Solution & Colligative Properties Complete Chapter Notes For IIT

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Solution and
Chapter
3
Colligative
Properties
Key Concepts
Solute (Solid/Liquid/Gas) + Liquid solvent h DH vap.
Liquid solution (Homogeneous Mixture) DS =
T
Vapour Pressure of Pure Liquid RT DH
At equilibrium dP = dT
P T
Rate of evaporation = Rate of condensation P2 T2
dP DH dT ln P
Evaporation Condensation Ú P
=
R Ú T2
P1 T1
P2 DH È 1 1˘
ln = -
R ÍÎ T1 T2 ˙˚
1/T
It is the equilibrium pressure exerted by the vapours of the P1
liquid on the liquid surface. -DH
or lnP = + C from indefinite integration
Factors affecting vapour pressure of pure liquid RT
d DH
(1) Nature of liquid or (ln P) = differential form for pure liquid at a
Intermolecular forces Ø fi volatility≠ or B.P. Ø fi V.P. ≠ dT RT 2
(2) Temperature effect given temperature its vapour pressure is fixed it is indepen-
Temperature ≠ Æ more vapour pressure ≠ dent of size or shape of the vessel.
Variation of Vapour Pressure with temperature is given by
classius – Clapeyron’s equation Boiling Point ____________________________
P DH vap. È 1 1˘ It is the temperature at
ln 2 = ÍT - T ˙ which vapour pressure of 1 atm
P1 R Î 1 2˚ l V
liquid becomes equal to P
H 2O(l) H 2O(g) external pressure. When ex-
∂( DG) = DV ∂P - DS ∂T ternal pressure is 1 atm it is
called normal boiling point.
At equilibrium DG = 0
fi It is difficult to cook
DV = Vg – Vl Vg food on mountains or hilly BP T
Since Vg >>> Vl areas because boiling point
RT decreases as external pressure is less.
= (for 1 mole) fi It is convenient to cook the food in pressure cooker be-
P
cause boiling point increases as external pressure is high.
nRT
= for n mole
P
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IIT JEE PC-V2_03.indd 1 5/13/2017 10:56:28 AM
3.2 Physical Chemistry-II for JEE (Main & Advanced)
Raoult’s Law ____________________________

For two miscible and volatile liquids 1
PB°
PA μ x A fi PA = PAo ◊ x A P = PA + PB 1
P 1
PB μ xB fi PB = PBo ◊ xB PA°
m
at a given temperature PA and
yA = 0 ¨ mole fraction Æ yA = 1
PB are the partial pressure of the
A+B yB = 1 yB = 0
vapours of A and B respectively.
yA 1 - yA 1
PAo and PBo
vapour pressure of + =
pure liquid A and B respectively. PAo PBo P
xA and xB mole fraction of A and B in solution or in liquid 1 Ê 1 1 ˆ 1
= – yA + o
phase. P ÁË PAo PBo ˜¯ PB
Total vapour pressure of solution
P = PA + PB PAo – PBo 1 ( PBo - PAo ) y A + PAo
P= =
P = PAo x A + PBo xB (i) ( PBo – PAo ) y A + PAo P PAo - PBo
P vs yA graph will be a curve definitely.
P= PAo x A + PBo (1 - xA )
P= ( PAo - PBo ) x A + PBo P P°
A
If xA = 1 – xB from (i)
P°
P = ( PBo - PAo ) xB + PAo B
o o yA = 0 yA = 1
Example, If P = 90 + 120xB find PA and PB if PAo = 90 mm Hg
yB = 1 yB = 0
If xB = 1; x A = 0 \ P = PBo = 210 mmHg
Graphical Representation of Compositions in Liquid
xB = 0; x A = 1\ P = PAo = 90 mmHg phase, Vapour phase and Effect of Pressures
Graphical Representation of Raoult’s Law ___ Pmax P°
A
P Liquid
Pressure
ia
ilibr
+ PB°
xB P°
B (P) Equ Pmin
°x A L V
P = PA P°B
Vapour phase
P P°A
P° PA xA
B
PA=
xA = 0 Malefaction xA = 1
PB PB =
PA PB°x xB = 1 xB = 0
B
xA = 0 xA = 1 fi If Psystem > Pmax fi only liquid phase will exist there.
xB = 1 Composition xB = 0
fi If Psystem < Pmax > Pmin fi L m V will exist.
(mole fraction)
fi If Psystem < Pmin fi only vapour phase will exist.
Relationship between mole fraction in liquid phase (xA) and Case 1
mole fraction in vapour phase in distillate (yA) When for vapour mixture of A and B pressure is increased.
PA = PAo x A = y A P by gaseous state Dalton’s law Effect:
If (nA = 1 and nB = 1)
PA = mole fraction in gas phase (yA) ¥ total Pressure (P)
Condition (a)
PB = PBo xB = yB P At P = Pmin fi first drop of liquid is formed, so it is called
Dew Point.
1 1
TOTAL V. PRESSURE OF yA = yB =
SOLUTION IN TERMS OF yA 2 2
Condition (b)
xA + xB = 1
at P = Pmax. fi last bubble of vapour remains
P ◊ y A P ◊ yB
+ =1 xA =
1
xB =
1
PAo PBo 2 2
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Solution and Colligative Properties 3.3
Case 2 nB No of moles of solute

For liquid mixture of A and B pressure is decreased. Molality m = ¥ 1000 =
wA weight of solvent in kg
If (nA = 2; nB = 1)
nB nB
Condition (a) = ¥ m A (mol wt. of solvent)
at P = Pmax fi first bubble of vapour is formed, so it is called n A wA
Bubble Point. nB m P 0 - PS
fi = ¥ mA = A
2 1 n A 1000 PS
x A = ; xB =
3 3
PAo - PS 1000
Condition (b) \ ¥ =m
PS mA
at P = Pmin fi Last drop of liquid remains
2 1 Mixture of two immiscible liquid
yA = yB = They will behave like two separate liquids.
3 3
Raoult’s Law When non-volatile solute (B) is added to PA = PAo and PB = PBo
pure solvent (A). Total vapour pressure of mixture
Total pressure of solution P or PS P = PAo + PBo P = PA° + PB°
B is non-volatile so no vapour will be there but xB π 0. \ xA < 1,
Two immiscible liquid behave like
i.e., vapour pressure will decrease.
separate pure liquids so that partial
A+B
PS = PAo x A + PBo xB ( PBo = 0) pressure will be equal to their pure
form.
PS = PAo (1 - xB )
PS = PAo - PAo xB Note:
As vapour pressure of the mixture is greater than both the
PAo - PS two components in pure form, so boiling point becomes
xB =
PAo lesser than both the two components in pure form.
xB = mole fraction of non-volatile solute
T < TAo ; T < TBo
PAo - PS = DP = Lowering in vapour pressure
PA = P \ y A = PAo ; PB = P \ yB = PBo
DP
= relative lowering in vapour pressure. PAo y A n A wA /m A
PAo So = = =
PBo yB nB wB /mB
Note:
nA, nB are moles of A and B in vapour phase.
On adding non-volatile solute vapour, pressure decreases
and according to Raoult’s Law, mole fraction of non-vol- Ideal solutions
atile solute becomes equal to relative lowering in vapour 1. These solutions obey the Raoult’s Law.
pressure. i.e., PA = PAo x A ; PB = PBo xB
PAo - PS nB P = PAo x A + PBo xB

=
PAo n A + nB 2. Strength of intermolecular forces remain unchanged,
before and after the mixing.
PAo n +n n
= A B = A +1 FA–B = FA–A = FB–B
PAo - PS nB nB 3. DHmix = 0 ( no changes in intermolecular forces)
PAo P n hence no change in interaction.
-1fi o S = A 4. DVmix = 0 Vf = VA + VB
PAo - PS PA - PS nB
No change in intermolecular forces.
PAo – PS nB 5. DSmix = +ve (for both ideal and non-ideal solution)
= always correct for any solution di- 6. DGmix = –ve (has spontaneity for both ideal and non-
PS n A lute or concentrate solution.
ideal solution)
PAo - PS nB DGmix = DHmix – TDSmix
= for dilute solution only
PAo nA Since DHmix = 0
Since If nB << nA \ DG = –TDSmix = –ve
nA + nB = nA
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Since 3. DHmix = –ve (heat releases)

PA = xAPA° 4. DVmix = –ve; Vf < (VA + VB)
PB = xB PB°
Examples:
P°x B P°A 1. Acid + Water (form more stronger H bond)
Pressure
°x A + B
P = PA 2. CH3COCH3 + CHCl3 (accetone + Chloroform)
P°B PA°x A
Ø Ø Ø
PB°xB Form H-bond with Polar-polar Van der
xA = 0 xA = 1 chloroform due to Waal forces
xB = 1 xB = 0 which volatility decreases
Øes > C = 0 .............. H.
Examples:
fi Benzene + Toluene Graphical Representation
fi Methanol + Ethonal (Homologues)
fi Ethyl chloride + Ethyle bromide
PB°x B P°A
fi Clorobenzene + Bromo benzene P
PA°xA +
fi Very dilute solution P°
B PA°xA PA < xAPA°
PA PB
Non-Ideal solution PB < xBPB°
PB°xB
They do not obey the Rault’s law.
xA = 0 xA = 1
PA π PAo x A ; PB π PBo xB ; P π PAo x A + PBo xB xB = 1 xB = 0
Non-ideal solution can be of two types:
Showing positive deviation from Rault’s law. Azeotropic Mixture OR Constant Boiling
Showing negative deviation from Rault’s law. Mixture_________________________________
* Showing positive deviation from Rault’s law: These are the liquid mixtures which distill off without change
1. Volatility more compare than the ideal solution, i.e., in their composition.
PA > PAo x A ; PB > PBo xB ; P > PAo x A + PBo xB . Azeotropism observed in non-ideal solution at a given
pressure for the fixed composition.
2. Strength of intermolecular forces decreases At this condition separation of two liquids is not possible.
3. DHmix = +ve (heat absorbed) Azeotropic mixtures can be of two types.
4. DVmix = +ve, Vf > (VA + VB) (bond formed is weak so
distance between the particle increases) Minimum Boiling Azeotrops
1. B.P. of azeotropic mixture is less than both the two
Example:
components.
Alcohol + Water
2. It is formed by the solution which shows +ve deviation
{Intermolecular H bonding comparatively weaker than pure
from R Law.
water)
CH3COCH3 + CCl4 or CS2 (Interaction weaker) Graphical Representation
Ø Ø (high pressure)
Polar Nature Non-Polar Liquid phase
Vapour Pressure
Graphical Representation
Temperature
Vapour phase P°A

T°
B
(higher temp.)
T° P°B Vapour Phase
P > PA + PB A
P°A
Pressure
Liquid phase
PA > xAPA°
P°B PA°xA Azeotrope Azeotrope
PB > xBPB° xA = 0 Mole xA = 1 xA = 0 Mole xA = 1
PA PB xB = 1 xB = 0 xB = 1 xB = 0
PB°xB fracion fraction
in liq. phase
xA = 0 xA = 1
xB = 1 xB = 0
Example:
Showing Negations Deviation From Raoult’s Law: Boiling point of C2H5OH + H2O
1. Volatility decreases compare to the ideal solution, i.e., (96%) (4%) By weight
Mixture 78°C and Bolling Point of H2O = 100°C Bolling
PA < PA x A ; PB < PB xB ; P < PA x A + PB xB
o o o o
point of ethenol = 78.6°C which is less than BP of ethanol
2. Strength of intermolecular forces increases is or water.
FA - B > FA - A , FB - B
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Maximum Boiling Areotrope:

PAo - PS Decrease in mass of solvent
1. Bolling point of the mixture is more than both the two o
=
components. PA Increase in mass of the dehydrating agent
2. It is observed in those solution which show –ve devia- PAo - PS Decrease in mass of solvent
tion. =
PS Decrease in mass of solution
Graphical Representation
Elevation in Boiling Point:
Vapour
On adding non-volatile solute vapour pressure decreases so
Vapour Pressure
Boiling Points
T°A T°B boiling point increases. Then elevation in boiling point DTb
Liquid T°A
T°B Liquid DTb = Tb - Tbo
Vapour phase Tb OR (Tb)s – boiling point of solution
xA = 0 Mole xA = 1 xA = 0 Mole xA = 1 Tbo – boiling point of pure solvent
xB = 1 fraction xB = 0 xB = 1 fraction xB = 0
DTb μ DP Lowering is vapour pressure
in liquid phase
DP nB m ¥ m A
Example: = =
PS n A 1000
HNO3 + H2O
(68%) (32%) by weight at 1 atm. pressure mA = Molarmass of solvent
B.P. (mixture) = 120.6°C, Which is greater than Boiling Point m = molality
of water (100°C) and Boiling Point of HNO3 (80°C) Solvent
Solution-1
Solution-2
COLLIGATIVE PROPERTIES Vapour pressure
These are the properties of dilute solutions which depends

only on the number of particles of the solute but independent
of its nature. DTb
There are four colligative properties:
T°
b Tb Temperature
DP
1. Relative lowering of vapour pressure o = xB
(x = mole fraction of solute). PA DP μ m
B
2. Elevation in boling point. DTb μ m
3. Depression in freezing point. DTb = Kbm
4. Osmotic pressure
Osmotic pressure are mainly used to find molar mass Kb Molal elevation constant
of unknown solute. DTb = Kbm
Measurement of Relative Lowering of Vapour Pressure wB ¥ 1000
by Ostwald and Walker Method: DTb = K b ¥
mB ¥ wA
Since PAo > PS
mB = molarmass of solute.
PS P°
A Here solute is neither associating nor dissociating.
moist
dryair air Dehydrating
dryair Molal elevation constant (Kb):
agent
It is the characteristic property of the solvent.
Solution Pure R(Tbo ) 2 ¥ m A

Kb =
(wt. decrease) solvent (wt. increase) 1000 ¥ DH vap.
(wt. decrease)
DHvap. molar heat of vapourisation (should in per mole)
Decrease in mass of solution μ PS
Kb for water = 0.52 K kg Mol–1
Decrease in mass of pure solvent μ PAo - PS
Unit of Kb = K molal–1 or K kg mol–1
Increase in mass of dehydrating agent = Decrease in mass of
Depression in freezing point:
(solution + solvent) μ PAo
Freezing point is the temperature at which vapour pressure of
solution and liquid phase becomes equal.
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Solvent Osmotic Pressure (p):

Solution-1
Solution-2 h fi height
l h raised due
(More, non volatile
solute) to osmosis
Pressure
Solution
S V Pure
Solvent
DTf
TF T°
F Temperature SPM
At Freezing Point p = hdg
Liquid Solvent in Solution m Solid Solvent It is the hydrostatic pressure developed on the solution
So, at Freezing Point only solvent solidify, so that amount of
which stops the osmosis.
solvent remains unchanged in the solution and concentration
It is the external pressure applied on the solution that just
of solution increases.
stops the osmosis.
or
On adding non-volatile solute vapour pressure decreases so 1. If Pext = p no osmosis
Freezing Point also decreases depression in Freezing Point. 2. If Pext < p osmosis will occur
3. If Pext > p reverse osmosis
DTF = TFo - TF
(Solvent particles moves in reverse direction)
TFo = Freezing Point of pure solvent or towards dilute solution
TF = Freezing Point of solutions. Reverse Osmosis:
DTF μ DP μ m Solvent particles move in the reverse direction, i.e., from so-
DTF μ m lution to the solvent.
DTF = KF ¥ m This method is used in purification of sea water.
KF = Molal depression constant or Cryoscopic con- Vant-Hoff’s Equation for Dilute Solution:
stant p = CST
w ¥ 1000 p = CRT
DTF = K F B
mB ¥ wA p = osmotic pressure
Molal depression constant (KF) n
It is the characteristic property of the solvent. C= [C - concentration of solution (Mol L–1)]
V
R(TFo ) 2 ¥ m A
KF = Solution constant S = R = 0.0821 atm L K–1 mol–1
1000 ¥ DH fusions
n
KF for water = 1.86 K molal–1 or K. kg mol–1 p= RT
V
For dilute aqueous solutions molality molarity
m M pV = nRT
Osmosis: n-moles of solute
It is the spontaneous phenomena in which solvent particles
move from lesser concentrated solution to higher concen- Note:
trated solution through a semi-permeable membrane. (SPM) 1. For two different solution if p1 = p2 isotonic solution
2. If p1 π p2
Solution with higher osmotic pressure forms hyper-
tonic solution.
Dilute Higher Where solution is with lower osmotic pressure
solution Solvent concentration known as hypotonic solution.
● The solvent particle moves from hypotonic to
SPM hypertonic
● To just stop the osmosis external pressure
should be applied on more concentrate solution

