Solution
Ideal solution
1. Must follow Rault’s law at all concentration and temperature.
2. ∆Vmix=0
Reason: A─A interaction = B─B interaction = A─B interaction
3. ∆Hmix=0
Reason: Heat absorbed for breaking A─A interaction and B─B
interaction is equal to Heat released in the formation of A─B
interaction.
4. Force of attraction between A─A interaction = B─B interaction
= A─B interaction
5. ∆Smix > 0
6. ∆Gmix < 0
The p-x diagram for an ideal solution of two
completely miscible liquid
Examples 1. n-hexane + n- heptane Same size and same polar nature
2 Benzene and toluene
Non- Ideal solution
• 1. Do not follow Rault’s law at all concentration and temperature.
• Ptot ≠p0 A + p0
• 2. ∆Vmix ≠0
• Reason: A─A interaction ≠ B─B interaction ≠ A─B interaction
• 3. ∆Hmix ≠0
• Reason: Heat absorbed for breaking A─A interaction and B─B
interaction is not equal to Heat released in the formation of A─B
interaction.
• 4. Force of attraction between A─A interaction ≠ B─B interaction ≠
A─B interaction
• 5. ∆Smix > 0
• 6. ∆Gmix < 0
Two types of Non Ideal solutions
A. Shows Positive deviation from Raoult’s law
B. Shows negative deviation from Raoult’s law
Non Ideal solutions Showing negative deviation from Raoult’s law
1. Do not follow Rault’s law at all concentration and temperature.
Ptot < p0 AXA + p0B XB
Reason : A─A interaction and B─B interaction < A─B interaction, which means the
A─B interaction is stronger and vapour formed is less.
2. ∆Vmix<0
Reason: The A─B interaction is stronger so molecules will come closer and volume
will decrease
3. ∆Hmix < 0
Reason: Heat released in the formation of A─B interaction is greater( as the
interaction is stronger) than Heat absorbed for breaking A─A interaction and B─B
interaction .
4. Force of attraction between A─A interaction and B─B interaction < A─B
interaction
5. ∆Smix > 0
6. ∆Gmix < 0
Non Ideal solutions Showing negative
deviation from Raoult’s law
Ptot < p0 AXA + p0B XB
Example : Chloroform (CHCl3and
acetone CH3COCH3
Reason: Between CHCl3 and
CH3COCH3 , there is vander waal’s
force of attraction which is weak
but in the solotion there forms
Hydrogen bond is formed so
interaction becomes stronger and
over-all vapour pressure
decreases resulting in negative
deviation.
Strong acid and water forms
Non Ideal solutions Showing positive deviation from Raoult’s
law
1. Do not follow Rault’s law at all concentration and temperature.
Ptot > p0 AXA + p0B XB
Reason : A─A interaction and B─B interaction > A─B interaction, which means the
A─B interaction is weaker and vapour formed is more.
2. ∆Vmix>0
Reason: The A─B interaction is weaker so molecules will go far away from each
other and volume will increase.
3. ∆Hmix > 0
Reason: Over all heat absorbed in breaking A─A interaction and B─B interaction is
greater than Heat released in the formation of A─B interaction (as it is weaker).
4. Force of attraction between A─A interaction and B─B interaction > A─B
interaction
5. ∆Smix > 0
6. ∆Gmix < 0
Non Ideal solutions Showing positive
deviation from Raoult’s law
Ptot >p0 AXA + p0B XB
Example : Water and Benzene
Reason: Hydrogen bond present between
water is broken by benzene. So force of
attraction decreased and vapour pressure
increased.
Colligative property
Those property of dilute solution which
depend on number of solute particles and not
on nature of solute particles.
Four Properties of Colligative property
1. Relative lowering of vapour pressure
2. The elevation of boiling point
3. The depression of freezing point
4. Osmotic pressure
The elevation of boiling point
When we add non-volatile solute in a solution, vapour pressure decreases and boiling point increases.
