Solutions- Lecture 1

Class XII- CHEMISTRY

Dr. Swati Srivastava
VAPOUR PRESSURE OF LIQUID SOLUTION
• LIQUID-LIQUID SOLUTIONS
• SOLID- LIQUID SOLUTIONS
These are the two types of the solutions . Either one of the component is
volatile. The liquid solvent is volatile usually . The solute may or may not be
VAPOUR PRESSURE OF LIQUID-LIQUID
volatile.

SOLUTION
Let’s consider two volatile liquids A and B . These liquids when kept in closed
vessel , eventually develops an equilibrium between vapour phase and liquid
phase. Let,
ptotal = total vapour pressure of the solution
pA and pB = partial pressure of the two components A and B
χA and χB = mole fraction of two components A and B
RAOULT’s The law states ‘for a solution of volatile liquids
the partial pressure of each component of the
LAW solution is directly proportional to its mole
fraction present in the solution.’
pA ∝ χA
pA = pA° χ A
pB = pB° χ B Dalton’s law of
partial pressure

pA°and pB° represents the vapour

pressure of pure components A and The total pressure (ptotal) over the solution phase, will
B at same temperature be sum of the partial pressures of the components in
the solution

Conclusions from equation:

ptotal = pA° χA +pB° χB • Total pressure can be related to mole fraction of any
= (1- χB) pA° +pB° χB one component.
• Total vapour pressure (VP) varies linearly with mole
= pA° +(pB° - pA°) χB fraction χB
• total VP increases or decreases with increase in mole
fraction
 • The dashed lines (I and II) pressure of
the components (linear plot) . It pass
Plot of pA and pB versus the through the points for which χA and χB
mole fraction χA and χB are equal unity.
• The line III p total versus χB is also
linear.
• The minimum value of ptotal is pA° and
the maximum value pB°, assuming that
III
component A is less volatile than
II component B i.e. pA°< pB°

Composition of vapour pressure

equilibrium with solution is
determined by the partial pressure of
the component.
I p1=y1ptotal
p2 = y2 ptotal
If y1 and y2 are the mole fraction of
the components 1 and 2 in the
vapour phase. (Dalton’s law of partial
pressure)
VAPOUR PRESSURE OF SOLIDS IN LIQUIDS
SOLUTION
•The liquids at a given temperature vapourise and an equilibrium is developed
•Under this condition pressure exerted by the vapours of the liquid over the liquid phase is called vapour pressure.

•In a pure liquid all the surface is occupied by the molecules of liquid. Now when non-volatile solute is added .
•The vapour pressure becomes lower than the pure solvent. The Vapour pressure depends solely on the solvent alone

•In the presence of non volatile solute, the surface with solvent molecules is reduced. Hence vapour pressure is also reduced.
•The decrease in the vapour pressure depends on the quantity of non –volatile solute , irrespective of its nature.
 For any solution the partial
RAOULT’s LAW-
pressure of each volatile
General Form component in the solution is
directly proportional to its mole
fraction.
• Solvent(A) and • Let , pA be the
solute(B) vapour pressure,
Binary • Solute is non χA be mole
Raoult’
Solutio volatile , only fraction and pA°
s Law
n solvent be the VP of the
molecules pure state.
contribute • pA = pA ° χ A
Raoult’s law is special law of Henry’s
law

Raoult’s
p1 = p1 ° p = KH χ law
χ1 becomes a
special case
Raoult’s Henry law, when
of henry’s
law- one of the
law in
volatile component is so
which KH
component volatile it exists as
a gas. becomes
equal to
p1°.
 Questions Bank

