Solutions

Solution
It is a homogeneous mixture of two or more
chemically non-reacting substances whose Concept Ladder
composition can be changed within certain limits. A solution which contains
A solution is regarded as a singular phase having as much solute as it
more than one component. can dissolve at a given
A solution which contains two components is temperature is called a
known as binary solution. saturated solution.
A solution which contains
The component which is present in smaller
lesser solute than the
quantities is called the solute and the other
amount of solute if
which present in larger amount is known as the
can dissolve is called
solvent.
unsaturated solution.
The below table shows the list of solutions and
their examples.

Types of Solutions
Solutions of Solids in Liquids
y It is a solution which still in contact with Concept Ladder
excess of solute. A solution which contains
y The solubility of the solute is defined as the more solute than the
amount of solute dissolved per 100 g of solvent amount of solute it can
at a specific temperature for a saturated dissolve at a particular
solution. temperature is called a
Solutions

y For exothermic substances such as KOH, CaO, super saturated solution.

Ca(OH)2, M2CO3, M2SO4 etc.,

1.
 solubility is inversely proportional to
temperature. (M = Alkali metals) Rack your Brain
y For endothermic substances such as NaCl,
KNO3, NaNO2, glucose etc., solubility is directly Why do aquatic species like fish
proportional to temperature. feel more comfortable in the
lakes in winter than in summer?
Solubility of Gases
y Solubility of gases is mostly described in
terms of absorption coefficient, i.e., the
Previous Year’s Questions
volume of the gas (at normal temperature and
pressure), dissolved by unit volume of solvent,
The beans are cooked earlier in
at a specific temperature and 1 atm pressure.
pressure cooker because.
y The solubility factor for a gas in a liquid
[NEET]
depends upon:
(1) Boiling point increases with
1. Temperature
increasing pressure
Solubility have inverse relation with
(2) Boiling point decreases with
temperature as dissolution of a gas is
increassing pressure
exothermic in most cases.
(3) Extra pressure of pressure
Gas + liquid ⇒ Dissolved gas cooker softens the beans
(4) Internal energy is not lost
∆H = –ve
while cooking in pressure
2. Nature of gas cooker.
The gas which can be easily liquified are
more soluble as they contian higher value
of van der Waal’s force of attraction. For
Concept Ladder
example, SO2 and CO2 are more soluble in
water than O2, N2 and H2. Solubility of gases in
3. Nature of solvent liquids decreases with
Gases which can be ionized in aq. solution rise in temperature.
are more soluble in H2O as compared to When dissolved, the gas
the other solvents. molecules are present
4. Pressure of the gas (Henry’s law) in liquid phase and the
This law states that the solubility of a gas process of dissolution can
in a given volume of liquid at constant be considered similar to
temperature is directly proporitonal to condensation and heat is
the pressure of the gas. evolved in this process. As
m∝P dissolution is an exothermic
process. the solubility
m = KP should decrease with
increase of temperature.
Solutions

2.
 m
or = KH (At constant temperature)
p
Rack your Brain
P = Pressure of gas at equlilibrium with
solution Why does the solubility
m = The mass of gas dissolved by unit of exothermic substances
volume of solvent. decreases with increasing of
Here KH = Henry’s constant (Function of temperatrue?
nature gas)
When solubility is expressed as its mole
fraction (X)
P ∝ X or P = KH X
1
So lub ility ∝
KH

Concept Ladder
To increase the solubility of
CO2 in soft drinks and soda
water, the bottle is sealed
under high pressure.

y Henry’s law is obeyed only when

1. Gas does not dissociate.
2. Pressure is not too high.
3. In solvent, gas is not highly soluble.
4. Temperature is not too low.
5. Gas should be inert.
e.g. NH3 + H2O 
 NH4OH
Concept Ladder
y The volume of the dissolved gas does not
When air enters the lungs,
depend upon pressure at a particular
partial pressure of oxygen is
Temperature.
high. This oxygen combines
Applications of Henry’s Law: with haemoglobin to form
(1) Soft drinks bottles are sealed at high oxyhaemoglobin. Partial
pressures to increase solubility of CO2 in pressure of O2 in tissues is
water. low. Hence, O2 is released
(2) Sea divers used a mixture of O2 + He from oxyhaemoglobin
to minimize the painful effect by N2 in which is utilised for
decomposition. functions of the cells.
Solutions

3.
 (3) At higher altitudes, breathing becomes
tough as O2 is less available in the air due
to less pressure.

Expression of Concentration of Solution

Solubility
The amount of solute which is dissolved in a
specific amount/volume of solution. It is denoted
by C or S.
Concept Ladder
Weight of solute in gram W Air quality measurement
C or S = or g / L
Volume in litre V are commonly reported in
C= N × E terms of: micrograms per
cubic meter (mg/m3) part
N = Normality of solution, per meilion (ppm) or parts
E = Eqivalent weight of solute per billion (ppb)
Concentration in parts per million (ppm)
When any amount of solute is present in one
million (106) parts of the solution, then it is known
as ppm.
Mass of A
=ppm(A) × 106
Total mass of the solution
Concentration in parts per billion (ppb)
When any amount of solute is present in one
billion (109) parts of the solution, then it is known
as ppb.