The elevation of boiling point
m = No. of moles of non-volatile solute
∆Tb = Kb m
M
Mass of the solvent (in Kg) . This
means ∆Tb is a colligative property
• 18g of glucose is dissolved in 1Kg water. Find the boiling point
of solution.(BP of pure water is 373K, Kb for water
=0.52KKg/mol)
• Solution
• ∆Tb = Kb m
• = 0.52 x No. of moles of non-volatile solute
M Mass of the
solvent (in Kg)
= 0.56 x 18/180
• 1Kg
∆Tb = 0.52
Tb - T0b = 0.52
Tb = 0.52+ 373
= 373.52 K
6g of urea(NH2CONH2) and 9g of glucose are
dissolved in 300g of water. Find the BP of solution.
(Pure water BP=1000C, Kb for water =0.52K.Kg/mol)
Solution
No. of moles of solute=nu + ng
= 6/60 + 9/180
=0.1 + 0.05 =0.15moles
∆Tb = Kb m
= 0.52 x 0.15
300/1000
=0.26 K
Tb = T0b + 0.26
= 100 + 0.26 =100.260C
If Kb is not given (rare)
Kb= R (T0b)2 M
1000 ∆Hvap
R- Universal gas constant( 8.314J/molK, 2Calorie/molK
T0b = BP of pure solvent
M=Molar mass of solvent
∆Hvap Enthalpy of vaporization(amount of heat to vapourise 1
mole of substance)
∆Hvap = Lv x M(Latent heat- vapourisation of 1g )
The depression of freezing point
Or Kf cryoscopic
constant which
depends on
solvent only.
What amount of C2H5OH(assume non-volatile) must
be dissolved in 1Kg water so that it freezes at -20 ( FP
of water =00C, Kf for water =1.86KKg/mol)
Solution
∆Tf= Kf x m
0-(-2)=1.86 x No. of moles of non-volatile solute
M Mass of the solvent (in Kg)
2 = 1.86x n/46000
n = 2 x 46000
1.86
=50g
Osmotic pressure
When a semipermeable membrane is placed between a
solution and solvent, it is observed that solvent molecules
enter the solution through the semipermeable membrane and
the volume of the solution increases. The semi-permeable
membrane allows only solvent molecules to pass through it but
prevents the passage of bigger molecules like solute. This
phenomenon of the spontaneous flow of solvent molecules
through a semipermeable membrane from a pure solvent to a
solution or from a dilute to a concentrated solution is called
osmosis.
• The flow of solvent molecules through the semipermeable
membrane can be stopped if some extra pressure is applied
from the solution side. This pressure that just stops the flow of
solvent is called osmotic pressure of the solution.
Osmotic pressure is a colligative property as it
depends on the number of solute present and not on
the nature of the solute.
Experimentally it was proved that osmotic pressure
(⫪) is directly proportional to molarity(M) and
temperature(T).
Mathematically, ℼ = MRT
Where
R is the gas constant/Solution constant
R=0.0821atm/molK.
ℼ = Osmotic pressure
M= Molarity= No. of moles of solute = n
Vol. of solution in L V
⇒ ℼ = (n/V) RT
P= (n/V) RT
Here, V is the volume of solution in litres and n is
moles of solute
1atm=1.01x105
Pa=1.01bar=0.987atm=760mmHg=760torr
Calculate the osmotic pressure due to 5%(w/v)
cane sugar solution(C12H22O11) at 150C.
Solution
ℼ = MRT
ℼ = (n/V) RT %(w/v) -5g cane sugar in
= (5/ 342 ) x 0.0821 x288 100 L
solution
100/1000
n= mass given/Molar mass
=5/342
Different Solutions
Isotonic solution: Two solutions having the same osmotic pressure at a given temperature are
known as an isotonic solution. When such solutions are separated by a semi-permeable
membrane than there is no osmosis.
