EBD_7753

374 CHEMISTRY

16 Solutions

(iii) Weight – Volume Percentage (w/V)

COMPONENTS OF SOLUTION
A solution is a homogenous mixture of two or more components Weight of solute (gm)
called solute and solvent. Weight – volume percentage= × 100
Volumeof solution (ml)
(i) Solute : The component present in lesser amount than other (iv) Parts per Million
component in solution is called solute.
It is defined as:
(ii) Solvent : The component present in greater amount than any
or all other components is called the solvent. Number of parts of
A solution consisting of two components, i.e., one solute component
and one solvent is called a binary solution. Parts per = ´ 106
million Total number of parts of
TYPES OF SOLUTIONS all components of the
On the basis of physical state of solute and solvent : There may be solution
the following nine types of binary solutions :
(v) Normality
S.No. Solute Solvent Example
1. Gas Gas Air Number of gram equivalents of solute
Normality =
2. Gas Liquid CO2 in soda water Volumeof solution (lit)
3. Gas Solid Hydrogen in Pd/Pt.
Weight of solute (gm)
4. Liquid Gas Fog As Gram equivalents of solute =
5. Liquid Liquid Alcohol in water, Equivalent weight of solute
benzene in toluene (vi) Mole fraction
6. Liquid Solid Mercury in zinc It is defined as:
amalgam
7. Solid Gas Smog Number of moles of
8. Solid Liquid Sugar in water the component
Mole fraction of a =
9. Solid Solid Alloys component Total number of moles of
CONCENTRATION OF SOLUTIONS all the components
Composition of a solution can be described by expressing its (vii) Molarity (M)
concentration. There are several ways of expressing the It is defined as:
concentration of the solution quantitatively. Number of moles of solute
(i) Mass Percentage (w/W) Molarity =
Volume of solution ( in L )
It is given by
(viii) Molality (m)
Mass of the component It is defined as:
in the solution Moles of solute
mass% of a = ´ 100 Molality (m) =
component Total mass of the solution mass of solvent in kg
(ii) Volume Percentage (v/V) (ix) Formality
It is given by weight of solute (gm)
Formality =
Formula weight of solute
Volume of the component 1
volume% of a = ´ 100
Total volume of solution ×
component Volume of solution (lit.)
 Solutions 375

Note: Effect of pressure: The solubility of a gas increases with increase

(i) Mass %, ppm, mole fraction and molality are independent of in pressure. Henry’s law states that at a constant temperature,
temperature, whereas molarity is a function of temperature. It solubility of a gas in a liquid is directly proportional to the pressure
is because volume depends on temperature and mass does of the gas, i.e. Expressing solubility in terms of mole fraction of gas
not. in the solution Henry’s law can be written as,
(ii) The molarity equation is M1V1 = M2V2 p = KHx
(for dilution from volume V1 to V2) p ® partial pressure of the gas in vapour phase
For a reaction between two reactants, x ® mole fraction of the gas in solution
KH ® Henry’s law constant
M1V1 M 2V2 • Henry’s constant, KH is a junction of the nature of the gas.
=
n1 n2 • Greater the value of KH, lower is the solubility of the gas at
where n1 and n 2 are their stoichiometric coefficients in the the same partial pressure.
balanced equation. • The value of KH increases with increase in temperature.
SOLUBILITY 1 1
KH µ and K H µ T \ x µ
Solubility of a substance, is its maximum amount that can be x T
dissolved in a specified amount of solvent. It depends on nature It is due to this reason that aquatic species are more
of solute and solvent, temperature and pressure. comfortable in cold water than in hot water.
Solubility of a Solid in a Liquid Applications of Henry’s Law
(i) To increase the solubility of CO2 in soft drinks and soda
When a solid solute is added to the solvent, some solute dissolves
water, the bottle is sealed under high pressure.
(dissolution) while some solute particles get separated
(ii) To avoid bends as well as toxic effects of high concentrations
(crystallization). A stage is reached when the two processes occur
of nitrogen in the blood, the tanks used by scuba divers are
at the same rate and a state of dynamic equilibrium is reached. The filled with air diluted with helium, nitrogen and oxygen.
solution which is in dynamic equilibrium with undissolved solute (iii) At high altitudes, the partial pressure of oxygen is less which
is the saturated solution and contains the maximum amount of leads to low concentration of oxygen in blood, causing
solute dissolved in a given amount of solvent. The concentration climbers to become weak and unable to think clearly,
of solute in such a solution is its solubility. symptoms of a condition known as anoxia.
Thus, the solubility of a solid in a liquid at any temperature is
defined as the maximum amount of the solid in grams which can be VAPOUR PRESSURE OF LIQUID SOLUTIONS AND
dissolved in 100g of the liquid to form the saturated solution. RAOULT’S LAW
Effect of temperature: If dissolution process is endothermic (DH Vapour Pressure of Liquid-liquid Solutions
> 0), solubility increases with increase in temperature and if it is When two volatile liquids are taken in a closed vessel, a stage is
exothermic (DH < 0), solubility decreases. reached when an equilibrium is established between vapour phase
Nature of the solute and solvent: Ionic compound dissolves in and liquid phase. The relationship between them is given by
polar solvents due to strong electrostatic forces of attraction Raoult’s law i.e.,
between ions and polar solvent molecules. Non-polar compound It states that at a given temperature, the partial vapour pressure of
dissolve in non polar solvents due to similar solute-solute, solute- any component of the solution is equal to the product of the
solvent and solvent-solvent interactions. vapour pressure of the pure component and its mole fraction in
the solution.
Effect of pressure: Solids and liquids are incompressible and
practically remain unaffected by changes in pressure. p1 µ x1 and p1 = p1°x1
Solubility of a Gas in a Liquid p2 µ x2 and p2 = p2° x2
It is generally expressed in terms of absorption coefficient which where p1 and p2 are partial pressures of components 1 and 2
is defined as the volume of gas (reduced to NTP) dissolved by p1° and p2° are their partial pressures in pure state
unit volume of solvent at particular temperature and 1 atm. pressure x1 and x2 are mole fractions of component 1 and 2.
of gas. According to Dalton’s law of partial pressure,
Nature of the gas: Easily liquifiable gases are more soluble. Example: pTotal = p1 + p2 = x1p1° + x2p2°
CO2 is more soluble than O2 and H2. = (1 – x2)p1° + x2p2°
= p1° + (p2° – p1°) x2
Nature of the solvent: Gases capable of forming ions in aqueous
Diagrammatically, it is represented as:
solution are more soluble in water than in other solvent.
Example : HCl, NH3 etc. p2 p2°
= p1+
Vapour pressure

Effect of temperature: Solubility of a gas in a liquid decreases p T

2
p

with increase in temperature. It is an exothermic process p1°

i.e., Gas + Solvent Solution + Heat
p1
Applying Le Chatelier, principle, increase in temperature would
shift the equilibrium in backward direction, i.e, solubility will x1 = 1 Mole x1 = 0
decrease. x2 = 0 fraction x2 = 1
 EBD_7753
376 CHEMISTRY