Mass of A Previous Year’s Questions

=ppb(A) × 109
Total mass of the solution
Molarity (M) How many grams of concentrated
It is the no. of moles of solute present in one nitric acid solution should be
litre of the solution, and it is denoted by M. used to prepare 250 mL of 2.0 M
y When molarity of a solution is one, it is called HNO3? The concentrated acid is
one molar solution. 70% HNO3. [NEET]
Weight of solute in gram (1) 70.0 g conc. HNO3
M=
Molar mass × Volume in litre (2) 54.0 g conc. HNO3
In case of dilution or mixing, (3) 45.0 g conc. HNO3
M
=1 V1 M
=2 V2 M3 V3 (4) 90.0 g conc. HNO3
M1 V1 + M2 V2 M V − MB VB
MR = or A A
V1 + V2 VA + VB
A → Acid; 1 → So lute (1)
Solutions

B → Base; 2 → So lute (2)

(Both don't react with
each other) 4.
5.
Solutions
 Molality (m)
No. of moles of solute dissolved in 1 kg of
solvent. It is denoted by m.

Weight of solute in gram

m=
Molar mass × wt. of solvent in kg
Previous Year’s Questions

y If molality of a solution is one, it is called

If molality of the dilute solution
molal solution.
is doubled, the value of molal
y Concentration of one molal solution is less
depression constant (Kf) will be
than that of one molar solution.
[NEET]
y Molality is used preferably over molarity in
(1) halved
experimental calculations as molality is
(2) tripled
temperature independent while molarity is
(3) unchanged
affected by temperature.
(4) doubled
Normality (N)
It is the no. of gram equivalents of a solute
present in a litre of solution, and is denoted by N.

Weight of solute in gram

N=
Equivalent mass × Volume in litre

y Relation between normality and molarity.

N × Eq. wt. = Molarity × Molar mass

N = Molarity × Valency
Concept Ladder
N = Molarity × Number of H+ or OH ion. Normality is gram
Formality (F) equilvalents/L or number
It is the no. of gram formula present in a litre of miliequivalents (meq)
of solution for an ionic solute. It is denoted by F. per cc of the solution and
molarity is mol/L or number
Weight of solute in gram of milimoles (mmol) per cc
F=
Formula wt. × Volume in litre of the solution.
No. of equivalent of solute
y It is applicable for ionic solids like NaCl. in solution (V) = N × V
No. of Moles of solute in
solution (V) = M × V [V =
Volume of Solution]
Solutions

6.
7.
Solutions
 Mole fraction
Mole fraction of a component is given by
the moles of one component divided by the
total no. of moles present in that solution. It is Previous Year’s Questions
expressed by X, for example, for a binary solution
two component A and B, What is the mole fraction of
nA the solute in a 1.00m aqueous
Mole Fraction of A (XA ) =
nA + nB solution?
nB [NEET]
Mole Fraction of B (XB ) =
nA + nB (1) 1.770
nA = no. of moles of A. (Solute) (2) 0.0354
nB = no. of moles of B. (Solvant) (3) 0.0177
w  (4) 0.177
Weight per cent =  × 100  It is weight of
 W 
solute present in 100 g of solution.
v 
Volume per cent =  × 100  It is volume of
V 
solute present in 100 mL of solution.
Moles of solute
=Mole per cent × 100
Total moles present in solution

Mass fraction
The ratio of the mass of the component to
the total mass of the solution is known as Mass
Fraction. It is given for a solution which contains
wA g of A and wB g of B,
WA
Mass fraction of A (XA ) =
WA + WB

WB
Mass fraction of B (XB ) =
WA + WB
So, xA + xB = 1 Concept Ladder

Sum of mole fraction of

y When one mole of a solute is present in one solute and solvent will be
litre of solution at 0°C it is called one always equal to 1.
demal solution.
1 Molar > 1 molal.

Relation Between Molarity (M) and Molality (m)

⇒ Let Molarity = M
Molality = m
Solutions

8.
 =Mass of solute = w (in gram)
Mass of solvant (in gram) = W
M2 = Molar mass of solute
d = density of solution
So mass of solvent = 1000d – MM2 g Definitions
w 1000 Vapour pressure of a liquid/
As =
m ×
M2 W solution is the pressure exerted
M by the vapour in equilibrium
So m
= × 1000 with the liquid/solution at a
1000d − MM2
M particular temperature.
m=
MM2
d−
1000
Vapour Pressure
Vapour Pressure of a Liquid
y When the vapour phase is in equilibrium
with the liquid is for a given temperature
Rack your Brain
then the pressure forced by the vapours is
known as vapour pressure of a liquid. Nature
Which unit is useful in relating
of the liquid and temperature are the two
concentration of solution with
dependent properties for it.
its vapour pressure?
y Vapour pressure of a solution is always
lesser than the vapour pressure form of its
pure liquid state.
y For having an idea of attractive force between
the molecles of a liquid, vapour of a liquid is
used. Force of attraction has inverse relation
with vapour pressure.
e.g., → P°C2H5OC2H5 > P°C2H5OH > P°H2O > P°Glycol
Concept Ladder
y With increase in temperature, vapour
pressure of liquid increases as kinetic energy A substance with a
of molecules increases. high vapour pressure
y The variation of vapour pressure with at normal temperature
temperature can be given by Clausius- is often referred to as
Clapeyron equation as follows: volatile. So, alcohol is
more volatile than water
P2 ∆Hvap  T2 − T1  because of presence of
log 10 =  
P1 2.303 R  T1T2  hydrogen bonding between
molecules of water.
Solutions

9.
 Rack your Brain

Why vapour pressure of aqueous

solution of glucose lower than
that of water?.

