Chapter 1 : Colligative Properties

Relative Molecular [9%] Mass

It is the mass of an element or a compound as compared to the mass of 1/12th part of carbon-12
(C12)
It is calculated by summing up atomic mass of all the elements present in a molecule.
*Mole is the amount of any substance which contains as many elementary entities (atoms,
molecules, ions or particals) as there are carbon atoms in 12g of C-12.
Solution: Solutions is defined as a homogeneous mixtures of solute and solvent.
Solution = Solute + Solvent
Concentration
The amount of solute dissolved in a particular amount of solvent is called concentration of
solution or composition.
Modes of expressing Concentration/ concentration units.
1) Molarity (M)
It is the number of moles of solute dissolved per litre of solution at particular temperature.
*Molarity is dependent on temperature.
no . of moles of solute Weight ×1000
Molarity = OR = *m means molecular mass
Volume∈litre m×Volume ∈ml
n weight w ×1000
M= n= =
V molecular wt . m×V 0 l∈ml
Unit: Mol L-1/ molar/M
Q. Calculate the molarity of 0.98 grams of H2SO4in 100ml of solution. Ans- 0.1 M
Q. What is the molarity of a solution prepared by dissolving 75.5 g of pure KOH in 54o ml of
solution? [k=39, O=16, H=1) Ans-2.50
2 ) Molality (m)
It is defined as the number of moles of solute dissolved per kg of solvent.
*Molality is independent of temperature.
no . of moles of solute w × 1000
Molality = or =
mass∈kg m×W ∈gram
n weight
m= =
w mol . wt
Unit: mol kg -1 / molal /m
Q. 2.82 gram of glucose is dissolved in 30g of H2O. Calculate molality. Ans – 0.52
Q. What is the molality of an aqueous solution of ethanoic acid which contains 6 g of ethanoic
acid in 500g of the solution? Ans-0.2
3)Mole fraction
It is defined as the ratio of the number of moles of a component to the total number of all
components of solution.
Lets assume solution containing component A and B.
nA– be the number of moles of A.
nB– be the number of moles of B.
nA nB
XA= XB= XA + XB= 1
nA+ nB nA+ nB
Q) A solution to be used in hand lotion is prepared by mixing 90g of H2O, 9.2 g of ethyl alcohol
and 18.4g of glycerol. Calculate mole fraction of each of the component.