egg and Pext. = p2 – p1
Size of egg Size of egg
increases due Size decreases due
to exsosmosis H2 O of egg HCl to endosmosis
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Vant Hoff’s factor (i): 1. 0.1 M glucose, 0.1 M NaCl, 0.1 M BaCl2
Number of particles of solute finally Colligative Property μi ¥ C
i=
Number of particles of solute initially if C.P ≠ fi V.P of Solution decreases
Observed value of colligative properties C.P ≠ fi F.P of Solution decreases
=
Normal value of colligative properties C.P ≠ fi B.P of Solution increases
Normal molecular weight of solute C.P ≠ fi p (Osmotic pressure) increases
=
Observed molecular weight of solute 2. 0.1 % glucose, 0.1% urea, 0.1% sucrose. if i same then
(i) if i > 1 fi dissociation 1
(ii) if i < 1 fi association C.P μ
Molar mass
(iii) if i = 1 fi neither dissociation nor association
\ C.Pmax for urea \ V.P. and F.P. fi minimum
Examples:
BP and p fi maximum
(i) BaCl2 h Ba+2 + 2Cl– i = 3/1
(ii) K3[Fe(CN)6] h 3K+ + [Fe(CN)6]– i = 4 Concentration Term:-
(iii) thimerisation fi i = 1/3 Precent Strength
(iv) dimerisation fi i = 1/2
w weight solute
Relationship Between Degree of Dissociation (a) and i. %= ¥ 100
A m nB w weight of solution
Initially 1 – w
= B ¥ 100
Finally (1 – a) na w
(1 - a ) + na w weight of solute (in gram)
i= %= ¥ 100
1 V volume of solution (in ml)
i = 1 + (n – 1)a w w
% = B ¥ 100
i -1 V v
a= v volume of solute
n -1 %= ¥ 100
v volume of solution
Relationship between degree of association (a) and Vant- V V
Huff factor (i): % = B ¥ 100
V V
nA m An
1 – weight of solution w = (v ¥ d) of solution.
a Molarity (M ) No of moles of solute in one Liter Solution
1–a
n nB
M=
a V (Liter)
1- a +
i= n fi i = 1 + Ê 1 - 1ˆ a
ÁË ˜ If V in ml
1 n ¯
nB n
i -1 1- i M= = B ¥ 1000
a= ¥n a = ¥n V (ml) V ml
1- n n -1
1000
Modified Forms of Colligative Properties: w
Since, V=
DP d
= ixB = i ¥ (mole fraction of solute)
PAo wB 1000 wB 10 w 10
\ M= ¥ = ¥ 100 ¥ = %¥
mB V (ml) V mB V mB
DTb = iKbm
w 10d
DTf = iKfm M= %¥
w mB
p = iCRT
Normality N:- No of gram equivalent in 1 Liter solution.
Isotonic Solutions:
wB 1000 w 1000
p1 = p2 Condition for isotonic N= ¥ = nf ◊ B ¥ = n f [M ]
Eq. wt. V (ml) mB V (ml)
at a given temperature T
È w 10d ˘
i1C1RT = i2C2RT \ N = nf Í % ˙
Î w mB ˚
i1C1 = i2C2 Concentration should be mole based.
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È w 10 ˘ 2 Temperature:
\ N = nf Í % ˙ Gas + Liquid fi Solution + heat (exothermic)
ÎV mB ˚
As dissolution of gas in liquid is exothermic process.
Molarmass So on increasing the temperature solubility decreases.
Equivalent weight =
n - factor 3. Pressure:
On increasing the pressure solubility of gases in liquid
Molefraction:- ratio of number of moles of one component
increases. This effect is given by Henry’s Law.
to the total Number of moles of solution
nB Henry’s Law:
Mole fraction of solute xB = for binary solution. fi At a given temperature mass of the gas dissolve in the
n A + nB
given amount of the solvent is directly proportional to
nB
\ xB = …(i) partial pressure of gas.
Sn
mμP
nA
xA = = mole fraction of solvent m
n A + nB = constant
P
xA + xB = 1 from (i)
\ nB = xB ¥ Sn fi At constant temperature, mole fraction of the gas dis-
wB solve in liquid is directly proportional to partial pres-
= x B ¥ Sn sure of the gas.
mB
xg μ P
\ wB = xB ¥ Sn ¥ mB …(ii)
and wA = xA ¥ Sn ¥ mA …(iii) P = KHxg KH: Henry constant
we know molality m = No of moles of solute in one kg sol- Unit Æ Pressure units.
vent Value of KH depends on temperature and nature of gas
w 1000 and liquid.
\ m= B ¥
mB wA
ng
From (i) and (ii) P = KH ng – moles of gas dissolved
ng + nl
x Sn mB 1000 x 1000
m= B ¥ = B ¥ =m nl - moles of the liquid
mB x A Sn m A x A mA
but
mA = molar mass of solvent.
ng << nl
Relation between molality (m) and Molarity (M) :- ng + nl nl
fi
If molarity of solution (M) means M moles solute dissolve in
1000 ml solution, if density of solution d gm/ml ng
P = KH use this
weight of solution = V ¥ d = 1000 ¥ d nl
weight of solvent = weight of solution – weight solute
According to Henry’s law, at a constant temperature
wA = 1000 d – MmB
volume of gas dissolve in the given amount of solvent
wB 1000 is independent of the pressure.
\ Molality m = ¥
mB wA Applying ideal gas equation for dissolved gas,
M ¥ 1000 PV = nRT
m=
1000d - MmB PV =
Mass
RT
Mwt
w
Since, nB = B = M = No. of moles of solute in 1 liter solu- Ê M ˆ RT
mB V =Á ˜
tion. Ë P ¯ Mwt
Factors Affecting Solubility of Gases, in Liquid: V = Constant
1. Nature of gas and liquid:
In polar solvents like water polar gases are more solu- Limitations of Henry’ Law _________________
ble whereas, solubility of non-polar gases is lesser (like
1. Solubility of gases in liquid should not be too much.
dissolves like). Gases which can be liquefied easily are
2. Henry’ law is applicable at high temperature and low
comparatively more soluble in water.
pressure concentration.
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Solved Examples
1. If 0.4 g of NaOH is present in 40 mL of solution. What Sol. Weight of solution = 3.65 + 25.08 = 28.73 g
is the molarity and normality [M.wt. of NaOH = 40] 3.65
Sol. We know that Weight fraction = = 0.127
28.73
Given wB = 0.4 gram Weight percent = 0.127 ¥ 100 = 12.7%
V = 40 ml 8. A solution was prepared by adding 125 cm3 of isopro-
mB = 40 pyl alcohol to water until the volume of the solution
\
wB 1000 was 175 cm3. Find the volume fraction and volume per-
M= ¥
mB V (ml) cent of isopropyl alcohol in the solution.
0.4 1000 Sol. Volume of solute = 125 cm3
= ¥ = 0.25 M Volume of solution = 175 cm3
40 40
N = nf ¥ M 125
\ volume fraction = = 0.714
= 1 ¥ 0.25 175
= 0.25 N 125
2. The normality of 1.5M H3PO4 is and volume percent = ¥ 100 = 71.4%
175
Sol. Basicity of H3PO4 is 3 9. The density of a solution containing 13% by mass of
We know that N = nf ¥ M sulphuric acid is 1.09 g/mL. Calculate the molarity and
N = 1.5 ¥ 3 = 4.5 normality of the solution.
3. How much volume of 10 M HCl should be diluted with
w 10d
water to prepare 2.00 L of 5M HCl? Sol. M = %¥
Sol. In dilution the following equation is applicable: w mB
M1V1 = M2V2 13 ¥ 10 ¥ 1.09
=
10M HCl = 5M HCl 98
10 ¥ V1 = 5 ¥ 2.00 = 1.445 M
5 ¥ 2.00 10. Vapour pressure of solution containing 3 and 1 mol re-
V1 = = 1.00 L spectively of x and y is 550 mm at the same tempera-
10
N ture another solution (containing 4 and 1 mol x and y
4. Find out the weight of H2SO4 in 150 mL, H2SO4. respectively). The vapour pressure becomes 560 mm at
7
this temperature calculate vapour pressure of x and y in
Weight in gram pure form.
Sol. N =
Equivalent weight ¥ Volume 3 1
Sol. xx = xy = P = 550
Weight in gram = Equivalent weight ¥ N ¥ volume 4 4
1 150 21 4 1
= 49 ¥ ¥ = = 1.05 g yx = xy = P = 560
7 1000 20 5 5
5. Find out the molarity of 1 L of 93% H2SO4 and its den- P = xx Pxo + x y Pyo
sity is 1.84.
3 o 1 o
Sol. Molatrity 550 = Px + Py
4 4
w 10d 93 ¥ 1.84 ¥ 10
M= %¥ = 4 o 1 o
w mB 98 560 = Px + Py
5 5
= 78.68 M 2200 = 3Pxo + Pyo
6. A 100 cm3 solution is prepared by dissolving 2 g of
NaOH in water. Calculate the normality of the solution. 2800 = 4 Pxo + Pyo
wB 1000 – – –
Sol. N = ¥ –600 = –Pxo
Equivalent weight V (ml)
2200 = 1800 + Pyo
2.0 1000 N
= ¥ = Pxo = 600 Pyo = 400
40 100 2
11. Two liquids A and B are miscible over the whole range
7. Find the percentage by weight and weight fraction of of composition obeying the Raoults law at 350 K. The
aspirin in the solution prepared by dissolving 3.65 g of vapour pressure of pure A is 24 KPa and B is 12 KPa.
aspirin in 25.08 g of water.
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A mixture of 60% A and 40% B is distilled at this tem- 4

perature. A small amount of the distillate is collected \ yBo =
5
and read distill at 350 K. What is the composition of
second distillate. 1
(c) y A = yB =
2
Sol. PAo = 24 KPa PBo = 12 KPa
1 Ê 1 1 ˆ 1
60 40 = - yA + o
xA = xB = P ÁË PAo PBo ˜¯ PB
60 + 40 60 + 40
60 40 \ P = 240 torr
= =
100 100 4 1
(d) x A = xB = i.e., liquid phase composition
24K 12K 5 5
= PAo PBo = is asked.
0.6 0.4
Py A 240 ¥ 1/2 4
40K = PAo PBo = 30 K xA = = =
PAo 150 5
yA & yB yA¢ and yB¢ = yA≤ and yB≤
13. What mass of non-volatile solute is to be dissolved in
100 g of water to decrease the vapour pressure of water
by 25%.
DP nB
1st distillate 2nd distillate Sol. =
PS n A
xA = 0.6 x¢A = yA = 3/4
xB = 0.4 x¢B = yB = 1/4 PAo – PS nB 25 wB ¥ 18
= = =
PAo x A 24 ¥ 0.6 3 PS n A 75 60 ¥ 100
yA = = =
P 24 ¥ 0.6 + 12 ¥ 0.4 4 25 ¥ 60 ¥ 100
= wB
1 75 ¥ 18
yB =
4 10
¥ 100 = wB
3 9
24 ¥ 6
4
A = y ¢A =
x ¢¢ = 111 g = wB
3 1 7
24 ¥ + 12 ¥ 14. 1000 g of 0.6 molal sucrose solution in water cooled to
4 4 –3.2°C. What weight of ice would be separated out at
1 this temperature. Molar mass of sucrose = 342.
xB¢¢ =
7 Sol. Weight of ice = Weight of H2O initially – Weight of
12. A liquid mixture of A and B is composed of 1 mol of A H2O finally.
and 1 and of B. If the pressure over the mixture at 300 K 1000 g H2O have 0.6 mol sucrose.
is reduced, at what pressure does the first bubble of va- wsol. = 1000 + 0.6 ¥ 342 = 1205.2 g
pour is formed. What is the composition of first bubble 0.6
of vapour formed. If the pressure is reduced further. At Moles of sucrose in 1000 g solution = ¥ 1000
1205.2
what pressure does last drop of liquid disappear. What = 0.5
is the composition of last drop of liquid given. wH2O initially = 1000 – 0.5 ¥ 342 = 829 g
PAo = 150 torr and PBo = 600 torr
1.86 ¥ 0.5 ¥ 1000
DTf = 3.2 =
PAo- PBo WH2O finally
Sol. (a) P =
( PBo - PA ) y oA +
o
yBo ( wH2O )finally = 290.6
1 Weight of ice = 829 – 290.6 = 538.4 g
x A = xB =
2 15. Calculate the osmotic pressure of solution containing
1 1 0.4% urea and 3.42% sucrose at 27°C.
P = PAo xB + PBo xB 150 ¥
+ 600 ¥
2 2 Sol. Molecular Mass urea = 60
= 375 torr 75 + 300 fi 375 Molecular Mass sucrose = 342
(b) Composition of vapour phase is required. We know p = CRT
n
PAo x A 150 ¥ 1/2 1 = RT
So = yA fi = V
P 375 5
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Ê w 10 ˆ 19. A substance x Mwt = 94 associates in water to form

Ê w 10 ˆ
p = p1 + p2 = Á % RT + Á % RT dimer. A solution of 1.25 g of x in 50 g of water lower
Ë V mB ¯ urea Ë V mB ˜¯ sucrose
˜
the freezing point by 0.3°C calculate degree of associa-
Ê 0.4 ¥ 10 3.42 ¥ 10 ˆ tion of x. Kf = 1.86.
=Á + ˜ 0.082 ¥ 300
Ë 60 342 ¯ Sol. DTf = iKf m
p = 4.1 atm 1.86 ¥ 1.25 ¥ 1000
16. 100 mL aq. solution of glucose with osmotic pressure 0.3 = i
94 ¥ 50
1.2 atm at 25°C is mixed with 300 mL of aqueous solu-
0.3 ¥ 94 ¥ 50
tion of urea at 2.4 atm, at 25°C. Calculate the osmotic i=
pressure of the mixture. 1.86 ¥ 1.25 ¥ 1000
Sol. Must U = 60 Must 60 = Constant temperature i = 0.6
p1 = 1.2; T1 = 298 Ê1 ˆ
p2 = 2.4; T2 = 298 i = 1 + Á - 1˜ a
Ën ¯
At constant temperature
p V + p 2V2 Ê1 ˆ
0.6 = 1 + Á - 1˜ a
p mix = 1 1 Ën ¯
V1 + V2
1.2 ¥ 100 + 2.4 ¥ 300 Ê -1ˆ
0.6 = 1 + Á ˜ a
= Ë 2¯
400
1.2 + (2.4 ¥ 3) 1
= 0.6 = 1 - a
4 2
1.2(1 + 6) 1
= a = 0.4
4 2
8.4 a = 0.8 = 80%
fi 2.1 atm
4 20. At 20°C and 0.02 atm pressure. Calculate the solubility
17. The Van’ hoff factor for 0.1 M barium nitrate solution of oxygen in 1 L of water. Given KH for oxygen is 4.6
is 2.74. What is the degree of dissociation? ¥ 104 atm.
i = 2.74 C = 0.1 M Ba(NO3)2 Æ Ba +2 + 2NO3- Sol. KH = 4.6 ¥ 104
\n = 3 P = 0.02
i - 1 2.74 - 1 1.74 T = 293 K
Sol. a = = fi fi 0.87
n -1 3 -1 2 ng
P = KH ¥
18. The vapour pressure of 0.1 M solution of urea at 20°C nl
is 0.311 mm less than that of water and vapour pressure ng
of 0.1 M KCl solution is 0.574 mm less than that of 0.02 = 4.6 ¥ 104 ¥
nl
water. Calculate the apparent degree of dissociation of
KCl at this dilution. 0.02 ¥ nl
= ng
Sol. For urea 4.6 ¥ 104
DP nl = No. of moles of water in one liter
= i xB
PAo 1000
= = 55.55
0.311 18
= (i = 1) xB (1)
PAo 0.02 ¥ 55.5
\ ng =
fi since equal molal 4.6 ¥ 104
For KCl
Ê 0.02 ¥ 55.5 ˆ
0.574
= i xB (2) ÁË 4.6 ¥ 104 ˜¯ ¥ 32 = mass of O 2 per litre
PAo
(2) 0.574 7.7 ¥ 10–3 g/L
= = i = 1.845 21. 1 mole heptane (V.P. = 92 mm of Hg) is mixed with 4
(1) 0.311
mole Octane (V.P. = 31 mm of Hg), form an ideal solu-
i = 1 + (n – 1)a
tion. Find out the vapour pressure of solution.
1.845 – 1 = a
Sol. Total mole = 1 + 4 = 5
0.845 = a
Mole fraction of heptane = xA = 1/5
a = 84.5%
Mole fraction of octane = xB = 4/5
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PS = x A PAo + xB PBo DTb =

