of temperature. Its unit is g-mol/kg.

IWhen solvent used is water, a molar (1 M) solution is more

concentrated than a molal (1 M) solution.
(vii) Normality (N) The number of gram equivalents of solute
present in 1L of solution.
number of gram equivalents of solute
Normality
volume of solution (in L)
mass of solute in gram
Number of gram-equivalents of solute =
equivalent weight
Relationship between normality and molarity
Nxeg. weight = Mx mol. weight
If two solutions of the same solute having volumes and molarities
V,, M, and V, M, are mixed, the molarity of the resulting
solution is
M= V,M + VyM,
V + V2
Similarly, Normality ()= M+N,V,
To dilute V, mL of a solution having molarity M, to molarity M,
up to the final volume V, mL, the volume of water added is
V,-V,-M,.
M,
SimilarBy, V,-V,-Nv
N,
(viii) Formality (F) It is the number of formula weights of solute
present per litre of the solution.
moles of substance added to solution
Formality =
volume of solution (in L)
 Solutions 125

(ix) Mass fraction Mass fraction of any component in the solution is

the mass of that component divided by the total mass of the solution.
Mass % of a component = mass of the component
in the solution
X 100
total mass of the solution
Molality, mole fraction and mass fraction are preferred over
molarity, normality, etc., because former involve weights which
do not change with temperature.
(x) Demal (D) It represents one mole of solute present in lL of
solution at 0°C.

Solubility
The maximum amount of a solute that can be dissolved in a given
amount of solvent (generally 100 g) at a given temperature is termed
as its solubility at that temperature.
The solute can be either solid or gas. Likewise, solubility is defined as
the one of solid in liquid or the solubility of gas in liquid.
The solubility of a solute in a liquid depends upon the following factors:
Solubility of gases in liquids
All gases are soluble in water as well as in other liquids to a greater or
smaller extent.

Factors affecting solubility of gases

(i) Nature of the gas The gases which can be easily liquified, are
more soluble in common solvents.
(ii) Nature of the solvent The gases which are capable of forming
ions in aqueous solutions are much more soluble in water than
in other solvents.
(iii) Temperature The solubility of most gases in liquids decreases
with increase of temperature.
(iv) Pressure The solubility of a gases increase with increase in
pressure.

Henry's Law
The most commonly used form of Henry's law states the partial
pressure (p) of the gas in vapour phase is proportional to the mole
fraction (x) of the gas in the solution" and is expressed as
p= KHx
126 Handbookof Chemistry
Higher the value of KH at given pressure, the lower is the solubility of
the gas in the liquid. The value of Ky decreases with increase in the
temperature. Thus, aquatic species are more confortable in cold water
[more dissolved 0,] rather than warm water.

Partial
pressure
of solute

Mole fraction of component in its solution

Applications
1. In manufacture of soft drinks and soda water, CO, is passed at
high pressure to increase its solubility.
2. To minimise the painful effects (bends) accompanying the
decompression of deep sea divers, O, diluted with less soluble
He gas is used as breathing gas.
3. At high altitudes, the partial pressure of O, is less than that at
the ground level. This leads to low concentrations of 0, in the
blood of climbers which causes 'anoxia'.
Vapour Pressure
The pressure exerted by the vapour molecules above the liquid surface
in equilibrium with the liquid at a given temperature is called vapour
pressure.

Factors affecting vapour pressure

Vapour pressure gets affected by following factors.
() Purity of the liquid Pure liquid always has a vapour pressure
higher than its solution.
(ii) Nature of the liquid Liquids which have weak intermolecular
forces are volatile and have greater vapour pressure.
(i) Temperature The vapour pressure of a liquid increases with
increase in temperature.
(iv) Effect of adding solute When a liquid contains a solute, some
of the solvent molecules are replaced by the solute particles on
the liquid surface and therefore, the available surface area for
the escape of solvent molecule decreases. Therefore, rate of
evaporation as well as rate of condensation both decrease.
 Solutions 127

