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Solutions
Solutions
Solutions
Chemical Classification
of Matter
Pure
Mixtures
Substances
Homogeneous Heterogeneous
Homogeneous Mixtures Heterogeneous Mixtures
(1) (2)
Sugar Water Alcohol Water
Solid Liquid Liquid Liquid
50 gm 100 gm 50 gm 100 gm
Solute Solvent Solute Solvent
100 gm 50 gm 100 gm 50 gm
Solute Solvent Solvent Solute
Types of
solutions
Completely Miscible
Partially Miscible
Immiscible
Solution (solid in liquid)
Saturated Solution
Unsaturated Solution
Dissolution
When a solid solute is added to the solvent, some solute dissolves and
its concentration increases in solution. This process is known as
dissolution
crystallisation
Some solute particles in solution collide with the solid solute particles
and get separated out of solution. This process is known as
crystallisation.
Solubility
Solubility is affected by -
Temperature
Pressure
Nature of Solute and Solvent
1
sgas Ex- Na2CO3.H2O, Li2CO3
Temperature
Effect of pressure
Effect of Temperature
Effect of Pressure
Solubility of Gas in Liquid
Solubility of Gases in Liquid
Henry's Law
P = KH 𝝌
Here,
KH = Henry's Constant
Henry’s constant :
The Henry's law constant for the solubility of nitrogen gas in water
at 298 K is 1 × 105 atm. The mole fraction of nitrogen in air is
0.8. Calculate the number of moles of nitrogen from air dissolved in
10 moles of water at 298 K and 5 atm pressure of air.
Solution
The value of Henry’s law constant for some gases at 293 K is given
below. Arrange the gases in the increasing order of their solubility.
He : 144.97 kbar, H2 : 69.16 kbar,
N2 : 76.48 kbar, O2 : 34.86 kbar
(A) He < N2 < H2 < O2 (B) O2 < H2 < N2 < He
(C) H2 < N2 < O2 < He (D) He < O2 < N2 < H2
Solution
Ans. (A)
Alternate Statement of Henry’s Law
s P
m P
Variation of solubility of gas with pressure
s
P
Variation of solubility of some gases with equilibrium pressure
Oxygen
Nitrogen
s
Helium
P
Henry’s constant :
Important Points
Certain gases are highly soluble in water like NH3, HCl etc. and
certain gases are less soluble in water like O2, N2, He etc.
Those gases which can react with solvent do not follow Henry's Law.
e.g. NH3 in water.
For real gases Henry's Law can only be applied at low pressure and
high temperature conditions.
Limitations of Henry's Law
1. Pressure is low
2. Temperature is high
Solution
Solution
Ans : y = z > x
Example
Solution
Ans : (A)
Example
Solution
Ans : 3 × 10–4
Ans :2.6 285
2.7 1.846 gm
Vapour Pressure
We have a container filled with pure substance at a constant
temperature.
At dynamic equilibrium,
Rate of evaporation = Rate of condensation
Vapour Pressure
Dynamic equilibrium
established
Rate of evaporation
Rate
Time
Vapour Pressure of a Liquid
R O
H
If temperature increases
For an equilibrium
A(ℓ) ⇌ A(g)
Kp = PA
Kp = P1 (at T = T1)
1
Kp = P2 (at T = T2)
2
Factors affecting vapour pressure
K p2 ΔH 1 1
log = − ΔvapH > 0
K p1 2.303R T1 T2
P2 ΔH 1 1
∴ log = −
P1 2.303R T1 T2
Note
Evaporation
Evaporation vs. Boiling
The Raoult’s law states that 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.
According to Raoult's law
PA α xA PA = PA∘ xA
PB α xB PB = PB° xB
PTotal = PA + PB
Where,
xA, xB → Mole fraction of A and B in liquid solution at equilibrium.
PA° , PB° → Vapour pressure of pure component 1 and 2 at the same
temperature.
PA, PB → Vapour pressure contribution of A and B respectively.
xA + xB = 1
xA = 1 – xB
So, PTotal = xA PA° + (1 – xA) PB°
Y = c + mx
Graph of Raoult's law
P∘B
Vapour Pressure
P∘A
xA = 1 Mole Fraction xA = 0
xB = 0 xB = 1
P∘B
Vapour Pressure
d
P∘A
c
xA = 1 a xA = 0
xB = 0 Mole Fraction xB = 1
P∘B
Vapour Pressure
d
P∘A
c
xA = 1 a xA = 0
xB = 0 Mole Fraction xB = 1
Example
Two liquid A and B are mixed to form an ideal solution. If one mole of
A and 4 moles of B are mixed then the total vapour pressure of
solution becomes 540 mm of Hg. If 1 moles of B is further added then
total vapour pressure of solution increases by 8 mm of Hg, Then find
the value of PA° & PB° .
(A) 348 mm, 420 mm (B) 600 mm, 400 mm
(C) 588 mm, 348 mm (D) 348 mm, 588 mm
Solution
Ans : (D)
Example
Consider the graph of total vapour pressure (PS) for ideal solution of A
and B at Temperature (T) versus mole fraction of A (XA)
200
PS (mm Hg)
100
0 XA 1
Select the correct statement.
(A) Boiling point of pure A is more than B
(B) Vapour pressure of pure A at temperature T is 100 mm Hg
(C) Vapour pressure of pure B at temperature T is 200 mm Hg
(D) Boiling point of pure A is less than B
Solution
Ans : (D)
Example
Solution
Solution
Ans : (A,B)
Example
Solution
Ans : (1) 20mm, 17mm of Hg
(2) 37 mm of Hg
(3) Y(CH3OH) = 20/37
Example
Two liquids A & B are mixed to form an ideal solution. The total vapour
pressure of solution is 235 – 135 x. Then find the value of p°A & p°B . If x
is the mole fraction of B in solution.