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 Ans – XH20= 0.92 , XC2H5OH= 0.037, XC3H803= 0.037
Q. calculate the mole fraction of each of the components of a mixture made by dissolving 10g
NaOH and 12.7 g Iodine in 54 g of water. [I=126]
4)Normality
It is the number of gram equivalent of solute dissolved per litre of solution at particular
temperature.
no . of g . eq of solute Wt . of solute ×1000 w ×1000
N= N= N= eq.wt=
Volume Eq . wt of solute × Vol.∈ml E ×Vol .∈ml
moleculer mass N 1V 1+ N 2V 2+ N 3 V 3
N mix=
acidity∨basicity∨valency V 1+V 2+V 3
Equivalent weight: is defined as number of parts by mass of a given substance which combines
with or displaces 1.008 parts by mass of hydrogen.
Equivalent weight of acid: molar mass/no. of replaceable H+ ions
Equivalent weight of Base: molar mass/no. of OH- ions furnished
Equivalent weight of salt: formula mass/charge on cation
Unit : g eq. L-1
Q. Find the equivalent weight of the following; i. H2SO4 ii. NaOH. iii. Na2CO3
Q. Calculate the normality of a solution containing 8g of sodium hydroxide in 2 litre of solution.
Ans – 0.1
Q. Calculate normality of solution obtained by mixing 10ml of N/5 HCl and 30ml of N/10 HCl.
Ans= 0.125
Q. calculate the normality of 970g of H3PO4 in water to make a 10 L solution. Ans-2.97
Vapour pressure
The pressure exerted by the vapour of a liquid on its surface when liquid and vapour phases are
in equilibrium at any definite temperature is called vapour pressure of the liquid.
Factors affecting vapour pressure:
1)Nature of liquids –intermolecular forces-Volatile liquids have higher vapour pressure than
non-volatile liquids.
2)Temperature – Vapour pressure increases with a rise in temperature.
3)Impurities- Non-volatile impurities decreases the vapour pressure of a liquid solution while
volatile impurities increases.
Raoult’s Law
This law applies to the ideal solution where it assumes that the interaction between the solvent
molecule is the same as the interaction between solute and solvent molecules.
Raoult’s law states that- The vapour pressure of any solution containing non-volatile solute in
volatile solvent is directly proportional to mole fraction of the solvent in the solution.
PS=P°A×XA where PS- vapour pressure of solution.P0A- vapour pressure of pure solvent. XA-
mole fraction of solvent.
Ideal and Non-Ideal Solutions
Ideal solutions – A solution of two or more completely miscible liquid is termed as ideal
solution when it obeys Raoults Law at all concentration and temperature.
Conditions for the formation of Ideal solution
1)The component must possess identical intermolecular forces.
2)They must be similar in structure and polarity. Eg: Benzene and Toulene ,
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 Chlorobenzene and Bromobenzene
Characteristics of an ideal solution
I)Solution and its component obey Raoults Law.
PA=P°A×XA PB=P°B ×XB P=PA+PB
II)The change in volume on mixing is zero that is ∆V mixing=0
III)The change in enthalpy on mixing is zero, i.e. ∆H mixing=0
Non-Ideal solutions
-The solution which donot obey Raoults Law is called Non-Ideal Solution.
Conditions for the formation of Non-Ideal solution
1.The component does not possess identical intermolecular forces.
2.They must not be of same structure and polarity.
Characteristics of Non-Ideal solution
i.Solution and its component don’t obey Raoults Law.
PA≠P°A×XA PB≠P°B×XB P≠PA+PB
ii.The change in the volume is not equal to zero
iii.The change in enthalpy is not equal to zero.
Colligatives Properties / Democratic Properties
It is a property of the solution that depends on the number of solute particles present in a given
amount of solvent.
It does not depend upon the chemical nature of solute.
Types of Colligative Properties
1. Relative Lowering of Vapour Pressure.
2. Elevation in Boiling Point.
3. Depression in Freezing Point.
4. Osmotic Pressure.

1)Relative Lowering of Vapour Pressure (Ostwalds and Walkers method)

Raoults law for solution containing non-volatile solute
-V.P of solution (PS)- is the product of v.p of pure solvent (P°) and mole fraction of
solvent(Xsolvent) PS=P°×XSOLVENT……….i
-Since the v.p of pure solvent (P) is more than the v.p of the solution (PS), the change in v.p (∆P)
is given by ∆P=P°-PS …………………ii
-Substituting equation i and equation ii, we get
∆P=P°×XSOLVENT
∆P=P° (1-XSOLVENT)……iii
-As we know that, XA+XB=1
XSOLUTE+XSOLVENT=1 XSOLUTE=1-XSOLVENT
-Substituting XSOLUTE in equation iii, we get
∆P
∆P=XSOLUTE =XSOLUTE
P°
P ° −P s
=XSOLUTEWhere, P°-PS=Lowering of V.P
P°