The composition of the vapour phase is given by: Examples:

p1 = y1pTotal (i) Benzene and toluene
p2 = y2pTotal (ii) n-Hexane and n-Heptane
where y1 and y2 are the mole fractions of components 1 and (iii) Ethyl iodide and ethyl bromide
2 in the vapour phase. (iv) Chlorobenzene and bromobenzene
Vapour Pressure of Solutions of Solids in Liquids Non Ideal: Solution possesses the following characteristics:
If a non-volatile solute is added to a solvent to give a solution, the (i) The interactions between components are different from
vapour pressure of the solution will be from solvent alone and it is those in pure components.
lower than the vapour pressure of the pure solvent at the same ;
(ii) DV ¹ 0, DH ¹ 0 on mixing the components.
temperature. (iii) They do not obey Raoult’s law. They show positive or
Then, the total vapour pressure will be given by negative deviations from Raoult’s law, i.e., PA ¹ xAPA° and
pT = p1 + p2
PB ¹ xBPB°
as p2 = 0 (non-volatile solute)
(iv) They form azeotropes
\ pT = p1 = p1°x1
i.e., vapour pressure of solution µ mole fraction of the solvent in Azeotropic Mixtures
solution. They are binary mixtures of two liquids having same composition
Mole fraction of the solvent in solution, in liquid and vapour phase and boil at a constant temperature and
n1 can be distilled without any change in their composition. They are
x1 = n + n
1 2 formed by non–ideal solutions. They are of two type.
where n1 = moles of solvent and n 2 = moles of solute Minimum boiling azeotropes : it is formed by liquids showing
pT = p1°x1 positive deviation. Such azeotropes have boilig point lower than
pºT n1 either any of the pure component.
i.e., pº = n + n Maximum boiling azeotropes : It is formed by liquids showing
1 1 2
negative deviation such azeotropes have boiling point higher than
pº1 –pT n2
= either of the pure component.
pº1 n1 + n2 Non-Ideal Solutions are divided into two types:
pº1 –pT Non-ideal solutions showing positive deviations
where pº1 is called relative lowering of vapour pressure and 1. The interactions between components are less than in pure
components, i.e., A – B < A – A/B – B
n2 2. DVmixing = +ve °x
n1 + n 2 = mole fraction of the solute in the solution. ° x + pB B PB°
Vapour Pressure
3. DHmixing = – ve P = p A A lution
l S o
Limitations of Raoult’s Law 4. PA > xAPA°; PB > xBPB° I dea

(i) Raoult’s law is applicable only to very dilute solutions. Examples: PA°
(i) Acetone + ethyl alcohol
(ii) Raoult’s law is applicable to solutions containing non-volatile
solute only. (ii) Water + Ethylalcohol
(iii) Acetone + Benzene xA = 1 Mole Fraction xB = 1
(iii) Raoult’s law is not applicable to solutes which dissociates or xA = 0
xB = 0
associate in solution.
Non-ideal solutions showing negative deviations
IDEAL AND NON-IDEAL SOLUTIONS
1. The interactions between components are more than in pure
An Ideal solution possesses the following characteristics.
components, i.e., A – B > A – A/B – B
(i) The interactions between components are similar to those in
pure components. 2. DVmixing = – ve
(ii) There is no volume change and enthalpy change on mixing 3. DHmixing = – ve + p B°
xB PB°
Vapour Pressure

° xA
the components. (DV = 0, DH = 0) 4. PA < xAPA°, PB < xBPB° P = pA n
utio
(iii) Each component obeys Raoult’s law at all temperatures and Examples: dea l sol
PA° I
concentrations i.e, PA = xAPA° and PB = xBPB° (i) H2O + HCl
(iv) They do not form azeotropes (ii) CH3OH + CH3COOH
Their graphical behaviour is shown as:
(iii) H2O + HNO3
pB° (iv) Chloroform + Benzene
+ pB xA = 1 x =1
Vapour pressure

p Mole Fraction xB = 0
pT= p
A
xB = 0 A
B
pA° COLLIGATIVE PROPERTIES
pA Those properties of ideal solutions which depend only on the
number of particles of solute dissolved in a definite amount of the
xA = 1 Mole xA = 0 solvent and do not depend on the nature of the solute are called
xB = 0 fraction xB = 1
colligative properties.
 Solutions 377

The important colligative properties are : (iii) Depression in Freezing Point

(i) Relative Lowering of Vapour Pressure Vapour pressure of the solution is less than that of pure
It is given by: solvent. As freezing point is the temperature at which the
p° - ps n2 w 2 / M2 vapour pressure of the liquid and solid phase are equal,
= = therefore, for the solution, this will occur at a lower temperature
p° n1 + n 2 w1 / M1 + w 2 / M 2 (Q lower the temperature lower is the vapour pressure)
p° - ps n 2 w 2 / M 2 Graphically, it is represented as:
for very dilute solution, ; =
p° n1 w1 / M1
p° - ps n 2 w 2 / M2 t
for all solutions, = = v en
ps n1 w1 / M1 id sol
u
(dilute or concentrated) Liq n
t utio
Where n1, w1, M1 ® number of moles, mass in g, mol. mass en Sol
solv
of solvent.

Vapour pressure
lid
n2, w2, M2 ® number of moles, mass in g, mol. mass of So
solute.
(ii) Elevation of Boiling Point
The boiling point of the solution is always higher than that DTf
of the pure solvent. This is because vapour pressure of
solution is lower than that of pure solvent and hence, the T f°
Tf
solution has to be heated more to make the vapour pressure
equal to the atmospheric pressure. Temperature/K
Graphically, it is represented as If Tf° is freezing point of pure solvent and T f freezing point
of the solution, then Tf < Tf°. The depression in freezing
Atmospheric point DTf is given by
pressure nt DTf = Tf° – Tf
. of solve Quantitatively, it is given by
B.P
tion DTf = Kf × m
f solu
Vapour pressure

B.P.
o Tf° – Tf = Kf × m (m ® molality)
w 2 1000
= Kf × ´
M 2 w1
DTb
1000 ´ K f ´ w 2
M2 = (Kf = molal depression constant
DTf ´ w1
or cryoscopic constant)

Relation for molal depression constant :

Tb° Tb M1RTf2
Temperature Kf =
If Tb° is vapour pressure of solvent and Tb is vapour pressure 1000DHf
of the solution than where, Tf = Freezing point of pure solvent
Tb > Tb° DHf = Enthalpy of fusion of solvent
The difference DTb is called elevation in boiling point Note:
DTb = Tb – Tb° Depression in freezing point is used in:
Quantitatively, it is given by (a) making antifreeze solutions
(b) melting of ice on the roads
DTb = K b ´ m , where m = molality
w 1000 (iv) Osmotic Pressure
Tb - Tb ° = K b ´ m = K b ´ 2 ´ The net spontaneous flow of the solvent molecules from the
M 2 w1
solvent to the solution or from a less concentrated solution
1000 ´ K b ´ w 2 to a more concentrated solution through a semipermeable
M2 = (Kb = molal elevation constant or
DTb ´ w1 membrane is called osmosis.
ebullioscopic constant) The minimum excess pressure that has to be applied on the
Molal elevation constant is also given as solution to prevent the entry of the solvent into the solution
through the semi-permeable membrane is called osmotic
RM1Tb2 pressure.
Kb =
1000 DH v Quantitatively, it is given by
where, Tb = b. pt. of pure solvent pµC where p ® osmotic pressure
DHv = Enthalpy of fusion of solvent pµT C ® conc. of solution
M1 = Molar mass of solvent \ p µ CT T ® temperature
 EBD_7753
378 CHEMISTRY

(a) Relative lowering of vapour pressure

p = CRT R ® gas constant
p° - ps
n = ix 2
C= p°
V
where, n = number of moles of the solute (b) Elevation in boiling point
V = volume of solution DTb = Tb - Tb ° = ik b m
n (c) Depression in freezing point
p = RT
V DTf = Tf ° - Tf = ik f m
pV = nRT (d) Osmotic pressure
Note: n
p = iCRT = i RT
(i) When the semi-permeable membrane permits solvent v
molecules to come out through the membrane, it is called Note:
exo-osmosis and when the membrane permits solvent (i) i > 1 if there is dissociation of the solute in solution and i < 1
molecules to enter inside, it is called endo-osmosis. if there is association of the solute in solution.
(ii) If pressure higher than osmotic pressure is applied on the (ii) For 100% dissociation of the solute, i = number of ions
solution, the solvent will flow from the solution into the pure produced from one molecule of the solute.
solvent through the semi-permeable membrane. This process (iii) Degree of dissociation is defined as the fraction of the total
is called reverse osmosis and it is used in the desalination of substance that undergoes dissociation i.e.,
water i.e., removal of salts from sea water.
(iii) Such solutions which have the same osmotic pressure at the Number of moles dissociated
Degree of dissociation (a) =
same temperature are called isotonic solutions. If one solution Total number of moles taken
is of lower osmotic pressure, it is called hypotonic with respect (A)n nA
to more concentrated solution. The more concentrated Initial mole 1 0
solution is said to be hypertonic with respect to dilute Dissociation mole a na
solution. Equilibrium mole (1 – a) na
(iv) When an animal cell is placed in a hypotonic solution, the \ Total number of moles = [(1 – a) + na] mole
cell swells and bursts (hemolysis).When a cell is placed in = 1 + a(n – 1) mole
hypertonic solution, the cell contracts in size (plasmolysis).
1 + a (n –1)
When excess of fertilizers (like urea) are applied, plasmolysis \i= = 1 + na – a
takes place and plants dry up (wilt). 1

