SOLUTION

Solutions
Solution is a homogeneous mixture of solvent and solute.
Solution = solvent  solute
In a binary solution (containing two components only), the component which is present in smaller
amount is called the solute and the other present in larger amount is called the solvent. Types of
solutions
Depending upon the physical state of the component, the solutions are classified into following different
types:

S. No. Solute Solvent Examples

1. Solid Solid Alloys
2. Liquid Solid Hydrated salts
3. Gas Solid Dissolved gases in mineral
4. Solid Liquid Salt/Sugar solution in water
5. Liquid Liquid Alcohol in water
6. Gas Liquid Aerated drinks
7. Solid Gas Iodine vapour in air
8. Liquid Gas Water vapour in air
9. Gas Gas Air

Henry's law
The solubility of the gas in a liquid increases with increase of pressure or decrease of temperature.
This law deals with dissolution of gas in liquid i.e. mass of any gas dissolved in any solvent per unit volume
is proportional to pressure of gas in equilibrium with liquid
x= kp
Different methods of expressing the concentration of a solution.
Name Symbol and Formula Definition Effect of temp.
Percentage Mass of solute Number of parts by No effect
% (w / W ) =  100 mass of solute per
Mass of soln.
hundred parts of the
Mass of solute
% (w/V) =  100 solution
Volume of soln.
Volume of solute
% (V/V) =  100
Volume of soln.
Volume of solute
% (V/W) =  100
Mass of soln.
Strength Mass of solute in grams Amount of the solute Changes with change of
g /l= in grams present in temperature
Volume of soln. in litres

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 one litre of solution
Parts per million Mass of solute Number of parts by No effect
ppm =  10 6 mass of solute per
T otal mass of solution
10 6 parts of solution
Molarity Number of moles of solute Number of moles of Changes with change of
M solute per litre of temperature
Number of litres of solution
solution
w B 1000
 
MB V
Mass
(Number of moles  ),
Molecular mass
Molality Number of moles of solute Number of moles of No effect
m
Number of kilograms of the solvent solute present in 1kg

w B 1000 of the solvent.

 
mB wA
Normality Number of gram equivalent s of solute Number of gram Changes with change of
N equivalents of the temperature
Number of litres of solution
solute present in one
w 2 1000
  ( E 2  Eq. Wt. of solute) litre of the solution
E2 V
Mole fraction nA nB Ratio of number of No effect
XA  ; XB  moles of one
n A  nB n A  nB
component to the
XA  XB 1, XA 1  XB , XB 1  XA total number of
moles of solution
Formality Number of formula mass Number of formula Changes with change of
F mass in grams temperature.
Number of litres of solution
present per litre of
W2 1000
  ( F2  formula mass of solution
F2 V
solute)

Some important relations.

(1) Relation between molality and molarity –
1000  M 1000  m  d
m ; M
[1000  d  m  molecular mass of solute] 1000  m  M B

(2) Relation between Molarity and Normality –

M  Molecular wt. = S g /L
N  Eq. wt. = S g /L
 M  mole. wt. = N  eq. wt.
N mol. wt. N N
  , n, N nM ; M 
M eq. wt. M n

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 SOLUTION

(3) Relation between mole fraction, molarity and molality

Molality Mol. wt. of solvent
Mole fraction of solute 
1  molality  Mol. wt. of solvent

Molarity Mol. wt. of solvent


Molarity(Mol. wt. of solvent - Mol. wt. of solute)  d
where d  density of solution
Vapour pressure and Raoult’s law.
Vapour pressure of a liquid or solution is the pressure exerted by the vapour in equilibrium with the
liquid or solution at a particular temperature. The vapour pressure of a liquid decreases if some non-
volatile solute is dissolved in it because some molecules of the solvent on the surface are replaced by the
molecules of the solute.
Raoult’s law for volatile solutes states that “In a solution, the vapour pressure of a component at a
given temperature is equal to the mole fraction of that component in the solution multiplied by the vapour
pressure of that component in the pure state.” Thus for a solution containing components A and B.
p A  X A  p0 A , pB  X B  p0 B

 PTotal  PA  PB  X A P 0 A  X B P 0 B  (1  X B ) P 0 A  X B P 0 B

or PTotal  (P 0 B  P 0 A ) X B  P 0 A
Raoult’s law for non-valotile solutes states “The relative lowering of vapour pressure of a solution
containing a non-volatile is equal to the mole fraction of the solute in the solution”. Mathematically
PA0  PA nB
  XB
PA0 n A  nB

Ideal and Non Ideal solution .