w
¥ 1000 ¥ Kb
1 4 m¥W
= ¥ 92 + ¥ 31
5 5 0.15
0.216 = ¥ 1000 ¥ 2.16
= 43.2 mm of Hg. mB ¥ 15
22. At 88°C benzene has a vapour pressure of 900 torr and 0.15 ¥ 1000 ¥ 2.16
mB = = 100
toluene has a vapour pressure of 360 torr. What is the 0.216 ¥ 15
mole fraction of benzene in the mixture with toluene 26. The rise in boiling point of a solution containing 1.8 g
that will be boil at 88°C at 1 atm pressure, benzene – glucose in 100 g of a solvent is 0.1°C. The molal eleva-
toluene form an ideal solution. tion constant of the liquid is
Sol. PS = 760 torr, because solution boils at 88°C. Sol. DTb = Kb ¥ m
Now 760 = 900 ¥ mole fraction of C6H6 + 360 ¥ [1 – wB
mole fraction of C6H6] DTb = Kb ¥ ¥ 1000
mB ¥ wA
\ 760 = 900a + 360 – 360a
DTb ¥ mB ¥ wA
a = 0.74 where ‘a’ is mole fraction C6H6. \ Kb =
23. The vapour pressure of benzene at 90°C is 1020 torr. A 1000 ¥ wB
solution of 5 g of a solute in 58.5 g benzene has vapour DTb = 0.1°C
pressure 990 torr. What is the molecular weight of the mB = 180
solute? wA = 100
wB = 1.8
P 0 – PS nB wB m A
Sol. = = ¥ 180 ¥ 0.1 ¥ 100
PS n A mB wA Kb = = 1.0
1000 ¥ 1.8
1020 – 990 5 ¥ 78 27. If freezing point of a solution prepared from 1.25 g of a
=
990 mB ¥ 58.5 non-electrolyte and 20 g of water is 271.9 K, the molar
mass of the solute will be
mB = 220 Sol. Given = Tf = 271.9 K
24. Calculate the vapour pressure lowering caused by ad- wB = 1.25 g wA = 20 g Kf = 1.86
dition of 50 g of sucrose (molecular mass = 342) to 500 DTf = T0 – Tf
g of water if the vapour pressure of pure water at 25°C = 273 – 271.9
is 23.8 mm Hg. DTf = 1.1
Sol. According to Raoult’s law, DTf = molality ¥ Kf
DP nB wB
= xB = DT f = ¥1000 ¥ K f
P o
n A + nB mB ¥ wA
n wB ¥ 1000 ¥ K f
or DP = B ¥ P o mB =
nA DT f ¥ wA
50 500 1.25 ¥ 1000 ¥ 1.86
Given: nB = = 0.146; nA = = 27.78 and mB =
342 18 1.1 ¥ 20
Po = 23.8 mm Hg mB = 105.68
Substituting the values in the above equation, 28. Molal depression constant for water is 1.86°C. What
0.146 is the freezing point of a 0.05 molal solution of a non-
DP = ¥ 23.8 = 0.124 mm Hg electrolyte in water?
0.146 + 27.78
Sol. DTf = molality ¥ Kf
25. 0.15 g of a substance dissolved in 15 g of solvent boiled
= 0.05 ¥ 1.86 = 0.093°C
at a temperature higher by 0.216°C than that of the pure
solvent. What is the molecular weight of the substance. Tf = T o – 0.093 = 0 – 0.093
[Kb for solvent = 2.16°C] Tf = – 0.093 = Freezing point of solution
Sol. Given: Kb = 2.16°C 29. A cane sugar solution has an osmotic pressure of 2.46
wB = 0.15 g atm at 300 K. What is the strength of the solution?
DTb = 0.216°C Sol. p V = nST
wA = 15 g n
DTb = molality ¥ Kb or p = ST = CST
V
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p 2.46 here n = 3
or C= = = 0.1 M a = 0.2433 or 24.33%
ST 300 ¥ 0.0821
33. A solution containing 30 g of a non-volatile solute in
30. A solution containing 8.6 g urea in 1 L was found to exactly 90 g water has a vapour pressure of 21.85 mm
be isotonic with 0.5% (wt./vol.) solution of an organic, Hg at 25°C. Further 18 g of water is then added to the
non-volatile solute. What is the molecular weight of or- solution. The resulting solution has vapour pressure of
ganic solute? 22.15 mm Hg at 25°C. Calculate (a) molar mass of the
Sol. Solutions are isotonic solute, and (b) vapour pressure of water at 25°C.
so p1 = p2
P 0 – 21.85 30 ¥ 18
n1 n Sol. = for I case......I (i)
ST = 2 ST {S and T are constant} 21.85 90 ¥ mB
V1 V2
Now weight of solvent = 90 +18 =108 g
n1 n2
so, = P 0 – 22.15 30 ¥ 18
V1 V2 = for II case.......II (ii)
22.15 108 ¥ m
Ê w1 ˆ Ê w2 ˆ \ By eq. (i) P°mB – 21.85 mB = 21.85 ¥ 6 = 131.1
or ÁË m ¥ V ¯˜ =Á ˜
1 1 urea Ë m2 ¥ V2 ¯ organic By eq. (ii) P°mB – 22.15 mB = 22.15 ¥ 5 = 110.75
0.30 mB = 20.35
8.6 0.5
or = 20.35
60 ¥ 1000 m2 ¥ 100 \ mB = = 67.83
0.30
m2 = 34.89
On substituting in Eq. (i),
31. A very dilute saturated solution of a sparingly soluble
salt A3B4 has a vapour pressure of 20 mm of Hg at P 0 – 21.85 30 ¥ 18
=
temperature T, while pure water exerts a pressure of 21.85 90 ¥ 67.83
20.0126 mm Hg at the same temperature. Calculate the \ P° = 23.78 mm
solubility product constant of A3B4 at the same tem- 34. The freezing point of ether was lowered by 0.60°C on
perature. dissolving 2.0 g of phenol in 100 g of ether. Calculate
Sol. Ps = 20 P° = 20.0126 the molar mass of phenol and comment on the result.
P° – Ps 0.0126 nB wB m A Given: Kf (ether) = 5.12 K kg mol–1.
= = = ¥
Ps 20 n A mB wA wB 1000
Sol. DT f = K f ◊ m = K f ¥
moles of solute mB wA
= 0.00063
moles of H 2O 2 1000
0.6 = 5.12 ¥ ¥
1 mole H2O = 18 g = 18 mL mB 100
18 mL solution = 0.00063 mole 5.12 ¥ 2 ¥ 10
0.00063 mB = = 170.6
1 L solution = ¥ 1000 = 0.035 mole/L 0.6
18 = observed molar mass
Let solubility of salt A3B4 is S then Actual molar mass of phenol C6H5OH
7S = 0.035 72 + 6 + 16 = 94
S = 0.005 mole/L It means phenol dimerise in solution.
Ksp = 33 ¥ 44 ¥ (S)7 = 27 ¥ 256 ¥ (0.005)7 35. To 500 cm3 of water 3.0 ¥ 10–3 kg of acetic acid is
Ksp = 5.4 ¥ 10–13 added. If 23% of acetic acid is dissociated, what will be
32. A 5% solution of anhydrous CaCl2 at 0°C developed 15 the depression of freezing point? Kf and density of wa-
atm osmotic pressure. What is the degree of dissocia- ter are 1.86 K kg mol–1 and 0.997 g cm–3, respectively?
tion of CaCl2? Sol. DT = Kf ¥ molality ¥ (1 + a)
Sol. p = iCST For acetic acid: CH3COOH m CH3COO–+H+
È w 10 ˘ 1 0 0
15 = i Í % ˙ ST 1–a a a
ÎV mB ˚
Given, a = 0.23; Also,
È 5 ¥ 10 ˘
=i¥Í ¥ .0821 ¥ 273 Mole of acetic acid
Î 111 ˙˚ molality (m) =
Weight of water in kg
i = 1.4857
3 ¥ 10 –3 ¥ 103
i – 1 1.487 - 1 = = 0.10
a= = 500 ¥ 0.997
and
n –1 3 -1 60 ¥
103
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DT = Kf ¥ molality (1 + a) 105.3
DT = 1.86 ¥ 0.1 ¥ 1.23 = 0.229 p= atm
760
36. A 0.01 m aqueous solution of K3[Fe(CN)6] freezes at
105.3 (ii)
–0.062°C. What is the apparent percentage of dissocia- ¥ V2 = n ¥ S ¥ 298
tion? [Kf for water = 1.86] 760
Sol. DTf = i Kfm 0.062 = i ¥ 1.86 ¥ 0.01 \ by Eqs. (i) and (ii), we get
i -1 V1 283 105.3 V1 1
i = 3.33 and a= = ¥ =
n -1 V2 298 500 V2 5
3.33 – 1
afi a fi 0.777 \ 77.77%
4 –1 \ V2 = 5V1
37. A solution containing 0.011 kg of barium nitrate in 0.1 i.e., solution was diluted five times.
kg of water boils at 100.46°C. Calculate the degree of 40. A 0.1 M solution of potassium ferrocyanide is 46% dis-
ionisation of the salt. Kb (water) = 0.52 K kg mol–1. sociated at 18°C. What will be its osmotic pressure?
0.011 ¥ 10 –3 i –1
Sol. DTb = i Kbm 0.46 = i ¥ 0.52 ¥ Sol. p = i CST a =
0.1 ¥ 261 n –1
i –1 K4[Fe(CN)6] h 4K+ + [Fe(CN)6]–4
i = 2.098 a= \ n=5
n –1
2.098 – 1 i –1
fi a fi 0.55 0.46 =
5 –1
i = 2.84
3 –1
38. At 300 K, two solutions of glucose in water of con- p = 2.84 ¥ 0.1 ¥ 0.082 ¥ 291
centration 0.01 M and 0.001 M are separated by semi- p = 6.785 atm
permeable membrane. Pressure needs to be applied on 41. A 1 L solution is prepared by dissolving some solid
which solution, to prevent osmosis? Calculate the mag- lead-nitrate in water. The solution was found to boil at
nitude of this applied pressure? 100.15°C. To the resulting solution 0.2 mole NaCl was
Sol. added. The resulting solution was found to freeze at
–0.83°C. Determine solubility product of PbCl2. Given
For 0.01 M solution, For 0.001 M solution, Kb= 0.5 and Kf = 1.86. Assume molality to be equal to
n1 /V1 = 0.01 n1 /V2 = 0.001 molarity in all cases.
T = 300 K T = 300 K Sol. Pb[NO3]2 Æ Pb+2 + 2NO–3
Strong electrolyte completely ionise.
p1V1 = n1ST1 p2V2 = n2ST2 \ n=3
\ p1 = 0.01 ¥ 0.0821 \ p2 = 0.001 ¥ 0.0821 DTb = iKbm
¥ 300 ¥ 300 0.15 = 3 ¥ 0.5 ¥ m fi m = 0.1
= 0.2463 atm = 0.02463 atm Now, Pb(NO3)2 + 2NaCl h PbCl2 + 2NaNO3
The movement of solvent particles occurs from dilute 0.1 0.2 — —
to concentrate solution, i.e., 0.001 M to 0.01 M solu- — — 0.1 0.2
tion. Thus, pressure should be applied on concentrated Now, this solution contains two salts
NaNO3 strong Electrolyte \ Completely ionise
solution, i.e., on 0.01 M solution to prevent osmosis.
and PbCl2 partially ionise
Also, magnitude of external pressure = 0.2463 – 0.0246
= 0.2217 atm pressure on 0.01 M solution. PbCl2 h PbCl2 h Pb +2 + 2Cl-
Solid (aq) S 2S
39. At 10°C, the osmotic pressure of urea solution is 500
mmHg. The solution is diluted and the temperature is 0.446 = 0.4 + 3S
raised to 25°C, when the osmotic pressure is found to S = 1.54 ¥ 10–2
be 105.3 mmHg. Determine extent of dilution. \ KSP = [Pb+2] [Cl–]2
Sol. For initial solution, = 4S 3 = 1.46 ¥ 10–5
42. A protein has been isolated as sodium salt with their
500 molecular formula NaxP (this notation means that xNa+
p= atm , T = 283 K
760 ions are associated with a negatively charged protein
500 P–x). A solution of this salt was prepared by dissolving
¥ V1 = n ¥ S ¥ 283 (i) 0.25 g of this sodium salt of protein in 10 g of water
760
and ebulliscopic analysis revealed that solution boils at
After dilution, let volume becomes V2 and temperature
temperature 5.93 ¥ 10–3 °C higher than the normal boil-
is raised to 25°C, i.e., 298 K
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ing point of pure water. Kb of water 0.52 kg mol–1. Also 44. Two beakers A and B present in a closed vessel. Beaker
elemental analysis revealed that the salt contain 1% so- A contains 152.4 g aqueous solution of urea, contain-
dium metal by weight. Deduce molecular formula and ing 12 g of urea. Beaker B contains 196.2 g glucose
determine molecular weight of acidic form of protein solution, containing 18 g of glucose. Both solutions al-
HxP. lowed to attain the equilibrium. Determine weight % of
Sol. DTb = i ¥ Kb ¥ m Molar mass of NaxP = M glucose in its solution at equilibrium:
( x + 1) ¥ 0.52 ¥ 0.25 ¥ 1000 Sol. Beaker A:
5.93 ¥ 10–3 = wt. of water = (152.4 – 12) gram
M ¥ 10
= 140.4 gram
( x + 1) Mole fraction of urea
= 4.56 ¥ 10–4 (i)
M
12
M 0.2
= 23x (ii) = 60 = = 0.025
100 12 140.4 0.2 + 7.8
\ M = 2300 x +
60 18
\ x + 1 = 2300x ¥ 4.56 ¥ 10–4
x + 1 = 1.0488x Beaker B:
x = 20.34 20 wt. of water = 196.2 – 18
From Eqs. (i) and (ii) = 178.2 gram
Formula of protein = H20P 18
M = 2300 ¥ 20 – 20 ¥ 23 + 20 = 45560 amu Mole fraction of glucose =
180
fi 0.01
43. The vapour pressure of two miscible liquids (A) and 18 178.2
+
(B) are 300 and 500 mm of Hg respectively. In a flask 180 18
10 mole of (A) is mixed with 12 mole of (B). However, Mole fraction of glucose is less so vapour pressure
as soon as (B) is added, (A) starts polymerising into above the glucose solution will be higher than the pres-
a completely insoluble solid. The polymerisation fol- sure above urea solution, so some H2O molecules will
lows first-order kinetics. After 100 min, 0.525 mole of transfer from glucose to urea side in order to make the
a solute is dissolved which arrests the polymerisation solutions of equal mole fraction to attain equilibrium.
completely. The final vapour pressure of the solution is Let x mole of H2O transferred
400 mm of Hg. Estimate the rate constant of the poly-
merisation reaction. Assume negligible volume change 0.2 0.1
= fix=4
on mixing and polymerisation, and ideal behaviour for 0.2 + 7.8 + x 0.1 + 9.9 – x
the final solution.
Sol. A + B h An + B now mass of glucose solution = 196.2 – 18 ¥ 4 = 124.2
PS = PT = PM = Vapour pressure of solution. 18
weight % of glucose = ¥ 100 ¥ 100 fi 14.49 %
124.2
PM = PAo x A + PBo xB
45. The addition of 3 g of substance to 100 g CCl4 (M =
Let a mole of A are left due to polymerisation after 100 154 g mol–1) raises the boiling point of CCl4 by 0.60°C
min. of Kb (CCl4) is 5.03 kg mol–1 K. Calculate
Ê a ˆ Ê 12 ˆ (a) the freezing point depression.
PM = 300 Á ˜ + 500 Á (i)
Ë 12 + a ¯ Ë 12 + a ˜¯ (b) the relative lowering of vapour pressure.
(c) the osmotic pressure at 298 K.
2.303 10 (d) the molar mass of the substance.
K= log (ii)
100 a Given: Kf(CCl4) = 31.8 kg mol–1 K and r (density) of
in 2nd Case solution = 1.64 g/cm3.
After 100 minute solute is added and final vapour pres- DT f Kf 0.6 ¥ 31.8
sure is 400 mm Hg, i.e., Ps = 400 Sol. (a) = = DT f = = 3.793∞C
DTb Kb 5.03
PM – 400 0.525
= (iii) (b) Relative lowering of vapour pressure
400 (a + 12)
3
from Eqs. (i) and (iii) a = 9.9 n
= 251.5
2.303 10 = = 0.018
n+N 3 100
Putting this in eq. (ii) K = log = 1.0 ¥ 10–4 +
100 9.9 251.5 154
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n Sol. P = 179XB + 92
(c) p = CRT = RT PB = 271, PT = 92
V
n=
3
= 0.012 PBo = 271, PTo = 92
251.5 936 736
103 nB = = 12, nT = =8
V= = 62.8 mL 78 92
1.64 12
0.012 XB = = 0.6, X T = 0.4
p= ¥ 0.0821 ¥ 298 = 4.65 atm 20
0.0628 PT = 271 ¥ 0.6 + 92 ¥ 0.4 = 199.4
5.03 ¥ 3 ¥ 1000 271 ¥ 0.6
(d) 0.6 = fi mB = 251.5 YB = = 0.815
mB ¥ 100 199.4
46. If 20 mL of ethanol (density = 0.7893 g/mL) is mixed YT = 0.185
with 40 mL water (density = 0.9971 g/mL) at 25°C, On further condensation
the final solution has density of 0.9571 g/mL. Calculate XB = 0.815, XT = 0.185
the percentage change in total volume of mixing. Also PT = 271 ¥ 0.815 + 92 ¥ 0.185 = 237.844
calculate the molality of alcohol in the final solution.
271 ¥ 0.815
Sol. C2H5OH h V1 = 20 mL, d1 = 0.7893 g/mL YB = = 0.9286
237.844
m1 = 15.786 g = wB 48. The vapour pressure of a certain liquid is given by the
H2O Æ V2 = 40 mL, d2 = 0.9971 g/mL equation:
m2 = 39.884 g = wA 313.7
Log10P = 3.54595 – + 1.40655 log10T where P
T
Total mass = 55.65 g is the vapour pressure in mm and T = Kelvin Tempera-
dsol. = 0.9571 g/mL ture. Determine the molar latent heat of vaporisation as
Total mass of solution a function of temperature. Calculate its value at 80 K.
Vsol. = 58.14 mL =
density of solution d ln P DH
Sol. = …(i)
60 – 58.14 dT RT 2
% change = ¥ 100 = 3.1%
60 313.7
log P = 3.54595 – + 1.40655 log T
wB 1000 15.766 ¥ 1000 T
m= ¥ = = 8.6
mB wA 46 ¥ 39.884 313.7
ln P =3.54595 ¥ 2.303 – ¥ 2.303 + 1.40655 ln T
T
47. Vapour pressure of C6H6 and C7H8 mixture at 50°C is
given by P (mm Hg) = 179 XB + 92, where XB is the d ln P 313.7 ¥ 2.303 1.40655
= + …(ii)
mole fraction of C6H6. A solution is prepared by mix- dT T2 T
ing 936 g benzene and 736 g toluene and if the vapours Comparing Eqs. (i) and (ii)
over this solution are removed and condensed into liq- DH = R[313.7 ¥ 2.303 + 1.40655 T]
uid and again brought to the temperature of 50°C, what
at T = 80 K
would be mole fraction of C6H6 in the vapour state?
DH = 1659.9 Cal.
Exercise
LEVEL I x
PA0 (1 - x) 0
(c) (d) PA
(1 - x) x
1. If PA0 is the vapour pressure of a pure liquid A and the 2. In a mixture of A and B if the mole fraction of the com-
mole fraction of A in the mixture of two liquids A and ponent A in vapour phase is x1 and mole fraction of
B is x, the partial vapour pressure of A is component A in liquid mixture is x2 ( PA0 = vapour pres-
(a) (1 - x) PA0 (b) xPA0 sure of pure A; PB0 = vapour pressure of pure B), then
total vapour pressure of the liquid mixture is
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12. Arrange the following compounds in order of de-