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P ° −PS
= Relative lowering of V.P
P°
Raoult’s law states that “Relative lowering of Vapour Pressure of a solvent or solution
containing non-volatile solute is equal to the mole fraction of solute in the solution”
∆P w
= XSOLUTEn2= --no.of moles of solute
P° m
n2 W
X2= n1= –no.of moles of solvent
n 1+ n 2 M
-For a very dilute solution n2<<<n1 , hence n2 can be neglected in the denominator in the equation
below:
∆P n2 ∆ P n2
= ………i =
P ° n 1+ n 2 P° n1
∆P w/m ∆P w M
= = ×
P° W/M P° m W
P ° xwxM
m= …………ii Equation ii represents the determination of molecular mass of a
∆ PxW
solute by relative lowering of V.P
Q)The V.P of pure benzene is 640 mm of Hg. A non-volatile solute whose weight 2.175g is
added to 39g of benzene. The V.P of the solution becomes 600 mm of Hg. Determine the
molecular weight of the solute Ans – 69.6.
Q)The V.P of ethanol and methanol are 44.5 mm of Hg and 88.7 mm of Hg respectively. An
ideal solution is formed at the same temperature by mixing 60g of ethanol with 40g of methanol.
Calculate the total V.P of the solution and the mole fraction of methanol in the vapour.
Ans –V.P=66.158 mm Hg and Xmethanol=0.672
Q)Two liquids X and Y on mixing form an ideal solution. At 30° C, the V.P of the solution
containing 3 mole of X and 1 mole of Y is 550 mm Hg. But, when 4 mole of X and 1 mole of Y
are mixed, the V.P of the solution thus formed is 560 mm Hg. What would be the V.P of pure X
and pure Y at this temperature?
Ans -P°Y =400 mm Hg and P°X =600 mm Hg
2.Elevation in Boiling Point (Cottrell’s Method/ Ebullioscopy Method)
Boiling point – B.P of a substance is a temperature at which V.P of a substance becomes equal
to atmospheric pressure.
-the addition of non-volatile solute to a volatile solvent, lowers its V.P
-Therefore, inorder to increase the V.P and to make it equal to atmospheric pressure the
temperature has to be increased.
-The difference between the boiling point of the solution and pure solvent is called elevation of
boiling point.
-The increase in boiling point of solvent on addition of solute to it is called elevation in boiling
point.
-It is denoted by ∆Tb ∆Tb=Tb-T°bwhere ∆Tb= elevation in boiling point
Tb=boiling point of solution
Tb=boiling point of pure solvent/ solvent

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 w×M ×P°
-Experimentally, ∆Tb α ∆P We know, ∆P α
m×W
-P° and M1 are constant for a particular solvent, so
w
∆P = *P° and M1 = constant
m×W
w
∆Tb α ⸫ ∆Tb α molality
m×W
∆Tb = Kb × molality ……….i where Kb = Ebullioscopic constant or elevation of B.P constant.
Substituting molality = w/(mxW) in equation i, we get
Kb× w ×1000
m= *wand W should be in gram *unit of Kb = K molal-1/ K Kg mol-1
∆Tb × W
If molality is equal to 1 than ∆Tb=Kb and that is known as molal elevation constant.
-Kb is elevation in boiling point when the molality of solution is unity (when 1 mole of solute is
dissolved in 1000g of solvent)
Q)An aqueous solution glucose molecular weight 180, containing 12g in 100g of water was
found to boil at 100.34° C. Calculate Kb for water in Kelvin Kg/ mole Ans- 0.51 K Kg /mol
Q) 10g of non-volatile solute when dissolved in 100g of benzene raised its boiling point by 1°C.
what is the molecular mass of the solute? Kb for benzene 2.53 K Kg/mole Ans- 253g
Q) A current of dry air is passed through a bulb containing 5g of a solute in 100g of a water and
then through water alone. The loss in the weight of solution and pure water were respectively
0.78 g and 0.02g. Calculate
i. relative lower of V.P ans- 0.025g ii.molecular weight of solute. Ans-36g

3.Depression(lowering) of Freezing point (Cryoscopy/ Beckmann’s method)