Raoult's Law
The Raoult's law states "For a solution of two volatile liquids, the
vapour pressure of each liquid in the solution is less than the
respective vapour pressure of the pure liquids and the equilibrium
partial vapour pressure of the liquid is directly proportional to its mole
fraction.
For a solution containing two liquids A and B, the partial vapour
pressure of liquid A is
PA XA
or PA = kxA
where, XA =
(na + ng)
= mole fraction of liquid A
The proportionality constant is obtained by considering the pure liquid
when, xA =1then k= på, the vapour pressure of pure liquid, hence,
PA = PÅ XA
Similarly, PB = PBXB
The total vapour pressure of the solution,
PT = PA + PB
= PÅ XA t PB XB

Rault's Law as a Special Case of Henry's Law

According to Raoult's law, the vapour pressure of a volatile component
in a given solution is given by p =1 P. In the solution of a gas in a
liquid, one of the components is s0 volatile that it exists a a gas and we
have already seen that its solubility is given by Henry's law which
states that
p=Ky .
If we compare the equations for Raoult's law and Henry's law and
Henry's law, it can be seen that the partial pressure of the volatile
component of gas is directly proportional to its mole fraction in
solution. Only the proportionality constant Ky differs from p. Thus,
law becomes a special case of Henry's law in which KH becomes equal
to p.
128 Handbook of Chemistry
pressure
Vapour
IdealSolutions
Those solutions in which solute-solute
(B -B) and solvent-solvent (A-A) P,
interactions are almost similar to
PB
solvent- solute (A-B) interactions are
called ideal solutions. These solutions
satisfy the following conditions : PA
XA =1+ XA =0
(i) Solution must obey Raoult's law, i.e., 0
Xe Xe =1
Mole fraction
PA = PÅXA P = PXB
(ii) AHmix = 0(No energy evolved or absorbed)
(ii) AV,mix = 0 (No expansion or contraction on mixing)
Some solutions behave like nearly ideal solutions, e.g., benzene +
toluene, n-hexane + n-heptane, ethyl iodide + ethyl bromide,
chlorobenzene + bromobenzene.

Non-ideal Solutions
Those solutions which shows deviation fromn Raoult's law are called
non-ideal solutions.
For such solutions,
AHmi, #0
AVmix #0
(a) Non-ideal solutions showing positive deviation In such
a case, the A- B interactions are weaker than A- A or B- B
interactions and the observed vapour pressure of each
component and the total vapour pressure are greater than that
predicted by Raoult's law.
PA > PÅXAi PB> PÂ X%B
Protal > PiXA + PBXB
For such solutions
AH mix 0, AVmix >0
Vapour
pressure pB Max
PAt
p>
Tdealsolution PB
PA PB
PA

XA =1 Mole fraction
XB =0 Xa =1
Non-ideal solution showing positive deviation
 Solutions 129

Examples : Ethanol + water, CS, + acetone, CCl, + CçHÇy

CCl, + CeH, CH,, ethanol + cyclohexane, CCl, + CHCL.
(b) Non-ideal solution showing negative deviation In such
a case, the A - B interactions are stronger than A - A or B- B
interactions and the observed vapour pressure of each
component and the total vapour pressure are lesser than that
predicted by Raoult's law.
PA < PÅXA PB< PBXB
Protal < Pi XA + PåxB
For such solutions,
AH mi, <0, AV.mix
Vapour
pressure
ldealsolution
p<PAp8
PA
MIN
PB

PA

XA =1 Mole fraction XA =0
XB =0 X8 =1
Non-ideal solution showng negative deviation
Examples : CHCl, + CH,C0CH,, CHC, +CçHe, H,0 + HCI,
H,0 + HNO3, methanol + acetic acid.