ABNORMAL MOLECULAR MASSES i -1

a= (n ® number of ions produced on dissociation)
n -1
In case of aqueous solutions of electrolytes, inorganic bases and
salts, which dissociate completely or partially in the solution, or if M c - M o é M c ® normal molecular mass ù
association takes place in the solution as in the case of acetic acid or, a = M ( n - 1) ê M ® observed molecular massú
and benzoic acid, the number of particles in the solution changes o ë o û
(increases in case of dissociation and decreases for association). (iv) Degree of association is defined as the fraction of the total
As a result, value of colligative property also changes and as substance which exists in the form of associated molecules
i.e.,
1 nA (A)n
molecular mass µ colligative properties
a
\ observed molecular mass comes out to be different from Equilibrium (1 – a) mole
n
theoretical value. This observed molecular mass is called abnormal moles mole
molecular mass. a
Van’t Hoff Factor \ Total no. of moles = 1 – a +
n
The extent of association or dissociation can be determined with a
the help of van’t Hoff factor (i) It is defined as the ratio of normal 1– a +
mass to the observed molecular mass of solute i.e., i= n
1
Normal molar mass Number of moles associated
i= Degree of association (a) =
Abnormal molar mass Total number of moles taken
Observed colligative property n
or i = \ a = (1 – i)
Calculated colligative property n -1
n = number of molecules of the solute associated
Total number of moles of particles after association / dissociation
or i = M o - Mc n
Number of moles of particles before association / dissociation
or, a = Mo ( n - 1)
Thus, the modified colligative properties are:
Solutions 379

CONCEPT MAP
 EBD_7753
380 CHEMISTRY

1. Lowering in vapur pressrue is the highest for : 13. The osmotic pressure at 17ºC of an aq. solution containing
(a) 0.1 M glucose (b) 0.1 M BaCl2 1.75 gm of sucrose per 150 ml solution is :
(c) 0.2 M urea (d) 0.1 M MgSO4 (a) 0.08 atm (b) 8.1 atm (c) 0.8 atm (d) 9.1 atm
2. Formation of a solution from two components can be 14. An aqueous solution of glucose is 10% in strength. The
considered as volume in which 1 g mole of it is dissolved, will be :
(i) Pure solvent ® separated solvent molecules, DH1 (a) 9 litre (b) 1.8 litre (c) 8 litre (d) 0.9 litre
(ii) Pure solute ® separated solute molecules, DH2
15. 10 g of NaCl is dissolved in 10 6 g of the solution. Its
(iii) Separated solvent & solute molecules ® Solution,
DH3 concentration is :
Solution so formed will be ideal if (a) 100 ppm (b) 0.1 ppm(c) 1 ppm (d) 10 ppm
16. On adding a solute to a solvent having vapour pressure 0.80
(a) ΧHsoln < ΧH3 ,ΧH1 ,ΧH 2 atm, vapour pressure reduces to 0.60 atm. Mole fraction of
(b) ΧHsoln < ΧH1 ∗ ΧH 2 ∗ ΧH3 solute is :
(a) 0.25 (b) 0.75 (c) 0.50 (d) 0.33
(c) ΧHsoln < ΧH1 ∗ ΧH 2 ,ΧH3 17. If 0.44 gm of substance dissolved in 22.2 gm of benzene
(d) ΧHsoln < ΧH1 ,ΧH 2 ,ΧH3 lowers the freezing point of benzene by 0.567ºC, then the
3. An aqueous solution containing 1 gm of urea boils at molecular mass of substance is, the molal depression
100.25ºC. The aqueous solution containing 3 g of glucose in constant= 5.12ºC mol–1.
the same volume will boil at (mol. wt. of urea = 60 and of (a) 128.4 (b) 156.6 (c) 178.9 (d) 232.4
glucose = 180) : 18. 2.5 litres of NaCl solution contain 5 moles of the solute.
(a) 100.25ºC (b) 100ºC What is the molarity?
(c) 100.15ºC (d) 100.50ºC (a) 5 molar (b) 2 molar (c) 2.5 molar (d) 12.5 molar
4. The statement “If 0.003 moles of a gas are dissolved in 900 g 19. Which of the following statements, regarding the mole
of water under a pressure of 1 atmosphere, 0.006 moles will fraction (x) of a component in solution, is incorrect?
be dissolved under a pressure of 2 atmospheres”, illustrates (a) 0 £ x £ 1 (b) x £ 1
(a) Dalton’s law of partial pressure (c) x is always non-negative (d) None of these
(b) Graham’s law 20. When 10 g of a non-volatile solute is dissolved in 100 g of
(c) Raoult’s law benzene, it raises boiling point by 1ºC then molecular mass
(d) Henry’s law of the solute is (Kb for benzene = 2.53 km–1)
5. Which of the following modes of expressing concentration (a) 223 g (b) 243 g (c) 233 g (d) 253 g
is independent of temperature ? 21. The mole fraction of the solute in one molal aqueous
(a) Molarity (b) Molality solution is:
(c) Formality (d) Normality (a) 0.009 (b) 0.018 (c) 0.027 (d) 0.036
6. Molarity of liquid HCl will be, if density of solution is 22. When a solute is present in trace quantities the following
1.17 gm/cc expression is used
(a) 36.5 (b) 32.05 (c) 18.25 (d) 42.10 (a) Gram per million (b) Milligram percent
7. The molarity of a solution containing 5 gm of NaOH in 250 (c) Microgram percent (d) Parts per million
ml solution : 23. 5 ml of N HCl, 20 ml of N/2 H2SO4 and 30 ml of N/3 HNO3
(a) 0.5 (b) 1.0 (c) 1.5 (d) 2.0 are mixed together and volume made to one litre. The
8. Concentrated hydrochloric acid contains 37% HCl (by mass). normality of the resulting solution is
The density of this solution is 1.18 gm/ml. The molarity of N N N N
the solution is : (a) (b) (c) (d)
5 10 20 40
(a) 10 M (b) 12 M (c) 13 M (d) 14 M 24. The molal freezing point constant for water is 1.86ºC.
9. An X molal solution of a compound in benzene has mole Therefore, the change in freezing point of 0.1 molal of NaCl
fraction of solute equal to 0.2. The value of X is solution in water is expected to be
(a) 14 (b) 3.2 (c) 1.4 (d) 2 (a) 0.372ºC (b) –1.86ºC (c) –0.186ºC (d) –0.372ºC
10. The molarity of the solution containing 7.1 g of Na2SO4 in 25. Vapour pressure of benzene at 30°C is 121.8 mm Hg. When
100 ml of aqueous solution is 15 g of a non volatile solute is dissolved in 250 g of benzene
(a) 2 M (b) 0.5 M (c) 1 M (d) 0.05 M its vapour pressure decreased to 120.2 mm Hg. The molecular
11. The vapour pressure of pure benzene at 25°C is 640 mm Hg weight of the solute (Mo. wt. of solvent = 78)
and that of solution of solute A is 630 mm Hg. The molality (a) 356.2 (b) 456.8 (c) 530.1 (d) 656.7
of solution is – 26. If 20 g of a solute was dissolved in 500 ml. of water and
(a) 0.2 m (b) 0.4 m (c) 0.5 m (d) 0.1 m osmotic pressure of the solution was found to be 600 mm of
12. The molarity of pure water is : Hg at 15ºC, then molecular weight of the solute is :
(a) 50 M (b) 18 M (c) 55.6 M (d) 100 M (a) 1000 (b) 1200 (c) 1400 (d) 1800
 Solutions 381

