CHAPTER – 2 SOLUTIONS NOTES 

#Liquid in liquid solutions:- 

 Vapour pressure of liquid/solution V.P of a liquid is defined as the

pressure exerted by the vapours of liquid over the surface of liquid in
equilibrium with it at a particular temperature  

Vapour pressure of a liquid-liquid solution and Raoult’s Law :- 

For liquid-liquid solution, as both the component are volatile, each

component will exert a V.P when equilibrium is reached which is called its
partial V.P whose value depends upon the mole fraction of the component
in pure state. 

#Raoult’s law for a solution of volatile liquids may be stated as        :- 

. In a solution of volatile liquids, the V.P of a component at a given

temperature is equal to the product of its V.P in pure state and its mole
fraction in solution.  

Let A and B be the two components of solution having partial Pa and pb

respectively. pure state V.P Poa and Pob and mole fraction Xa and Xb  resp. 

 Then A.T. Rault’s law :- 

Pa= P 0a X  a                                                       P b= P ob X b 

According to Dalton’s law of partial pressure, the total V.P of the

components of soln  

P = Pa + Pb  = PoaXa  + PobXb  

 For a binary solution 

 

According to Dalton’s Law of  partial pressure, the  total pressure over it
the solution is the sum of the partial pressures of the component of
solutions  

P = Pa + P 

P =POAXA + POBXB 

For a binary soln 

Xa + Xb = 1  

Ptotal = Pob + ( Poa – Pob ) Xa  

This relation is also an eqlb of straight line of type  

Y = mx +c  

When Xa is 0 ( i.e, Xb = 1) the V.P of solution is equal to  Pob 

 Th
e  V.P is P btw these two extremes, the V.P varies linearly with Xa
o
a 

because Poa  and Pob  are constant. 

 
  

# V.P of a soln containing non-volatile solute :-  

. When a  non-volatile solute is added to a solvent, the V.P of soln is

found to be less than that of pure solvent. Because on soln, the surface
has both solute And solvent particles therefore, he fraction of surface
occupird by the particles of solvent gas reduced so the number of
solvent molecules escaping into the vapour phase is correspondingly
reduced, thus , the V.P is also reduced . 

The decrease in V.P of the solvent depends on the quantity of non-

volatile solute present in the soln  irrespective of its nature. 

#Raoult’s law for soln   containing non- volatile solute  

In a soln containing non-volatile solute  the V.P of soln will be due to

solvent only  because solute is non-volatile/  

V.P od soln   = V.P of solvent in soln 

P=Pa  

If Pa is the V.P of solvent or solnn containing non-volatile solute and Xz is its mole
fraction then ACC to RAoult’s law  
Psoln = P0aXa  

So, for a soln containing non-volatile solute

@   “ The relative lowering in V.P of a solutions containing non-volatile solute is

equal to the mole fraction of solute at a  given temperature 

# Raoult’s law as a special case of Henry’s law 

Acc to Raoult’s law, the V.P of a volatile component in a given solution is given
by the relation  
Pa = PoaXa 

In case of soln of gas in liquid, the gaseous components is volatile components.

Its solubility is governed by the Henry’s Law, which give the relation  

P =KhX 

Thus Raoult’s Law and Henry’s law become identical EXCEPT THAT THEIR
PROPOTIONALITY constants are different being equal to Poa in Raoult’s law and
Kh in henry’s Law  

# Ideal and non-ideal solutions  

 Ideal soln  - Ideal solutions are those which obey Raoult’s law over
entire range of concentration and temperature  

 Ideal solution are made by mixing two components which are

identicall in molecular size in structure and have almost identical
forces of attraction. In ideal solution the intermolecular interactions
in the solutions ( solute – solvent interaction one of same magnitude
as in pure components   

 If A is solvent, B is solute the A-B interactions are of same

magnitude as A-A and B-B interactions 

 No solutiona is ideal, veru dilute solution behave as near ideal

solutions 

# Graphical representation of ideal soln  

 
  

This relation is also an equation of straight line of the type y= mx + c

whrn Xa = 0 , vapour pressure of solution is equal to  Pob and when Xa  is ,
vapour pressure of solution is Poa . b/w these two extremes, the V.P
varies , linearly with Xa  becaude Poa and  Pob  are constt . A straight line is
obtained when P is plitted against Xa or Xb .  

