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Vapour Pressure
At equilibrium conditions the pressure exerted by the
vapours of the liquid over the liquid phase is called
vapour pressure.
Rate of Evaporation = Rate of Condensation
Q- Which of the following statements is correct if the
intermolecular forces in liquids A, B and C are in the order
A< B<C?
A B evaporates less readily than C
B B and C evaporates at the same time
C A and B evaporates at the same time
D A evaporates more readily than C
Q- Which of the following statements is correct if the
intermolecular forces in liquids A, B and C are in the order
A< B<C?
A B evaporates less readily than C
B B and C evaporates at the same time
C A and B evaporates at the same time
D A evaporates more readily than C
Raoult’s Law
For a solution of volatile liquids, the partial vapour pressure of each
component of the solution is directly proportional to its mole fraction present
in solution.
Raoult’s Law
Let A, B be to two volatile liquids in a closed container as shown.
Raoult’s Law
pA = xAPAº
Similarly, for liquid B we have,
pB = xBPBº
Total pressure over the solution PT ,
according to Dalton's law
PT = pA + pB = xAPAº + xB PBº
Raoult’s Law
Composition of vapour phase
Q- The vapour pressure of a pure liquid A is 70 torr at 27ºC. It
forms an ideal solution with another liquid B. The mole
fraction of B is 0.2 and total vapour pressure of the solution
is 84 torr at 27ºC. The vapour pressure of pure liquid B at
27ºC.
A 14
B 56
C 140
D 70
Q- The vapour pressure of a pure liquid A is 70 torr at 27ºC. It
forms an ideal solution with another liquid B. The mole
fraction of B is 0.2 and total vapour pressure of the solution
is 84 torr at 27ºC. The vapour pressure of pure liquid B at
27ºC.
A 14
B 56
C 140
D 70
Solution:
Advance Concept
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Advance Concept
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Advance Concept
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Advance Concept
j
Q- Two liquids A and B from ideal solutions. At 300 K, the
vapour pressure of solution containing 1 mole of A and 3
mole of B is 550 mm Hg. At the same temperature, if one
more mole of B is added to this solution, the vapour
pressure of the solution increases by 10 mm Hg. Determine
the vapour pressure of A and B in their pure states
(in mm Hg):
A 400, 600
B 500, 500
C 600, 400
D None of these
Q- Two liquids A and B from ideal solutions. At 300 K, the
vapour pressure of solution containing 1 mole of A and 3
mole of B is 550 mm Hg. At the same temperature, if one
more mole of B is added to this solution, the vapour
pressure of the solution increases by 10 mm Hg. Determine
the vapour pressure of A and B in their pure states
(in mm Hg):
A 400, 600
B 500, 500
C 600, 400
D None of these
Solution:
Q- The total vapour pressure of a 4 mole % solution of NH3 in
water at 293 K is 50.0 torr, the vapour pressure of pure water
is 17.0 torr at this temperature. Applying Henry’s and
Raoult’s laws, calculate the total vapour pressure for a 5
mole % solution:
A 58.25 torr
B 33 torr
C 42.1 torr
D 52.25 torr
Q- The total vapour pressure of a 4 mole % solution of NH3 in
water at 293 K is 50.0 torr, the vapour pressure of pure water
is 17.0 torr at this temperature. Applying Henry’s and
Raoult’s laws, calculate the total vapour pressure for a 5
mole % solution:
A 58.25 torr
B 33 torr
C 42.1 torr
D 52.25 torr
Solution:
Solution:
Henry Law
‘’the partial pressure of the gas in vapour phase (p) is
proportional to the mole fraction of the gas (x) in the solution”
P∝x
P = K Hx
KH = Henry’s law constant
Q- Molar solubility of helium, nitrogen and oxygen are
plotted against partial pressure of the gas at constant
temperature. Henry’s law constant for these gases will lie in
follow sequence
A O2 > N2 > He
B O2 < N2 < He
C O2 = N2 = He
D O2 > N2 < He
Q- Molar solubility of helium, nitrogen and oxygen are
plotted against partial pressure of the gas at constant
temperature. Henry’s law constant for these gases will lie in
follow sequence
A O2 > N2 > He
B O2 < N2 < He
C O2 = N2 = He
D O2 > N2 < He
Solution:
Ideal solution
Those solutions which obey Raoult's law over the entire range of
concentration are called ideal solutions.