27. A solution containing components A and B follows Raoult's 39. In the accompanied diagram, the ideal behaviour of a solution
law when is shown by the line/s
(a) A – B attraction force is greater than A – A and B – B pA+pB
C D
(b) A – B attraction force is less than A – A and B – B p0
(c) A – B attraction force remains same as A–A and B –B A =x
A p
(d) volume of solution is different from sum of volume of A
solute and solvent p0 p p0
A B B
28. The vapour pressure of two liquids ‘P’ and ‘Q’ are 80 and 0 =x B
60 torr, respectively. The total vapour pressure of solution p B
obtained by mixing 3 mole of P and 2 mole of Q would be A Mole fractions B
(a) 72 torr (b) 140 torr xA = 1 xA = 0
(c) 68 torr (d) 20 torr xB = 0 xB = 1
29. A mixture of components A and B will show –ve deviation (a) AD (b) CB
when (c) CD (d) AD, CB and CD
(a) D Vmix > 0 (b) D Hmix < 0 40. Which one of the following is non-ideal solution
(c) A – B interaction is weaker than A – A and B – B (a) Benzene + toluene
interactions (b) n-hexane + n-heptane
(d) A–B interaction is stronger than A–A and B–B
(c) Ethyl bromide + ethyl iodide
interactions.
30. A non-ideal solution was prepared by mixing 30 mL (d) CCl4 + CHCl3
chloroform and 50 mL acetone. The volume of mixture will be 41. The molal elevation constant is the ratio of elevation in
(a) > 80 mL (b) < 80 mL(c) = 80 mL (d) ³ 80 mL boiling point to:
(a) molality (b) mole fraction
31. The volume of gas decreases from 500 cc to 300 cc when a
sample of gas is compressed by an average pressure of 0.6 (c) molarity (d) none
atm. During this process 10 J of heat is liberated . The change 42. The azeotropic mixture of water (b.p.100°C) and HCl
in internal energy is. (b.p.85°C) boils at 108.5°C. When this mixture is distilled it is
(a) –2.16 J (b) 12.15 J (c) 2.16 J (d) 101.3 J possible to obtain
32. Which of the following liquid pairs shows a positive (a) pure HCl
deviation from Raoult’s law ? (b) pure water
(a) Water - Nitric acid (c) pure water as well as pure HCl
(b) Benzene - Methanol (d) neither HCl nor H2O in their pure states
(c) Water - Hydrochloric acid 43. The molar freezing point constant for water is 1.86 °C/mol. If
(d) Acetone - Chloroform 342 g of cane sugar (C12H22O11) is dissolved in 1000 g of
33. 18 g of glucose (C6H12O6) is added to 178.2 g of water. The water, the solution will freeze at :
vapour pressure of water for this aqueous solution is (a) – 1.86°C (b) 1.86°C
(a) 76.00 torr (b) 752.40 torr (c) – 3.92°C (d) 2.42°C
(c) 759.00 torr (d) 7.60 torr 44. Which will form maximum boiling point azeotrope
34. If all the four following compounds were sold at the same (a) HNO3 + H2O solution
price, which would be cheapest for preparing an antifreeze (b) C2H5OH + H2O solution
solution for a car radiator?
(c) C6H6 + C6H5CH3 solution
(a) C3H5(OH)3 (b) C2H4(OH)2
(c) C2H5OH (d) CH3OH (d) None of these
35. The value of P° for benzene is 640 mm of Hg. The vapour 45. The vapour pressure at a given temperature of an ideal
pressure of solution containing 2.5gm substance in 39gm. solution containing 0.2 mol of a non-volatile solute and 0.8
benzene is 600mm of Hg the molecular mass of X is – mol of solvent is 60 mm of Hg. The vapour pressure of the
(a) 65.25 (b) 130 (c) 40 (d) 75 pure solvent at the same temperature is
36. An ideal solution is formed when its components (a) 150 mm of Hg (b) 60 mm of Hg
(a) have no volume change on mixing (c) 75 mm of Hg (d) 120 mm of Hg
(b) have no enthalpy change on mixing 46. When a hard boiled egg after shelling is immersed in
(c) Both (a) and (b) are correct saturated brine:
(d) Neither (a) nor (b) is correct (a) it shrinks
37. All form ideal solution except (b) it grows is size
(a) C6H6 and C6H5CH3 (b) C2H6 and C2H5I (c) its size remains unchanged
(c) C6H5Cl and C6H5Br (d) C2H5 I and C2H5OH. (d) it initially grows in size and then shrinks
38. For which of the following parameters the structural isomers 47. The vapour pressure of a solvent decreases by 10 mm of Hg
C2H5OH and CH3OCH3 would be expected to have the same when a non-volatile solute was added to the solvent. The
values?(Assume ideal behaviour) mole fraction of the solute in the solution is 0.2. What should
(a) Boiling points be the mole fraction of the solvent if the decrease in the
(b) Vapour pressure at the same temperature vapour pressure is to be 20 mm of Hg ?
(c) Heat of vaporization (a) 0.8 (b) 0.6 (c) 0.4 (d) 0.2
(d) Gaseous densities at the same temperature and pressure
 EBD_7753
382 CHEMISTRY

48. A solution of acetone in ethanol 61. The freezing point of a 3% aq. solution of A is equal to the
(a) shows a positive deviation from Raoult’s law freezing point of 9% aq. solution of B. If the molecular weight
(b) behaves like a non ideal solution of ‘A’ is 60, then the molecular wt. of B is
(c) obeys Raoult’s law (a) 45 (b) 90 (c) 180 (d) 360
(d) shows a negative deviation from Raoult’s law 62. 1.00 g of a non-electrolyte solute (molar mass 250 g mol–1)
49. Azeotropic mixture of water and HCl has the percentage of was dissolved in 51.2 g of benzene. If the freezing point
HCl. depression constant, Kf of benzene is 5.12 K kg mol–1, the
(a) 20.2% (b) 26.4% (c) 48% (d) 68% freezing point of benzene will be lowered by
50. Which of the following aqueous solution has minimum (a) 0.3 K (b) 0.5 K (c) 0.4 K (d) 0.2
freezing point ? 63. The normality of mixture obtained by mixing 100 ml of 0.4 M
(a) 0.01 m NaCl (b) 0.005 m C2H5OH H 2SO4 and 200 ml of 0.2 M HCl is
(c) 0.005 m MgI2 (d) 0.005 m MgSO4.
(a) 0.0267 (b) 0.2670 (c) 1.0267 (d) 1.1670
51. On adding 0.750 gm of compound in 25 gm of solvent, the
64. Brownian movement is found in
freezing point is depressed by 0.502°C. The molecular wt. of
(a) unsaturated solution (b) saturated solution
the substance is [The molecular depression constant =
(c) colloidal solution (d) suspension solution
50.2°C per 100 gm of solvent]
65. A solution is formed by diluting 250 ml. of 0.400 N H2SO4 with
(a) 100 (b) 200 (c) 300 (d) 400
one litre of water. The normality of above formed solution is :
52. 5 gm of CH 3COOH is dissolved in one litre of ethanol. (a) 0.400 N (b) 0.899 N (c) 0.040 N (d) 0.080 N
Suppose there is no reaction between them. If the density of 66. In a 0.2 molal aqueous solution of a weak acid HX the degree
ethanol is 0.789 gm/ml then the molality of resulting solution of ionization is 0.3. Taking kf for water as 1.85, the freezing
is point of the solution will be nearest to
(a) 0.0256 (b) 0.1056 (c) 0.1288 (d) 0.1476 (a) – 0.360ºC (b) – 0.260ºC
53. Which one of the following is a colligative property ? (c) + 0.481ºC (d) – 0.481ºC
(a) Boiling point (b) Vapour pressure 67. Which one of the following aqueous solutions will exihibit
(c) Osmotic pressure (d) Freezing point highest boiling point ?
54. If 0.1 M solution of glucose and 0.1 M solution of urea are (a) 0.015 M urea (b) 0.01 M KNO3
placed on two sides of the semipermeable membrane to equal (c) 0.01 M Na2SO4 (d) 0.015 M glucose
heights, then it will be correct to say that 68. The amount of dibasic acid present in 100 ml of the aq.
(a) there will be no net movement across the membrane solution to give solution of [mol. wt. = 200] normality of 0.1
(b) glucose will flow towards urea solution N is
(c) urea will flow towards glucose solution (a) 0.5 gm (b) 1 gm (c) 1.5 gm (d) 2 gm
(d) water will flow from urea solution to glucose 69. The elevation in boiling point of a solution of 13.44 g of
55. When 800 gm of a 40% solution by weight was cooled, 100 CuCl2 in 1 kg of water using the following information will
gm of solute precipitated. The percentage composition of be (Molecular weight of CuCl2 = 134.4 g and Kb= 0.52 K
remaining solution is kg mol-1)
(a) 31.43% (b) 5.56% (c) 6.78% (d) 6.96% (a) 0.16 (b) 0.05 (c) 0.1 (d) 0.2
56. At 25°C, the highest osmotic pressure is exhibited by 0.1 M 70. The molecular weight of benzoic acid in benzene as
solution of determined by depression in freezing point method
(a) CaCl2 (b) KCl (c) glucose (d) urea corresponds to :
57. Which one of the following salts will have the same value of (a) ionization of benzoic acid.
van’t Hoff factor (i) as that of K4[Fe(CN)6]. (b) dimerization of benzoic acid.
(a) Al2(SO4)3 (b) NaCl (c) Al(NO3)3 (d) Na2SO4. (c) trimerization of benzoic acid.
58. Which of the following 0.10 m aqueous solutions will have (d) solvation of benzoic acid.
the lowest freezing point ? 71. A 0.5 molal solution of ethylene glycol in water is used as
(a) Al2(SO4)3 (b) C6H12O6 coolant in a car. If the freezing point constant of water be
(c) KCl (d) C12 H22 O11 1.86°C per mole, the mixture shall freeze at
59. Which of the following colligative property can provide (a) 0.93°C (b) –0.93°C(c) 1.86°C (d) –1.86°C
molar mass of proteins (or polymers or colloids) with greatest 72. The rise in the boiling point of a solution containing 1.8 g of
precision ? glucose in 100 g of solvent is 0.1°C. The molal elevation
(a) Osmotic pressure constant of the liquid is
(b) Elevation of boiling point (a) 0.01 K/m (b) 0.1 K/m (c) 1 K/m (d) 10 K/m
(c) Depression of freezing point 73. The solutions which have same osmotic concentrations are
(d) Relative lowering of vapour pressure known as
60. Camphor is often used in molecular mass determination (a) Normal (b) Isotonic
because (c) Hypotonic (d) Hypertonic
(a) it is readily available 74. The normal boiling point of the solution is the temperature
(b) it has a very high cryoscopic constant at which the vapour pressure of the solution is –
(c) it is volatile (a) equal to 1 torr (b) equal to 76 mm Hg
(d) it is solvent for organic substances (c) equal to 2.0 atm (d) equal to 1 atm
 Solutions 383