Vapour Pressure of a Solution

y When the pure solvent is added to a miscible
solute then they form a solution. There is
decrease in escaping tendency of solvent
molecules as some molecules of solute
replace the molecules of the solvent from the Concept Ladder
surface. This causes decrease in the vapour In a solution, the vapour
pressure. prssure of a componenet
y The vapour pressure of a pure solvent is more at a given temperature is
than that of its solution. equal to the mole fraction
y If the vapour pressure of a solvent is po and of that component in the
that of solution is ps then, lowering of vapour solution multiplied by the
pressure = po – ps vapour pressure of that
y When there is decrease in surface area component in the pure
occupied by the solvant molecules and state.
increase in density, the vapour pressure of a
solution decreases.

Raoult’s Law
Raoult’s Law for Volatile Solutes
It states that for a given solution, the vapour
pressure of a component for a given temperature Previous Year’s Questions
is equal to the multiplication of mole fraction
of the component in the solution and V.P. of In which case Raoult’s Law is not
that component in its pure state for the same applicable?
temperature. For a solution containing two [AIIMS]
components A and B the total vapour pressure P (1) 1M NaCl
is : (2) 1M Urea
pA = p0A × xA (3) 1M glucose
(4) 1M sucrose
pb = p0b × xB

P = pA + pB = p0A xA + p0B xB
Solutions

10.
As we know that:
xA + xB = 1

xA = (1 – xB) Concept Ladder

P = (1 – xB) p0A + p0B xB The relative lowering

of vapour pressure of a
P = (p0B – p0A) xB + p0A solution containing a non-
As P0A, P0B are constant at a particular temperature volatile solute is equal to
hence PT is a linear function of the mole fraction the mole fraction of the
(xB). solute in the soluton.

Raoult’s Law for Non-volatile Solutes

Raoult’s law states that the relative lowering
of vapour pressure of a solution containing a
non-volatile solute is equal to the mole fraction
of the solute in the solution.
0
Previous Year’s Questions
P − Ps n2
= = x2
P0 n1 + n2 Which of them is not equal to
Here, zero for an ideal solution?
x2 = Mole fraction of solute [NEET]
n1 = Moles of solvent (1) DVmix
n2 = Moles of solute (2) DP = Pobserved — PRoult
ps = Vapour pressure of the solution (3) DHmix
p0 = Vapour pressure of pure solvent (4) DSmix

Ideal Solutions
Ideal solutions are the solutions in which
solute-solute and solvent-solvent interactions
are almost similar to solute-solvent interactions
(A—B = A—A or B—B interactions) and such
solutions satisfy the following requirements:
1. They obey Raoult’s law for all ranges of Definitions
concentrations and temperature.
2. ΔH (mix) = 0 An ideal solution is that solution
3. ΔV(mix) = 0 in which each component
4. (V·P)obs = (V·P)exp. obeys Raoult’s law under all
(B·P)obs = (V·P)exp. conditions of temperature and
5. No dissociation or association takes place concentrations.
here.
Solutions

11.
 6. No chemical reaction between solute and
solvent.
7. It does not form azeotrope mixture. Previous Year’s Questions
Examples:
1. Benzene + toluene A solution containing components
2. Hexane + heptane A and B follows Raoult’s law
3. Ethyl bromide + ethyl iodide [AIPMT]
4. Chlorobenzene + bromobenzene (1) A—B attraction force is greater
5. CCl4 + SiCl4 than A—A and B—B.
6. All dilute solutions (2) A—B attraction force is less
than A—A and B—B.
(3) A—B attraction force is
remains same as A—A and
B—B.
(4) Volume of solution is different
from sum of volume of solute
and solvent.

Non-ideal Solutions
Non-ideal solutions are the solutions in which
solutesolvent interactions are different from
solute-solute and solvent-solvent interactions.
These solutions do not obey Raoult’s law for all
concentrations and:
1. ΔH (mix) ≠ 0
2. ΔV (mix) ≠ 0 Definitions
Types of Non-ideal Solutions A non-ideal solution is that
(a) Non-ideal solutions showing positive solution in which solute and
deviations: Positive deviation occurs when solvent molecules interact with
total vapour pressure for any mole fraction one another with a different force
is more than what is expected according to than the forces of interaction
Raoult’s law. This happens when the new between the molecules of the
interactions are weaker than the interaction pure components.
in the pure component (A—B < A—A or B—B
interactions).
Solutions

12.
y ΔH = +ve, ΔV = +ve, ΔS = +ve, (V.P)obs > (V.P)exp.
PA > PA0 · XA, PB > PB0 · XB
Previous Year’s Questions
PT > PA0 XA + PB0· XB
y It forms minimum boiling azeotrops, for A solution of acetone in ethanol
example, C2H5OH + cyclohexane. The H- [AIPMT]
bonding present in pure C2H5OH are cut off (1) obeys Raoult’s Law
on adding cyclohexane. For such solution, ΔV (2) shows a negative deviation
and ΔH are positive. from Raoult’s Law
Examples: (3) shows a positive deviation
1. Acetone + carbon disulphide, from Raoult’s Law
2. Acetone + benzene (4) behaves like a near ideal
3. Carbon tetrachloride + chloroform or Toluene solution.
4. Methylalcohol + water
5. Acetone + C2H5OH

Rack your Brain

Why does a solution of ethanol

and cyclohexane show positive
deviation from Raoult’s Law?