PA0 x2 PA0 x1 PB0 x1 PB0 x2
(a) (b) (c) (d) creasing the depression in freezing point of aqueous
x1 x2 x2 x1 solution.
3. At 40°C, the vapour pressure in torr of methanol and (i) Acetic acid
ethanol solution is P = 119x + 135, where x is the mol. (ii) Trichloroacetic acid
fraction of methanol. Hence (iii) Trifluoroacetic acid
(a) vapour pressure of pure methanol is 119 torr. (a) i > ii > iii (b) ii > iii > i
(b) vapour pressure of pure ethanol is 135 torr. (c) iii > i > ii (d) iii > ii > i
(c) vapour pressure of equimolar mixture of each is 13. During depression of freezing point in a solution,
127 mm. which of the following are in equilibrium?
(d) mixture is completely immiscible. (a) liquid solvent, solid solvent
4. A solution that obeys Raoult’s law is (b) liquid solvent, solid solute
(a) non-ideal (b) colloid (c) liquid solute, solid solute
(c) ideal (d) saturated (d) liquid solute, solid solvent
5. In a mixture A and B components show negative devia- 14. Nitrobenzene freezes at 278.98°C. 0.25 molal solution
tion as of a solute in nitrobenzene causes freezing point de-
(a) DVmix = +ve pression of 2°C. Kf for nitrobenzene is
(b) DHmix = –ve (a) 2 K m–1 (b) 4 K m–1
–1
(c) A–B interaction is weaker than A–A and B–B in- (c) 8 K m (d) 12 K m–1
teraction. 15. 0.15 g of a substance dissolved in 15 g of a solvent is
(d) None of the above. boiled at a temperature higher by 0.216°C than that of
6. 100 mL of liquid A was mixed with 25 mL of liquid B the pure solvent. Find out the molecular weight of the
to give a non-ideal solution of A–B mixture. The vol- substance. (Kf for solvent is 2.16 k.kg. m–1).
ume of this mixture would be (a) 1.01 (b) 10.1 (c) 100 (d) 10.0
(a) 75 mL 16. The freezing point of equimolal aqueous solution will
(b) Either less or more than 125 mL. be highest for
(c) Close to 125 mL but not exceeding 125 mL. (a) C6H5NH3Cl (aniline hydrochloride)
(d) Just more than 125 mL. (b) Ca(NO3)2
7. Which of the following liquid pairs shows a positive (c) La(NO3)3
deviation from Raoult’s law? (d) C6H12O6 (glucose)
(a) Water-nitric acid 17. When mercuric iodide is added to the aqueous solution
(b) Benzene-methanol of potassium iodide, the
(c) Water-hydrochloric acid (a) freezing point is raised.
(d) Acetone-chloroform (b) freezing point is lowered.
8. Liquids A and B form an ideal solution. (c) freezing point does not change.
(a) The enthalpy of mixing is zero. (d) boiling point does not change.
(b) The entropy of mixing is zero. 18. Which of the following is not a colligative property?
(c) The free energy of mixing is zero. (a) Osmotic pressure
(d) The free energy as well as the entropy of mixing (b) Elevation in B.P.
(c) Vapour pressure
are each zero.
(d) Depression in freezing point
9. Which of the following solution (in H2O) has the high-
19. Arrange the following in order of decreasing solubility
est boiling point elevation?
in H2O.
(a) 0.2 m urea (b) 0.1 m K4[Fe(CN)6]
Phenol (i), Toluene (ii), Chloroform (iii)
(c) 0.2 m K2SO4 (d) 0.3 m Glucose (a) (i) > (ii) > (iii) (b) (iii) > (ii) > (i)
10. When mango is placed in dilute aqueous solution of (c) (i) > (iii) > (ii) (d) (iii) > (i) > (ii)
hydrochloric acid, it 20. A X molal solution of a compound in benzene has mole
(a) shrinks (b) swells fraction of solute equal to 0.2. The value of X is
(c) brusts (d) Nothing happens (a) 14 (b) 3.2 (c) 1.4 (d) 2.0
11. If 32 g of an unknown molecule (assumed to be union- 21. What will be the mass percentage of aspirin (C9H8O4)
ised in solution) dissolved in 200 g of H2O of, then in acetonitrile (CH3CN) when 6.5 g of C9H8O4 is dis-
elevation in boiling point is found to be 1.04°C . Find solved in 450 g of CH3CN?
out the molar mass of the unknown molecule (given Kb (a) 2.848% (b) 1.424%
for H2O = 0.52 kg mol–1) (c) 14.24% (d) 28.48%
(a) 160 g/mole (b) 80 g/mole 22. The vapour pressure of a solvent decreased by 10 mm
(c) 40 g/mole (d) 320 g/mole Hg when a non-volatile solute was added to the sol-
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vent. The mole fraction of solute in solution is 0.2. 32. The values of observed and calculated molecular
What would be mole fraction of the the solvent if de- weights of silver nitrate are 92.64 and 170 respectively.
crease in vapour pressure is 20 mm of Hg? The degrees of dissociation of silver nitrate is
(a) 0.8 (b) 0.6 (c) 0.4 (d) 0.2 (a) 60% (b) 83.5% (c) 46.7% (d) 60.23%
23. What is the mole fraction of toluene in vapour which is 33. For a dilute solution, Raoult’s law states that
in equilibrium at 30°C with a benzene-toluene solution (a) the lowering of vapour pressure is equal to the
with a mole fraction of benzene of 0.400? mole fraction of the solute.
( PBo = 119 torr and PTo = 37.0 torr) (b) the relative lowering of vapour pressure is equal
(a) 0.0237 (b) 0.337 (c) 0.437 (d) 0.237 to the mole fraction of the solute.
24. At a given temperature, total vapour pressure in torr of (c) the relative lowering of vapour pressure is propor-
a mixture of volatile components A and B is given by tional to the amount of the solute in solution.
(d) the vapour pressure of the solution is equal to the
PTotal = 120 – 75XB hence, vapour pressure of pure A
mole fraction of the solvent.
and B respectively (in torr) are
34. Benzene and toluene form ideal solution over the en-
(a) 120, 75 (b) 120, 195
tire range of composition. The vapour pressure of pure
(c) 120, 45 (d) 75, 45
benzene and naphthalene at 300 K are 50.71 mm Hg
25. Liquids A and B form an ideal solution and the former and 32.06 mm Hg respectively. What will be the mole
has stronger intermolecular forces. If XA and X A¢ are fraction of benzene in vapour phase if 80 g of benzene
the mole fractions of A in the solution and vapour phase is mixed with 100 g of naphthalene?
in equilibrium, then (a) 0.0675 (b) 0.675 (c) 0.35 (d) 0.5
X A¢ X A¢ 35. Benzene and toluene form nearly ideal solutions. At
(a) =1 (b) >1
XA XA 20°C, the vapour pressure of benzene is 75 torr and
that of toluene is 22 torr. The partial vapour pressure (in
X A¢
(c) <1 (d) X A¢ + X A = 1 torr) of benzene, at 20°C for a solution containing 78 g
XA of benzene and 46 g of toulene, is
26. What will be the mass of a non-volatile solute (molar (a) 50 (b) 25 (c) 37.5 (d) 53.5
mass 40 g mo1–1) which should be dissolved in 114 g 36. The vapour pressure of pure liquid A is 0.80 atm. On
octane to reduce its vapour pressure to 80%? mixing a non-volatile B to A, its vapour pressure be-
(a) 10 g (b) 4 g (c) 2 g (d) 16 g comes 0.6 atm. The mole fraction of B in the solution is
27. Vapour pressure of water at 293 K is 17.535 mm Hg. (a) 0.150 (b) 0.25 (c) 0.50 (d) 0.75
What will be the vapour pressure of water at 293 K 37. 100 g of liquid A (molar mass 140 g mo1–1) was dis-
when 25 g of glucose is dissolved in 450 g of water? solved in 1000 g of liquid B (molar mass 180 g mol–1).
(a) 17.44 mm Hg (b) 174.4 mm Hg The vapour pressure of pure liquid B was found to be
(c) 34.88 mm Hg (d) 8.72 mm Hg 500 torr. What will be the vapour pressure of pure liquid
28. The modal elevation constant is the ratio of the eleva- A and its vapour pressure in the solution respectively if
tion in B.P. to the total vapour pressure of the solution is 475 torr?
(a) molarity (a) 28.7 torr and 32 torr (b) 280.7 torr and 32 torr
(b) molality (c) 28.7 torr and 3.2 torr (d) 280.7 torr and 3.2 torr
(c) mole fraction of solute 38. 3.0 molal NaOH solution has a density of 1.110 g/mL.
(d) mole fraction of solvent The molarity of the solution is
29. The boiling point of an aqueous solution of a non-vola- (a) 2.9732 (b) 3.05
tile solute is 100.15°C. What is the freezing point of an
(c) 3.64 (d) 3.0504
aqueous solution obtained by diluting the above solu-
39. When 5.0 g of BaCl2 is dissolved in water to have 106
tion with an equal volume of water? The values of Kb
g of solution. The concentration of solution is
and Kf for water are 0.512°C and 1.86°C molality–1.
(a) 2.5 ppm (b) 5 ppm
(a) –0.544°C (b) –0.512°C
(c) –0.272°C (d) –1.86°C (c) 5M (d) 5 g L–1
30. Which of the following 0.1 M aqueous solution will 40. At a certain hill station pure water boils at 99.725°C. If
have the lowest freezing point? Kb for water is 0.513°C kg mol–1, the boiling point of
(a) Potassium sulphate (b) Sodium chloride 0.69 m solution of urea will be
(c) Urea (d) Glucose (a) 100.079°C (b) 103°C
31. What will be the osmotic pressure of a solution pre- (c) 100. 359°C (d) unpredictable
pared by dissolving 25 mg of K2SO4 in 2 L of water at 41. The freezing point of 1 molal NaCl solution assuming
25°C, assuming that it is completely dissociated? NaCl to be 100% dissociated in water is
(a) 5.27 ¥ 10–3 atm (b) 52.7 ¥ 10–3 atm (a) –1.86°C (b) –3.72°C
(c) 26.3 ¥ 10 atm
–3
(d) 2.63 ¥ 10–3 atm (c) +1.86°C (d) +3.72°C
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42. 10 g of solute with molecular mass 100 g mol–1 is dis- 2. 0.2 molal acid HX is 20% ionised in solution. Kf = 1.86
solved in 100 g solvent to show 0.3°C elevation in boil- K molality-1 the freezing point of the solution is
ing point. The value of molal ebullioscopic constant (a) –0.45°C (b) –0.90°C
will be (c) –0.31°C (d) –0.53°C
(a) 10 (b) 3 3. How much the amount of CaCl2 (i = 2.47) dissolved in
(c) 0.3 (d) unpredictable 2.5 L of water such that its osmotic pressure is 0.75 atm
43. If the observed and theoretical molecular mass of NaCl at 27°C?
is found to be 31.80 and 58.50, then the degree of dis- (a) 0.3 mole (b) 0.03 mole
sociation of NaCl is (c) 3 mole (d) 0.003 mole
(a) 83.96% (b) 8.39% 4. Boiling point of pure H2O is 373.15 K. If 32.5 g of
(c) 90% (d) 100% KCN is dissolved in 100 mL of H2O, what will be the
44. The substance A when dissolved in solvent B shows the boiling point of solution? (Given Kb for H2O = 0.52 K.
molecular mass corresponding to A3. The Vant Hoffs kg mol–1 and molar mass of KCN= 65 g/mole)
factor will be (a) 105.28°C (b) 100.52°C
(a) 1 (b) 2 (c) 3 (d) 1/3 (c) 373.67 K (d) 373.75 K
45. A 5% solution of cane sugar is isotonic with 0.877 % of 5. The freezing point of a solution of acetic acid (mole
X. The molecular weight of substance X is fraction is 0.02) in benzene is 277.4 K. Acetic acid ex-
(a) 59.98 (b) 119.96 (c) 95.58 (d) 126.98 ists partly as a dimer 2A m A2. Determine the equi-
46. The osmotic pressure of equimolar solutions of urea, librium constant for dimerisation. Freezing point of
BaCI2 and AlCI3 will be in which order? benzene is 278.4 K and (Kf for benzene is 5).
(a) AlCl3 > BaCl2 > Urea (a) 3.39 kg mol–1 (b) 33.9 kg mol–1
–1
(b) BaCl2 > AlCl3 > Urea (c) 1.68 kg mol (d) 16.8 kg mol–1
(c) Urea > BaCl2 > AlCl3 6. Which one of the following pairs of solution can we
(d) BaCl2 > Urea > AlCl3 expect to be isotonic at the same temperature?
47. A certain substance ‘A’ tetramerises in water to the ex- (a) 0.1 M urea and 0.1 M NaCl
tent of 80%. A solution of 2.5 g of A in 100 g of water (b) 0.1 M urea and 0.2 M MgCl2
lowers the freezing point by 0.3°C. The molar mass of (c) 0.1 M NaCl and 0.1 M Na2SO4
A is (d) 0.1M Ca(NO3)2 and 0.1 M Na2SO4
(a) 122 (b) 31 (c) 244 (d) 62 7. The osmotic pressure of a 5% aqueous solution of cane
48. Which of the following solutions will exhibit highest sugar at 150°C is (Mol. Wt. of cane sugar = 342)
boiling point? (a) 4 atm (b) 3.4 atm
(a) 0.01 M Na2SO4 (b) 0.01 M KNO3 (c) 5.07 atm (d) 2.45 atm
(c) 0.015 M urea (d) 0.015 M glucose 8. If the solution of mercuric cyanide of strength 3 g/L
49. What is the osmotic pressure of 12% solution of can has an osmotic pressure 0.3092 ¥ 105 Nm–2 at 298 K,
sugar (mol. wt. 342) at 17°C? what is the apparent molecular weight and degree of
(a) 8.35 atm (b) 9.35 atm dissociation of Hg(CN)2 respectively? (Hg = 200.61, C
(c) 5.36 atm (d) 7.35 atm = 12, N = 14)
50. Mixture of volatile components A and B has total va- (a) 240.2, 2.45% (b) 480.4, 2.45%
pour pressure (in torr): (c) 480.4, 24.5% (d) 240.2, 24.5%
P = 254 – 119xA, where xA is mole fraction of A in mix- 9. Concentrated nitric acid used in laboratory work is 68%
ture. nitric acid by mass in aqueous solution. What should be
Hence PAo and PBo are (in torr) the molarity of such a sample of the acid if the density
of the solution is 1.504 g mL–1?
(a) 254, 119 (b) 119, 254
(a) 1.623 M (b) 16.23 M
(c) 135, 254 (d) 154, 119
(c) 162.3 M (d) 0.1623 M
10. Heptane and octane form an ideal solution. At 373 K,
the vapour pressures of the two liquid components are
LEVEL II 105.2 kPa and 46.8 kPa respectively, what will be the
vapour pressure of a mixture of 26.0 g of heptane and
1. A solution is obtained by mixing 300 g of 25% solu- 35 g of octane?
tion and 400 g of 40% solution by mass. What will be (a) 7.308 kPa (b) 73.08 kPa
the mass percentage of the solute and solvent resulting (c) 730.8 kPa (d) 7308 kPa
solution? 11. The vapour pressure of water is 12.3 k pa at 300 K.
(a) 23% and 77% (b) 12.5% and 87.5% What will be the vapour pressure of 1 molal solution of
(c) 33.6% and 66.4% (d) 50% and 50% a non-volatile solute in it?
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(a) 24.16 k pa (b) 1.208 k pa (a) 1 (b) NA/20 (c) 2 (d) 0.1 NA
(c) 2.416 k pa (d) 12.08 k pa 20. 1.0 molal aqueous solution of an electrolyte X3Y2 is
12. The boiling point elevation constant for toluene is 25% ionised. The boiling point of the solution is (Kb for
3.32 K kg mol-1, the normal boiling point of toluene H2O = 0.52 K kg/mol):
is 110.7°C. The enthalpy of vaporisation of toluene (a) 375.5 K (b) 374.04 K
would by nearly (c) 377.12 K (d) 373.25 K
(a) 17.0 k Jmol–1 (b) 34.0 kJ mol–1 21. The molal boiling point constant of water is 0.573°C
(c) 51.0 kJ mol –1
(d) 68.0 kJ mol–1 kg mole–1. When 0.1 mole of glucose is dissolved in
13. A 5% solution (by mass) of cane sugar in water has 1000 g of water, the solution boils under atmospheric
freezing point of 271 K. What will be the freezing point pressure at
of 5% glucose in water if freezing point of pure water is (a) 100.513°C (b) 100.0573°C
273.15 K? (c) 100.256°C (d) 101.025°C
(a) 273.15 K (b) 279.07 K 22. The boiling point of an aqueous solution of a non-vola-
tile solute is 100.15°C. What is the freezing point of an
(c) 269.07 K (d) 293.07 K
aqueous solution obtained by diluting the above solu-
14. At 300 K 36 g of glucose present in a litre of its solu-
tion with an equal volume of water. The values of Kb
tion has osmotic pressure of 4.98 bar. lf the osmotic
and Kf for water are 0.512 and 1.86°C mol–1:
pressure of the solution is 1.52 bars at the same tem-
(a) –0.544°C (b) –0.512°C
perature, what would be its concentration? (c) –0.272°C (d) –1.86°C
(a) 0.061 M (b) 0.61 M 23. An aqueous solution of acetone, CH3COCH3, is 10%
(c) 0.0061 M (d) 6.1 M acetone by weight. What is the mole percentage of ac-
15. The ratio of the value of any colligative property for etone in this solution:
KCl solution to that for sugar is nearly ____ times (a) 3.332% (b) 5.000%
(a) 1 (b) 0.5 (c) 2 (d) 2.5 (c) 10.00% (d) 11.11%
16. When 0.6 g of urea dissolved in 100 g of water, the 24. The freezing point of an aqueous solution of a non-
water will boil at (Kb for water = 0.52 kJ. mol–1 and electrolyte is –0.14°C. The molality of this solution is
normal boiling point of water = 100°C): [Kf (H2O) = 1.86 K kg mol–1]:
(a) 373.052 K (b) 273.52 K (a) 1.86 m (b) 1.00 m (c) 0.15 m (d) 0.075 m
(c) 372.48 K (d) 273.052 K 25. Dry air was passed successively through a solution of
17. A solution prepared by dissolving a 2.50 g sample of 5 g of a solute in 180 g of water and then through pure
an unknown compound dissolved in 34.0 g of benzene, water. The loss in weight of solution was 2.5 g and that
C6H6 boils at 1.38°C higher than pure benzene. Which of pure solvent 0.04 g. The molecular weight of the sol-
expression gives the molar mass of the unknown com- ute is
pound? (a) 31.25 (b) 3.125
Compound Kb (c) 312.5 (d) None of these
C6H6 2.53°C.m–1
2.50
(a) 2.53 ¥
1.38 LEVEL III
34.0
(b) 1.38 ¥ ¥ 2.50
2.53 1. Match the columns:
2.53 1
(c) 2.50 ¥ 103 ¥ ¥ Column I Column II
34.0 1.38
1.38 (a) CH3COOH in H2O (p) Neither association
(d) 2.50 ¥ 103 ¥ ¥ 2.53 nor dissociation
34.0
18. When 1.20 g of sulphur is melted with 15.00 g of naph- (b) CH3COOH in benzene (q) When a non-vola-
thalene, the solution freezes at 77.2° C. What is the mo- tile solute is added.
lar mass of this from of sulphur. Data for Napthalene (c) Polymer in water (r) Molecular mass
Melting point, m.p 80°C Freezing point, depression observed greater
constant, Kf = 6.80°C m–1 than molecular
(a) 180 g mol–1 (b) 194 g mol–1 mass actual.
–1
(c) 260 g mol (d) 450 g mol–1
19. 12.2 g benzoic acid (M = 122) in 100 g H2O has eleva- (d) Vapour pressure of a (s) DTb(obs) > DTb(calc.)
tion of boiling point of 0.27°C, Kb = 0.54 K kg/mole. If liquid decreases
there is 100% dimerisation, the number of molecules of (t) van’t Hoff factor,
benzoic acid in associated state is i>1
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2. Match the columns: Comprehension I