75. The temperature at which 10% aqueous solution (w/v) of 87. The molal elevation constant for water is 0.52. What will be
glucose will exhibit the osmotic pressure of 14 bar is – the boiling point of 2 molar sucrose solution at 1 atm.
(a) 307.3°C (b) 307.3 K (c) 34 K (d) – 34°C pressure? (Assume B.P. of pure water as 100°C)
76. 4 gm castic soda is dissolved in 100 cc of solution. The (a) 101.04°C (b) 100.26°C
normality of solution is (c) 100.52°C (d) 99.74°C
(a) 0 (b) 0.5 (c) 1 (d) 1.5 88. A 0.0020 m aqueous solution of an ionic compound
77. If A contains 2% NaCl and is separated by a semipermeable Co(NH3)5(NO2)Cl freezes at – 0.00732 °C. Number of moles
membrane from B which contains 10% NaCl, then which of ions which 1 mol of ionic compound produces on being
event will occur ? dissolved in water will be (Kf = – 1.86°C/m)
(a) NaCl will flow from A to B (a) 3 (b) 4 (c) 1 (d) 2
(b) NaCl will flow from B to A 89. An aqueous solution is 1.00 molal in KI. Which change will
(c) Water will flow from A to B cause the vapour pressure of the solution to increase?
(d) Water will flow from B to A (a) Addition of NaCl
78. KBr is 80% ionized in solution. The freezing point of 0.4
molal solution of KBr is : (b) Addition of Na 2SO4
(c) Addition of 1.00 molal KI
K kg
K f (H 2 O) = 1.86 (d) Addition of water
mole 90. A solution of sucrose (molar mass = 342 g mol –1) has been
(a) 274.339 K (b) – 1.339 K prepared by dissolving 68.5 g of sucrose in 1000 g of water.
(c) 257.3 K (d) – 1.339°C The freezing point of the solution obtained will be
79. Which of the following pairs of solution are isotonic at the (Kf for water = 1.86 K kg mol–1).
same temperature ? (a) – 0.372°C (b) – 0.520°C
(a) 0.1 M Ca(NO3)2 and 0.1 M Na2SO4 (d) + 0.372°C (d) – 0.570°C
(b) 0.1 M NaCl and 0.1 M Na2SO4
(c) 0.1 M urea and 0.1 M MgCl2 91. 25.3 g of sodium carbonate, Na 2CO3 is dissolved in enough
(d) 0.2 M urea and 0.1 M NaCl water to make 250 mL of solution. If sodium carbonate
80. The relationship between the values of osmotic pressure of dissociates completely, molar concentration of sodium ions,
0.1 M solutions of KNO3 ( P1 ) and CH3COOH ( P2 ) is : Na + and carbonate ions, CO 32– are respectively (Molar mass
P1 P2 of Na2CO3 = 106 g mol–1)
(a) = (b) P1 > P2 (a) 0.955 M and 1.910 M (b) 1.910 M and 0.955 M
P1 + P2 P1 + P2 (c) 1.90 M and 1.910 M (d) 0.477 M and 0.477 M
(d) P2 > P1 (d) P1 = P2 92. The freezing point depression constant for water is
81. Which of the following solutions will exhibit highest boiling – 1.86ºC m–1. If 5.00 g Na2SO4 is dissolved in 45.0 g H2O, the
point? freezing point is changed by – 3.82ºC. Calculate the van’t
(a) 0.01 M Na2SO4 (aq) (b) 0.01 M KNO3 (aq) Hoff factor for Na2SO4
(c) 0.015 M urea (aq) (d) 0.015 M glucose (aq) (a) 2.05 (b) 2.62 (c) 3.11 (d) 0.381
82. What is the freezing point of a solution containing 8.1 g HBr 93. The van’t Hoff factor i for a compound which undergoes
in 100 g water assuming the acid to be 90% ionised ? dissociation in one solvent and association in other solvent
(Kf for water = 1.86 K kg mol–1) : is respectively :
(a) 0.85K (b) – 3.53K(c) 0K (d) – 0.35K (a) less than one and greater than one.
83. Osmotic pressure of 0.4% urea solution is 1.64 atm and that (b) less than one and less than one.
of 3.42% cane sugar is 2.46 atm. When the above two (c) greater than one and less than one.
solutions are mixed, the osmotic pressure of the resulting (d) greater than one and greater than one.
solution is : 94. Mole fraction of the solute in a 1.00 molal aqueous solution is
(a) 0.82 atm (b) 2.46 atm (a) 0.1770 (b) 0.0177 (c) 0.0344 (d) 1.7700
(c) 1.64 atm (d) 4.10 atm 95. A 0.1 molal aqueous solution of a weak acid is 30% ionized.
84. The freezing point of 1% solution of lead nitrate in water will If Kf for water is 1.86°C/m, the freezing point of the solution
be : will be :
(a) 2°C (b) 1°C (c) 0°C (d) below 0°C (a) – 0.18°C (b) – 0.54°C (c) – 0.36°C (d) – 0.24°C
85. A solution of urea (mol. mass 56 g mol-1) boils at 100.18°C 96. 200 mL of an aqueous solution of a protein contains its 1.26 g.
at the atmospheric pressure. If Kf and Kb for water are 1.86 The osmotic pressure of this solution at 300 K is found to be
and 0.512 K kg mol-1 respectively, the above solution will 2.57 × 10–3 bar. The molar mass of protein will be (R = 0.083 L
freeze at bar mol–1 K–1)
(a) 0.654°C (b) - 0.654°C (a) 51022 g mol–1 (b) 122044 g mol–1
(c) 6.54°C (d) - 6.54°C (c) 31011 g mol–1 (d) 61038 g mol–1
N N N 97. PA and PB are the vapour pressure of pure liquid components,
86. If 50 ml H2SO4, 30 ml HNO3, 10 ml HCl is mixed A and B, respectively of an ideal binary solution. If XA
10 3 2
and solution is made to 1L. Then normality of resultant represents the mole fraction of component A, the total
solution is pressure of the solution will be.
N N N (a) PA + XA (PB – PA) (b) PA + XA (PA – PB)
(a) (b) (c) (d) N (c) PB + XA (PB – PA) (d) PB + XA (PA – PB)
20 40 50
 EBD_7753
384 CHEMISTRY