Azeotropic Mixture
A mixture of two liquids which boils at a particular temperature like a
pure liquid and distils over in the samne composition is known as
constant boiling mixtures. These are formed by non-ideal solutions.
i) Minimum boiling azeotropes are formed by those liquid
pairs which show positive deviation from ideal behaviour. Such
azeotropes have boiling points lower than either of the
components, e.g. C,H,OH (95.57%) + H,0 (4.43%) (by mass).
(ii) Maximum boiling azeotropes are formed by those liquid
pairs which show negative deviation from ideal behaviour. Such
azeotropes have boiling points higher than either of the
components, e.g. H,O(20.22%) + HCI [79.78%] by mass.
130 Handbook of Chemistry

Colligative Properties
[Colligative : from Latin = Co means together; ligate means to bind]
Colligative properties are those properties which depend only upon the
number of solute particles in a solution irrespective of their nature.
Relative Lowering of Vapour Pressure
When a non-volatile solute is added to a solvent, to vapour pressure is
solvent. Relative lowering in vapour pressure is the ratio of lowering in
vapour pressure to vapour pressure of pure solvent. The relative lowering
in vapour pressure of solution containing a non-volatile solute is equal to
the mole fraction of solute in the solution.
På PA= XB

where, PA PA = relative lowering of vapour pressure of pure solvent

PÅ
PÅ - PA r
for dilute solutions, n << n .
Hence,
PA - PA nB
n

P, - PA_ W; x M¡
M¡ x WA

Mp = WB MA X PA
WA (p - PA)
Above expression is used to find the molecular weight of an unknown
solute dissolved in a given solvent. where, Wh and W, = mass of solute
and solvent respectively, Ma and M, = molecular weight of solute and
solvent respectively.
Ostwald and Walker method is used to determine the relative lowering
of vapour pressure.
 Solutions 131

Elevation in Boiling Point (AT,)

Boiling point
Boiling point of a liquid is the Boiling point
of solvent of solution
temperature at which its vapour Vapour
pressure
becomes equal to the 1 atm
pressure S o l v e n t

ution

atmospheric pressure. As the vapour S o l u t i o

pressure of a solution containing a

non-volatile solute is lower than that
of the pure solvent, then it's boiling
point will be higher than that of the
pure solvent as shown in figure. The Temperature
(K)
increase in boiling point is known as
elevation in boiling point, AT,
AT, = T, - T;
AT, = Kb m (where, m= molality)
K, is molal elevation constant or ebullioscopic constant. Molecular
mass of solute can be calculated as
K, Wa x 1000
AT,= Mz x WA
WE 1000
Ma=Kb
WA AT,
where, W and WA = mass of solute and solvent respectively.
K, has units of K/m or K kg mol, for water, K, = 0.52 K kg mol'.
Depression in Freezing Point (AT;)
Freezing point of a liquid is the Pureliquid
temperature at which vapour pressure of
F r o zseonl v e n t

Vapour
pressure
the solvent in its liquid and solid phase Solution
become equal. As we know that vapour
pressure of solution containing
non-volatile solute is lower than that of
pure solvent, solid form gets separated out
at a lower temperature as shown in the
figure. T T?

This decrease in freezing point of a liquid Temperature

(K)
is known as depression in freezing point.
Depression in freezing point (AT;) =T; - T;
AT, = K,m= K, WBX
MB
1000
WA
132 Handbook of Chemistry
To find molecular mass of solute,
K, Wp x 1000
Mp =
AT,· WA
where, K, is molal depression constant or cryoscopic constant.
K, has units of K/m or K kg moll.
Ethylene glycol is usually added to water in the radiator to lower its
freezing point. It is called antifreeze solution.

l Common salt (NaCl) and anhydrous CaCl, are used to clear snow on
the roads because they depress the freezing point of water. The
freezing point depression is determined by Beckmann method or Rast
method.
Calculations of molal elevation constant (K;) and molal
depression constant (K,)
K, M, R(T;
1000 x AH,
M R(T;
K, = AH,x 1000
T; = boiling point of solvent
T;= freezing point of solvent
AH,= molar enthalpy of fusion
AH, = molar enthalpy of vaporisation
where, M, is molar mass of solvent in kg mol, R= gas constant.
K, AT,
K, AT,
Osmosis and Osmotic Pressure
Osmosis is the phenomenon of spontaneous flow of the solvent
molecules through a semipermeable membrane from pure solvent to
solution or from a dilute solution to concentrated solution. It was first
observed by Abbe Nollet.
Some natural semiperneable nembranes are animal bladder, cell
membrane etc.
Cu, [Fe(CN);] is an artificial semipermeable membrane which does not
work in non-aqueous solutions as it dissolves in them.
 Solutions 133