(b)
Non-ideal solutions showing negative
deviations: Negative deviation is seen when
total vapour pressure for any mole fraction
is less than that expected from Raoult’s law. Rack your Brain
This happens when the new interactions are
stronger than the interactions in the pure
Two liquids A and B on mixing
components
produce a warm solution. Which
(A—B > A—A or B—B interactions).
type of deviation from Raoult’s
y ΔH = –ve, ΔV = –ve, ΔS = +ve
law does it show?
(V·P)obs. < V·Pexp.
PA < PA0 . xA, PB < PB0· xB ; PT < PA°.xA + PB°.xB
Solutions

13.
 y It forms maximum boiling azeotrope, for
example, CHCl3 + CH3COCH3 . For such
solutions, ΔV and ΔH are negative.

Rack your Brain

Cutting onions taken from the

fridge is more comfortable than
Examples: cutting those lying at room
1. Chloroform + benzene ordiethyl ether temperature. Why?
2. Acetone + aniline
3. Nitric acid (HNO3) + water
4. Acetic acid + pyridine

Concept Ladder

Azeotropic mixtures cannot

be separated into their
constituents by fractional
distillation. For example,
Azeotropic Mixture
if we try to concentrate a
It is a mixture of two liquids having the same
dilute solution of alcohol,
boiling point. Because of same boiling point
we can do so only till it
the two liquids cannot be separated by simple
becomes 95.4% because
distilation. These mixtures are therefore called
after that it becomes a
constant boiling mixtures. These are formed by
constant boiling mixture
non-ideal solutions.
(azeotrope). The mixture
Azeotropic mixture and composition curves
containing 95.4% alcohol
y These are the mixture of two liquids which
and 4.6% water is called
boils at one particular temperature like a pure
rectified spirit.
liquid and distils over in the same composition
i.e., these are constant boiling mixtures. These
are formed by non-ideal solutions.
Solutions

14.
15.
Solutions
 y For the separation of constituent particles of
the liquid mixtures by distilation, the study of
vapour pressure curves of the mixtures will
make it easy.
y By fractional distilation method the separation
will be possible only when the composition
of vapour phase is different from that of the
boiling liquid phase. Concept Ladder

To obtain pure alcohol

Types of azeotropic mixtures
(100% alcohol) called
These are of the following two types:
absolute alcohol from
1. Azeotropic mixtures with minimum boiling rectified spirit, the method
point: Azeotropic mixture is the mixture of used to called azeotropic
two liquids in which the boiling point of the distillation. For this
mixture is lesser than either of the two pure purpose, rectified spirit
components. is mixed with a suitable
y It is formed by the composition of a non-ideal amount of benzene. The
solution which shows positive deviation to the mixture is then subjected
solution having maximum vapour pressure. to fractional distillation.
y This mixture consists non-ideal solutions
showing positive deviation Raoult’s law and
for which, the vapour pressure is maximum.
For example, C2H5OH (95.5%) + H2O (4.5%)
mixture boils at 351.5 K.
(B.P. of C2H5OH = 78.1° C, B.P. of H2O = 100° C)
Solutions

16.
y Such mixtures on distillation will give first
fraction upto point M in pure state. After this
the temperature will rise and the second
component will pass over. Hence in such Rack your Brain
solutions also complete separation is not
possible. The dissolution of ammonium
y The figure shows maximum vapour pressure chloride in waster is an
at point M and therefore solution has lowest endothermic process but still it
boiling point. dissolves in water readily. Why?

2. Azeotropic mixtures with maximum boiling

point: Azeotropic mixture is the mixture of
two liquids in which the boiling point of the
mixture is larger than either of the two pure
components.
y It is formed by the composition of a non-ideal
Concept Ladder
solution which shows negative deviation to
the solution having minimum vapour pressure. Tertiary azeotrope is a
E.g., Nitric acid (68%) + water (32%) mixture mixture of water (7.4%),
Benzene (74.1%) and
boils at 393.5 K.
Alcohol (18.5%). Whereas
An aqueous solution of HCl initally gives pure binary azeotrope is a
water when subjected to distillation and mixture of Benzene (67.7%)
later forms a constant boiling mixture at a and Alcohol (32.2%).
temperature of 100°C containing 20.24% acid.
y During distillation when two volatile liquids
A and B are mixed, for condition having A
is more volatile and present in excess, the
vaopur part will be richer in component A and
liquid part will be for component B. Lastly, A Rack your Brain
point is reached ‘N’ where the boiling point
is maximum and the vapour pressure is Can we separate the
minimum as shown in the figure. componenets of azeotropic
y For this stage from this type of solution, mixture by distillation?
complete separation of components into its
pure state is impossible.
Solutions