1. Calculate the vapor pressure of a mixture containing 252 g of n-pentane (MW= 72 g) and 1400 g of n-
heptane (MW = 100 g) at 20oC. The vapor pressure of n-pentane and n-heptane are 420 mm Hg and 36
mm Hg respectively.
2. What happens to vapor pressure when you add a solute to a solution?
(a) It lowers the vapor pressure.
(b) It has no effect.
(c) It raises the vapor pressure.
(d) It causes the reaction to reach equilibrium.
3. How many grams of nonvolatile compound B (molar mass= 97.80 g/mol) would need to be added to 250.0 g
of water to produce a solution with a vapor pressure of 23.756 torr? The vapor pressure of water at this
temperature is 42.362 torr.
4. How many grams of testosterone , C19H28O2, a nonvolatile, non electrolyte (MW = 288.4 g/mol), must be
added to 207.8 grams of benzene to reduce the vapor pressure to 71.41 mm Hg? (Benzene = C 6H6 = 78.12
g/mol. The vapor pressure of benzene is 73.03 mm Hg at 25.0 °C.)
 IDEAL AND NON IDEAL SOLUTIONS

• Obey Raoult’s law in the entire range of concentration.

• Examples : n-Hexane and n-Heptane , bromoethane and
chloroethane , benzene and toluene

Ideal solutions
 When the solution doesn’t obey Raoult’s
Non-Ideal solution law over the entire range of
concentration, then it is called non-
ideal solution. The Vapour pressure of
such solution can be higher or lower than
Raoult’s law

If the Vapour Pressure is higher , the solutions exhibits

positive deviation and if it is lower , it exhibits negative
deviation.
 Intermolecular
attractive forces
between solute-
solvent Nature of interaction :
A-B interaction is
molecules are
weaker than those
weaker than
between A-A and B-B.
those between
solute-solute and
This means that in such
solvent-solventsolutions molecules of A
(or B) will find it easier to
escape than in pure state.

This will increase the

vapour pressure and
result in positive
deviation. Positive
deviation
Mixtures of ethanol and acetone. In pure ethanol , molecules are hydrogen bonds. On adding acetone ,
its molecules get in between the host molecules and break some of the hydrogen bonds .

Solution of carbon disulphide and acetone , dipole interactions between solute –solvent molecules
weaker than the respective interaction among the solute-solute and solvent-solvent molecules.

Examples
T

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The escaping tendency
of molecules decreases
and consequently the
vapour pressure
decreases
AZEOTROPES

Some liquids, which are binary mixtures have same composition in

liquid and vapour phase and boil at constant temperature. The
components cannot be separated by fractional distillation. There
are two types of Azeotropes

Minimum boiling Maximum

azeotropes (large boiling
positive azeotropes (large
deviation from negative
Raoult’s law) deviation from
Raoult’s law)
 Examples of
Azeotrope
Nitric
Ethanolacid
–water
and mixture
water is is
anan
example
example
of minimum
maximumboiling
boilingazeotrope
azeotrope..
This
On fractional
azeotropedistillation
has approximate
95% bycomposition
volume of ethanol
68% nitric
is produced.
acid and
32% water(Minimum
by mass with
boiling
boiling
azeotrope)
point of 393.5K.
Minimum boiling azeotrope Maximum boiling azeotrope
L- liquid phase
V- vapour phase
 Question Bank

Q1 Which of the following is maximum boiling azeotropic?

a) CH3COOH+C5H5N(pyridine)
b) H2O + ethanol
c) cyclohexane +ethanol
d) H2O + methanol
Q2 Which of the following mixture will have same composition in liquid and vapour phase?
(a) Benzene –Toluene (b) Water and Nitric acid (c) Water- Ethanol (d) n-Hexane – n- Heptane
Q3 Can we separate an azeotropic mixture by distillation? Why do we call it a mixture ?
Q4 What are the values of ∆H and ∆V for positive deviation from ideality ? Give one
example?
Colligative All these properties depend on the number
properties of solute particles (irrespective of their
nature) relative to the total number of
particles present in the solution . Such
Co- Liga
properties Co
are called colligative properties
re
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mea
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When a non volatile solute is added to volatile solvent there
are many properties which changes.
•Relative lowering of vapour pressure of the solvent
•Elevation of boiling point of thesolvent

•Depression of freezing point of the solvent.

•Osmotic pressure of solution
 Relative lowering of vapour
pressure

The vapour pressure of a solvent in solution is less than that of

pure solvent. Lowering of vapour pressure depends only on the
concentration of solute particles and independent of their
identity.