Types of Non-ideal Solutions 

 
 . Non ideal showing + ve deviation from Raoult’s law 
. Non ideal showing  - ve deviation from Raoult’s law 
 

# . Non ideal showing + ve deviation from Raoult’s law 

 

In these solutions, the intermolecular attractive forces between solute –

solvent molecules are weaker than those b/w solute-solvent and
solvent-solvent molecule . 

AB interactions are weaker than A-A and B-B interactions in pure

liquids/  

So, the escaping tendency of A and B types of molecule from the

solution become more than that from pure liquids. As a result each
component of solutions has partaial V.P greater than ecpected from
Raoult’s law and the total V.P of solution will be greater than the  

Corresponding  V.P in case of ideal soln of same composition  

 Mathematically for a solution showing + ve deviation  

  Pa > PoaXa     ,                          Pb >  PobXb  

P = Pz + Pb    > PoaXa  

#Characteristics of non-ideal solutions showing +ve deviation 

1.  P = Pa + Pb > PoaXa + PobXb 

 2. ∆mixing H > 0  

Because energy is required to break stronger A-A and B-B attractive

forces. Since, A-B interaction are weaker i.e dissolution process is
endothermic and due to this, increase in temperature, increase the
solubility in such a solution 

3. ∆mixing v > 0 

I.e the volume of solution is greater than sum of volume of its

components. This is due to weakining of attractive forces which results
in increase in volume and intermolecular distance 

#Graphical representation of showing +ve deviation 

#Non-ideal solution showing -ve deviation 

In the solution, solute and solvent A-B interaction are stronger than
solute-solute (B-B) and solvent-solvent (A-A) interaction so, the escaping
tendency of A &B types of molecules from the solution is less than pure
liquids so, observe V.P of both components and solutions are lower than
the ideal value expected from Raoult's law . 

 MATHEMATICALLY FOR A SOLN SHOWING – VE DEVIATION

 Pa < PoaXA PB < POBXB

P = PA + PB < POAXA + POBXB

 In case of +ve deviation from Raoult’s law, we get minimum boiling
azeotropes. In these azeotropes, the boiling point of solution is less than
boiling point of either of its pure component.

In case of -ve deviation from Raoult’s law, maximum boiling azeotropes are
formed and boiling point of azeotropes are formed and boiling point of
azeotrope is higher than that of either of its components

#Colligative properties

Certain physical properties of dilute solution containing non-volatile solure

depend upon the no. of solute particles in soln, net on their nature. These
properties are called colligative properties

# Four colligative properties are :-

1 Relative lowering in vapour pressure

2 Elevation in B.P

3 Drepression in freezing point

4 osmotic pressure

# Relative lowering in Vapour pressure

As established earlier  

2. Elevation in boiling point

Boiling point of a liquid is temperature at which its V.P become equal to

atmospheric pressure. The V.P becomes equal to atmospheric pressure.
The V.P of solution containing non-volatile is less than that of pure
solvent. So, solution has to be heated to a higher temperature. So, that
its V.P becomes equal to atmospheric pressure. So, the boiling point of
solution containing non-volatile solute is higher than that of pure
solvent. This difference in B.P is known as elevation in boiling point
So, ebullioscopic constt on molal elevation constant may be defined as
elevation in boiling point for one molal solution i.e, the solution
containing one mole solute in thousand grain solvent
Unit of Kb = K
-----
Mol

# Determination of molar mass of solute from elevation in boiing point

Wa = mass of solvent
Wb = mass of solute
Ma = molar mass of solvent
Mb = molar mass of solute