98. A mixture of ethyl alcohol and propyl alcohol has a vapour (a) The solution is non-ideal, showing – ve deviation from
pressure of 290 mm Hg at 300 K. The vapour pressure of Raoult’s Law.
propyl alcohol is 200 mm Hg. If the mole fraction of ethyl (b) The solution is non-ideal, showing + ve deviation from
alcohol is 0.6, its vapour pressure (in mm Hg) at the same Raoult’s Law.
temperature will be (c) n-heptane shows + ve deviation while ethanol shows
(a) 360 (b) 350 (c) 300 (d) 700 – ve deviation from Raoult’s Law.
99. A binary liquid solution is prepared by mixing n-heptane (d) The solution formed is an ideal solution.
and ethanol. Which one of the following statements is correct 100. The molarity of a solution obtained by mixing 750 mL of
regarding the behaviour of the solution? 0.5(M) HCl with 250 mL of 2(M) HCl will be :
(a) 0.875 M (b) 1.00 M (c) 1.75 M (d) 0.975 M

1. p1, p2, p3 and p4 atm are the osmotic pressures of 5% (mass/ 7. The mole fraction of water in 20% aqueous solution (By
volume) solutions of urea, fructose, sucrose and KCl weight) of H2O2 is
respectively at certain temperature. The correct order of their 77 68 20 80
magnitudes is : (a) (b) (c) (d)
68 77 80 20
(a) p1 > p 4 > p 2 > p3 (b) p1 < p 4 < p 2 < p3 8. Molarity of H2SO4 is 18 M. Its density is 1.8 g/ml. Hence
(c) p 4 > p1 > p 2 > p3 (d) p 4 > p1 > p3 > p 2 molality is
(a) 36 (b) 200 (c) 500 (d) 18
2. The osmotic pressure (at 27° C) of an aqueous solution 9. The solution containing 4.0 gm of a polyvinyl chloride
(200mL) containing 6 g of a protein is 2 × 10–3 atm. If polymer in 1 litre of dioxane was found to have an osmotic
R = 0.080 L atm mol–1K–1, the molecular weight of protein is pressure 6.0 × 10–4 atmosphere at 300K, the value of R used
(a) 7.2 × 105 (b) 3.6 × 105 is 0.082 litre atmosphere mole–1K–1. The molecular mass of
(c) 1.8 ×10 5 (d) 1.0 × 105 the polymer was found to be
3. The freezing point of equimolal aqueous solutions will be (a) 3.0 × 102 (b) 1.6 × 105 (c) 5.6 × 104 (d) 6.4 × 102
highest for : 10. At temperature 327°C and concentration C osmotic pressure
(a) C6H5NH3Cl (aniline hydrochloride) of a solution is P, the same solution at concentration C/2 and
(b) Ca(NO3)2 at temperature 427°C shows osmotic pressure of 2 atm, value
(c) La(NO3)3 of P will be
(d) C6H12O6 (glucose)
12 24 6 5
4. Which of the following has been arranged in the increasing (a) (b) (c) (d)
order of freezing point? 7 7 5 6
(a) 0.025M KNO 3 < 0.1M NH 2 CSNH 2 11. In countries nearer to polar region, the roads are sprinkled
with CaCl2. This is
< 0.05 M BaCl 2 < 0.1M NaCl (a) to minimise the snow fall
(b) 0.1M NaCl < 0.05M BaCl 2 (b) to minimise pollution
< 0.1M NH 2 CSNH 2 < 0.025 M KNO 3 (c) to minimise the accumulation of dust on the road
(c) 0.1M NH 2 CSNH 2 < 0.1M NaCl (d) to minimise the wear and tear of the roads
12. If a is the degree of dissociation of Na2SO4, the Vant Hoff’s
< 0.05M BaCl 2 < 0.025M KNO 3 factor (i ) used for calculating the molecular mass is
(d) 0.025M KNO 3 < 0.05M BaCl 2 (a) 1 + a (b) 1 – a (c) 1 + 2a (d) 1 – 2a
< 0.1M NaCl < 0.1M NH 2 CSNH 2 13. The correct relationship between the boiling points of very
5. The volume of 4 N HCl and 10 N HCl required to make 1 litre dilute solutions of AlCl3 (t1) and CaCl2 (t2), having the same
of 6 N HCl are molar concentration is
(a) 0.75 litre of 10 N HCl and 0.25 litre of 4 N HCl (a) t1 = t2 (b) t1 > t2 (c) t2 > t1 (d) t2 ³ t1
(b) 0.50 litre of 4 N HCl and 0.50 litre of 10 N HCl 14. If the various terms in the given below expressions have
(c) 0.67 litre of 4 N HCl and 0.33 litre of 10 N HCl usual meanings, the van’t Hoff factor (i) cannot be calculated
(d) 0.80 litre of 4 N HCl and 0.20 litre of 10 N HCl by which one of the following expressions
6. A solution of Al2(SO4)3 {d=1.253 gm / ml} contain 22% salt by (a) pV = inRT
weight. The molarity, normality and molality of the solution is (b) DT f = iK f .m
(a) 0.805 M, 4.83 N, 0.825 m (c) DTb = iK b .m
(b) 0.825 M, 48.3 N, 0.805 m P° -P æ n ö
(c) 4.83 M, 4.83 N, 4.83 m (d) solvent solution = i ç ÷
(d) None of these
°
Psolvent è N+nø
 Solutions 385