Freezing point- defined as the temperature at which liquid and solid states of substance have the
same V.P or the liquid and solid states of substance are in equilibrium with each other.
Tf- freezing point of soln
T°f- freezing point of solvent. ⸫ ∆Tf=T°f-Tf
The depression of freezing point is directly proportional to lowering of vapour pressure.
Experiments reveal that ∆Tf is directly proportional to molality.
w × kf × 1000
∆Tf α molality ∆Tf = kf × molality m2=
∆ Tf ×W
wherekf = cryoscopic constant or molal depression constant.
-If molality =1 then ∆Tf= Kf
-Cryoscopic constant or molal depression constant (kf)- depression in freezing point which
would be produced by dissolving 1 mole of solute in 1000g of solvent.
-Unit of kf = K Kg mol-1/ K molal-1/ °C molal-1
*Freezing point of a volatile solvent decreases upon the addition of non-volatile solute. This is
due to the lowering of V.P upon the addition of solute.
Q) the cryoscopic constant of water is 1.86 k kg / mol. An aqueous solution of cane sugar freezes
at -0.372°C. Calculate the molality of solution. Ans – 0.2 molal
Q) the normal freezing point of nitrobenzene is 278.82 K. A 0.25 molal solution of a certain
solute in nitrobenzene causes a freezing point depression of 2°. Calculate the value of kf for
nitrobenzene. Ans – 8 K molal-1

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Q) water is used in car radiator. In winter season ethylene glycol is added to water so that water
may not freeze. Assuming ethylene glycol to be non-volatile, calculate the minimum amount of
ethylene glycol that must be added to 6 kg of water to prevent if from freezing at -0.3°C.The
molal depression constant of water is 1.86 K kg mol-1. Ans – 60 g
Q) Addition of 0.643 g of a compound to 50ml of benzene( density=0.879 g/ml) lowers the
freezing point from 5.51°C to 5.03°C. If kf for benzene is 5.12 K kg/mol , calculate the molar
mass of the compound. Ans – 156.06
Q) Calculate the amount of ice that will separate out on cooling a solution containing 50g of
ethylene glycol in 200g of water to -9.3°C. Kf for water is 1.86 K Kg/mol . Ans- 38.71g

Osmotic Pressure (л)

Berkeley and Hartley’s method
Osmosis
- The spontaneous flow of the solvent through a semipermeable membrane from a pure solvent
to a solution or a dilute solution to concentrated solution.
Osmotic Pressure
-Can be defined as the excess pressure which must be exerted on the solution side in order to
prevent the flow of solvent molecules towards the solvent side when both are separated by semi-
permeable membrane.
Van’t Hoff theory of dilute solutions.
-Van’t Hoff found that the dilute solution obey boyle’s law and Charle’s law exactly as the gases
do and this laws came to be called as Boyle-Van’t Hoff Law and Charles-Van’t Hoff Law.
1)Boyle-Van’t Hoff Law
-Temperature remaining constant, the osmotic pressure of dilute solution is inversely
proportional to the volume of solution or directly proportional to concentration.
1
Лα Л α C------i
V
2)Charles’-Van’t Hoff law
-Concentration remaining constant, Osmotic pressure is directly proportional to absolute
temperature.
Л α T…………………ii
3)Avogadro’s – Van’t Hoff law
-The Osmotic Pressure is directly proportional to number of moles of solute.
Л α n………………….iii
-Combining all three equation, we get
n ×T
Лα
V
nRT
Л= *R = gas constant (0.0821)L atm
V
ЛαCRTsince *C = n/ V
*Temperature should be in kelvin.
wt w
Л=nRT/V *n = ( )
mol . wt m

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 WRT WRT
Л= *m =
mV лV
*Unit for л : Pascal, atm , torr
Q) Calculate the OP of solution containing 3.42g of sucrose in 1 litre of water at 127°C.
Ans- 0.3284 atm
Q) Calculate the OP of a decimolar solution of solution of sucrose at 300K.
Ans- 2.463 atm
Q) A 5% solution of cane sugar (molecular weight = 342) is isotonic with 0.877% solution of
Urea. Find the molecular weight of Urea. Ans- 59.99
Notes:
-The condition for obtaining right molecular weight in all above method
I. The solution must not be too concentrated.
-If the solution is concentrated the solute particles interacts with each other and with solvent.
Thus the V.P starts depending upon the nature of solvent and not just on the nature of solute
particles.
II. The solute must not dissociate or associate.
-The number of solute particles change if they undergo association or dissociation.