Relation between vapour pressure of the solvent and

mole fraction
n1 and n2
p1 = p1 ° χ 1 are
The reduction in vapour pressure of the solvent (∆p1) number of
∆p1= p1°-p1= p1°- p1° χ1 = p1°(1- χ1 )= p1° χ2 moles of
∆p1/p1° = p1°-p1/p1° = χ2 = n2/n1+n2 solvent
and solute
 Relative lowering of vapour pressure and is equal the mole
fraction of the solute.
For dilute solutions n2<<n1 hence neglecting n2 in the
denominator.

p1°-p1/p1° = n2/n1+n2 = w2 x M1/ M2 x

w1
Here , w1 and w2 are the
masses and M1 and M2 If in a solution, there are many
non- volatile solutes, the
are the molar masses of
lowering of vapour pressure
the solvent and solute
depends on the sum of mole
respectively.
fraction of different solutes.
Back Exercise

Q2.17 The vapour pressure of water is 12.3kPa at 300K. Calculate

the vapour pressure of 1 molal solution of non- volatile solute in
it.

1 molal solution means that 1 mole of the solute is dissolved in 1

kg of the solvent. The density of water (solvent) as 1 g/mL
Mass of solution = mass of the solvent
χB =mass of the solute / mass of the solute + (1000/Mass of
solvent)
= m /m+(1000/18) = 1/1+55.55 = 1/56.55
Now ,
∆pA/pA° = pA°-pA/pA° = χB= n2/n1+n2 = 12.3 –pA / 12.3 = 1/56.55
12.3 – pA= 12.3/56.55 = pA= 12.3 – 12.3/56.55 = 12.08 kPa.
Q2.19 A solution containing 30 g of non volatile solute exactly in
90 g of water has a vapour pressure of 2.8 kPa at 298K. Further
18 g of water is then added to the solution and the new vapour
pressure becomes 2.9kPa at 298K. Calculate (i) molar mass of the
solute (ii) vapour pressure of water at 298K

pA°-pA/pA° = χB= nB/nB+nA

1- pA/pA° = (WB/MB)/(WB/MB)+(WA/MA)
1- 2.8/ pA° = (30/M)/ (90/18) (WB/MB)<<<(WA/MA)
2.8/pA°= 1-(M/6) = (M-6)/M(1)

Similarily , 2.9/pA°= (M-6)/(M-5)(2)

Dividing (1) by (2)
0.1M = 3.4 , M = 34 g/mol
Substituting in (1) we get pA°= (34 x 2.8)/28 = 3.4 kPa
Assignment: Try back questions
related to lowering of vapour
pressure(Q 2.15,2.18 and 2.34).
 ELEVATION IN BOILING POINT
Boiling point of liquid is the temperature at which vapour
pressure is equal to its atmospheric pressure. Boiling
point of water is 373.15K (100°C) because at this
temperature the vapour pressure of water is 1.013 bar (1
atm)

When a non-volatile solute is added to a solvent, the boiling

point increases. This is because upon adding non-volatile solute
the vapour pressure of the solution decreases as part of the
surface is occupied by the non-volatile solute which hinders the
 Vapour pressure of the solution is lower than that of the
pure solvent and vapour pressure increases with increase in
temperature. Hence solution has to be heated more to make
the vapour pressure equal to the atmospheric pressure.

For example: vapour pressure of aqueous solution of sucrose is less

than that of pure water 1.013 bar (373.15K). In order to make the
solution boil, the vapour pressure must be raised above the boiling
temperature. Thus boiling point is higher than that of the pure
solvent.
 Plot of vapour pressure versus temperature

ATOMOSPHERIC
PRESSURE
B Tb° is the
D boiling
point of the
pure
solvent Tb
A is boiling
C point of the
solution
Relations

Dilute solutions
 Molal Elevation Constant
(Kb) Ebullioscopi
c constant

Molal elevation constant may be defined as the elevation in boiling

point when the molality of the solution is unity (1 mole of the
solute is dissolved in 1 kg of the solvent) . The units are therefore
degree/molality, K/m, °C/m or K kg/mol
 Calculation of molal elevation constant from enthalpy of
vaporization
Molar mass of Boiling point of
the solvent the pure solvent