Solution
Vapour phase
yA + yB = 1
Liquid phase
xA + xB = 1
pA = yA pT pB = yB pT
Calculation of YA & YB from Dalton’s law
xA p°A = yA pT
xB p°B = yB pT
xA p∘A
yA =
pT
xB p∘B
yB =
pT
In a liquid phase, sum of the mole fractions of all components = 1
x A + xB = 1
yA pT yB pT
+ = 1
p°A p°B
yA yB 1
+ =
p°A p°B pT
yA yB 1
+ =
p°A p°B pT
p°B
p°A
0 1
Mole fraction of B
in vapour phase
yA yB 1
+ =
p°A p°B pT
100% liquid
p°B
p°A
P 100% vapours
0 1
Mole fraction of B
Vapour Pressure V/S Vapour Composition
The V.P. of ideal solution always lie in between the V.P. of pure
components.
Below vapourous curve, the system will by 100 % vapour & above
liquidous and curve, 100% liquid. Both the physical states exists only
in between the curves.
At any pressure in between pA° and pB°, the physical state of system
may be changed by changing the composition.
Example
Solution
Ans : 0.4
Example
Solution
Ans : 0.2
Example
Solution
Ans : (1) 70 mm
(2) 75 mm
(3) 65 mm
Ans : 0.3 and 0.7
What happens when
a non-volatile solute
is added to a volatile
liquid ?
Non-volatile solute :
Glucose, Sugar, Urea, NaCl
etc.
What happens when a non-volatile solute is added to a
volatile liquid ?
pS = p°A xA + p°B xB
p°B = 0
pS = p°A xA = p° xSolvent
Calculation of vapour pressure
p°A
pS
0 xA 1
Solution
Ideal Non-Ideal
Positive Negative
Deviation Deviation
Ideal solutions
Those solutions which obey Raoult's law over the entire range of
concentration are known as ideal solutions.
+ =
Non-Ideal solutions
Those solutions which do not obey Raoult's law over the entire range
of concentration, then they are called non-ideal solutions.
+ =
Non-Ideal solutions
Those solutions which do not obey Raoult's law over the entire range
of concentration, then they are called non-ideal solutions.
+ =
Difference between ideal and non ideal solutions
Positive Negative
Properties Ideal Solutions
Deviation Deviation
Intermolecular
A-----A or B-----B = A-----B A–A or B–B > A–B A–A or B–B < A–B
interactions
Vapour
ps = p∘A xA + p∘B xB ps > p∘A xA + p∘B xB ps < p∘A xA + p∘B xB
Pressure
Difference between ideal and non ideal solutions
Positive Negative
Properties Ideal Solutions
Deviation Deviation
Intermolecular
A-----A or B-----B = A-----B A–A or B–B > A–B A–A or B–B < A–B
interactions
Intermolecular Intermolecular
Intermolecular distances are
distances increase. distances decreases.
same.
Difference between ideal and non ideal solutions
Positive Negative
Properties Ideal Solutions
Deviation Deviation
Intermolecular
A-----A or B-----B = A-----B A–A or B–B > A–B A–A or B–B < A–B
interactions
Positive Negative
Properties Ideal Solutions
Deviation Deviation
Intermolecular
A-----A or B-----B = A-----B A–A or B–B > A–B A–A or B–B < A–B
interactions
Positive Negative
Properties Ideal Solutions
Deviation Deviation
Intermolecular
A-----A or B-----B = A-----B A–A or B–B > A–B A–A or B–B < A–B
interactions
p°B
Vapour Pressure
p°A
xA = 1 Mole Fraction xA = 0
xB = 0 xB = 1
Examples of ideal Solution
p°B
Vapour Pressure
p°A
xA = 1 Mole Fraction xA = 0
xB = 0 xB = 1
Examples of non-ideal solutions with positive deviation
p°B
Vapour Pressure
p°A
xA = 1 xA = 0
Mole Fraction
xB = 0 xB = 1
Examples of non-ideal solutions with negative deviation
(i) The boiling point of ideal solution always lie in between the boiling
points of pure liquids.
(ii) Below liquidous curve, the system in 100% liquid and above vaporous
curve, the system is 100% vapour. Both the physical states exists
only in between the curves.
(iii) At any composition, the physical state of system may be changed
by changing the temperature.
(iv) At any temperature in between TA° and TB° , the physical state of
system may be changed by changing the composition.
100 % vapour
T°A
T
T°B
100 % liquid
0 Mole Fraction of B 1
Distillation
(ii) With the elimination of vapor above the liquid, the boiling point of
residual liquid increases.
(iii) The boiling point of distillate is less than that of original liquid.
Azeotropes
0 X 1 0 X 1
Mole Fraction of B Mole Fraction of B
T°A
PB
°
P L
L V T°B
PA
°
T
Hydrogen chloride-
79.8% Water 108.6°C
Water
Example
10 ml of liquid A (B.P. = 368K) and 10 mL of liquid B (B.P. = 415 K) are
mixed to obtain 19.92 ml of a constant boiling mixture then B.P. of the
solution is
(A) < 368 K (B) > 368 K but < 415 K
(C) > 415 K (D) Unpredictable
Solution
Ans : (_)
Example
Solution
Ans : (C)
Example
Solution
Ans : (_)
Example
Solution
Ans : (_)
Example
Solution
Ans : (_)