Properties of Ideal Solution
❏ Raoult's law is obeyed
❏ ∆Hmix = 0, there should not be enthalpy change when
components of ideal solutions are mixed
❏ ∆Vmix = 0, there should not be change in volume on mixing
Example-
● n-Hexane and n-Heptane
● Ethyl bromide and Ethyl iodide
● Benzene and Toluene
Q- For an ideal solution of two components A and B, which of
the following is true?
A ΔHmixing < 0 (zero)
B ΔHmixing > 0 (zero)
C A - B interaction is stronger than
A - A and B - B interactions
D A - A, B - B and A - B
interactions are identical
Q- For an ideal solution of two components A and B, which of
the following is true?
A ΔHmixing < 0 (zero)
B ΔHmixing > 0 (zero)
C A - B interaction is stronger than
A - A and B - B interactions
D A - A, B - B and A - B
interactions are identical
Solution:
Solutions in which solute - solute and solvent-solvent
interactions are almost similar to solute solvent
interactions are known as ideal solution.
Non-Ideal solution
Those solutions which do not obey Raoult's Law over the entire
range of concentration are called non-ideal solution.
Properties of non-Ideal Solution
❏ Raoult's law not obeyed
❏ ∆Hmix ≠ 0, there should be enthalpy change when
components of solutions are mixed
❏ ∆Vmix ≠ 0, there should be change in volume on mixing
when components of solutions are mixed
Non-Ideal Solutions Showing Positive Deviation From Raoult’s Law
Non-Ideal Solutions Showing Positive Deviation From Raoult’s Law
Non-Ideal Solutions Showing Positive Deviation From Raoult’s Law
● ∆Hmix > 0, Less heat is evolved when the new attractions are
set up
● ∆Vmix > 0, Volume increase because less interaction between
solute and solvent
● ∆Smix > 0, mixing of solute and solvent , increase number of
particles so entropy change is positive.
● ∆Gmix < 0, mixing of solute and solvent is a spontaneous
process so Gibbs free energy change will negative.
Non-Ideal Solutions Showing Positive Deviation From Raoult’s Law
Examples:
1. Chloroform and water
1. Ethanol and CCI4
1. methanol and chloroform
1. Benzene and methanol
1. acetic acid and toluene
1. acetone and ethanol
1. methanol and H2O
1. C2H5OH + cyclohexane.
Non-Ideal Solutions Showing Negative Deviation From Raoult’s Law
Non-Ideal Solutions Showing negative Deviation From Raoult’s Law
Non-Ideal Solutions Showing negative Deviation From Raoult’s Law
Non-Ideal Solutions Showing negative Deviation From Raoult’s Law
● ∆Hmix < 0, More heat is evolved when the new
attractions are set up
● ∆Vmix < 0, Volume decrease because more interaction
between solute and solvent
● ∆Smix > 0, mixing of solute and solvent , increase
number of particles so entropy change is positive.
● ∆Gmix < 0, mixing of solute and solvent is a spontaneous
process so Gibbs free energy change will negative.
Non-Ideal Solutions Showing negative Deviation From Raoult’s Law
Examples:
1. Chloroform and methyl acetate
1. H2O and HCI
1. H2O and HNO3
1. Acetic acid and pyridine
1. Phenol and Aniline.
1. Acetone and Chloroform
Q- The diagram given below is a vapour pressure
composition diagram for a binary solution of A and B. The
force of attraction between A - B is
A similar to A - A and B - B
interactions
B greater than A - A and B - B
interactions
C Smaller than A - A and B - B
interactions
D unpredictable
Q- The diagram given below is a vapour pressure
composition diagram for a binary solution of A and B. The
force of attraction between A - B is
A similar to A - A and B - B
interactions
B greater than A - A and B - B
interactions
C Smaller than A - A and B - B
interactions
D unpredictable
Solution:
Azeotrope
Azeotropes are constant boiling mixtures which have same
composition in liquid phase as well as in vapour phase. They are
further classified into :
❖ Minimum boiling Azeotropes: Non-ideal solutions which
boil at a lower temperature than boiling point of each
component in the pure state, e.g., 95.5 % ethyl alcohol and
4.5 % water by mass.
❖ Maximum boiling Azeotropes : Non-ideal solutions which
boil at a higher temperature than the boiling point of each
component in a pure state, e.g., 68 % nitric acid and 32 %
water by mass.