17.
 3. Mixture Showing ideal behaviour or zeotropic
mixture: Zeotropic mixture is defined as the
liquid mixture which get distilled whenever
Concept Ladder
there is change in its concentration.
y For zeotropic mixture, the vapour pressure Absolute alcohol is
composition curve for liquids A and B is a prepared by azeotropic
straight line. A will be collected distillate as it distillation method.
become more volatile on distillation. Rectified spirit is mixed
y The remaining fraction will be richer in B with a suitable amount of
and poorer in A. We can get A and B in their benzene and subjected to
pure state, on repeating the process of fractional distillaton.
distillation again and again, e.g., methanol-
water mixture.
Solutions

18.
Solubility of Partially Miscible Liquids
Conjugate solutions
Many liquids are partially miscible and form
two liquid layers at a particular temperature. Such
liquid solutions in which different compositions
of components coexist are called conjugate
solutions, for example, phenol and water.
Critical temperature Definitions
With change in temperature the miscibility of Those properties of ideal
liquids changes. For a certain temperature the two solutions which depend only
layers become completely miscible. This certain on the number of particles of
temperature is termed as critical temperature or the solute (molecules or ions)
consolute temperature. dissolved in a definite amount
of the solvent and do not
Colligative Properties depend on the nature of solute
The properties of a solution which depend are called colligative properties.
only on the number of particles like molecules
or ions of the solute in a definite amount of the
solvent but not on the nature of the solute, are
termed as Colligative Properties. These are as
follows:
1. Relative lowering of vapour pressure
2. Osmotic pressure
3. Elevation in boiling point
4. Depression in freezing point
y VP, BP, FP, MP and Osmosis are not colligative Previous Year’s Questions
properties.
y These are properties of dilute solution non- Pure water can be obtained from
volatile solute without any dissociation or sea water by
association. [AIPMT]
(1) centrifugation
Relative Lowering of Vapour Pressure (2) plasmolysis
When a non-volatile solute is mixed with a (3) reverse osmosis
volatile solvent, the vapour pressure of solution (4) sedimentation
becomes less than the vapour pressure of pure
solvent. It is due to increase in density which
decreases rate of evaporation.
1
Mathematically, p ∝ d

If p0 = vapour pressure of pure solvent

p = vapour pressure of solvent in solution
Solutions

19.
 y The lowering of vapour pressure

Δp = (p0 – p)

y The ratio in the lowering of vapour pressure

and the vapour pressure of pure solvent
is define as the relative lowering of vapour
pressure.

∆p p0 − p
= = Relative lowering of vapour pressure
p0 p0

y When a solution is prepared by

mixing the non-volatile solute B and
solvent A
xA + xB = 1

xB = 1 – xA
Here, xB is the mole fraction of solute.

pA
As = xA Previous Year’s Questions
p0A
p
1 − 0A =1 − xA =xB ; (  1 − xA =xB ) A solution has a 1 : 4 mole
pA
ratio of pentane to hexane. The
p0A − pA ∆p n
= x=
B = vapour pressures of the pure
pAo
pA n + N
0
hydrocarbons at 20°C are 440
Here, n = Number of moles of the solute mm Hg for pentane and 120 mm
N = Number of moles of the solvent Hg for hexane. The mole fraction
y In a dilute solution, N is far greater than n, of pentane in the vapour phase
and hence, would be
[AIPMT]
n w / m wM (1) 0.200
x=
B = =
N W / M Wm (2) 0.549
Here, (3) 0.786
W = Weight of solvent (4) 0.478
w = Weight of solute
M = Molecular weight of solvent
m = Molecular weight of solut

p0A − pA ∆p wM m × M
So, = = =
p0A p0 Wm 1000
Solutions

20.
y The molecular weight of a solute can be
determined with the help of the relative
lowering of vapour pressure method
Previous Year’s Questions

y R.L.V.P is measured by ostwald walker method. During osmosis, flow of water

through a semipermeable
P0 − PS Loss in Mass of Solvent bulbs
= membrane is
p0 Gain in CaCl 2 tube [AIPMT]
Osmosis (1) from solution having lower
In osmosis, there is a net flow of solvent molecules concentration only
from a less concentrated solution to a more (2) from solution having higher
concentrated solution or from the solvent to the concentration only
solution or across a semi-permeable membrane (3) from both sides of
(membranes of animal origin, membranes made semipermeable membrane
from with equal flow rates
(4) from both sides of
Cu2[Fe(CN)6], Ca3(PO4)2 etc.) semipermeable membrane
with unequal flow rates.
Osmosis was first observed by Abbe Nollet in
1748. e.g.
(1) Absorption of water from soil by cell walls of
roots.
(2) Water movement from root to upper parts of
plants.

Osmotic Pressure
y When the column is formed as a result of
osmosis, then the equilibrium hydrostatic Rack your Brain
pressure is known as Osmotic Pressure.
y To restrict the entry of the solvent into
What will happen if pressure
the solution through the semi-permeable
greater than the osmotic
membrane, the min. pressure that is to be
pressure is applied on the
applied on the solution is osmotic pressure.
solution separated by a semi-
y It is the min. pressure needed to apply on a
permeable membrane from the
solution for making its vapour pressure equal
solvent?
to vapour pressure of the solvent.
y It is denoted by P or p.
y It is measured by Pfeffer’s method, Berkely-
Hartley’s method, Townsend’s method.
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21.
 Van’t Hoff equation of osmotic pressure
p = CST
Here,
Concept Ladder
p = Osmotic pressure When the membrane
S or R = Solution constant permits the solvent
(≈ 0.0821 Latm/K. mol) molecules to come out
C = Concentration of solution in mol/L through the membrane,
T = Absolute temperature in K it is called exomosis
So, p ∝ C (At constant temperature) (exo-osmosis). When the
n membrane permits the
=p =ST (C n/ V) solvent molecules to
V
enter inside, it is called
p V = nST endosmosis (endo-
Here, osmosis).
n = Numbers of moles the solute,
V = Volume of solution