Column I Column II According to Raoult’s law (which is applicable for a mixture
(a) Azeotropes (p) Molality of volatile liquids) the partial vapour pressure of a liquid is
directly proportional to the mole fraction of that component.
(b) A mixture of CHCl3 (q) Intermolecular at-
Further assuming ideal behaviour for vapours and applying
and benzene shows traction negative
Dalton’s law we can write different equations as follows:
deviation from
ideal behaviour. PA = PAo x A , PB = PBo xB
(c) The ratio of observed (r) van’t Hoff factor PTotal = PA + PB = PAo x A + PBo xB = PBo + ( PAo - PBo ) x A
molecular mass to
theoretical molecu- Further mole fraction of a component in vapour phase is
lar mass equal to the ratio of partial vapour pressure to total vapour
pressure of mixture.
(d) The number of moles (s) Solutions with
The vapour pressure of two pure liquids A and B which
of solute dissolved in same composition
form an ideal solution are 300 and 500 torr respectively at
1000 g of solvent in vapour and liq-
temperature T. A mixture of the vapours of A and B for which
uid phase.
the mol fraction of A is 0.25 is slowly compressed at tem-
(t) Constant boiling perature T.
mixtures. 5. The total pressure when first drop of condensate is
3. Match the columns: formed will be
(a) 428 torr (b) 400 torr
Column I Column II
(c) 388 torr (d) 358 torr
(a) CCl4 + CHCl3 (p) Raoult’s law 6. The pressure when only the last bubble of vapour re-
mains will be
(b) + H2 O (q) Nearly ideal solution (a) 350 torr (b) 375 torr
(c) 525 torr (d) 450 torr
(c) PA μ xA (r) Non-ideal solution 7. The mole fraction of B in the last bubble of vapour will
with –ve deviation be
(a) 0.16 (b) 0.84 (c) 0.20 (d) 0.80
(d) CHCl3 + acetone (s) Non-ideal solution
with +ve deviation Comprehension II
(t) Hydrogen bonding A solution of sucrose (molar mass = 342) has been prepared
4. Match the columns: by dissolving 68.4 g of sucrose in one kg of water. Kf for
DHf = Molar heat of fusion of ice; Lf = Latent heat of water is 1.86 K kg mol–1 and vapour pressure of water at 298
fusion of ice (g–1) K is 0.024 atm.
DHv = Molar heat of vaporisation of water; Lv = Latent 8. The vapour pressure of the solution at 298 K will be
heat of vaporisation of water (g–1) (a) 0.230 atm (b) 0.235 atm
(c) 0.236 atm (d) 0.0235 atm
Column I Column II 9. The osmotic pressure of the solution at 298 K will be
(a) Molal depression (p) (a) 4.29 atm (b) 4.49 atm
18 ¥ 373 ¥ 373 ¥ R
constant of water (c) 4.69 atm (d) 4.89 atm
1000 DH v 10. The freezing point of the solution will be
(b) Molal elevation (q) (a) –0.684°C (b) –0.342°C
373 ¥ 373 ¥ R
constant of water (c) –0.372°C (d) –0.186°C
1000 Lv
Comprehension III
(c) DTf of solution (r) 18 ¥ 273 ¥ 273 ¥ R A system of greater disorder of molecules is more probable.
containing 9.0 g of 1000 DH f The disorder of molecules is reflected by the entropy of the
glucose in 50 g of system. A liquid vaporises to form a more disordered gas.
water When a solute is present, there is additional contribution to
(d) DTb of solution (s) 273 ¥ 273 ¥ R the entropy of the liquid due to increased randomness. As the
containing 3.0 g entropy of solution is higher then that of pure liquid, there
1000 L f
of urea in 50 g of is weaker tendency of it to form the gas. Thus, a solute (non
water volatile) lowers the vapour pressure of a liquid, and hence a
(t) Kf higher boiling point of the solution.
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Similarly, the greater randomness of the solution opposes (c) Statement 1 is True, Statement 2, is False
the tendency to freeze. In consequence, a lower temperature (d) Statement 1 is False, Statement 2 is True
must be reached for achieving the equilibrium between the 14. Statement 1: If a solution is heated such that keeping
solid (frozen solvent) and the solution. rest of all things unchanged, volume is changed, then
Elevation of boiling point (DTb) and depression of freezing it also brings changes to colligative properties related
point (DTf) of a solution are the colligative properties which with it.
depend only on the concentration of particles of the solute, Statement 2: The molarity of solution changes on
not their identity. For dilute solutions, DTb and DTf are pro- changing the volume of solution for same amount of
portional to the molality of the solute in the solution. solute.
2
RTbo M 15. Statement 1: The vapour pressure of a liquid is the
DTb = Kbm Kb = Ebulliscopic cons tan t = equilibrium pressure of liquid-vapour equilibrium at
1000 DH vap
and DTf = Kf m; the given temperature.
2 Statement 2: The ratio of the lowering of vapour pres-
RT fo M sure of a solvent upon dissolution of a non-volatile sol-
K f = Cryoscopic constant =
1000 DH fus ute, to the vapour pressure of pure solvent increases
(M = molecular mass of the solvent) with temperature.
The values of Kb and Kf do depend on the properties of the 16. Statement 1: Reverse osmosis is used to purify saline
water.
DH vap
solvent. For liquids, is almost constant. For solutes Statement 2: Solvent molecules pass from concentrat-
Tbo ed to dilute solution through semipermeable membrane
undergoing change of molecular state is solution (ionisation if high pressure is applied on solution.
or association), the observed DT values differ from the calcu- 17. Statement 1: The boiling point of 0.1 M urea solution
lated ones using the above relations. In such situations, the is less than that of 0.1 M KCl solution because
relationships are modified as DTb = iKbm; DTf = iKfm where Statement 2: Elevation of boiling point is directly pro-
i = Van’t-Hoff factor, greater than unity for ionisation and portional to the number of species present in the solu-
smaller than unity for association of the solute molecules in tion.
solutions. 18. Statement 1: Gases always tend to be less soluble in
11. Depression of freezing point of which of the follow- liquids as the temperature is raised.
ing solutions does represent the cryoscopic constant of Statement 2: Vapour pressure of liquids increase with
water? increase in temperature.
(a) 6% by mass of urea in aqueous solution. 19. Statement 1: Azeotropic mixtures are formed only by
(b) 100 g of aqueous solution containing 18 g of glu- non-ideal solutions.
cose. Statement 2: Boiling point of an azeotrope is either
(c) 59 g of aqueous solution containing 9 g of glucose. higher than both the components or lower than both the
(d) 1 M KCl solution in water. components.
12. Dissolution of a non-volatile solute into a liquid leads 20. Statement 1: The vapour pressure of 0.1 M sugar solu-
to the? tion is more than 0.1 M KCl solution because
(a) Decrease of entropy. Statement 2: Lowering of vapour pressure is directly
(b) Increase in tendency of the liquid to freeze. proportional to the number of species present in the so-
(c) Increases in tendency to pass into the vapour lution.
phase. 21. Statement 1: One molar solution is always more con-
(d) Decrease in tendency of the liquid to freeze. centrated than one molal solution because
13. To aqueous solution of NaI, increasing amounts of sol- Statement 2: The amount of solvent in 1 M and 1 m
id HgI2 is added. The vapor pressure of the solution aqueous solution is not equal.
(a) decreases to a constant value 22. Statement 1: Out of various colligative properties, os-
(b) increases to a constant value motic pressure is used for determination of molecular
(c) increases first and then decreases masses of polymers because
(d) remains constant because HgI2 is sparingly solu- Statement 2: Polymer solutions do not possess con-
ble in water stant boiling point or freezing point.
23. Statement 1: If a liquid solute more volatile than the
Assertion and Reasoning Code
solvent is added to the solvent, then the vapour pres-
(a) Statement 1, is True, Statement 2 is True; Statement 2 sure may increase i.e., Ps > Po because
is a correct explanation for Statement 1 Statement 2: In the presence of a more volatile liquid
(b) Statement 1 is True, Statement 2 is True; Statement 2, solute, only solute will form the vapours and solvent
is NOT a correct explanation for Statement 1 will not.
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24. Statement 1: van’t Hoff factor is equal to unity if the 30. The colligative properties of a solution are
elecrolytic solute undergoes 100% dissociation be- (a) μ molality
cause 1
Statement 2: van’t Hoff factor for sucrose solution is (b) μ
molecular mass of the solute
unity.
(c) Proportional to each other.
Multiple Correct Type (d) Independent of the nature of the solute, i.e., elec-
25. When a solute is added to a pure solvent, the trolyte or non-electrolyte.
(a) vapour pressure of the solution becomes lower 31. Identify the correct statements.
than that of the pure solvent. (a) The solution formed by mixing equal volumes of
(b) rate of evaporation of the pure solvent is reduced. 0.1 M urea and 0.1 M glucose will have the same
(c) solute does not affect the rate of condensation. osmotic pressure.
(d) rate of evaporation of the solution is equal to the (b) 0.1 M K4[Fe(CN)6] and 0.1 M Al2(SO4)3 are iso-
rate of condensation of the solution at a lower tonic solutions.
vapour pressure than that in the case of the pure (c) For association of a solute in a solution, i > 1.
solvent. (d) The ratio of van’t Hoff factors for 0.2 M glucose
26. Which is/are correct statement(s)? and 0.1 M sucrose is 2: 1.
(a) When mixture is less volatile, there is positive de-
0
32. 1 mole benzene ( Pbenzene = 42 mm) and 2 mole toluene
viation from Raoult’s law. ( Ptoulene = 36 mm) will have
0
(b) When mixture is more volatile, there is negative (a) total vapour pressure 38 mm
deviation from Raoult’s law. (b) mole fraction of vapours of benzene above liquid
(c) When mixture is less volatile, there is negative mixture is 7/19.
deviation from Raoult’s law. (c) positive deviation from Raoult’s law.
(d) When mixture is more volatile, there is positive (d) negative deviation from Raoult’s law.
devation from Raoult’s law. 33. A binary liquid (AB) shows positive deviation from
27. According to Raoult’s law, the relative decrease in the Raoult’s law when
solvent vapour pressure over the solution is equal to 0 liq 0 liq
(a) the mole fraction of the solvent. (a) p A > p A X A and p A > pB X B
(b) the mole fraction of the solute if solute does not (b) Intermolecular forces: A-A, B-B > A-B
undergo association or dissociation. (c) DVmix > 0
(c) the number of moles of the solute. (d) DHmix > 0
(d) i times the mole fraction of the solute which un- 34. The azeotropic solutions of two miscible liquids
dergoes dissociation or association in the solvent (a) can be separated by simple distillation.
(i = van’t Hoff factor). (b) may show positive or negative deviation from
28. Which of the following statements are correct for a Raoult’ law.
binary solution which shows negative deviation from (c) are supersaturated solutions.
Raoult’s law? (d) behave like a single component and boil at a con-
(a) The negative deviation from linearity diminishes stant temperature.
and tends to zero as the concentration of the solu- 35. If P0 and Ps are the vapour pressures of the solvent and
tion component approaches unity. its solution respectively and N1 and N2 are the mole
(b) When solutions form, their volumes are smaller fractions of the solvent and solute respectively, then
than the sum of the volumes of their components.
(c) Heat is released during the formation of the solu- (a) PS = P0N2
tion. (b) P0 – PS = P0N2
(d) Heat is absorbed during the formation of the solu- (c) PS = P0N1
tion. (d) (P0 – PS)/PS = N1/(N1 + N2)
29. In the depression of freezing point experiment, it is 36. Which of the following form ideal solution?
found that the
(a) C6H5Cl and C6H5Br (b) C6H6 and C6H5CH3
(a) vapour pressure of the solution is less than that of
pure solvent. (c) Hexane and Heptane (d) Ethanol + Cyclohexane
(b) vapour pressure of the solution is more than that 37. At constant temperature, the osmotic pressure of a so-
of pure solvent. lution is
(c) only solute molecules solidify at the freezing (a) directly proportional to the concentration.
point. (b) inversely proportional to the molecular weight of
(d) only solvent molecules solidify at the freezing the solute.
point.
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(c) directly proportional to the square of the concen- ing point is 0.112°C lower than that of pure benzene.
tration. Deduce the value of x. (Atomic mass of Se = 78.8 g
(d) directly proportional to the square root of the con- mol–1).
centration. 46. The vapour pressure of pure benzene at a certain tem-
38. Ideal solution is formed when its components perature is 640 mm Hg. A non-volatile solid weighing
(a) have zero heat of mixing. 2.175 g is added to 39.0 g of benzene. The vapour pres-
(b) have zero volume change. sure of the solution is 600 mm Hg. What is the molar
(c) obey Raoult’s law. mass of the solid substance in nearest integer?
(d) can be converted into gases. 47. Addition of 0.643 g of a compound to 50 mL of ben-
39. In the depression of freezing point experiment, it is zene (density: 0.879 g mL–1) lower the freezing point
found that from 5.51°C to 5.03°C. If Kf for benzene is 5.12 K kg
(a) the vapour pressure of the solution is less than that mol–1, calculate the molar mass of the compound in
of pure solvent. nearest integer.
(b) Freezing point of 1 m sucrose solution greater 48. The vapour pressure of two pure liquids A and B, that
than 1 m NaCl solution at same temperature. form an ideal solution are 100 and 900 mm Hg respec-
(c) only solute molecules solidify at the freezing tively at temperature T. This liquid solution of A and B
point. is composed of 1 mole of A and 1 mole of B. What will
(d) only solvent molecules solidify at the freezing be the pressure, in mm Hg when 1 mole of mixture has
point. been vaporised?
Integer and Subjective Question 49. Mixture of two liquids A and B is placed in cylinder
containing piston. Piston is pulled out isothermally so
40. At 20°C, the osmotic pressure of urea solution is 400 that volume of liquid decreases but that of vapour in-
mm. The solution is diluted and the temperature is creases. When negligibly small amount of liquid was
raised to 35°C, when the osmotic pressure is found to remaining, the mole fraction of A in vapour is 0.4. Giv-
V en P°A = 0.4 atm and P°B = 1.2 atm at the experimental
be 105.3 mm. Find final
Vinitial temperature. Calculate the total pressure at which the
41. An aqueous solution containing 5% by weight of urea liquid has almost evaporated. (Assume ideal behav-
and 10% by weight of glucose. What will be the DTf of iour)
solution? Kf¢ for H2O is 1.86° mol–1 kg? 50. 1.5 g of monobasic acid when dissolved in 150 g of
42. A certain mass of a substance when dissolved in 100 water lowers the freezing point by 0.165°C. 0.5 g of the
g C6H6 lowers the freezing point by 1.28°C. The same same acid when titrated, after dissolution in water, re-
mass of solute dissoved in 100 g of water lowers the quires 37.5 mL of N/10 alkali. Calculate the degree of
freezing point by 1.40°C. If the substance has normal dissociation of the acid (Kf for water = 1.86° C mol–1).
molecular weight in benzene and is completely disso- 51. The molar volume of liquid benzene (density = 0.877
cated in water, into how many ions does it dissociate in g mL–1) increase by a factor of 2750 as it vaporises
water? Kf of H2O and C6H6 are 1.86 and 5.12 K mol–1 at 20°C and that of liquid toluene (density = 0.867 g
respectively. mL–1) increases by a factor of 7720 at 20°C solution
43. A complex is represented as COCl3. xNH3. Its 0.1 mol- has a vapour pressure of 46.0 torr. Find the mole frac-
al solution in aqueous solution shows DTf = 0.558°. Kf tion of benzene in the vapour above the solution.
for H2O is 1.86 K molality–1. Assuming 100% ionisa- 52. Calculate the boiling point of a solution containing 0.61
tion of complex and coordination number of Co as six, g of benzoic acid in 50 g of carbon disulphide assuming
find the value of x. 84% dimerisation of the acid. The boiling point and Kb
44. A very small amount of a non-volatile solute (that does of CS2 are 46.2°C and 2.3 K kg mol–1, respectively.
not dissociate) is dissolved in 56.8 cm3 of benzene 53. At 25°C, 1 mol of A having a vapour pressure of 100
torr and 1 mol of B having a vapour pressure of 300
(density 0.89g cm–3). At room temperature, vapour
torr were mixed. The vapour at equilibrium is removed,
pressure of this solution is 98.88 mm Hg while that of
condensed and the condensate is heated back to 25°C.
benzene is 100 mm Hg. If the freezing temperature of
The vapour now formed are again removed, recon-
this solution. If the freezing temperature of this solu-
densed and analysed. What is the mole fraction of A in
tion is 0.73 degree lower than that of benzene, what
this condensate?
is the value of molal freezing depression constant of
54. 30 mL of CH3OH (d = 0.7980 g cm–3) and 70 mL of
benzene in nearest integer?
H2O (d = 0.9984 g cm–3) are mixed at 25°C to form a
45. The molal freezing point depression constant for ben- solution of density 0.9575 g cm–3. Calculate the freez-
zene (C6H6) is 4.90 K kg mol–1. Selenium exists as ing point of the solution. Kf(H2O) is 1.86 kg mol–1 K.
a polymer of the type Sex. When 3.26 g of selenium Also calculate its molarity.
is dissolved in 226 g of benzene, the observed freez-
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55. When the mixture of two immiscible liquids (water 0.1 M KI solution dissolves 12.5 g/L of I2. Calculate
and nitrobenzene) boils at 372 K and the vapour pres- the equilibrium constant Kc for the above equilibrium.
sure at this temperature are 97.7 kPa (H2O) and 3.6 kPa Also calculate the freezing point of the resulting so-
(C6H5NO2). Calculate the weight % of nitrobenzene in lution. Assume molarity to be equal to molality and
the vapour. also assume that conc. of I2 in all saturated solutions is
56. The molar volume of liquid benzene (density = 0.877 same. [Kf for water = 1.86 K kg mol–1].
g mL–1) increases by a factor of 2750 as it vaporises 63. Two solutions of non-volatile solutes A and B are pre-
at 20°C while in equilibrium with liquid benzene. At MA 1
27°C when a non-volatile solute (that does not dissoci- pared. The molar mass ratio, = . Both are pre-
MB 3
ate) is dissolved in 54.6 cm3 of benzene vapour pres-
sure of this solution, is found to be 98.88 mm Hg. Cal- pared as 5% solutions by weight in water. Calculate the
culate the freezing point of the solution. ( DT f ) A
ratio of the freezing point depressions, of the
Given: Enthalpy of vaporization of benzene (l) = ( DT f ) B
394.57 J/g. solutions. If the two solutions are mixed to prepared
Molal depression constant for benzene = 5.12 K kg. two new solutions, S1 and S2, the mixing ratio being
mol–1. 2:3 and 3:2 by volume for S1 and S2 respectively what
Freezing point of benzene = 278.5 K. ( DT f ) S1
57. An ideal solution was prepared by dissolving some would be the ratio ?
( DT f ) S2
amount of cane sugar (non-volatile) in 0.9 moles of wa-
ter. The solution was then cooled just below its freezing 64. The vapour pressures of two pure liquids A and B that
temperature (271 K), where some ice get separated out. form an ideal solution are 300 and 800 torr, respectively,
The remaining aqueous solution registered a vapour at temperature T. A mixture of the vapours of A and B
pressure of 700 torr at 373 K. Calculate the mass of ice for which the mole-fraction of A is 0.25 is slowly com-
separated out, if the molar heat of fusion of water is 96 kJ. pressed at temperature T. Calculate
58. The freezing point depression of a 0.109 M aqueous (a) the composition of the first drop of the conden-
solution of formic acid is –0.21°C. Calculate the equi- sate.
librium constant for the reaction, (b) the total pressure when this drop is formed.
HCOOH (aq) m H+ (aq) + HCOOQ (aq) (c) the composition of the solution whose normal
Kf for water = 1.86 kg mol–1 K boiling points is T.
59. 10 g of NH4Cl (mol. weight = 53.5) when dissolved in (d) the pressure when only the last bubble of vapour
1000 g of water lowered the freezing point by 0.637°C. remains.
Calculate the degree of hydrolysis of the salt if its de- (e) composition of the last bubble.
gree of dissociation is 0.75. The molal depression con- 65. At solution containing 12.5 g of non-electrolyte sub-
stant of water is 1.86 kg mol–1 K. stance in 175 gram of water gave boiling point eleva-
60. The freezing point of 0.02 mol fraction solution of ace- tion of 0.70 K. Calculate the molar mass of the sub-
tic acid (A) in benzene (B) is 277.4 K. Acetic acid ex- stance. Molal elevation constant (Kb) for water 0.52 K
ists partly as a dimer 2A = A2. Calculate equilibrium kg mol–1.
constant for the dimerisation. Freezing point of ben- 66. What weight of the non-volatile solute, urea (NH2 –
zene is 278.4 K and its heat of fusion DHf is 10.042 kJ CO – NH2) need to be dissolved in 100 g of water, in
mol–1. order to decrease the vapour pressure of water by 25%?
61. Tritium, T (an isotope of H) combines with fluorine to What will be the molality of the solution?
form weak acid TF, which ionises to give T+. Tritium is 67. Ethylene dibromide (C2H4Br2) and 1,2-dibromo pro-
radioactive and is a b-emitter. A freshly prepared aque- pane (C3H6Br2) form a series of ideal solution over the
ous solution of TF has pT (equivalent of pH) of 1.5 whole range of composition. At 85°C, the vapour pres-
and freezes at –0.372°C. If 600 mL of freshly prepared sures of these pure liquids are 173 mm Hg and 127 mm
solution were allowed to stand for 24.8 years, calculate Hg respectively.
(i) ionisation constant of TF. (ii) Number of b-particles (a) If 10 g of ethylene dibromide is dissolved in 80
emitted. g of 1, 2-dibromo propane. Calculate the partial
(Given: Kf for water = 1.86 kg mol K–1, t1/2 for tritium pressures of each components and the total pres-
= 12.4 years.) sure of the solution at 85°C.
62. The freezing point of an aqueous saturated solution of (b) Calculate the composition of the vapour in equi-
I2 is –0.0024°C. More than this can dissolve in a KI librium with the above solution and express as
solution because of the following equilibrium: mole fraction of ethylene dibromide.
-
(c) What would be the mole fraction of 1,2-dirbomo
I 2(aq) + I aq I 3- (aq) propane in solution at 85°C equilibriated with
50:50 mole mixture in the vapour?
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68. A dilute solution contains m mol of solute A in 1 kg of 3. A solution of non-volatile solute in water freezes at
a solvent with molal elevation constant Kb. The solute –0.30°C. The vapour pressure of pure water at 298 K
dimerises in solution as 2A m A2. Show that equilib- is 23.51 mm Hg and Kf for water is 1.86 degree/molal.
rium constant for the dimer formation is Calculate the vapour pressure of this solution at 298 K.
K ( K m – DTb ) [IIT-JEE, 1998]
K= b b 4. To 500 cm3 of water, 3 ¥ 10–3 kg of acetic acid is added.
(2 DTb – K b m) 2
If 23% of acetic acid is dissociated, what will be the
Where DTb is the elevation of the boiling point for the depression in freezing point? Kf and density of water
given solution. Assume molarity = molality. are 1.86 K kg mol–1 and 0.997 g cm–3 respectively.
69. Distribution coefficient of an organic acid between wa- [IIT-JEE, 2000]
ter and benzene is 4.1 in favour of C6H6. If 5 g of acid 5. 1.22 g of benzoic acid is dissolved in 100 g of acetone
is distributed in between 50 mL of benzene and 100 and 100 g of benzene separately. Boiling point of the
mL of water, calculate the concentration of acid in two solution in acetone increases by 0.17°C, while that in
solvents. the benzene increases by 0.13°C; kb for acetone and
70. Heptane and octane form ideal solution. At 373 K, the benzene is 1.7 K kg mol–1 and 2.6 K kg mol–1. Find
vapour pressures of the two liquids are 105.2 kPa and molecular weight of benzoic acid in two cases and jus-
46.8 kPa respectively. What will be the vapour pres- tify your answer. [IIT-JEE, 2004]
sure, in bar, of a mixture of 25g of heptane and 35 g of 6. For a dilute solution containing 2.5 g of a non-volatile
octane? non-electrolyte solute in 100 g of water, the elevation
71. The freezing point depression of 0.001 m Kx[Fe(CN)6] in boiling point at 1 atm pressure is 2°C. Assuming
is 7.10 ¥ 10–3 K. Determine the value of x. Given, Kf = concentration of solute is much lower than the concen-
1.86 K kg mol–1 for water. tration of solvent, the vapour pressure (mm of Hg) of
72. The composition of vapour over a binary ideal solu- the solution is (take Kb = 0.76 K kg mol–1).
tion is determined by the composition of the liquid. If [IIT-JEE, 2012]
xA and yA are the mole fractions of A in the liquid and (a) 724 (b) 740 (c) 736 (d) 718
vapour, respectively find the value of xA for which (yA 7. Consider separate solution of 0.500 M C2H5OH (aq),
– xA) has maximum. What is the value of the pressure 0.100 M Mg3(PO4)2 (aq), 0.250 M KBr (aq) and 0.125
at this composition? M Na3PO4 (aq) at 25°C. Which statement is true about
these solution, assuming all salts to be strong electro-
lytes? [2014 Main]
PREVIOUS YEARS’ QUESTIONS (a) They all have the same osmotic pressure.
OF JEE (MAIN & ADVANCED) (b) 0.100 M Mg3(PO4)2 (aq) has the highest osmotic
pressure.
1. The degree of dissociation of Ca(NO3)2 in a dilute (c) 0.125 M Na3PO4 (aq) has the highest osmotic
aqueous solution, containing 7.0 g of the salt per 100 g pressure.
water at 100°C is 70 per cent. If the vapour pressure of (d) 0.500 M C2H5OH (aq) has the highest osmotic
water at 100°C is 760 mm, calculate vapour pressure of pressure.
the solution. [IIT-JEE, 1991] 8. The vapour pressure of acetone at 20°C is 185 torr.
2. Addition of 0.643 g of a compound to 50 mL of ben- [2015 Main]
zene (density 0.879 g/mL) lowers the freezing point When 1.2 g of a non-volatile substance was dissolved
from 5.51°C to 5.03°C. If K¢f for benzene is 5.12 k m–1. in 100 g of acetone at 20°C, its vapour pressure was
Calculate the molecular weight of the compound. 183 Torr. The molar mass of the substance is
[IIT-JEE, 1992] (a) 32 (b) 64 (c) 128 (d) 488
Answer Key
LEVEL I
1. (b) 2. (a) 3. (b) 4. (c) 5. (b) 6. (b) 7. (b) 8. (a) 9. (c) 10. (a)
11. (b) 12. (d) 13. (a) 14. (c) 15. (c) 16. (d) 17. (a) 18. (c) 19. (c) 20. (b)
21. (b) 22. (b) 23. (d) 24. (c) 25. (c) 26. (a) 27. (a) 28. (b) 29. (c) 30. (a)
31. (a) 32. (b) 33. (b) 34. (b) 35. (a) 36. (b) 37. (b) 38. (a) 39. (b) 40. (a)
41. (b) 42. (c) 43. (a) 44. (d) 45. (a) 46. (a) 47. (d) 48. (a) 49. (a) 50. (c)
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LEVEL II
1. (c) 2. (a) 3. (b) 4. (a) 5. (a) 6. (d) 7. (c) 8. (a) 9. (b) 10. (b)
11. (d) 12. (b) 13. (c) 14. (a) 15. (c) 16. (a) 17. (c) 18. (b) 19. (b) 20. (b)
21. (b) 22. (c) 23. (a) 24. (d) 25. (a)
LEVEL III
1. (A) Æ s, t; (B) Æ r; (C) Æ p; (D) Æ q 2. (A) Æ s, t; (B) Æ q; (C) Æ r; (D) Æ p