ℼ = MRT
For 2 solutions, ℼ1 = ℼ2 , Temp being the same, so, M1=M2
Hypotonic solution: A hypotonic solution has a lower osmotic pressure than that of the
surrounding i.e, the concentration of solute particles is less than that of the surrounding. If
the hypotonic solution is separated by semipermeable membrane then water moves out of
the hypotonic solution.
ℼ1 < ℼ2
Hypertonic solution: A hypertonic solution has a higher osmotic pressure than that of the
surrounding i.e, the concentration of solute particles is more than that of the surrounding. If
the hypertonic solution is separated by semipermeable membrane then water moves inside
the hypertonic solution.
ℼ1 > ℼ2
Van’t Hoff Factor
1. P0A-PA /P0A= Xsolute= nsolute / nsolute + nsolvent
2. ∆T = K m= K X No. of moles of solute/Mass of solvent(in kg)
b b b
3. ∆T = K m= K X No. of moles of solute/Mass of solvent(in kg)
f f f
4. ℼ = MRT = No. of moles of solute nxRxT
Vol. of solution (in L) V
In all these cases, the solute taken was non-
electrolyte like urea, sugar etc. They did not
dissociate in the solution. No dissociation or
association.
When the solute used was electrolyte, the
observed colligative property differed from
the calculated colligative property.
NaCl→ Na+ + Cl-
1mole 1mole 1 mole
Sometimes molecules will associate or join together to reduce the number of
moles and observed colligative property will reduce.
Van’t Hoff Factor(i)
How much or how many times the
particles are increasing or decreasing is
given by colligative property
i= Total no. of solute after dissociation/association
Total no. of solute before dissociation/association
Dissociation of electrolyte
NaCl→ Na+ + Cl-
1mole 1mole 1 mole
i= 2/1=2
1MgCl2 → 1Mg2+ + 2Cl-
i=1+2/1 =3
K4[Fe(CN)6 → 4K+ + [Fe(CN)6]4-
i = 5/1 = 5
α- Degree of dissociation
NaCl→ Na+ + Cl-
Initial 1 0 0
Equilibrium 1-α α α
Suppose α molecules of NaCl dissociate, so
1-α molecules of NaCl did not dissociate
i= 1-α+α+α = 1+α
1
If α=1, i=1+1=2
i= observed CP
Calculated CP
1. P0A-PA /P0A= Xsolute x i
2. ∆Tb = Kb m x i
3. ∆Tf = Kf m x i
4. ℼ = MRT x i
• At a given temperature which of the following will have maximum
osmotic pressure-
1M NaCl, 1M Na2SO4, 1M Al2(SO4)3
Solution
ℼ = MRT x i
ℼ= i (M,R,T are the same)
• Al2(SO4)3→ 2Al + 3SO42-
i=Total no. of solute after dissociation/association i= 5/1
Total no. of solute before dissociation/association
• Na2SO4 → 2Na+ + SO42- i= 3/1 = 3
NaCl →Na+ + Cl- i= 1
i more so more no. of particles so observed CP more,
more osmotic pressure
Ans
1M Al2(SO4)3
1% urea(NH2CONH2), 1% NaCl and 1% Na2SO4 is given
in W/V. Find the osmotic pressure.
Solution
ℼ = MRT x i
(1% means 1g in 100 mL)
ℼ= M x i = 1/60 = 1/6
100/1000
1% NaCl = 1/58.5 x 2 = 1
100/1000 2.92
1% Na2SO4 = 1/142 x 3 = 1
100/1000 4.7
Ans ℼNaCl > ℼ Na2SO4 > ℼ NH2CONH2
• A 2 molal NaCl soluton in water has elevation in boiling point
of 1.88K. If Kb for water is 0.52KKg/mol. Calculate i and
degree od dissociation α foe NaCl.
Solution
• NaCl→ Na+ + Cl-
Initial 1 0 0
Equilibrium 1-α α α
i= 1-α+α+α = 1+α
1
∆Tb = Kb m x i
1.88 = 0.52 x 2 x i
i = 1.8
i = 1-α 1.8= 1- α α=0.8 i.e 80%dissociation