w
pV = RT
M
As n = w/M
M = Molar mass of solute
w = Gram weight of solute

Determination of molecular weight from osmotic

pressure
p = CST
C = n/V Previous Year’s Questions
C = Concentration of solution.
n = No. of moles of solute in solution. From the colligative properties of
y When solute is dissolved in V litre then solution, which one is the best
method for the determination of
=pV nST= (n W/ M)
molecular weight of proteins and
W polymers?
pV = ST
M [AIPMT]
W × ST (1) Osmotic pressure
M=
p×V (2) Lowering in vapour pressure
y Accurate molecular weight is obtained under (3) Lowering in freezing point
the following conditions: (4) Elevation in boiling point
Solutions

22.
1. Solution must be very dilute.
2. Solute must be non-volatile.
3. Solute should not undergo dissociation or Concept Ladder
association in the solution.
y When height is involved then, p = hdg If two solutions have
y d = density of solution. same osmotic pressure
y h = hight difference in both vessel (due to and hence same molar
osmosis) concentration, they are
Isotonic solution called isotomic. If of
Solutions having equal molar concentrations lower osmotic pressure,
or equal osmotic pressures are called isotonic it is called hypotonic
solutions. For example, 0.91% solution of pure with respect to the more
aqueous NaCl is isotonic with human RBC. concentrated solution.
The more concentrated
P1 = P2 or p1 = p2
solution is said to be
w1 w2 hypertonic with respect to
=
M1 V1 M2 V2 the dilute solution.
y In an isotonic solution net osmosis is zero.
When RBCs are placed in distilled water
(Hypotonic medium) they swell as water
flows into them, but when they are taken in
5% NaCl solution (Hypertonic) they shrink as
water comes out from the cells.
Elevation in Boiling Point Concept Ladder
Boiling point is the temperature of a liquid at
which its vapour pressure becomes equal to the RT02 M1RT02
=Kb =
atmospheric pressure. 1000l v 1000 ∆ vapH
∆ vapH
where, l v =
M1
T0 = Boiling point of the
liquid (pure solvent)
lv = latent heat of
vaporisation (per gm)
DvapH = latent heat of
vaporisation (per mole)
M1 = M.M of solvent
R = Gas constant
Solutions

23.
 y Elevation in the boiling point is also termed
as ebullioscopy. Definitions
y It is the increase in boiling point of a solvent
Molal elevation constant may
due to the addition of non-volatile solute in
be defined as the elevation of
it. It is denoted by ΔTb.
boiling point when the molality
y It is measured by Lands Berger’s method and
of the solution is unity, i.e., 1
Koltrell’s method.
mole of the solute is dissolved
y The elevation in B.P. is given as
in 1 kg (1000 g) of the solvent.
m = molality of solution The units of Kb are, therefore,
degree/molality, i.e. K/m or °C/m
∆ Tb α m or ∆ Tb =
Kb .m or K kg mol-1.
w 1000
So, ∆ Tb = Kb × ×
M W
Mw = kb × w × 1000
Molecular weight of solute, MW
∆Tb × W
Here,
W = Weight of solvent Rack your Brain
w = Weight of solute
Kb = Molal elevation constant or ebullioscopic
Why elevation of boiling point is
constant.
a colligative properte?
If molality of the solution is one, then

∆ Tb =
Kb
RT2
Kb =
1000 L v
∆Hv
Lv =
M
Here, Lv = Latent heat of vaporization.
y If molar elevation in boiling point constant (K) Previous Year’s Questions
is to be calculated, then replace 1000 with
100 in the above mentioned formula, that is, The freezing point depression
K = 10 Kb. constant for water is -1.86°C
m-1. If 5.00g Na2SO4 is dissolved
Depression in Freezing Point in 45.0g H2O, the freezing point
Freezing point is a measure of temperature for is changed by -3.82­°C. Calculate
the substance having the same solid and liquid the van’t Hoff factor for Na2SO4.
forms in equilibrium, also having same vapour [AIPMT]
pressure. Solid form of a solution separates out (1) 2.05 (2) 2.63
at a lower temperature because of lower vapour (3) 3.11 (4) 0.381
pressure of the solution.
Solutions

24.
y It is the decrease in freezing point of a solvent
due to the addition of a non-volatile solute.
Rack your Brain
y This is also termed as cryoscopy.
y Depression in freezing point (ΔTf) = Freezing
Sodium chloride solution freezes
point of pure solvent – Freezing point of
at lower temperature than water
solution
but boils at higher temperature
y It is measured by Beckmann’s thermometer
than water. Explain.
method and Rast’s method.
∆Tf = Kf.m.