15. A 0.001 molal solution of [Pt(NH3)4Cl4] in water had a freezing 26. A 5% solution of cane sugar (molar mass 342) is isotonic
point depression of 0.0054°C. If K f for water is 1.80, the with 1% of a solution of an unknown solute. The molar mass
correct formulation for the above molecule is of unknown solute in g/mol is :
(a) [Pt(NH3)4 Cl3]Cl (b) [Pt(NH3)4 Cl2]Cl2
(a) 171.2 (b) 68.4 (c) 34.2 (d) 136.2
(c) [Pt(NH3)4 Cl]Cl3 (d) [Pt(NH3)4 Cl4]
27. –1
Kf for water is 1.86 K kg mol . If your automobile radiator
16. The amount of urea to be dissolved in 500 c.c. of water
(K = 1.86°C mol–1) to produce a depression of 0.186°C in the holds 1.0 kg of water, how many grams of ethylene glycol
freezing point is : (C2H6O2) must you add to get the freezing point of the
(a) 9 g (b) 6 g (c) 3 g (d) 0.3 g solution lowered to –2.8ºC ?
17. Which has the minimum freezing point ? (a) 72 g (b) 93 g (c) 39 g (d) 27 g
(a) One molal NaCl aq. solution
28. When 20 g of naphthoic acid (C11H8O2) is dissolved in 50 g
(b) One molal CaCl2 aq. solution
(c) One molal KCl aq. solution of benzene (Kf = 1.72 K kg mol–1), a freezing point depression
(d) One molal urea aq. solution of 2 K is observed. The Van't Hoff factor (i) is
18. On mixing 3 g of non - volatile solute in 200 mL of water, its (a) 0.5 (b) 1 (c) 2 (d) 3
boiling point (100°) becomes 100.52°C. If Kb for water is 0.6 29. The Henry’s law constant for the solubility of N2 gas in
K/m then molecular wt. of solute is : water at 298 K is 1.0 × 105 atm. The mole fraction of N2 in air
(a) 10.5 g mol -1 (b) 12.6 g mol -1 is 0.8. The number of moles of N2 from air dissolved in
(c) 15.7 g mol -1 (d) 17.3 g mol -1 10 moles of water at 298 K and 5 atm pressure is
19. 1 mol each of the following compounds is dissolved in 1L of (a) 4.0× 10– 4 (b) 4.0 × 10–5
solution. Which will have the largest DTb value? (c) 5.0 × 10– 4 (d) 4.0 × 10–6
(a) HF (b) HCl (c) HBr (d) HI.
30. Dissolving 120 g of urea (mol. wt. 60) in 1000 g of water gave
20. Equal masses of methane and oxygen are mixed in an empty
container at 25°C. The fraction of the total pressure exerted a solution of density 1.15 g/mL. The molarity of the solution is
by oxygen is (a) 1.78 M (b) 2.00 M (c) 2.05 M (d) 2.22 M
1 273 31. The freezing point (in °C) of a solution containing 0.1 g
(a) 1/2 (b) 2/3 (c) ´ (d) 1/3.
3 298 of K3[Fe(CN)6] (Mol. wt. 329) in 100 g of water (Kf = 1.86 K
21. A 5.25% solution of a substance is isotonic with a 1.5% solu- kg mol–1) is
tion of urea (molar mass = 60 g mol–1) in the same solvent. If (a) –2.3 × 10–2 (b) –5.7 × 10–2
the densities of both the solutions are assumed to be equal to –3
(c) –5.7 × 10 (d) –1.2 × 10–2
1.0 g cm–3, molar mass of the substance will be
(a) 210.0 g mol–1 (b) 90.0 g mol–1 32. For a dilute solution containing 2.5 g of a non-volatile non-
(c) 115.0 g mol –1 (d) 105.0 g mol–1. electrolyte solute in 100 g of water, the elevation
22. At 80° C, the vapour pressure of pure liquid ‘A’ is 520 mm Hg in boiling point at 1 atm pressure is 2°C. Assuming
and that of pure liquid ‘B’ is 1000 mm Hg. If a mixture solution concentration of solute is much lower than the concentration
of ‘A’ and ‘B’ boils at 80° C and 1 atm pressure, the amount of solvent, the vapour pressure (mm of Hg) of the solution is
of ‘A’ in the mixture is (1 atm = 760 mm Hg) (take Kb = 0.76 K kg mol–1)
(a) 52 mol percent (b) 34 mol percent
(a) 724 (b) 740 (c) 736 (d) 718
(c) 48 mol percent (d) 50 mol percent
23. The vapour pressure of water at 20°C is 17.5 mm Hg. If 18 g 33. If sodium sulphate is considered to be completely
of glucose (C6H12O6) is added to 178.2 g of water at 20°C, dissociated into cations and anions in aqueous solution,
the vapour pressure of the resulting solution will be the change in freezing point of water (DTf ), when 0.01 mol
(a) 17.325 mm Hg (b) 15.750 mm Hg of sodium sulphate is dissolved in 1 kg of water, is (Kf = 1.86
(c) 16.500 mm Hg (d) 17.500 mm Hg K kg mol–1)
24. Two liquids X and Y form an ideal solution. At 300 K, vapour (a) 0.372 K (b) 0.0558 K
pressure of the solution containing 1 mol of X and 3 mol of Y
is 550 mm Hg. At the same temperature, if 1 mol of Y is further (c) 0.0744 K (d) 0.0186 K
added to this solution, vapour pressure of the solution 34. Which observation(s) reflect(s) colligative properties?
increases by 10 mm Hg. Vapour pressure ( in mm Hg) of X (i) a 0.5 m NaBr solution has a higher vapour pressure
and Y in their pure states will be, respectively: than a 0.5 m BaCl2 solution at the same temperature
(a) 300 and 400 (b) 400 and 600
(ii) pure water freezes at the higher temperature than pure
(c) 500 and 600 (d) 200 and 300
methanol
25. On mixing, heptane and octane form an ideal solution. At
373 K, the vapour pressures of the two liquid components (iii) a 0.1 m NaOH solution freezes at a lower temperature
(heptane and octane) are 105 kPa and 45 kPa respectively. than pure water
Vapour pressure of the solution obtained by mixing 25.0 g of Choose the correct answer from the codes given below
heptane and 35 g of octane will be (molar mass of heptane
(a) (i), (ii) and (iii) (b) (i) and (ii)
= 100 g mol–1 and of octane = 114 g mol–1)
(a) 72.0 kPa (b) 36.1 kPa (c) 96.2 kPa (d) 144.5 kPa (c) (ii) and (iii) (d) (i) and (iii)
 EBD_7753
386 CHEMISTRY

35. When a gas is bubbled through water at 298 K, a very dilute 42. The system that forms maximum boiling azeotrope is
solution of the gas is obtained. Henry’s law constant for the (a) carbondisulphide – acetone
gas at 298 K is 100 kbar. If the gas exerts a partial pressure of (b) benzene – toluene
1 bar, the number of millimoles of the gas dissolved in one (c) acetone – chloroform
litre of water is (d) n-hexane – n-heptane
(a) 0.555 (b) 5.55 43. Which one of the following gases has the lowest value of
(c) 0.0555 (d) 55.5 Henry’s law constant?
36. 1.5 g of a non-volatile, non-electrolyte is dissolved in 50 g (a) N2 (b) He
benzene (Kb = 2.5 K kg mol–1). The elevation of the boiling (c) H2 (d) CO2
point of the solution is 0.75 K. The molecular weight of the 44. A solution is prepared by dissolving 10 g NaOH in 1250 mL
of a solvent of density 0.8 mL/g. The molality of the solution
solute in g mol–1 is
in mol kg–1 is
(a) 200 (b) 50
(a) 0.25 (b) 0.2
(c) 75 (d) 100
(c) 0.008 (d) 0.0064
37. Which one of the following statements is false? 45. The freezing point of equimolal aqueous solution will be
(a) Raoult’s law states that the vapour pressure of a highest for
component over a binary solution of volatile liquids is (a) C6H5NH3+Cl– (b) Ca(NO3)2
directly proportional to its mole fraction (c) La(NO3)2 (d) C6H12O6
(b) Two sucrose solutions of the same molality prepared
in different solvents will have the same depression of DIRECTIONS for Qs. 46 to 50 : These are Assertion-Reason
freezing point type questions. Each of these question contains two statements:
(c) The correct order of osmotic pressures of 0.01 M Statement-1 (Assertion) and Statement-2 (Reason). Answer these
questions from the following four options.
solution of each compound is BaCl2 > KCl > CH3COOH
> glucose (a) Statement-1 is true, Statement-2 is true, Statement-2 is a
(d) In the equation osmotic pressure p = MRT, M is the correct explanation for Statement-1
molarity of the solution (b) Statement-1 is True, Statement-2 is True ; Statement-2 is
38. At 300 K the vapour pressure of an ideal solution containing NOT a correct explanation for Statement-1
1 mole of liquid A and 2 moles of liquid B is 500 mm of Hg. (c) Statement-1 is True, Statement-2 is False
(d) Statement-1 is False, Statement-2 is True
The vapour pressure of the solution increases by 25 mm of
46. Statement-1 : If one component of a solution obeys Raoult’s
Hg, if one more mole of B is added to the above ideal solution
law over a certain range of composition, the other component
at 300 K. Then the vapour pressure of A in its pure state is
will not obey Henry’s law in that range.
(a) 300 mm of Hg (b) 400 mm of Hg Statement-2 : Raoult’s law is a special case of Henry’s law.
(c) 500 mm of Hg (d) 600 mm of Hg 47. Statement-1 : Lowering of vapour pressure is directly
39. Henry’s law constant of oxygen is 1.4 × 10–3 mol. lit–1. atm–1 at proportional to osmotic pressure of the solution.
298 K. How much of oxygen is dissolved in 100 ml at 298 K Statement-2 : Osmotic pressure is a colligative property.
when the partial pressure of oxygen is 0.5 atm? 48. Statement-1 : If a liquid solute more volatile than the solvent
(a) 1.4 g (b) 3.2 g is added to the solvent, the vapour pressure of the solution
(c) 22.4 mg (d) 2.24 mg may increase i.e., ps > po.
40. 1 g of a non-volatile, non-electrolyte solute of molar mass Statement-2 : In the presence of a more volatile liquid solute,
250 g/mol was dissolved in 51.2 g of benzene. If the only the solute will form the vapours and solvent will not.
freezing point depression constant Kf of benzene is 5.12 49. Statement-1 : Azeotropic mixtures are formed only by
kg K mol–1. The freezing point of benzene is lowered by non-ideal solutions and they may have boiling points either
(a) 0.3 K (b) 0.5 K greater than both the components or less than both the
(c) 0.2 K (d) 0.4 K components.
41. Negative deviation from Raoult’s law is observed in which Statement-2 : The composition of the vapour phase is same
one of the following binary liquid mixtures? as that of the liquid phase of an azeotropic mixture.
(a) Ethanol and acetone 50. Statement-1 : Camphor is used as solvent in the
(b) Benzene and toluene determination of molecular masses of naphthalene,
(c) Acetone and chloroform anthracene etc.
(d) Chloroethane and bromoethane Statement-2 : Camphor has high molal elevation constant.
 Solutions 387