3. (A) Æ p, q; (B) Æ s, t; (C) Æ p, q; (D) Æ r 4. (A) Æ r, t; (B) Æ p; (C) Æ r, s, t; (D) Æ p, q
5. (a) 6. (d) 7. (b) 8. (d) 9. (d) 10. (c) 11. (c) 12. (d) 13. (b) 14. (b)
15. (c) 16. (a) 17. (a) 18. (b) 19. (b) 20. (a) 21. (d) 22. (c) 23. (c) 24. (d)
25. (a, b, c, d) 26. (c, d) 27. (b, d) 28. (a, b, c) 29. (a, d) 30. (a, b, c)
31. (a, b) 32. (a, b) 33. (a, b, c, d) 34. (b, d) 35. (b, c) 36. (a, b, c) 37. (a, b)
38. (a, b, c) 39. (a,b,d) 40. (4) 41. (3) 42. (3) 43. (5) 44. (5) 45. (8)
46. (65) 47. (156) 48. (300) 49. (0.66 atm) 50. (18.27%) 51. (0.732) 52. (46.31°C)
53. (0.1 and 0.9) 54. (–19.91°C, 7.63 M) 55. (20.11%) 56. (277.51 K)
57. (12.54 gram) 58. (1.44 ¥ 10–4) 59. (h = 0.109) 60. (3.225)
61. (Ka = 7.3 ¥ 10–3, 3.7 ¥ 1022 b-particle) 62. (707.2 and 272.62 K) 63. 9/11
64. (a) XA = 0.47 (b) 565 torr (c) XA = 0.08 (d) 675 torr (e) XA≤ = 0.11 65. (53) 66. (111.118 gram) and (18.52 m)
67. (a) PA = 20.42 mm Hg; PB = 112.04 mm Hg (b) 0.154 (c) 0.5 and 0.5 68. Derivation
69. 67.22 gram/litre and 16.39 gram/litre 70. (73.08 kPa) 71. (3) 72. PAo PBo
PREVIOUS YEARS’ QUESTIONS OF JEE (MAIN & ADVANCED)
1. (746.24 mmHg) 2. (156.06) 3. (23.44 mmHg) 4. (0.229) 5. (122 and 244) 6. (a)
7. (a) 8. (b)
Hints and Solutions

7. (b) mixture of polar CH3OH and non polar benzene
LEVEL I show +ve deviation.
8. (a) For an ideal solution DHmix = 0; DSmix > 0; DGmix <
1. (b) PA = x PAo 0.
2. (a) Mole fraction of A in vapour 9. (c) DTb μ i ¥ m: Higher the value of i ¥ m. more will be
DTb order of DTb b > c > d > a.
PA P0 x 10. (a) The H+ ion concentration in the medium is lower
= = A 2 = x1 = y A
Ptotal P than that of H+ concentration present in the mango
PA x2 juice, therefore osmotic pressure inside the mango is
\ Ptotal = Ps = higher than that of aqueous hydrochloric acid. There-
x1
fore, H2O will be passes out from the mango into aque-
3. (b) PT = PA + PB, for pure ethanol, x = 0 ous hydrochloric acid. Therefore mango shrinks,
\ 0
Pethanol = (119 ¥ 0 + 135) torr w 1000
11. (b) DTb = iKb ◊ m = iK b B ¥
\ vapour pressure of pure ethanol = 135 torr mB wA
4. (c) Ideal solution obey Roult’s law. i=1
5. (b) For a non-ideal solution with negative deviation, 1 ¥ 0.52 ¥ 32 ¥ 1000
DHmix = –ve \ DTb = = 1.04
mB ¥ 200
DVmix = –ve
6. (b) Either less than or more than 125 mL because \ mB = 80 g/mole
DVmixing = 0 for ideal solution. 12. (d) ‘i’ value of CF3COOH > CCl3COOH > CH3COOH
Since, i μ acidic strength
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13. (a) On freezing a solution, only solvent freeze, but not wB = 10 gram.
solute. P0 - PS 17.5 - PS nB 25/180
DT f 2 27. (a) = = =
14. (c) K f = = = 8 Km -1 P0 17.5 nB + n A 25
+
450
m 0.25 180 18
1000 ¥ K f ¥ wB 1000 ¥ 2.16 ¥ 0.15 Relative lowering of vapour pressure
15. (c) DT f = fi 0.216 =
wA ¥ mB 15 ¥ mB
P o - Psolution
\ mB = 100 = xsolute ;
Po
16. (d) Higher the value of ‘i’ less will be freezing point. 25 25
17. (a) 2KI + HgI2 Æ K2[HgI4] 17.535 - Ps
= 180 ª 180 ;
18. (c) Relative lowering of vapour pressure is a colligative 450 25 450
17.535 +
property.
18 180 18
19. (c) Solubility of phenol > chloroform > toluene due to
\ Ps = 17.44 mm Hg
H-bonding.
xB ¥ 1000 0.2 ¥ 1000 DTb
20. (b) m = = = 3.2 28. (b) K b =
(1 - xB ) ¥ m A 0.8 ¥ 78 m
Since, DTb = Kb ◊ m
21. (b) Mass percentage of solute 29. (c) DTb = Kb ◊ m and DTf = Kf ◊ m
Weight of solute ¥ 100 DTb = 0.15°C; 0.15 = Kb ¥ m
=
Weight of [solute + solvent] On diluting the above solution with equal volume of
Mass percentage of aspirin in acetonitrile water molality becomes approximately half.
6.5 DT f Kf 1 DT 1.86 1
= ¥ 100 = 1.424% = ¥ ; 1 = ¥ ; DT f = 0.272°C
(450 + 6.5) DTb Kb 2 0.15 0.512 2
Dp 10 30. (a) DTf = i ¥ Kf ¥ m ; i value of K2SO4 is maximum, so

22. (b) = = 0.2 fi P o = 50 the freezing point is least.
Po Po
31. (a) p = iCST; K2SO4 h 2K+ + SO 24- ; Van’t Hoff
DP 20
= = 0.4 Factor, i = 3
Po Po n
\ xsolvent = 0.6 osmotic Pressure, p = i RT ;
V
23. (d) Total pressure of the solution is given by
25 ¥ 10 –3
PTotal = X B PBo + X T PTo p =3¥ ¥ 0.0821 ¥ 298 ; p = 5.27 ¥ 10–3 atm
174 ¥ 2.0
= 0.4 ¥ 119 + 0.6 ¥ 37 = 47.6 + 22.2
Observed molecular weight
= 69.8 torr 32. (b) i = ;
Applying Dalton’s law for mole fraction in vapour Calculated molecular weight
phase Normal molecular weight
i for AgNO3 = =1+a
PB 47.6 Observed molecular weight
yB = = = 0.763
PTotal 62.4 170
a= - 1 = 0.835 = 83.5%
yT = 1 – 0.763 = 0.237 92.64
24. (c) Given PTotal = 120 – 75 xB 33. (b) Roult’s Law states that the relative lowering of va-
pour pressure is equal to mole fraction of solute.
P = x A PA0 + xB PB0 0 0
34. (b) PT = x A PA + xB PB
For pure A, XB = 0; PAo = 120 torr
P P
y A = A or yB = B
For pure B, XB = 1; PBo = 120 – (75 ¥ 1) = 45 torr PT PT
PA PAo x A x¢ Po P0 - PS nA
25. (c) x ¢A = = fi A = A <1 35. (a) =
PS PS xA P P0 n A + nB
78 46
(Since the liquid A is less volatile, PAo < PS) n A + nB = + = 1 + 0.5
DP nB wB m A 78 92
26. (a) = = ¥ 1
PS n A mB wA PB = PBo ¥ = 75 ¥ 0.66 = 50
1.5
20 wB 114
fi = ¥
80 40 114
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P0 - PS i = 1 – a + a/3 a = 100%
36. (d) = xB 1 1
P0 =1–1+ =
3 3
0.8 - 0.6 0.2
= = = 0.25 45. (a) 5% solution means 100 mL solution contain 5 g
0.8 0.8 cane sugar.
37. (b) P = x A PA0 + xB PB0 0.877% means 100 mL solution contain 0.877 g X iso-
tonic solution C1 = C2
PT = PA + PB = PA0 x A + PB0 xB = PB0 (1 - x A )
p1 = p 2
100
140 \ C1ST = C2 ST
xA = = 0.11
1000 100 C1 = C2
+
180 140 5 0.877
=
\
0
4.75 = PA ¥ 0.11 + 500(1 – 0.11) 342 ¥ 100 M wt. ¥ 100
0.877
PA0 =
31.0
= 280.7 torr Mwt = ¥ 342 = 59.98
0.11 5
PA = PA0 ¥ x A = 280.7 ¥ 0.11 = 32 torr 46. (a) Osmotic pressure μ Colligative properties
OP = iCRT
M ¥ 1000
38. (a) m = AlCl3 (i = 4), BaCl2 (i = 3), Urea (i = 1)
d ¥ 1000 – M ¥ Molar mass of solute
1– i Ê 1- i ˆ
M ¥ 1000 47. (d) a= = n
3= 1 ÁË 1 - n ˜¯
1110 – M ¥ 40 1–
n
3330 – 120M = M ¥ 1000 1– i
3330 0.8 = ; i = 0.4
3330 = M(1120) \ M= 1
1120 1–
M = 2.97 n
39 (b) The concentration of solution (ppm) DT = iKf ¥ m
Weight of solute 5 wB ¥ 1000
= ¥ 106 = 6 ¥ 106 = 5 ppm 0.3 = 0.4 ¥ 1.86 ¥
Weight of solvent 10 mB ¥ wA
40. (a) DTb = m ¥ Kb
2.5 ¥ 1000
DTb = 0.69 ¥ 0.513°C 0.3 = 0.4 ¥ 1.86 ¥
mB ¥ 100
DTb = 0.69 ¥ 0.513°C mB = 62
Tsolution – Tsolvent = 0.3597 48. (a) DT = i ¥ Kb ¥ m
Tsolution – 99.725°C = 0.3597 i ¥ m of Na2SO4 is highest, hence its boiling point will
Tsolution = 100.0789°C also be highest
41. (b) DTf = i ¥ m ¥ Kf [NaCl = Na+ + Cl–] Na2SO4 i ¥ m = 3 ¥ 0.01 = 0.03
KNO3 i ¥ m = 2 ¥ 0.01 = 0.02
DTf = 2 ¥ 1 ¥ 1 ¥ 1.86 Since, i = 2
Urea i ¥ m = 1 ¥ 0.015 = 0.015
DTf = 3.72
Glucose i ¥ m = 1 ¥ 0.015 = 0.015
Tsolvent – Tsolution = 3.72
n
0° – Tsolution = 3.72 49. (a) p = ST
V
Tsolution = – 3.72°C 12 1
42. (c) DTb = m ¥ Kb = ¥ ¥ 0.0821 ¥ 290
342 0.1
10 ¥ 1000 = 8.35 atm
0.3 = ¥ Kb
100 ¥ 100
50. (c) When xA = 0, xB = 1
Kb = 0.3
\ P = PBo
M – M 0 58.50 – 31.80
43. (a) a = T = = 0.8396 = 83.96%
M0 31.80 \ PBo = 254,
44. (d) 3A h A3 when xA = 1, xB = 0
1– a a/3 \ PAo = P = 254 – 119 = 135
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Hence the molality of A after dimer is formed = (1 – a)