w 1000
• ∆=
Tf Kf ×
mw W
Kf × w × 1000 Concept Ladder
• M or mw =
∆ Tf × W
Here, RT02 M1RT02
=Kf =
W = Weight of solvent 1000l f 1000 ∆ fusH
w = Weight of solute ∆ fH
where, l f =
Kf = Molal depression constant or cryoscopic M1
constant
T0 = freezing point of the
y If molality of the solution is one, then liquid (pure solvent)
lf = latent heat (per gram)
ΔTf = Kf
DfusH = latent heat of fusion
RT2 M1 = M.M of solvent
• Kf =
1000 Lf R = Gas constant
Solutions

∆Hf
Lf =
M
25.
Solutions

26.
 RTf 2
Kf =
l f × 1000 Definitions
Here, lf = Latent heat of fusion
Molal depression constant may
y If molar depression in freezing point constant
be defined as the depression of
(K) is to be calculated, then replace 1000 with
freezing point when the molality
100 in the above-mentioned formula, that is,
of the solution is unit i.e., one
K = 10 Kf
mole of the solute is dissolved
in 1000 g (1 kg) of the solvent.
Van’t Hoff Factor
The units of Kf are, therefore,
y Certain solutes which undergo dissociation
degrees/molality i.e., K/m or [K]
or association in solution, are found to show
[kg] [mol]-1
abnormal molecular mass. Due to this, the
colligative property becomes abnormal which
can be explained by Van’t Hoff factor.

Normal molar mass

i=
Observed molar mass Rack your Brain
Observed colligative property
i=
Normal colligative property Value of i (Van’t Hoff Factor) for
Actual number of particles or species aqueous KCl solution is close to
i= 2, while the value of ethanoic
Expected number of particles or species
acid in benzene is nearly 0.5
why?
y For solutes showing dissociation, the van’t
Hoff factor i > l.
For example, Fe3+ + 3Cl − 
→ Fe3+ + 3Cl − Here i = 4

i = 2 for MX, MNO3 , MSO4 

Concept Ladder
i = 3 for MX2 , M2O, M(NO3 )2 
i 4 for= MX3 , K3 [ Fe(CN)6 ]  When α 1 Van’t Hoff factor, (i)

i = 5 for M2 X3 , M2 (SO4 )3 ,  • i > 1 (in case of
M3 (PO4 )2 ,K4 [Fe(CN)6 ] dissociation)
• i < 1 (in case of
association)
y For solutes showing association, the van’t
Hoff factor i < 1. For example, dimerization of
acids like benzoic acid in benzene.
y For solutes showing neither dissociation nor
association, the van’t Hoff factor i is 1, for
example, urea, glucose, sucrose.
Solutions

27.
Solutions

28.
 i−1
y Degree of dissociation, α =
n−1
Here n = Number of species formed after
dissociation

n(1 − i)
Degree of association, α =
n−1
Here n = Number of species formed after
association.
Measuring Molecular Mass of Polymers
Molecular mass of polymers is best determined
by osmotic pressure method; firstly, because the
values given by other colligative properties are
so low that they cannot be measured accurately,
and secondly, osmotic pressure measurements
can be made at room temperature and do not
require heating which may change the nature of
the polymer.

Q.1 Distinguish between the boiling point of a liquid and the normal boiling point
of a liquid.

A.1 B.P. is the temperature at which the vapour pressure of the liquid becomes
equal to the surrounding pressure. The normal B.P. is the temperature at
which the vapour pressure is 1 atm.

Q.2 Briefly explain the underlying principle of the purification of water by reverse
osmosis.

A.2 When pressure greater than osmotic pressure is applied on the salt water
side of a semi-permeable membrane, water molecules flow through the
membrane towards pure water side.
Solutions

29.
 Q.3 Components of a binary mixture of two liquids A and B were being separated
by distillation. After some time separation of components stopped and the
composition of the vapour phase became the same as that of a liquid phase.
Both the components started coming in the distillate. Explain why this
happened.

A.3 Both the components started coming for distillation, the liquid and vapour
phase will have the same composition. This shows an azeotropic mixture.
Therefore it can’t be separated by distillation.

Q.4 Explain why on the addition of 1 mol of NaCl to 1 litre of water, the boiling point
of water increases, while the addition of 1 mol of methyl alcohol to one litre of
water decreases its boiling point.

A.4 NaCl is a non-volatile solute. On adding NaCl to water, vapour pressure is

lowered and hence boiling point of water increases. Methyl alcohol is more
volatile than water. On adding methyl alcohol into water, vapour pressure of
solution is greater than that of water. hence, boiling point of water decreases.

Q.5 Explain the solubility rule “like dissolves like” in terms of intermolecular forces
that exist in solutions.

A.5 For one substance to dissolve into another substance, the two substances
should have similar intermolecular interactions. This is so only when either
both the substances (solute and solvent) are polar or both are non-polar. This
rule is called “like dissolves like”.

Q.6 Concentration terms such as mass percentage, parts per million, mole fraction
and molality are independent of temp., however, molarity is a function of
temperature. Explain.

A.6 Change in molarity of a solution is due to the change in volume which is cause
due to change in temperature. Hence, terms such as ppm, mole fraction,
mass percentage and molality are independent of temp., as their calculations
are based on mass and do not involve volume.
Solutions

30.
Q.7 What is the significance of Henry’s Law constant KH?

A.7 Higher the value of Henry’ss law constant, KH, lower is the solubility of gas in
the liquid

Q.8 Why are aquatic species more comfortable in cold water in comparison to
warm water?