Mb = 1000 * Kb * Wb
-------------------------
^Tb * Wa

# Normal boiling point : Normal boiling point of a liquid is temperature

at which its V.P becomes 1 atm

# Depression in freezing point

Freezing point of a liquid is the tmeprature at whoch the solid and liquid
state of substance co-exist in equilibrium because the two states have
same V.P at this temperature. When a non-volatile solute is added to a
solvent the freezing point of solution is always lower than that of pure
solvent, this is called depression in freezing.
This is because the V.P of solution is less than that of pure solvent and
since, freezing point is that temperature at which the V.P of liquid phase
and solid phase are equal. SP for the solutions, this will occur at lower
temperature causing depression in freezing point.

^Tf = Tf1 – Tf2

Tf1 : Freezing point of pure solvent

Tf2 : Freezing point od solution ( non-volatile solute )

Experimentally, it has been found

^tf = Kfm

Molal freezing point, depression constant or chryoscopic constant

If m = 1
^ Tf = K f
 SO, Chryoscopic constant may be defined as depression in freezing point
for one molal solutiojn

Unit of Kf = K Kg mol-1

 Calculation of molar mass of solute from depression in freezing point

^ T f = Kf m

M = Wb * 1000
---------------
Mb * Wa
# Common salt or anhydrous calcium chloride are used to clear si=now in the
areas which experience snow fall because these substance being non-volatile
depresses the freezing point of water. So, ice or snow meets off easily at the
prevailing temperature.

# Osmosis and osmotic pressure : Osmosis may be defined as spontaneous

flow of solvent molecules from less concentration solution to more
concentration, solution through a semi-permeable membrane is called
osmosis. When the membrane permits a solvent molecules to come out
through the membrane it is called exosmosis and if it perits solvent molecules
to enter inside, it is called endosmosis

Difference between osmosis and diffusion

Osmosis

- SPM is used
- Flow of solvent molecules only that too sthrough SPM
- IT takes place form lower to conc to higher concentration
- It applies in solution only
- It can be stopped or reversed

Diffusion

- SPM is not used

- Movement of bpth solute and solvent particles
- It takes place from hogher to lower concentration solution
- It takes in gases as well as solution
- It cannot be stopped or reversed
3. Osmotic pressure (π)
The external pressure which must be applied on solution side in order to
prevent the movement of solvent into it through SPM
 *Expression for osmotic pressure

Osmotic pressure of a solution is deirectly proportional to the molar

concentration of solutiojn at a particular temperature

Παc
ΠαT
Π = CRT
R is constant and its value is same as that of gas constant

C is molarity of solution

πV = nRT
This equation is called Van’t haff equation for dilute solution

 Isotonic solutions
Solutions having same osmotic pressure at same tempr are called
isotonic solution
Equimolar solution at same temperature ar isotonic when such solution
are separated by SPM , No osmosis take place

 Hypertonic and hypotonic

When two solution have unequal osmotic pressures at same temperature the
one with osmotic pressure is called hypotonic and the other with higher
osmotic pressure os called hypertonic
When two such solution are separated by SPM, direction of osmosis is from
hypotonic solutiions

The fluid inside human RBC is isotonic with 0.91 % ( w/v) NaCl solution. SO,
normal saline water is safe to inject intsavenously.
If RBC’s are placed in distilled water or in NaCl solution having salt concnn less
than 0.91 % i.e, hypertonic solution endosmosis will take place and RBCs will
swell or may even burst, it is also known as hemolysis. If RBCs are placed in
hypertonic solutipm then it will shrink it iss known as plasmolysis
People taking a lot of salty food experienced water retention in tissues, cells
and intercellular spaces because od osmosis to balance osmotic pressure of
body fluids. This lead to puffiness or swelling in body which is edema

# Reverse osmosis

When external pressure greater than osmotic pressure is applied on the

solution side], the solvent will move from solution to solvent through SPM is
directional of osmosis gets reversed, this is known as reverse osmosis