Minimum boiling Azeotropes
Maximum boiling Azeotropes
Colligative Properties
Properties of the solution which do not depend upon the nature of
the solute but depend only on the number of solute particles
The four important colligative properties are :
(i) Relative lowering in vapour pressure
(ii) Elevation in boiling point
(iii) Depression in freezing point
(iv) Osmotic pressure
Relative Lowering in Vapour Pressure
Vapour Pressure of a solution of a non volatile solute (solid
solute) is always found to be less than the vapour pressure of
pure solvent.
Relative Lowering in Vapour Pressure
Q- At room temperature, a dilute solution of urea is
prepared by dissolving 0.60 g of urea in 360 g of water. If the
vapour pressure of pure water at this temperature is 35 mm
Hg, lowering of vapour pressure will be:
(molar mass of urea = 60 g mol-1)
A 0.027 mmHg
B 0.028 mmHg
C 0.017 mmHg
D 0.031 mmHg
Q- At room temperature, a dilute solution of urea is
prepared by dissolving 0.60 g of urea in 360 g of water. If the
vapour pressure of pure water at this temperature is 35 mm
Hg, lowering of vapour pressure will be:
(molar mass of urea = 60 g mol-1)
A 0.027 mmHg
B 0.028 mmHg
C 0.017 mmHg
D 0.031 mmHg
Solution:
Boiling Point
Temperature at which its vapour pressure becomes equal to
the atmospheric pressure (1 atm)
Elevation in Boiling Point
Elevation in Boiling Point
The difference in the boiling point points of the solution (Tb) and
pure solvent (Tb0) is called the elevation in boiling point.
Let ∆Tb be the elevation in boiling point, then
Tb = Tb0 + ∆Tb ⇒ ∆Tb = Tb - Tb0
From experiments,
∆Tb ∝ m ⇒ ∆Tb = Kbm
Kb : molal boiling point elevation constant or
Ebullioscopic constant of solvent
m : molality of the solution
Elevation in Boiling Point
Q- The molal b.p. constant for water is 0.513ºC kg mol-1.
When 0.1 mole of sugar is dissolved in 200g of water, the
solution boils under a pressure of 1 atm at
A 100.513ºC
B 100.0513ºC
C 100.256ºC
D 101.025ºC
Q- The molal b.p. constant for water is 0.513ºC kg mol-1.
When 0.1 mole of sugar is dissolved in 200g of water, the
solution boils under a pressure of 1 atm at
A 100.513ºC
B 100.0513ºC
C 100.256ºC
D 101.025ºC
Solution:
Freezing Point
Temperature at which vapour pressure of solid becomes equal
to vapour pressure of liquid is called freezing point of liquid .
Depression in Freezing Point
Depression in Freezing Point
Depression in Freezing Point
Q- What mass of sugar, C12H22O11 (M = 342) must be
dissolved in 4.0 kg of H2O to yield a solution that will freeze
at –3.72°C. (Take Kf = 1.86°C/m)
A 2736 gm
B 2196 gm
C 1123 gm
D 3212 gm
Q- What mass of sugar, C12H22O11 (M = 342) must be
dissolved in 4.0 kg of H2O to yield a solution that will freeze
at –3.72°C. (Take Kf = 1.86°C/m)
A 2736 gm
B 2196 gm
C 1123 gm
D 3212 gm
Solution:
Osmosis
The phenomenon of the passage of pure solvent into
solution or from less concentrated solution to more
concentrated solution through a semipermeable
membrane is called osmosis.
Semi-permeable membrane
Osmotic Pressure
The excess pressure that must be applied to a solution to
prevent the passage of solvent through a semipermeable
membrane
Osmotic Pressure
The osmotic pressure (𝜋) is given as:
𝜋 = CRT
C = molar concentration of solution (molarity)
T = temperature
R = gas constant
Isotonic Solution
Two or more solutions having equal osmotic pressure
under given conditions are called isotonic solutions
𝜋1 = 𝜋2
C1RT = C2RT
or C1 = C2
Q- A solution containing 4 g of polyvinyl chloride in 1 litre of
dioxane was found to have an osmotic pressure of
6 × 10-4 atm at 300 K. The molecular mass of polymer is:
A 3 × 103
B 6.4 × 102
C 5 × 104
D 1.6 × 105
Q- A solution containing 4 g of polyvinyl chloride in 1 litre of
dioxane was found to have an osmotic pressure of
6 × 10-4 atm at 300 K. The molecular mass of polymer is:
A 3 × 103
B 6.4 × 102
C 5 × 104
D 1.6 × 105
Solution:
Van’t Hoff Factor
In order to know about the extent of association or
dissociation of solutes in solution van’t Hoff
introduced a factor(i).