Abnormal Molecular Masses

-Colligative properties are used for determining the molecular mass of solute.
-The value of mass of non-electrolyte (like sugar, Urea, Glucose, etc) obtained from colligative
properties (observed properties) are found to be same as normal value.
-In certain cases with electrolyte’s and organic compounds the observed or experimental mass is
either higher or lower than normal value. This difference in molecular mass is called abnormal
molecular masses.
1
*No.of particles α colligative properties α
mol . mass
i.Molecular Association
-The association of solute leads to formation of bigger molecular molecules leading to decrease
in its number in the solution.
-Certain molecules or solute like acetic acid, benzoic acid, etc will undergo molecular
association to give dimer, trimer, tetramer, etc. to form bigger molecule.
-In such cases number of particles decreases, this decreases the magnitude of colligative
properties because number of particles α colligative property.
ii.Molecular Dissociation
-Certain compounds like NaCl, HCl, Kbr, etc. undergo dissociation when dissolved in solvent.
-When molecules undergo dissociation, the number of particles in the solution increases and
hence colligative properties increases while molecular mass decreass.
Van’t Hoff’s Factor (i)
-It is the ratio of the observed(experimental) value of a colligative property to the normal
(calculated) value of the same property is termed as Van’t Hoff’s Factor.
∆ obs ∆ Pobs ∆ Tbobs
i= i= i=
∆ nor ∆ Pnor ∆ Tbnor
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 ∆ Tfobs Number of particles present∈the solution
i= i=
∆ Tfnor Normal numbers of particles
Normal molecular mass
i=
Observed molecular mass

-For electrolytic solution

i) i > 1 undergo dissociation
ii) i< 1 undergo association
iii) i =1 Unaffected

Modified equation of colligative properties

Equation for colligative property
When solute remains normal When solute undergoes
Colligative Property
association/ dissociation
P ° solv−Psoln P ° solv−Psoln
= Xsolute = i x Xsolute
1.Relative Lowering of V.P P ° solv P ° solv

2.Elevation of boiling point ∆Tb= Kb×m ∆Tb = i x Kb × m

3.Depression of freezing point ∆Tf= kf×m ∆Tf =i x kf × m

4.Osmotic Pressure Л = CRT Л = i x CRT

Review Questions-Compulsorily should be solved in the note book!
Q)Calculate the amount of KCl which must be added to 1 kg of H2O so that the freezing point is
depressed by 2 kelvin.(kf for water = 1.86 K kg/mol) Ans- 40.05
Q)A decinormal solution of NaCl exerts an osmotic pressure of 4.6 atm at 27°C. Calculate its
degree of dissociation. Ans-0.8699
Q) A 17% solution of silver nitrate is isotonic with 3.4% of glucose. Calculate the degree of
dissociation of silver nitrate. Ans-0.9
Q)Calculate mole fraction of acetic acid in aqueous solution containing 20% by mass of acetic
acid. Ans- 0.069
Q)Calculate the lowering of vapour pressure caused by the addition of 100g of sucrose
(molecular mass = 342) to the 1000g of water if the vapour pressure of pur water at 25°C is 23.8
mm of Hg. Ans- 0.125
Q)A solution of non-volatile solute with molecular mass 342 is obtained by dissolving 17.1g of it
in 500g of water. Calculate the osmotic pressure of solution at 27°C. Ans-2.463 atm

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Q)A 2.5g of non-volatile solute dissolved in 50g of benzene, depresses the freezing point by
1.2K. If the normal mass is 122, Calculate the observed molar mass and Van’t Hoff Factor (kf
for benzene =5.12K kg/mol) Ans- m2=213.33 and i=0.572
Q)45g of ethylene glycol is mixed with 600g of water.(kf for water = 1.86 K kg/mol). Calculate
a) freezing point depression and b)Freezing point of the solution.Ans-a.2.25 K and b) 270.75 K
Q)A mountain trecker carries a bottle each of pure water and an energy drink containing 100g
per litre of glucose. At what temperature would this two liquids freeze. Give your reason fot your
answer.( kf for water = 1.86 K kg/mol) Ans- 271.97 K
Q)Boiling point of 0.1 M BaCL > 0.1 M NaCl. Why?

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