0 2 0 2
R (T ) M 1 R (T )
Kb  b
 b
Latent heat of
1000H V 1000lV vapourization
per gram of the
solvent
Latent heat of
vapourization per
mole of the solvent Nature of the
solvent
 Q1 •10g of a non volatile solute when dissolved in 100g of benzene raises its boiling point by 1°. What is the
molecular mass of the solute ?(K b for benzene = 2.53 K/m)

Weight of the solute w2 = 10g, weight of solvent w1=

100g
∆Tb = 1°, Kb = 2.53 K/m
1000 K b w2
M2 
w1 Tb
1000 g / kg 2.53Kkg / mol 10 g

100 g 1K
253 g / mol
 Q2 •A solution containing 6 g of a solute is dissolved in 250 cm3 of water gave a pressure of 4.5 atm at 27°C. Calculate the
boiling point of the solution . The molal elevation constant for water is 0.52°C per 1000g.

W2 = 6 g, V= 250 cm3 = 0.25 litre

P= 4.5 atm,
T=27+273 = 300K
R = 0.0821 litre atm/degree/mole
PV=nRT
4.5 X 0.25 = n X0.0821 X 300
n = 0.0457 mole
i.e. 0.0457 mole of the solute are present in 250 mL of water (or 250 g of
water)
Molality of the solution = (0.0457 X 1000)/250 = 0.1828 mol/Kg
∆Tb = Kb m
= 0.52 X 0.1828 = 0.095° C
Boiling point of solution (Tb) = Tb°+ ∆Tb = 100 + 0.095 = 100.095 ° C
Assignment :
Q1 Calculate the molal boiling point constant for chloroform
from the fact that its boiling point is 61.2 °C and 0.1 molal
solution of an organic substance in chloroform boiled at 61.579
°C.
Q2 When 1.80 g of non volatile compound is dissloved in 25.0 g
of acetone ,the solution boils at 56.86 °C while pure acetone
boils at 56.38 °C under the same atomospheric pressure.
Calculate the molar mass of the compound . The molal elevation
constant for acetone is 1.72°.
Q3 Find the boiling point of a solution containing 0.520g of
glucose(C6H12O6) dissolved in 80.2 g of water. (Kb for water is
0.52K/m)
DEPRESSION IN FREEZING POINT

Freezing point of the substance is the temperature at

which the liquid and the solid form of the same substance
are in equilibrium and have the same vapour pressure.

Vapour pressure of the A solution will freeze when

liquid and solid phase are its vapour pressure equals
equal the vapour pressure of the
pure solid solvent
Raoult’s law stated that when non – volatile solid
is added to the solvent its, vapour pressure
decreases. As vapour pressure is lowered ,
temperature is also lowered.

Now the freezing point , the temperature at

equilibrium of solid and liquid phase , is at low
temperature. Thus the freezing point is lowered.
 Plot of vapour pressure versus temperature

On, cooling the vapour pressure of the solvent

decreases along the curve AB. At B, the solids A
start appearing and the vapour pressure
decreases steeply along the path BC . At B D
there is equilibrium between solid and liquid B

Tf° is the
freezing point
of the pure
E solvent

C
Tf is freezing
point of the
solution
Vapour pressure decreases as the solute
is added. So the graph is lower and the
value is also less as seen by DE . At E
there is equilibrium or its freezing point.
Relations
 Molal Depression
Constant (Kf) Cryoscopic
constant

Molal depression constant may be defined as the depression in

freezing point when the molality of the solution is unity (1 mole of
the solute is dissolved in 1 kg of the solvent) . The units are
therefore degree/molality, K/m, °C/m or K kg/mol
 Calculation of molal depression constant from enthalpy of
fusion Freezing point
Molar mass of of the pure
the solvent solvent

0 2 0 2
R (T ) M 1
f R (T )
f
Kf  
1000H f 1000l f Latent heat of
fusion per gram
of the solvent

Latent heat of
fusion per mole of
the solvent Nature of the
solvent
 • A 5%solution (by mass)of cane
sugar in water has freezing point
of 271K. Calculate the freezing
Q2.20(NCERT)
point of 5% glucose in water. If
the freezing point of pure water
is 273.15K
T f 273.15  271.0 2.15 K
In case of Freezing point of the
T f K f m
K f 51000 sugar solution of 5% glucose
2.15 
34295 In the in water
K f 51000 case of
T f 
18095 glucose
2.15 180

Dividing the
T f 342 two equations
= 273.15-4.085 =
T f 4.085 K
269.065K
 • An aqueous solution of an organic
compound containing 0.6 g in 21.7 g of
water freezes at 272.187K. If the value of
Q2 Kf for water is 1.86 deg/molality and it
freezes at 273K , what is the molar mass
of the organic compound.