Van’t hoff factor and degree of association
Van’t hoff factor and degree of dissociation
Colligative Properties
If van’t Hoff factor is known, the various colligative properties
would be given by
Q- We have three aqueous solutions of NaCl labelled as ‘A’,
‘B’ and ‘C’ with concentration 0.1M, 0.01M and 0.001M,
[Link] value of van’t hoff factor for these
solutions will be in the order
A iA< iB< iC
B iA> iB> iC
C iA = iB = iC
D iA < iB > iC
Q- We have three aqueous solutions of NaCl labelled as ‘A’,
‘B’ and ‘C’ with concentration 0.1M, 0.01M and 0.001M,
[Link] value of van’t hoff factor for these
solutions will be in the order
A iA< iB< iC
B iA> iB> iC
C iA = iB = iC
D iA < iB > iC
Solution:
The value of van’t hoff’s factor will be iA = iB = iC due to complete
dissociation of strong electrolyte (NaCl) in dilute [Link] complete
dissociation value of i for NaCl is 2
Q- Depression of freezing point of 0.01 molal aq. CH3COOH
solution is 0.02046 ℃. One molal urea solution freezes at -
1.86 ℃. Assuming molality equal to molarity, pH of CH3COOH
solution is?
A 1
B 2
C 3
D 4
Q- Depression of freezing point of 0.01 molal aq. CH3COOH
solution is 0.02046 ℃. One molal urea solution freezes at -
1.86 ℃. Assuming molality equal to molarity, pH of CH3COOH
solution is?
A 1
B 2
C 3
D 4
Solution:
Q- Column-I and Column II contains four entries each.
Entries of column-I are to be matched with some entries
of column-II. One or more than one entries of column-I
may have the matching with the same entries of
column-II
Column-I Column-II
Can be separated by fractional
(a) n-hexane + n-heptane (p)
distillation
(b) Acetone + chloroform (q) Maximum boiling azeotrope
Chloro-benzene and Cannot be separated by fractional
(c) (r)
bromo-benzene distillation completely
(d) Ethanol + water (s) Minimum boiling azeotrope
Q- Column-I and Column II contains four entries each.
Entries of column-I are to be matched with some entries
of column-II. One or more than one entries of column-I
may have the matching with the same entries of
column-II
Column-I Column-II
Can be separated by fractional
(a) n-hexane + n-heptane (p)
distillation
(b) Acetone + chloroform (q) Maximum boiling azeotrope
Chloro-benzene and Cannot be separated by fractional
(c) (r)
bromo-benzene distillation completely
(d) Ethanol + water (s) Minimum boiling azeotrope
A → P; B→Q,R; C→P; D→R,S
Q- Column-I and Column II contains four entries each.
Entries of column-I are to be matched with some entries
of column-II. One or more than one entries of column-I
may have the matching with the same entries of
column-II
Column-I Column-II
(Solute) (Van’t Hoff factor, i)
(a) AlCl3 if α = 0.8 (p) i = 3.4
(b) BaCl2 if α = 0.9 (q) i = 2.8
(c) Na3PO4 if α = 0.9 (r) i = 3.8
(d) K4[Fe(CN)6] if α = 0.7 (s) i = 3.7
Q- Column-I and Column II contains four entries each.
Entries of column-I are to be matched with some entries
of column-II. One or more than one entries of column-I
may have the matching with the same entries of
column-II
Column-I Column-II
(Solute) (Van’t Hoff factor, i)
(a) AlCl3 if α = 0.8 (p) i = 3.4
(b) BaCl2 if α = 0.9 (q) i = 2.8
(c) Na3PO4 if α = 0.9 (r) i = 3.8
(d) K4[Fe(CN)6] if α = 0.7 (s) i = 3.7
A → P; B → Q; C → S; D→R
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Mohit Ryan
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Mohit Ryan Sir
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