A.8 Due to the increase in solubility and availability of O2, aquatic species are
more comfortable in cold water

Q.9 Why soda water bottle kept at room temperature fizzes on opening?

A.9 Both pressure inside the bottle and solubility of carbon dioxide reduces, when
a soda water bottle is opened at room temp. and normal pressure conditions,
therefore causing the gas bubbles to escape and soda water fizzing.

Q.10 Why is the vapour pressure of an aqueous solution of glucose lower than that
of water?

A.10 In pure water, the entire surface is occupied by water molecules which are
volatile. On adding glucose, some water molecules on the surface are replaced
by glucose molecules which are non-volatile. Hence, vapour pressure is
lowered.

Q.11 Mixing of acetone with chloroform takes place with reduction in volume ?
What type of deviation from Raoult’s law is shown in this case ?

A.11 The solution has negative deviation from Raoult’s law because decrease
in volume indicates strong forces of interaction between the molecules in
solution.
Solutions

31.
 Q.12 How does sprinkling of salt help in clearing the snow-covered roads in hilly
areas? Explain the phenomenon involved in the process.

A.12 When salt is spread over snow covered roads, depression in freezing point of
water takes place. At the ambient temperature, snow starts melting and it
helps in clearing the roads.

Q.13 What is a “semi-permeable membrane”?

A.13 A semi-permeable membrane is a continuous sheet or film of suitable material

(natural or synthetic) which has pores such that solvent molecules can pass
through but big molecules of the solute cannot.

Q.14 Write an example of a material used for making semi-permeable membrane

for carrying out reverse osmosis.

A.14 Cellulose acetate and polyamides are the examples of materials used for the
semi-permeable membrane include.

Q.15 Molarity of H2SO4 is 0.8 and its density is 1.06 g/cm3. What will be its concentration
in terms of molality and mole fraction?

A.15 Molarity of H2SO4 = 0.8, it means 0.8 mole H2SO4 are present in 1 L of the
solution 0.8 mole H2SO4 = 0.8 × 98g = 78.4 g;
1L H2SO4 solution = 1000 × 1.06g = 1060g
∴ Mass of solvent (water) = 1060 - 78.4g = 981.6 g = 981.6 moles = 54.53moles
18

Thus, 981.6g of water contain 0.8 mole of H2SO4.

0.8mol
∴ Molality = × 1000 mol kg −1 =
0.815mol kg −1
981.6 g

Further, the solution contains 0.8 mole of solute in 54.53 moles of solvent.
∴ Mole fraction= 0.8
of solute = 0.014
0.8 + 54.53
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32.
Q.16 At a given temperature, the vapour pressure in mm of Hg of a solution of two
volatile liquids A and B is given by the equation p = 120 - 80 XB (XB = mole
fraction of B)
Calculate the vapour pressures of a pure A and B at the same temperature.

A.16 When XB = 0, we have pure A ∴ pA0 = 120 - 80 × 0 = 120 mm

The given expression can be written as p = 120 - 80 (1 - XA)

When XA = 0, we have pure B ∴ pB° = 120 - 80 (1 - 0) = 40 mm

Alternatively, for pure B, xB = 1. Hence, pB0 = 120 - 80 × 1 = 40 mm

Q.17 CCl4 and water are immiscible whereas ethanol and water are miscible in
all proportions. Correlate this behavior with molecular structure of these
compounds.

A.17 CCl4 is a non-polar covalent compound hence it can neither form H-bonds
with water molecules nor it can break H-bonds in water molecules whereas
water is a polar compound. Therefore, CCl4 is insoluble in water.

Ethanol is a polar compound hence it can form H-bonds with water. Therefore,
it is miscible with H2O in all proportions.

Solutions

33.
 Chapter Summary

y Alloys are solutions of solids in solid

y Henry’s Law determines solubility of gas in a liquid.
y When two non-reacting solutions of different normalities are mixed, the normality of
final solution can be calculated by using following equation.
N1V1 + N2V2 = N3(V1 + V2)
y Human RBC is isotonic with 0.91% NaCl
y Osmotic pressure is best colligative property to determine molecular mass of a non
volatile solute and polymers.
y Plasmolysis is shrinking of living (plant or animal) call when placed in hypertonic
solution.
y Reverse osmosis takes place when pressure applied on solution is more than osmotic
pressure. The solvent starts flowing from solution to pure solvent e.g., desalination
of sea water to obtain pure water.
y Substance having high vapour pressure evaporate easily.
y Clausius Clapeyron equation is used to calculate boiling point of solution at given
temperature when boiling point at some other pressure is given.

P2 H  1 1 
log    
P1 2.303 R  T1 T2 
y (i) Aerosol - solid in gas or liquid in gas
(ii) Gel - liquid in solid
(iii) Emulsion - liquid in liquid
y Bredig’s arc method and petisation are method of preparation of colloids and dialysis
is method of purification of colloid.
y Negatively charged colloids are metals and coagulated by +vely charged ions.
y Colloidal gold is called purple of cassius.
y Colloidal antimony is used in treatment of kalazar.
y Proteins are coagulated by Ag+.
y CMC is critical micellisation concentration, the surfactants at this concentration
associate to form micells. For soaps, the CMC value to 10-3 mole/litre.
y Surface tenstion of lyophilic colloids is lower than water.
Solutions

34.