Depression in freezing point ∆Tf = 273-272.187 =

0.813 K
w2 = 0.6 g , w1 = 21.7 g
Kf = 1.86 deg/molality
M2 = (1000 X Kf Xw2)/(w1 X ∆Tf)
= (1000 X 1.86 X 0.6)/(21.7 X 0.813)
= 63.26 g/ mol
Assignment :
Q1 A solution of urea in water has a boiling point of 100.128 °C .
Calculate the freezing point of the same solution. Molal cons
tant of water Kb and Kf are 1.86 °C and 0.512 °C respectively
Q2 1.0 g of an non –electrolyte solute dissolved in 50.0 g of
benzene lowered the freezing point of benzene by 0.40 K . The
freezing point depression constant of benzene is 5.12 K kg/ mol.
Find the molar mass of the solute.
Q3 a solution containing 34.2 g of cane –sugar (C12H22O11)
dissolved in 500 cm3 of water froze at -0.374°C . Calculate the
freezing point depression constant of water.
Q 2.21 of NCERT.
Osmosis
and
Osmotic
Pressure
The net spontaneous flow of the solvent molecules from the solvent to the solution or from less
concentrated to a more concentrated solution through a semi permeable is called osmosis
The spontaneous mixing of the particles
of solute and the solvent to form a
homogenous mixture is called diffusion

Flow of solvent through semi permeable membrane. Applies in solution

only

Solute and solvent move directly

into each other.
Applies in gases as well as solutions
It can be stopped or reversed by applying pressure on the solution
with high concentration

It cannot be stopped or
reversed
Semi – permeable
membrane Vegetable
membrane

Natural semi Animal

membrane
rmeable membrane
Parchment
paper
Artificial semi
rmeable membrane Cellophane
OSMOSIS

Osmotic Pressure may be defined as the equilibrium

hydrostatic pressure of the column set up as result of
osmosis
Osmotic pressure is the equilibrium
hydrostatic pressure of the column set up as a
result of osmosis.

It is the minimum pressure that must be

applied on the solution to prevent the entry of
the solvent into the solution through the semi­
permeable membrane.
For dilute solutions, that osmotic pressure is proportional to
molarity , c of the solution at given temperature T.
 W2 RT
M2  Determination of molecular mass from
V osmotic pressure

This method is
used to
•Molarity is used instead of
determine molar molality. They are used for bio
masses of molecules as they are generally
proteins, not stable at high temperature
and polymers have poor
polymers and solubility.
other
macromolecules
Intext 2.12 Calculate the osmotic pressure in pascals exerted by a
solution prepared by dissolving 1.0 g of polymer of molar mass
185,000in 450 mL of water at 37°C

Given : Volume (V) of solution = 450 mL = 0.45 L = 0.45 X 10-3

m3
Now, πV = nRT
Π x 0.45 X 10-3 = (1 x 8.314 Pa X 310 K)/ 185000
Π= (1 x 8.314 Pa X 310 K)/ 185000 X 0.45 X 10-3
Π= 30.96 Pa
Q2. At 300 K , 100 cm3 of a solution containing 3.0
g of a solute exhibits an osmotic pressure of 2.052
atm. What is the molar mass of the solute ? [R =
0,.082 L atm mol-1 deg-1 ].