An ideal solution of the components A and B is defined as the solution in which the intermolecular
interactions between A and B are of the same magnitude as between the pure components or it is a solution
in which there is no volume change and enthalpy change on mixing ( Vmixing  0,  H mixing  0) or it is a
solution in which each component obeys Raoult’s law at all temperatures and concentrations.

For ideal solution: Obeys Raoults law , PA  PAo . X A ; PB  PBo. X B

The interaction between the components are similar to those in the pure component.
Non-ideal solution
A non-ideal solution is a solution in which A–B interactions are of different magnitude than those in
the pure components or for which  Vmixing  0,  H mixing  0 or which does not obey Raoult’s law.

For non ideal solution: PA  PA0 . X A , PB  PB0 . X B

The interaction between the components are different from those of pure components.

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 Types of non-ideal solutions

Showing positive deviations Showing negative deviations

1. Interaction < in the pure components Interactions > pure components
2.  Vmix.  ve ;  H mix.  ve  Vmix.  ve ;  H mix.  ve
3. PA  PA0 . X A ; PB  PB0 . X B PA  PA0 . X A ; PB  PB0 . X B
4. Form minimum boiling azeotropes. Form maximum boiling azerotropes.
Ex– CH 3 COCH 3  CS 2 / CH 3 COCH 3  C 2 H 5 OH / Ex– CHCl 3  C 6 H 6 / CHCl 3  C 2 H 5 OC 2 H 5 CH 3
CH 3 COCH 3  C 6 H 6 / C 2 H 5 OH  H 2 O / CCl 4  CHCl 3 COCH 3  C 6 H 5 NH 2 / HCl  H 2 O / HNO 3  H 2O

Some important points

(1) With the help of Raoult’s law for non-volatile solute, mole. mass (M B ) can be determined -

PA0  PA 1 WB M A
 XB  
PA0 M B WA
(2) Mol. wt. by Raoults law is for dilute solutions of non-electrolytes.
(3) The pressure under which liquid and its vapour can co-exist in equilibrium is known
as saturated vapour pressure.
(4) A substance is deliquescent, if its V. P. is less than water vapour in the air so that it
can absorb water vapour from the air.
(5) If PAo  PBo , it means A is more volatile.
(6) For ideal solution – Its components can be separated by fractional distillation.
(7) When H–bonding occurs in mixing solution shows negative deviations.
(8) Higher the concentration, lower is the V. P.
(9) Lowering of V. P. is not a colligative properties.
Azeotropic mixtures.
Azeotropic mixture is a mixture of two liquids which boils at one particular temperature like a pure
liquid and distils over in the same composition i.e. these are constant boiling mixtures. These are formed by
non- ideal solutions. These are of two types;
(1) Azeotropic mixtures with minimum boiling point i.e. whose boiling point is less than either
of the two pure components. This is formed by that composition of a non-ideal solution showing positive
deviation for which the vapour pressure is maximum.

Components Boiling point (K)

A B Mass % of B A B Azeotrope
H 2O C2 H 5 OH 95 .57 373 351.3 351.1
H 2O C2 H 5 CH 2OH 71.69 373 370 350.72
CHCl 3 C2 H 5 OH 67 334 351.3 332.3
(CH 3 )2 CO CS 2 6.8 329.25 320 312.2

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 SOLUTION

(2) Azeotropic mixtures with maximum boiling point i.e. whose boiling point is more than
either of the two pure components. This is formed by that composition of a non-ideal solution showing
negative deviation for which the vapour pressure is minimum.

Components Boiling point (K)

A B Mass % of B A B Azeotrope
H 2O HCl 20.3 373 188 383

H 2O HNO 3 58.0 373 359 393.5

H 2O HClO 4 71.6 373 383 476

For azerotropes :
b. p. < liquid mixed [+ deviation]
b. p. > liquid mixed [– deviation]
Boiling point is the temperature at which vapour pressure becomes equal to the atmospheric
pressure. As vapour pressure of solution is lower than that of the solvent, its boiling point is higher. The
increase is called elevation in boiling point i.e.  Tb  T  T0 .