Osmosis may be
i) Exosmosis It is outward flow of water or solvent from a cell
through semipermeable membrane.
(ii) Endosmosis It is inward flow of water or solvent from a cell
through a semipermeable membrane.
The hydrostatic pressure developed on the solution which just prevents
the osmosis of pure solvent into the solution through a semipermeable
membrane is called osmotic pressure.
WB

C-M,V)
Osmotic pressure () = RCT;

WRT
Ma=
dRT
Mp
where, d = density, R=solution contant,
T= temperature, M¡ = molar mass of solute
Osmotic pressure can be determined by any one of the method listed below
(i)) Pfeffer's method
(i1) Berkeley and Hartley's method (very good method)
(ii) Morse and Frazer's method
On the basis of osmotic pressure, the solution can be
(i) Hypertonic solution A solution is called hypertonic if its
Osmotic pressure is higher than that of the solution from which it
is separated by a semipermeable membrane.
When a plant cell is placed in a hypertonic solution, the fluid
from the plant cell comes out and cell shrinks, this phenomenon
iscalled plasmolysis.
(ii) Hypotonic solution A solution is called hypotonic if its
osmotic pressure is lower than that of the solution from which it
is separated by a semipermeable membrane.
(iii) Isotonic solution Two solutions are called isotonic if they
exert the same osmotic pressure. These solutions have same
molar concentration. 0.91% solution of pure NaCl is isotonic with
human RBC's.
Two solutions are isotonic if they have the same molar
concentration, e.g. if x% solution of X is isotonic with y %
solution of Y, this means molar concentration of X = Molar
concentration of Y
134 Handbook of Chemistry
1000 yx 1000 y
100 M7 100 x My M7 My
Osmotic pressure method is the best method for determining the
molecular masses of polymers since observed value of any other
colligative property is too small to be measured with reasonable
accuracy.

Reverse osmosis When the external pressure applied on the solution is more than
osmotic pressure, the solvent flows from the solution to the pure solvent, which is
called reverse osmosis. Desalination of sea water is done by reverse osmosis.

Abnormal Molecular Masses

In some cases, observed colligative properties deviate from their
normal calculated values due to association or dissociation of
molecules. As we know,
1
Colligative property «
Ma
Hence, higher and lower values of molar mass is observed in case of
association and dissociation respectively, e.g. in benzene, acetic acid
gets associated, so, its observed molecular mass is 120. Similarly KCI
undergoes dissociation in aqueous solution, so its observed molecular
mass is 37.25.
These observed values are corrected by multiplying with van't Hoff
factor ().

van't Hoff Factor ()

It is the ratio of observed value of colligative property to the calculated
value of colligative property.
i=
observed value of colligative property
calculated value of colligative property
normal molecular mass
i=
observed molecular mass
i=
number of particles after association or dissociation
number of particles initially
So to correct the observed value of molar mass, van't Hoff factor
() must be included in different expressions for colligative properties.
AT, = iK, m
AT, = ik, m
 Solutions 135

I=i CRT
Ap

i for several strong electrolytes (Complete dissociation)

For KCl, NaCl and MgSO4, iapproaches 2 as the solution becomes
very dilute. As expected, the value of i gets close to 3 for K,S0,.
Degree of Dissociation (a) and van't Hoff Factor ()
If one molecule of a substance gets dissociated into n particles or
molecules and a is the degree of dissociation then
’ nP
Initially 1mol 0
At eq 1-a no

Total number of moles at equilibrium

=l- +na
i-l-0a + na
1
i-1
n-]

Degree of Association () and van't Hoff Factor (i)

If n molecules of a substance A associate to form A, and c is the degree
of association then
nA A
Initially 1 mol 0

At equilibrium 1-a
n

Total number of moles at equilibrium

=1- +

1-a+*
i= n

i-1
a =
1
-1

van't Hoff factor (i)> 1 for solutes undergoing dissociation and it is < 1
for solutes undergoing association.