Here we are given that, Mass of the solute w = 3.0 g ,

Volume , V = 100 cm3 = 100/1000 = 0.1 L
Osmotic pressure , P = 2.051 atm
Temperature T= 300 K
Molar Mass , m = w RT/ PV
=( 3 x 0.082 X 300 )/ 2.051 x 0.1 = 360 g/mol
 HYPOTONIC,
HYPERTONIC AND
ISOTONIC
SOLUTIONS
Two solutions having same
If a solution has more If a solution has less osmotic
osmotic pressure at a given
osmotic pressure than other pressure than other solution
temperature are called
solution it is called it is called hypotonic
isotonic solutions.0.9% NaCl
hypertonic solution. If the solution. If the salt
solution is isotonic with
solution is containing more concentration is less than
human blood. So its used for
than 0.9% NaCl , water will 0.9% NaCl , water will flow
intravenous injections so that
flow out cells and they would into the cells if placed in the
the blood cells neither swell
shrink. solution and would swell
nor shrink
Examples
 • At 300 K, 36 g of glucose present in a
litre of its solution has an osmotic
pressure of 4.98 bar. If the osmotic
Q2.22(NCERT)
pressure of the solution is 1.52 bar at the
same temperature , what would be its
1 C1 concentration?

 2 C2
36
4.98
 180
1.52 C2
36 1.52
C2 
180 4.98
0.061mol / L
•In a mixture of two solutions, the solution with lower osmotic
pressure is hypotonic while solution with higher osmotic pressure is
hypertonic.

•The outflow of fluid from the plant cells placed in a hypertonic

solution is known a plasmolysis (shrinkage of plant cell).
 Reverse
Osmosis

The direction of
osmosis can be
reversed if the pressure
larger than osmotic
pressure is applied to
the solution side . Now
pure solvent flows out
of the solution through
the semi permeable
membrane .This
phenomena is Reverse
Osmosis(RO)
Desalination of sea water
 Portable The workable
When on the
water
solution side, porous
pressure is membrane is a
film of
applied which
cellulose
is quite high , acetate placed
the pure over a suitable
water is support. This
squeezed out cellulose
of the sea acetate allows
water to water not
impurities and
through the
ions present in
membrane sea water.
ABNORMAL
MOLECULAR
MASSES
Molecular masses can be calculated by
measuring any of the colligative properties. The
relation between colligative properties and
molecular mass of the solute is based on
following assumptions.
(1) The solution is dilute, so that Raoult’s law is
obeyed.
(2) The solute neither undergoes dissociation nor
association in solution
In case of solutions where above assumptions are not valid
we find discrepancies between observed and calculated
values of colligative properties. These anomalies are
primarily due to
(i) Association of solute molecules.
(ii) Dissociation of solute molecules
Dissociation of solute molecules : A number of electrolytes
dissociate in solution to give two or more particles (ions).
Therefore, the number of solute particles, in solutions of such
substances, is more than the expected value. Accordingly, such
solutions exhibit higher values of colligative properties. Since
colligative properties are inversely proportional to molecular
masses, therefore, molecular masses of such substances as
calculated from colligative properties will be less than their
normal values.
VANT HOFF’S
FACTOR (i)

The value of “i” is less than unity in the case of association and
greater than unity in case of dissociation
Q2.32(NCERT)
•Calculate the depression in the freezing point of water when 10 g of CH 3CH2CHClCOOH is added to 250 g
of water . Ka = 1.4 X10-3, Kf = 1.86 K Kg mol -1.

Molecular weight, CH3CH2CHClCOOH = 122.5 g/mol

m = (10X1000)/ 122.5X250 = 40/122.5
Ka = Cα2/1-α
α <<<1
Ka= C α2
= 40/122.5 X α2
1.4X10-3 = 40/122.5 X α2 , α2 = 42.875 X10-4
α = 6.54 X 10-2 = 0.0654 = (i-1)/ n-1 (Dissociation)
0.0654 = i-1/2-1
i = 1.0654
∆Tf = i Kf m = (1.0654 X 1.86 X 40) /122.5 = 0.65°
Q2.41(NCERT) •Determine the osmotic pressure of a solution prepared by dissolving 25 mg of K 2SO4 in 2 litres of water at
25°C, assuming that it is completely dissociated.

K 2 SO4  2 K   SO22
i n 3
V inB RT
3 25 10  3 0.082 298
 2 
174
3 25 10  3 0.082 298

174 2
5.27 10  3 atm
Questions Please !!!!!