Freezing point is the temperature at which they liquid and the solid form of the same substance are
in equilibrium and hence have the same vapour pressure, Due to lower vapour pressure of the solution.
Solid form of a solution separates out at a lower temperature.
Colligative properties.
Which depend only on number of particles are :
(1) Relative lowering of vapour pressure
(2) Osmotic pressure
(3) Elevation in boiling point ( Tb )
(4) Depression in freezing point ( T f )
All colligative properties are used for calculation of molecular masses.
(1) Relative lowering of vapour pressure : It is the ratio of lowering in vapour pressure and
vapour pressure of pure selvent. It is equal to the mole fraction of solute.
PA0  PA
 XB; Where – PA0  vapour pressure of pure solvent, PA  vapour pressure of solution
PA0

X B  male fraction of salute , PA0  PA  lowering of vapour pressure

(2) Osmosis and Osmotic pressure
solvent molecules
In Osmosis lower conc.    Higher conc.
flow
The outflow of water from a cell is called exosmosis where as inflow is called endosmosis.
(i) Experiments of osmosis [By Abble Nollet in 1748]

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 (ii) Osmotic pressure : It is the minimum pressure that must be applied on the solution to prevent the
entry of the solvent into the solution through semipermeable membrane. It is represented by  .
(iii) Measurement of  is best carried out by Barkley-Hartley method. It is a Colligative property.
n W RT  in atm, V in litres 
  CRT or   RT ,   B   
V MB V R  0.0821 L.atm. k -1 mol 1 
(iv) Isotonic – Having same 
Hyper tonic – Having more  to the given solution
Hypotonic – Having less  to the given solution.
(v) In equimolar solution of C 6 H 12 O6 , NaCl and BaCl 2 .
The order of  is as follows – BaCl 2  NaCl  glucose
(vi) A 0.91% solution of pure NaCl is isotonic with human red blood corpuscles (RBC)
(vii) of dil. Solution  ionic concentration.
(3) Elevation in boiling point : The boiling points elevates when a non-volatile solute is added to a
volatile solvent. Which occurs due to lowering of vapour pressure.
The boiling point of a liquid may be defined as the temperature at which its vapour pressure becomes
equal to atmospheric pressure.
So when a non-volatile solute is added to a volatile solvent results lowering of vapour pressure and
consequent elevation of boiling point.
Tb  P  X B , Tb  elevation in b.pt., P  lowering of V.P.
or Tb  KX B X B  mole fraction of solute, K  elevation constant
wB M A n
or Tb  K   K B MA
M B WA WA
nB
If W A is the weight of solvent in kg. then is equal to molality (m) of the solution.
WA
Tb  KM A m or Tb  K b m
Where K b is molal elevation constant or molal ebullioscopic constant.
When molality m of the solution is equal to one, then Tb  K b
Hence molal elevation constant of the solvent may be defined as the elevation in its boiling point when
one mole of non-volatile solute is dissolved per kg (1000 gm) of solvent. The unit of K b are K kg mol 1 .
w B 1000
Because molality of solution m  .
M B WA
WB 1000 1000  K b  WB
So, Tb  K b . , MB 
M B WA Tb  WA
When the volume is taken as 1000 ml. then elevation in boiling point is known as molar elevation
constant.
(4) Depression in freezing point : The freezing point of a pure liquid is fixed. If a non-volatile
solute is dissolved in a liquid the freezing point of the solution is lowered. The freezing point is that

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 SOLUTION

temperature at which the solvent has the same vapour pressure in two phases, liquid solution and solid
solvent. Since the solvent vapour pressure in solution is depressed, its vapour pressure will become equal to
that of the solid solvent at a lower temperature
nB wB / M B
So, T f  P  X B or T f  KX B  K K
n A  nB W A / M A  WB / M B
wB W w
For dilute solution  A and hence B can be neglected in the denominator. So
MB MA MB
wB / M B n MA
T f  K K B
WA / M A WA
nB
If W A is the mass of solvent in kg, then is equal to molality (m) of the solution.
WA
T f  KM A m or T f  K f m (K  M A  K f )
Where K f is molal depression constant. When molarity (m) of the solution is one, then T f  K f
Hence molal depression constant or molal cryoscopic constant may be defined as “the depression
in freezing point when one mole of non-volatile solute is dissolved per kilogram (1000 gm) of solvent” and
molar depression constant is defined as “the depression in freezing point when one mole of non-volatile
solute is dissolved per litre (1000 ml) of solvent.”
The molecular mass of the non-volatile solute may be calculated by the use of following
K f  WB  1000
mathematical equation, M B 
W A  T f

Van’t Hoff factor.

Van’t Hoff factor (i) – It is the ratio of the experiments value of the colligative properties to the
Experimental value of the colligative property
calculated value of the colligative property i.e. i  .
Calculated value of the colligative property
1 Calculated molecular mass (Mc )
As molecular mass  , Hence i  , modified formulae for
Colligative property obs. molecular mass (Mo )
substances.
Undergoing dissociation or association in the solution are –
h
 Tb  i k b m ;  T f  i k f m ;   i RT ; where i (Vant Hoff factor)>1 [for solutes undergoing
V
dissociation]
i < 1 [for solutes undergoing association]

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