LEVEL II ¥ Initial molality = (1 – 0.48) ¥ initial molality = 0.52 ¥
0.262
300 ¥ 25 a
1. (c) Weight of solute in 300 g solution =
100
= 75 g Molality of A2 after dimer is formed = ¥ molality =
2
400 ¥ 40 0.48
Weight of solute in 400 g solution = = 160 g = 0.24 ¥ 0.26 = 0.06288
100 2
\ Total weight of solute in resultant solution = 75 + The equilibrium constant
160 = 235 g [ A2 ] 0.06288
Keq = = = 3.39 kg mol–1
Total weight of solution = 300 + 400 = 700 g [ A]2
(0.13624) 2
Mass percentage of solute in resulting solution
\ mA = 100
235 6. (d) Number of ions in solution of NaCl = 2
= ¥ 100 = 33.6%
700 MgCl2 = 3; Urea = 1; Na2SO4 = 3; Ca(NO3)2 = 3
Mass percentage of solvent in resulting solution
= (100 – 33.6)% = 66.4% \ iC = 3 ¥ 0.1 = 0.3 for both Ca(NO3)2 and Na2SO4
2. (a) DTf = i ¥ Kf ¥ m n
7. (c) p = CRT = RT
0 – Tf = (1 + 0.2) ¥ 1.86 ¥ 0.2 = 0.4464 V
\ Tf = –0.4464°C Êw 10 ˆ
3. (b) p = iCST; Osmotic Pressure; p = iCRT =Á %¥ ¥ RT
ËV mB ˜¯
n
or p = i RT 10
V =5¥ ¥ 0.0821 ¥ [150 + 273]
n 342
\ 0.75 = ¥ 0.0821 ¥ 300 ¥ 2.47 = 5.07 atm
2.5
0.75 ¥ 2.5 8. (a) Let the apparent molecular weight = mo
n= ; \ n = 0.03 mole
0.0821 ¥ 300 ¥ 2.47 n w 1
Osmotic pressure = p = ¥ RT = ¥ ¥ RT
w B 1000 V mo V
4. (a) DTb = iKb ¥
mB wA 3 ¥ 10-3 1
or 0.3092 ¥ 105 = ¥ -3 m3 ¥ 8.314 ¥ 298
32.5 1000 mo 10
= 2 ¥ 0.52 ¥ ¥
64 100 \ mo = 240.2 ¥ 10 kg
–3
= 240.2 gram/mole
DTb = 5.28 Since,
\ Tf = 100 + 5.28 = 105.28°C
Number of particles after dissociation
5. (a) Let acetic acid = A; Benzene = B i=
Assume, a part of A forms dimer Number of particles before dissociation
2A m A2 N ormal molecular weight
=
1 0 Initially moles Observed molecular weight
1–a a/2 Moles after dimer is formed
\ Hg(CN)2 m Hg++ + 2CN–
(1 - a ) + a /2 1–a a
\ i= = 1 - a /2 2a
1 \ Number of particles after dissociation
Molecular fraction of A = xA = 0.02; = (1 – a) + a + 2a = 1 + 2a
= mole fraction of solute
1 + 2a 252.61 ¥ 10-3
Molecular fraction of B = xB = 0.98 \ i= = ;
= mole fraction of solvent 1 240.2 ¥ 10-3
0.02 1000 a = 0.02457 or 2.4567%
Molality of A in B = ¥
78 0.98 w
= 0.262 mol kg–1 of Benzene 9. (b) Given % = 68%
w
Since, DTf = Kf ¥ i ¥ molality mB = 63 and d = 1.504 gmL–1
278.4 – 277.4 = 5 ¥ i 0.262 or, 1 = 5 ¥ i ¥ 0.262
w 10d 68 ¥ 10 ¥ 1.504
1 M= % = = 16.23 M
i= = 0.763; 1 – a/2 = 0.763 fi a = 0.48 w mB 63
5 ¥ 0.262
10. (b) P = x A PAo + xB PBo
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o
PHeptane = 105.2 kPa 1000 Kb wB 1000 ¥ 0.52 ¥ 0.6
16. (a) DTb = Tb - Tbo = =
o mB wA 60 ¥ 100
POctane = 46.8 kPa
Tb – 373 = 0.052 Tb = 373.052
Ê 26 ˆ Ê 35 ˆ
Á 100 ˜ Á 114 ˜ 1000 ¥ Kb ¥ w2 1000 ¥ 2.53 ¥ 2.5
PS = 105.2 ¥ Á + 46.8 ¥ Á 17. (c) mB = mB =
26 35 ˜ 26 35 ˜ DTb w1 1.38 ¥ 34
ÁË + ˜¯ ÁË + ˜
100 114 100 114 ¯ 1000 K f wB
= 73.08 kPA 18. (b) DT f =
mB wA
PAo - PS 1000 1000 ¥ 6.8 ¥ 1.2
11. (d) ¥ =m mB = \ mB = 194.2 g/mole
PS mA 2.8 ¥ 15
12.3 - PS 1000 1000 Kb wB 0.27 ¥ 122 ¥ 100
¥ =1 19. (b) DTb = i ¥ i=
PS 18 mB wA 1000 ¥ 0.54 ¥ 12.2
1018 ¥ PS = 12300 a
i = 0.5 i=1–a+
12300 n
\ PS = = 12.082 KPa
1018 weight 12.2
No. of moles = = = 0.1 mole
RTb2¥ mA Molar mass 122
12. (b) K b = 2C6H5COOH (C6H5COOH)2
1000 ¥ DHV
0.1 0
R(Tbo ) 2 m A 0.1
DHV = 0 mole
1000 ¥ K b 2
= 33919 J ª 34 KJ 0.1 0.1 N
mole = NA = A
13. (c) Let the mass of solution = 100 g 2 2 20
20. (b) 1–a 3a 2a
( DT f )1
273 - 271
( DT f )1 = K f m1 fi K f = = DTb = i Kbm x3y2 h 3x+2 + 2y+3
m1 5 1000
¥ i = 1– a + 3a + 2a i = 0.75 + 1.25
342 95
i=2 Tb – T bo = 2 ¥ 1 ¥ 0.52
For glucose (DTf)2 = Kf m2 and (Tf)2 = T f – DTf
0
Tb = 373 + 1.04 Tb = 374.04
273.15 – Tf = Kf ¥ m2 21. (b) DTb = Kbm Tb – T bo = 0.573 ¥ 0.1
273 - 271 5 1000 Tb = 373.0573 K
= ¥ ¥
5 1000 180 95 22. (c) DTb = Kbm 0.15 = 0.512 ¥ m
¥
342 95 m = 0.292 DTf = Kfm¢
Tf(glucose) = 269.07 K 0.292
14. (a) p = CRT m¢ = m/2 Tf – T fo = 1.86 ¥
T = –0.27°C 2
We know that f
p1V1 = C1RT1 and p2V2 = C2RT2 23. (a) Acetone = 10 gm Water = 90 gm
Since, (V1 = V2, T1 = T2) 10/58
mole % of acetone = ¥ 100 = 3.33%
10/58 + 90/18
p1 p 2
\ = 0.14
C1 C2 24. (d) DTf = Kfm m= = 0.075 molal
1.86
p 2C1 1.52 ¥ 36 P° – PS Loss in weight of solvent
\ C2 = = = 0.061 M 25. (a) = (i)
p1 4.98 ¥ 180 PS Loss in weight of solution
(C.P)1 i1 Exp. colligative property P° – PS wB m A
15. (c) = ; iKCl = = ¥ (ii)
(C.P) 2 i2 Normal colligative property PS mB wA
from eq. (i) and (ii)
Number of particle furnished by KCl
= =2 0.04 5 ¥ 18
Number of particles before dissociation =
2.5 180 ¥ mB
For an ideal solution of sugar isugar = 1
mB = 31.25
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LEVEL III 7. (b) P = x A PAo + xB PBo

PA
yA = , yB = 1 - y A
1. (A - s, t), (B - r), (C - p), (D - q) PT
1. CH3COOH in H2O undergoes dissociation.
P o - PS 1000 w 1000
2. CH3COOH in C6H6 undergoes dimerisation 8. (d) ¥ =m= B ¥
3. Polymer in water undergoes neither association PS mA mB wA
nor dissociation. 0.024 - PS 1000 68.4 1000
¥ = ¥
2. (A – s, t) (B – q) (C – r) (D – p) PS 18 342 1000
(a) Azeotropes or constant boiling mixtures with
PS = 0.0239 atm
equal composition in both vapour phase and liq-
uid phase. 9. (d) p = CST ; p = C ¥ R ¥ T;
(b) CHCl3 in benzene shows negative deviation be- 68.4
= ¥ 0.0821 ¥ 298; p = 4.89 atm
cause of increase in molecular interactions. 342
Observed molecular mass 1L
(c) i =
Theoritical molecular mass 10. (c) DTf = i ¥ Kf ¥ m; T f0 - T f = i ¥ K f ¥ m
Weight of solute 1000
(d) m = ¥ 0 – Tf = 1 ¥ 11.86 k kg mol–1 ¥
68.4
mol/kg
Molar mass of solute Weight of solvent 342
3. (A - p,q), (B - s,t), (C -p, q), (D - r) = 0.372°C 1
(a) CCl4 and CHCl3 are similar in structure and pos- Tf = –0.372°C
sess similar interaction so they are nearly ideal
11. (c) DTf = Kf.m for a solution with m = 1, DTf = Kf
solution and obeys Roult’s law.
Cryoscopic constant Kf = DTf of solution having unit
(b) C6H6 in H2O, weakness the hydrogen bonding in
molality of normal solutes (means i = 1)
H2O and exhibit positive deviation.
9 ¥ 1000
(c) In ideal solution, PA μ XA Molality of glucose solution in m = =1
(d) For non-ideal solution with negative deviation (59 - 9) ¥ 180
P < x A PAo 12. (d) Since the solution has greater entropy (disorder)
4. (A - r,t), (B - p), (C - r, s, t), (D - p,q) than the pure liquid, so former has lesser tendency to
freeze, i.e., the temperature has to be lowered to freeze
(Match the Column) the solution. It has lesser tendency to pass into the va-
2 2 pour phase.
RT fo RT fo m A
+ - + 2-
(a) K f = = ; 13. (b) 2Na (aq) + 2I(aq) + HgI2(s) h 2Na (aq) + HgI4(aq)
1000 L f 1000 DH f
The number of mole particles decreases from 4 = (2Na+
T fo (water) = 273 K, mA = 18
+ 2i–) to 3 = (2Na+ + HgI 24- ). Hence, the colligative
2 2
RT fo RT fo m A property will decrease or, the vapour pressure will in-
(b) K f = = ; crease to a constant value until NaI is completely con-
1000 L f 1000 DH f sumed
T fo (water) = 373 K, mA = 18 14. (b) On heating a solution, volume decreases and mo-
larity increases. Therefore, colligative property also
9 ¥ 1000 changes
(c) DT f = K f ¥ m = K f ¥ = Kf
180 ¥ 50 P DH È 1 1˘
15. (c) ln 2 = ¥Í - ˙
3 ¥ 1000 P1 R Î T1 T2 ˚
(d) DTb = K b ¥ m = K b ¥ = Kb
60 ¥ 50 16. (a) In the process of reverse osmosis, solvent flows
from concentrated side to dilute side of the so saline
5. (a) P = x A PA + xB PB
o o
water can be purified.
P
y A = A , yB = 1 - y A 17. (a) DTb = iKb ◊ m
PT i for urea < KCl
18. (b) Follow Henry’s Law
6. (d) P = x A PAo + xB PBo 19. (b) Azeotropes the boiling point of solution is either
= 300 ¥ 0.25 + 500 ¥ 0.75 = 450 torr lower (+ve deviation to R-Law) or higher (–ve devia-
P tion to R-Law) than that pure components.
y A = A , yB = 1 - y A
PT
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DP 34. (b, d) In azeotrofric mixture, both components will boil

20. (a) = i ¥ xA at same temperature.
Po
i for KCl > urea P o - PS
35. (b, c) = 1 - xsolvent
n n Po
21. (d) M = solute ; m = solute Po – Poxsolvent = Po – PS
V(solution) W(solvent)
–Poxsolvent = –PS
22. (c) Since molecular weight of polymers is very high,
DTf and DTb will be very small so that accurate values PS
\ = xsolvent = N1
cannot be obtained. But osmotic pressure of polymer Po
solution can be measured accurately. \ PS = PoN1
23. (c) Vapours formed above a solution in composed of P o - PS
both volatile solute and solvent. = xsolute = N 2
24. (d) For 100% ionisation, i is equal to number of ions Po
produced from one mole of solute. e.g., For 100% ioni- \ Po – PS = PoN2
sation of NaCl, i = 2 36. (a, b, c) Components with similar molecular structure
25. (a, b, c, d) When a non-volatile solute is added to a and similar molecular interaction will form an ideal so-
pure solvent, the solution vapour pressure is less than lution.
that of pure solvent. e.g. C6H5Cl and C6H5Br, C6H6 and C6H5CH3;
26. (c, d) If a mixture is less volatile then the solution ex- 37. (a, b) p = iCST
hibits negative deviation and if the mixture is more vol- 38. (a, b, c) Ideal solution: Obeys Roult’s law
atile then the solution exhibits positive deviation from DHmix = DVmix = 0
Roult’s Law. 39. (a, b, d) When a non-volatile solute is added to a pure
P0 - Ps solvent to form a solution vapour pressure of solution
27. (b, d) = X solute decreased compared to that of a solution. At freezing
P0
point, only solvent freezes in a solution DTf = iKf m.
28. (a, b, c) For a solution with negative deviation, DHmix < 0; p C
DVmix < 0. 40. (4) p1 = C1ST; p2 = C2ST; 1 = 1
p 2 C2
29. (a, d) When a non-volatile solute is added to a pure
solvent to form a solution vapour pressure of solution 400
For initial solution, p = atm, T = 293 K
decreased compared to that of a solution. At freezing 760
point, only solvent freezes in a solution. 400
30. (a, b, c) Colligative property μ molality ¥ V1 = n ¥ S ¥ 293 (i)
760
1 After dilution, let volume becomes V2 and temperature
μ
Molecular mass 105.3
is raised to 35°C, i.e., 308 K. p = atm
31. (a, b) 760
1. For both urea and glucose i = 1 105.3
¥ V2 = n ¥ S ¥ 308 (ii)
2. For both K4[Fe(CN)6] and Al2(SO4)3, i = 1 + 4a 760
3. For association of a solute in a solution i < 1 V 293 105.3
4. Glucose and sucrose do not undergo either asso- By Eqs. (i) and (ii) we get 1 = ¥
V2 308 400
ciation or dissociation
V1 1
32. (a, b) PT = Pbenzero
o
xbenzene + Ptoulene
o
X toulene =
V2 4
Pbenzene 14 7
ybenzene = = = V2 = 4V1
PT 38 19 i.e., solution was diluted to four times.
1 2 41. (3) DTf = (1.86)[(narea + nglucose)10]
PT = 42 ¥+ 36 ¥ = 38 mm
3 3 solution has 5% by weight urea and 10% by weight
33. (a, b, c, d) In case of non-ideal solution with positive glucose
deviation from Roult’s law. Weight of solute
% by weight = ¥ 100
Weight of solution
1. Ps > x A PA0 + xB PB0
\ Weight of water = 85 g; Weight of urea = 5 g; Weight
2. DHmix > 0 of glucose = 10 g
3. DVmix > 0 DTf = DTurea + DTGlucose
4. A-A and B-B later actions are more than of A-B
interaction 1000 ¥ 1.86 ¥ 5 1000 ¥ 1.86 ¥ 10
DT = + = 3.04
60 ¥ 85 180 ¥ 85
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42. (3) We know,

P o – Ps wB m A
1000 K f ¥ wB = ¥
DT f = Ps mB wA
mB ¥ wA
640 – 600 2.175 ¥ 78
1000 ¥ 5.12 ¥ w \ =
In C6H6: 1.28 = (i) 600 mB ¥ 59
mN ¥ 100
\ m = 65.25
1000 ¥ 1.86 ¥ w 47. Given
In H2O: 1.40 = (ii)
mexp ¥ 100 wB = 0.643 gram, Kf = 5.12 Kmol–1 kg
(Since given that solute behaves as normal in C6H6 and DTf = 5.51 – 5.03 = 0.48
dissociates in water.) By Eqs. (i) and (ii) wA = wt. of benzene = V ¥ d = 50 ¥ 0.879 g
1000 ¥ 5.12 ¥ 0.643
mN 1.40 5.12
= ¥ = 3.01 \ 0.48 =
mexp 1.28 1.86 mB ¥ 50 ¥ 0.879
wB 1000
mn (Normal molar mass) = DT f = K f ¥ ¥
Since, i = mB wA
mexp. (experimental molar mass)
\ mB = 156.06
i = 3.01 ª 3.0 48. Let nB mole of B present in 1 mole of mixture that has
43. (5) DTf = i ¥ Kf ¥ m been vaporised.
CoCl3. xNH3 h CoCl. xNH3 + nCl– Thus, yB = nB
1 3–n 0 xB =1 – nB
1–a a na P = PA°xA + PB°xB = PA° + xB(PB° – PA°)
Let n ions of Cl– are attached with Co. through prima-
ry valencies which undergo dissociation. All the NH3 P – PAo
xB = = 1 - nB
molecules are attached through secondary valencies. PBo – PAo
(NH3 behave as neutral ligand)
DTf = (1 – a + a + na) ¥ Kf ¥ molality PBo xB P o (1 - nB )
yB = fi nB = B
0.558 = (1 – 1 + 1 + n) ¥ 1.86 ¥ 1 ( a = 1) P P
\ n=2 nB P = PB - nB PB
o o (i)
Thus complex is [CoCl.xNH3].Cl2. PBo
Since coordination number of Co is six, thus x + 1 = 6 nB = (ii)
or x = 5. PBo + P
From Eqs. (i) and (ii)
P o - PS 1000 DT f
44. (5) ¥ =m= PBo P - Po P P - Po
PS mA Kf 1- = o Ao fi o = o Ao
PBo + P PB – PA PB + P PB - PA
100 - 98.88 1000
\ m= ¥ = 0.1452 On solving
98.88 78
DT f P = PAo PBo = 100 ¥ 900 fi 300 mm Hg
0.73
now K f = = = 5.027
49. PT = PA x A + PB xB = PA x A + PB (1 - x A )
o o o o
m 0.1452
100 - 98.88 1000 PT = PBo + x A = ( PAo – PBo )
\ m= ¥ = 0.1452
98.88 78
PAo x A PAo x A
45. (8) Given Kf = 4.9 yA = = o
PT PB + x A ( PAo - PBo )
wB = 3.26 wA = 226
0.4 x A
DTf = 0.112°C mB = x ¥ 78.8 0.4 =
1.2 - 0.8 x A
wB 1000
DT f = K f ¥ ¥ 1.2 = 1.8 ¥ xA
mB wA
2
4.9 ¥ 3.26 1000 xA =
0.112 = ¥ 3
x ¥ 78.8 226 1
so xB =
46. Given that, 3
P° = 640 mm, Ps = 600 mm, 2 1 2
wB = 2.175 g, wA = 39.0 g, mB = 78 PT = 0.4 ¥ + 1.2 ¥ = = 0.66 atm
3 3 3
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0.5 Tf = –19.91°C
50. = 3.75 ¥ 10–3 fi mB = 133.33 23.94
mB M= = 7.63 M
1.86 ¥ 1.5 ¥ 1000 32 ¥ 0.98
0.165 = (1 + a) ¥
133.33 ¥ 150 wt of Nitrobenzene
55. ¥ 100
1 + a = 1.1827 wt of Nitrobenzene + wt of water
a = 0.1827 = 18.27% 3.6 ¥ 123
= ¥ 100
78 3.6 ¥ 123 + 97.7 ¥ 18
51. VB = ¥ 2750 mL = 244.583 L
0.877 = 20.11%
92
VT = ¥ 7720 mL = 819.192 L 56. At 20°C:
0.867
78
1 ¥ 0.0821 ¥ 293 ¥ 760 For C6H6 Æ V = ¥ 2750 mL
PB = = 74.74 torr 0.877
244.583
PV = 1 ¥ 0.0821 ¥ 293
1 ¥ 0.0821 ¥ 293 ¥ 760 P = 74.74 mm Hg
PT = = 22.317
819.192 If vapour pressure of benzene at 27°C is P1 then
46 = 74.74 xB + 23.317(1 – xB) P1 DHV È 1 1 ˘
52.423xB = 23.683 ln = –
P R ÍÎ T T1 ˙˚
xB = 0.451
P1 394.57 ¥ 78 È 1 1 ˘
P o ¥ xB 74.74 ¥ 0.451 ln = –
yB = B = = 0.732 74.74 8.314 Î 293 300 ˙˚
Í
PT 46
P1 = 100.364 mm Hg
a 0.84
52. i = 1 – =1– = 0.48 P° – Ps 1000
2 2 m= ¥
0.48 ¥ 2.3 ¥ 0.61 ¥ 1000 Ps mA
DTb = = 0.1104 100.364 – 98.88 1000
122 ¥ 50 m= ¥ = 0.1924
Tb = 46.2 + 0.1104 = 46.31°C 98.88 78
1 DTf = Kf ¥ m = 5.12 ¥ 0.1924 = 0.985°C
53. PA° = 100, PB° = 300, xA = xB = Tf = 278.5 – 0.985 = 277.51 K
2
1 1 57. Initial moles of H2O = 0.9
PT = 100 ¥ + 300 ¥ = 200 torr DHf = 6 kJ
2 2
1 RT f2 M 8.314 ¥ (273) 2 ¥ 18
100 ¥ Kf = = = 1.86
yA = 2=1 1000DH f 1000 ¥ 6000
200 4
DTf = Kf ¥ m
1 3
On condensation x ¢A = , xB¢ = 2
4 4 m= = 1.075
1 3 1.86
PT¢ = 100 ¥ + 300 ¥ = 250 so in 1000 g H2O Æ 1.075 mole solute
4 4
25 1.075
y ¢A = = 0.1 in 1 g H2O Æ mole solute
250 1000
On further condensation 1.075
in 0.9 ¥ 18 g H2O Æ ¥ 0.9 ¥ 18 mole solute
A = 0.1
x ¢¢ 1000
Mole of solute (nB) = 0.0174.15
xB¢¢ = 0.9 means composition of 2nd distillate
P° – Ps nB 760 – 700
54. CH3OH Æ V1 = 30 mL, d1 = 0.798 g/mL = fi = 0.0857
Ps nA 700
m1 = 23.94 g = mass of CH3OH
H2O Æ V2 = 70 mL, d2 = 0.9984 g/mL 0.017415
m2 = 69.888 g = mass of water Moles of H2O (nA) = = 0.2032
0.0857
mT = 93.828 g = Total mass of solution Moles of Ice separate out = 0.9 – 0.2032 = 0.6968
dsolution = 0.9575 g/mL Mass of Ice separate out = 0.6968 ¥ 18 = 12.54 g
Vsolution = 98 mL 58. DTf = (1 + a) Kf ¥ m
1.86 ¥ 23.94 ¥ 1000 0.21 = (1 + a) ¥ 1.86 ¥ 0.109
DTf = = 19.91 1 + a = 1.0358
32 ¥ 69.888
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a = 0.0358 Moles of b-particle emitted = 0.06156

Ca 2
0.109(0.0358) 2 Number of b-particle emitted = 0.06156 ¥ 6.023 ¥ 1023
Ka = = = 1.44 ¥ 10-4 = 3.7 ¥ 1022
1–a 1 – 0.0358
62. 272.6256 K
59. NH4Cl h NH4+ + Cl–, NH4++H2OhNH4OH+H+
[ I 3- ]
C Ca Kc =
C–Ca Ca Ca Ca – Cah Cah Cah [ I 2 ][ I - ]
C – Ca + Ca + Ca – Ca h + Ca h + Ca h DTf = i ¥ Kf ¥ M(M = m)
i= DTr = Kfm
C
= (1 + a + ah) 0.0024
m= = 0.0013 mole/kg
DTf = i ¥ Kf ¥ m 1.86
-
(1 + a + a h) ¥ 1.86 ¥ 10 I2(aq) + I (aq) m I 3- (aq)
0.637 =
53.5 0.0492 0.1 0 Initial
1 + a + ah = 1.832 and (0.0492 – x) (0.1x) x Equilibrium
since a = 0.75, h = 0.109 Now, 0.0492 – x = 0.0013, because of conc. of I2 in all
8.314 ¥ (278.4) 2 ¥ 78 saturated solutions is same
60. Kf = =5
1000 ¥ 10042 x = 0.0479
0.02 ¥ 1000 [ I 3- ]
m= = 0.2614 Kc =
0.98 ¥ 78 [ I 2 ][ I - ]
DTf = i ¥ Kf ¥ m (0.0479)
Kc =
a (0.0013) (0.0521)
i=1– = 0.7643
2 Kc = 707.2 I –3 + I2 + I – + K+
a = 0.4713 DTf = 1.86(0.0479 + 0.0013 + 0.0521 + 0.1)
2A m A2 \ freezing point of the resulting solution = 272.6256 K
C 63. 9/11
C–Ca Ca/2 ( DT f )1 M 2
Ca /2 a =
K eq = = ( DT f ) 2 M1
(C – Ca ) 2
2C (1 – a ) 2 5
0.4713 ( DT f ) = K f ¥ ¥ 1000;
K eq = = 3.225 95M A
2 ¥ 0.2614(1 – 0.4713) 2 5
( DT f ) = K r ¥ ¥ 1000
61. TF h T+ + F– 95M B
C–Ca Ca Ca ( DT f ) A
\ MB 3
C - Ca + Ca + Ca = =
i= =1+ a ( DT f ) B MA 1
C
for dilute solution C = M = m (molality) Further for solution S1, molality
\ DTf = iKf ◊ m = iKf ◊ C = È 5 ¥ 1000 ˘ ¥ 2 + È 5 ¥ 1000 ˘ ¥ 3
PT = 1.5 fi [T+] = 0.0316 = Ca Í 95M ˙ 5 Í 95M ˙ 5
(i) Î A ˚ Î B ˚
0.372 = 1.86 ¥ C (1 + a) For solution S2, molality
C + Ca = 0.2 (ii)
È 5 ¥ 1000 ˘ 3 È 5 ¥ 1000 ˘ 2
from Eqs. (i) and (ii) = Í ˙¥ +Í ˙¥
C = 0.1684, a = 0.1876 Î 95M A ˚ 5 Î 95M B ˚ 5
Ca 2 0.1684(0.1876) 2 ( DT f ) S1 molality of S1
Ka = = = 7.3 ¥ 10–3 =
1–a (1 – 0.1876) ( DT f ) S2 molality of S2
In 600 mL solution [TF] = C–Ca = 0.1368 mole/L 3 ˘ È 3 2 ˘
È 2
So moles = 0.1368 ¥ 0.6 = 0.08208 =Í + ˙ /Í + ˙
Since, 24.8y = 2t1/2 ÎM A MB ˚ ÎM A MB ˚
0.08208 MA 1
Moles left after 24.8 years = = 0.02052 2+3 2+3¥
4 MB 3= 3 = 9
Moles disintegrated =
MA 1 2 11
= 0.08208 – 0.02052 = 0.06156 3+3 3+2¥ 3
MB 3 3
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64. (a) XA = 0.47 (b) 565 torr (c) XA = 0.08 (d) 675 torr (e) 0.25 wB 18
XA≤ = 0.11 fi = ¥ \ wB = 111.118
0.75 60 100
x A p oA xB pBo 111.11 1000
x ¢A = and xB¢ = \ molality = ¥ = 18.52
p p 60 100
xA po ¥ xA 67. (a) PA = 20.42 mm Hg, PB = 112.014 mm Hg
= oA
xB pB (1 - x A ) (b) yA = 0.154
(c) yA = 0.5
Given
PA0 = 300 torr, PB0 = 800 torr We know PT = x A PA0 + xB PB0
X A¢ = 0.25, X B¢ = 1 - 0.25 = 0.75 nA

xA = , xB = 1 - x A
n A + nB
(a) By the condensation of only one drop, we can as-
PA
sume that composition of the vapour remains the yA = , yB = 1 - y A
same PT
PA0 X A P0 X Let C2H4Br2 = A, mA = 24 + 4 + 160, where mA = mo-
X A¢ = and X B¢ = B B lecular weight of A
P P
mB = molecular weight of B and B is C3H6Br2 = mB =
X A¢ 0
P X
or = 0 A A 36 + 6 + 160 = 202 Moles of A,
X B¢ PB (1 - X A )
wA 10
Putting various known values, we get nA = = = 0.053 Moles of B,
m A 188
XA = 0.47 and XB = 0.53
(b) P = 300 ¥ 0.47 + 800 ¥ 0.53 = 565 torr wB 80
(c) 760 = 300 XA + 800 XB nB = = = 0.396
mB 202
XA = 0.08 and XB = 0.92
(d) When only the last bubble of vapour remains, nB 0.396
\ xB = = = 0.882
we can assume composition of vapour is now the n A + nB 0.053 + 0.396
composition of the condensate. \ xA + xB = 1
Hence, P = 0.25 ¥ 300 + 0.75 ¥ 800 = 675 torr \ xA = 1 – 0.882 = 0.118
(e) Composition of the last bubble; (a) We know, total pressure
PAo X A 0.25 ¥ 300 PT = PA + PB Where PA, PB are partial pressures of
X A¢¢ = = = 0.11 A and B respectively.
P 675
X B¢¢ = 0.89 = PA0 ◊ x A + PB0 ◊ xB , where PA0 , PB0 are partial
pressures of pure component of A and B.
wB 1000 PT = 173 ¥ 0.118 + 127 ¥ 0.882 = 20.42 + 112.014
65. DTb = Kb ¥ ¥
mB wA = 132.43 mm Hg
Kb ¥ wB ¥ 1000 Here partial pressure of A, PA = 20.42 mm Hg
\ mB = Here partial pressure of B, PB = 112.014 mm Hg.
DTb ¥ wA
(b) Mole fraction of ethylene dibromide in the vapour
According to available data
Partical Pressure of A 20.42
Mass of solute (wB) = 12.5 g yA = = = 0.154
Total pressure 132.43
Mass of water (wA) = 1.75 g
Molal elevation constant (Kb) = 0.52 K kg mol–1 (c) In vapour phase nA : nB = 50:50 yA = 0.5, yB = 0.5
Elevation in boiling point temperature (DTb) = 0.70 K nB
=
n A + mB
(0.052 K kg mol-1 ) ¥ (12.5 g) ¥ 1000
\ mB = 68. 2A m A2
(0.70 K) ¥ (175 g)
m 0 initially
= 53 g mol-1 ma
(m – ma) after dimerisation
P 0 - Ps wB m A 2
66. = ¥
P0 mB wA ma
m(1 – a)
75 2
Po - Po ¥ where a is the degree of dimerisation and m is molal-
fi 100 = w ¥ 18
75 ity which is also molarity (given for dilute solution)).
Po ¥ 60 100
Hence due to dimerisation, final molality = m
100
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ma Ê aˆ 70. (a) Heptane C7H16 mA = 100

m(1 – a) + = m ÁË1 - ˜¯ (b) Octane C8H18 mB = 114
2 2
i = 1 + (n – 1)a wA 25 35
nA = = = 0.25 ; nB = = 0.3
Ê1 ˆ m A 100 114
i = 1 + Á - 1˜ a
Ë2 ¯
0.25 0.3
Ê aˆ xA = = 0.45 xB = = 0.55
= Á1 - ˜ 0.25 + 0.30 0.25 + 0.30
Ë 2¯
= 0.45
Ê aˆ
DTb = Kb ¥ m ¥ i = Kb ¥ m Á1 - ˜ P = PA0 x A + PB0 xB
Ë 2¯
= 105.2 ¥ 0.45 + 46.8 ¥ 0.55
2( Kb m - DTb )
\ a= = 47.34 + 25.74 = 73.08 kPa
Kb m 71. DTf = i ¥ Kf ¥ m
Equilibrium constant K for the dimer formation is 7.10 ¥ 10–3 = i ¥ 1.86 ¥ 0.001
ma i = 3.817
[ A2 ] a i –1
K= = 2 2 = from Eq. (i) a=
[ A]2
m (1 – a ) 2
2m(1 – a ) 2 n –1
2 3.817 – 1
È K m – DTb ˘ È 2( Kb m – DTb ) ˘ a=
K = 2Í b ˙ 2m Í1 – ˙ ( x + 1) – 1
Î Kb m ˚ Î Kb m ˚
x = 2.817 ª 3
Kb ( K b m – DTb ) \ molecular formula of the compound is K3[Fe(CN)6].
K=
( K b m – 2 K b m + 2DTb ) 2 72. Since
K b ( K b m – DTb ) x A PAo
K= Proved yA =
(2 DTb – K b m) 2 PBo + ( PAo – PBo ) x A
69. Let the amount of organic acid in Subtracting xA from both the sides, we get
C6H6 layer = a g
x A PAo
Volume of C6H6 = 50 mL y A - xA = – xA
a PBo + ( PAo – PBo ) x A
\ concentration of acid in C6H6 = g mL–1
50 Differentiating this with respect to xA, we get
Since total amount of acid = 5 g d ( y A – xA ) PAo
\ amount of acid in H2O layer = (5 – a) g = o
and volume of H2O = 100 mL
dx A PA + ( PAo – PBo ) x A
Ê 5 – aˆ g x A PAo ( PAo – PBo )

\ Concentration of acid in H2O = ÁË ˜ - –1
100 ¯ mL {PBo + ( PAo – PBo ) x A }2
Concentration of acid in C6 H 6 The value of xA at which yA – xA has a maximum value
Now, K = can be obtained by setting the above differential equal
Concentration of acid in H 2O
to zero. Thus, we have
a 100
= ¥
50 (5 – a ) PAo
-
(
x A PAo PAo – PBo ) –1
a 100 PAo + ( PAo – PBo ) x A {PBo + ( PAo – PBo ) x A }2
\ 4.1 = ¥
50 (5 – a )
PAo PBo – PBo
or a = 3.361 g. Solving for xA, we get x A =
\ Amount of acid in 50 mL PAo – PBo
C6H6 = 3.361 g The value of P at this composition is
3.361 or P = x A PAo + xB PBo
\ acid concentration in C6H6 = ¥ 1000
50
P = PBo + ( PAo - PBo ) x A
= 67.22 g/L
Also, amount of acid in 100 mL H2O = 5 – a = 5 – 3.361 Ê Po Po - Po ˆ
= 1.639 g. or P = PBo + ( PAo - PBo ) Á Ao B o B ˜
1.639 Ë PA - PB ¯
\ acid concentration in H2O = ¥ 1000
100 or P = PAo PBo
= 16.39 g/L
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PREVIOUS YEARS’ QUESTIONS 5. Since, DTb = K b

wB 1000
¥
OF JEE (MAIN & ADVANCED) mB wA
Kb ¥ wB ¥ 1000
1. Ca(NO3)2 m Ca2+ + 2NO3- \ mB =
Before dissociation 1 0 0 DTb ¥ wA
After dissociation 1–a a 2a
\ total mole at equilibrium = (1 + 2a) ( a = 0.7) For acetone solution:
= (1 + 2 ¥ 0.7) = 2.4 1000 ¥ 1.7 ¥ 1000
For Ca(NO3)2: mB = = 122
0.17 ¥ 100
P o - PS n For benzene solution:
=i B
PS nA 1000 ¥ 2.6 ¥ 1.22 ¥ 1000
mB = = 244
760 - PS 7 18 0.13 ¥ 100
= 2.4 ¥ ¥ = 0.01844
PS 164 100 Molecular weight of C6H5COOH is 122 and thus it is
evident that benzoic acid remains as normal molecu-
760
PS = = 746.24 mm Hg lar species in acetone but shows 100% dimerisation in
1.01844 C6H6, i.e., in C6H6 it exists as (C6H5COOH)2.
2. Given wB = 0.643 gram, Kf = 5.12 Kmol–1 kg wB 1000
6. (a) DTb = K b ¥
DTf = 5.51 – 5.03 = 0.48 mB wA
wA = Weight of benzene = V ¥ d = 50 ¥ 0.879 g wB DTb ¥ wA
= nB =
1000 ¥ 5.12 ¥ 0.643 mB K b ¥ 1000
\ 0.48 =
mB ¥ 50 ¥ 0.879 2 ¥ 100 5
= =
wB 1000 0.76 ¥ 1000 19
= DT f = K f ¥ ¥
mB wA [For very dilute solution (nA + nB = nA)]
\ mB = 156.06 P o - PS nB n w m
3. DTf = Kf ¥ m = xB = = B = B ¥ A
P o
n A + nB n A mB wA
DT f P o - PS 1000 760 - PS 5 18
\ m= = ¥ = ¥
Kf PS mA 760 19 100
760 - PS 9
0.30 23.51 - PS 1000 =
= ¥ 760 190
1.86 PS 18
760 - PS = 36
1002.9 PS = 23510
PS = 760 - 36 = 724 mmHg
\ PS = 23.44 mmHg
7. (a) Given Salts are completely ionise
4. DTf = i ¥ Kf ¥ M, i = (1 + a) Since, colligative properties μ i ¥ M
DTf = Kf ¥ molality ¥ (1 + a) and i ¥ M for C2H5OH = 1 ¥ 0.5 = 0.5
For acetic acid: CH3COOH m CH3COO– + H+ For Mg3(PO4)2 = 5 ¥ 0.1 = 0.5
C 0 0 For KBr = 2 ¥ 0.25 = 0.5
(1 – a) Ca Ca For Na3PO4 = 4 ¥ 0.125 = 0.5
Given, a = 0.23; \ all have same osmotic pressure because (i ¥ M
same) p = [i ¥ M]RT
Mole of acetic acid
Also, molality = P∞- Ps wB m A
Weight of water in kg 8. (b) = ¥
Ps mB wA
3 ¥ 10-3 ¥ 103
=
500 ¥ 0.997 185 - 183 1.2 58
60 ¥ = ¥
103 183 mB 100
C = 0.10 1 1.2 ¥ 58
DTf = Kf ¥ molality (1 + a) =
183 mB ¥ 100
DTf = 1.86 ¥ 0.1 ¥ 1.23
= 0.229 mB = 63.68
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Solution & Colligative Properties Complete Chapter Notes For IIT

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Solution & Colligative Properties Complete Chapter Notes For IIT

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3.2 Physical Chemistry-II for JEE (Main & Advanced)

Raoult’s Law ____________________________

Solution and Colligative Properties 3.3

Case 2 nB No of moles of solute

PAo - PS nB P = PAo x A + PBo xB

3.4 Physical Chemistry-II for JEE (Main & Advanced)

Since 3. DHmix = –ve (heat releases)

Vapour phase P°A

Solution and Colligative Properties 3.5

Maximum Boiling Areotrope:

These are the properties of dilute solutions which depends

Solution Pure R(Tbo ) 2 ¥ m A

3.6 Physical Chemistry-II for JEE (Main & Advanced)

Solvent Osmotic Pressure (p):

should be applied on more concentrate solution

Solution and Colligative Properties 3.7

3.8 Physical Chemistry-II for JEE (Main & Advanced)

Solution and Colligative Properties 3.9

3.10 Physical Chemistry-II for JEE (Main & Advanced)

A mixture of 60% A and 40% B is distilled at this tem- 4

Solution and Colligative Properties 3.11

Ê w 10 ˆ 19. A substance x Mwt = 94 associates in water to form

3.12 Physical Chemistry-II for JEE (Main & Advanced)

PS = x A PAo + xB PBo DTb =

Solution and Colligative Properties 3.13

3.14 Physical Chemistry-II for JEE (Main & Advanced)

Solution and Colligative Properties 3.15

3.16 Physical Chemistry-II for JEE (Main & Advanced)

Solution and Colligative Properties 3.17

12. Arrange the following compounds in order of de-

3.18 Physical Chemistry-II for JEE (Main & Advanced)

Solution and Colligative Properties 3.19

3.20 Physical Chemistry-II for JEE (Main & Advanced)

Solution and Colligative Properties 3.21

2. Match the columns: Comprehension I

3.22 Physical Chemistry-II for JEE (Main & Advanced)

Solution and Colligative Properties 3.23

3.24 Physical Chemistry-II for JEE (Main & Advanced)

Solution and Colligative Properties 3.25

3.26 Physical Chemistry-II for JEE (Main & Advanced)

Solution and Colligative Properties 3.27

1. (A) Æ s, t; (B) Æ r; (C) Æ p; (D) Æ q 2. (A) Æ s, t; (B) Æ q; (C) Æ r; (D) Æ p

PREVIOUS YEARS’ QUESTIONS OF JEE (MAIN & ADVANCED)

Hints and Solutions

3.28 Physical Chemistry-II for JEE (Main & Advanced)

Dp 10 30. (a) DTf = i ¥ Kf ¥ m ; i value of K2SO4 is maximum, so

Solution and Colligative Properties 3.29

3.30 Physical Chemistry-II for JEE (Main & Advanced)

Hence the molality of A after dimer is formed = (1 – a)

Solution and Colligative Properties 3.31

3.32 Physical Chemistry-II for JEE (Main & Advanced)

LEVEL III 7. (b) P = x A PAo + xB PBo

Solution and Colligative Properties 3.33

DP 34. (b, d) In azeotrofric mixture, both components will boil

3.34 Physical Chemistry-II for JEE (Main & Advanced)

42. (3) We know,

Solution and Colligative Properties 3.35

3.36 Physical Chemistry-II for JEE (Main & Advanced)

a = 0.0358 Moles of b-particle emitted = 0.06156

Solution and Colligative Properties 3.37

X A¢ = 0.25, X B¢ = 1 - 0.25 = 0.75 nA