Exemplar Questions 10. The unit of ebullioscopic constant is

1. Which of the following units is useful in relating (a) K kg mol–1 or K (molality)–1
concentration of solution with its vapour pressure? (b) mol kg K–1 or K–1 (molality)
(a) Mole fraction (b) Parts per milion (c) kg mol–1 K–1or K–1 (molality)–1
(c) Mass percentage (d) Molality (d) K mol kg–1or K (molality)
2. On dissolving sugar in water at room temperature solution 11. In comparison to a 0.01 M solution of glucose, the depression
feels cool to touch. Under which of the following cases in freezing point of a 0.01 M MgCl2 solution is ....... .
dissolution of sugar will be most rapid? (a) the same (b) about twice
(a) Sugar crystals in cold water (c) about three time (d) about six times
(b) Sugar crystals in hot water 12. An unripe mango placed in a concentrated salt solution to
(c) Powdered sugar in cold water prepare pickle shrivels because .......... .
(d) Powdered sugar in hot water (a) it gains water due to osmosis
3. At equilibrium the rate of dissolution of a solid solute in a (b) it loses water due to reverse osmosis
volatile liquid solvent is ....... (c) it gains water due to reverse osmosis
(a) less than the rate of crystallisation (d) it loses water due to osmosis
(b) greater than the rate of crystallisation 13. At a given temperature, osmotic presure of a concentrated
(c) equal to the rate of crystallisation solution of a substance ............ .
(d) zero (a) is higher than that of a dilute solution
4. A beaker contains a solution of substance 'A'. Precipitation (b) is lower than that of a dilute solution
of substance 'A' takes place when small amount of 'A' is (c) it gains water due to reverse osmosis
added to the solution. The solution is ........ . (d) it loses water due to osmosis
(a) saturated (b) supersaturated
14. Which of the following statements is false?
(c) unsaturated (d) concentrated
(a) Two different solutions of sucrose of same molality
5. Maximum amount of a solid solute that can be dissolved in
prepared in diffferent solvents will have the same
a specified amount of a given liquid solvent does not
depression in freezing point.
depends upon ......... .
(b) The osmotic pressure of a solution is given by the
(a) temperature (b) nature of solute
(c) pressure (d) nature of solvent equation p = CRT (where, C is the molarity of the
6. Low concentration of oxygen in the blood and tissues of solution)
people living at high altitude is due to ............ . (c) Decreasing order of osmotic pressure for 0.01 M
(a) low temperature aqueous solutions of barium chloride, potassium
(b) low atmospheric pressure chloride, acetic acid and sucrose is
(c) high atmospheric pressure BaCl2 > KCl > CH3COOH > sucrose
(d) both low temperature and high atmospheric pressure (d) According to Raoult's law, the vapour pressure exerted
7. Considering the formation, breaking and strength of by a volatile component of a solution is directly
hydrogen bond, predict which of the following mixtures will proportional to its mole fraction in the solution
show a positive deviation from Raoult's law? 15. The value of van't Hoff factors for KCl, NaCl and K2SO4
(a) Methanol and acetone respectively are ............ .
(b) Chloroform and acetone (a) 2, 2 and 2 (b) 2, 2 and 3
(c) Nitric acid and water (c) 1, 1 and 2 (d) 1, 1 and 1
(d) Phenol and aniline 16. Which of the following statement is false?
8. Colligative properties depend on ............ . (a) Units of atmospheric pressure and osmotic pressure
(a) the nature of the solute particles dissolved in solution are same
(b) the number of solute particles in solution (b) In reverse osmosis, solvent molecules move through a
(c) the physical properties of the solution particles semipermeable membrane from a region of lower
dissolved in solution concentration of solute to a region of higher
(d) the nature of solvent particles concentration
9. Which of the following aqueous solutions should have the (c) The value of molal depression constant depends on
highest boiling point? nature of solvent
(a) 1.0 M NaOH (b) 1.0 M Na2SO4 (d) Relative lowering of vapour pressure, is a dimensionless
(c) 1.0 M NH4NO3 (d) 1.0 M KNO3 quantity
 EBD_7753
388 CHEMISTRY

17. Value of Henry's constant KH ............. . 22. Two beakers of capacity 500 mL were taken. One of these
(a) increases with increase in temperature beakers labelled as "A" was filled with 400 mL water whereas
(b) decreases with increase in temperature the beaker labelled "B" was filled with 400 mL of 2M solution
of NaCl. At the same temperature both the beakers were
(c) remains constant
placed in closed containers of same material and same
(d) first increases then decreases capacity as shown in figure.
18. The value of Henry's constant, KH is ............. .
(a) greater for gases with higher solubility
(b) greater for gases with lower solubility A B
(c) constant for all gases
(d) not related to the solubility of gases Water NaCl solution
19. Consider the figure and mark the correct option.
At a given temperature, which of the following statement is
correct about the vapour pressure of pure water and that of
Piston (A) Piston (B)
NaCl solution?
SPM (a) Vapour pressure in container (A) is more than that in
container (B)
(b) Vapour pressure in container (A) is less than that in
Fresh water Concentrated container (B)
(A) sodium chloride (c) Vapour pressure is equal in both the containers
solution in
water (B) (d) Vapour pressure in container (B) is twice the vapour
pressure in container (A)
(a) Water will move form side (A) to side (B) if a pressure 23. If two liquids A and B form minimum boiling azeotrope at
lower than osmotic pressure is applied on piston (B) some specific composition then
(b) Water will move from side (B) to side (A) if a pressure (a) A — B interactions are stronger than those between
greater than osmotic pressure is applied on piston (B) A — A or B — B
(c) Water will move from side (B) to side (A) if a pressure (b) vapour pressure of solution increases because more
equal to osmotic pressure is applied on piston (B) number of molecules of liquids A and B can escape
from the solution
(d) Water will move from side (A) to side (B) if pressure
(c) vapour pressure of solution decreases because less
equal to osmotic pressure is applied on piston (A)
number of molecules of only one of the liquids escape
20. We have three, aqueous solutions of NaCl labelled as 'A', 'B' from the solution
and 'C' with concentrations 0.1 M,0.01M and 0.001 M,
(d) A — B interactions are weaker than those between
respectively. The value of van't Hoff factor for these solutions
A — A or B — B
will be in the order ........... .
24. 4 L of 0.02 M aqueous solution of NaCl was diluted by adding
(a) iA < iB < iC (b) iA > iB > iC
1 L of water. The molality of the resultant solution
(c) iA = iB = iC (d) iA < iB > iC is .................
21. On the basis of information given below mark the correct (a) 0.004 (b) 0.008
option. (c) 0.012 (d) 0.016
Information 25. On the basis of information given below mark the correct
(i) In bromoethane and chloroethane mixture option.
intermolecular interactions of A — A and B — B type Information On adding acetone to methanol some of the
are nearly same as A — B type interactions. hydrogen bonds between methanol molecules break.
(ii) In ethanol and acetone mixture A — A or B — B type (a) At specific composition methanol-acetone mixture will
intermolecular interactions are stronger than A — B form minimum boiling azeotrope and will show positive
type interactions. deviation from Raoult's law
(iii) In chloroform and acetone mixture A — A or B — B (b) At specific composition methanol-acetone mixture will
type intermolecular interactions are weaker than form maximum boiling azeotrope and will show positive
A — B type interactions. deviation from Raoult's law
(a) Solution (ii) and (iii) will follow Raoult's law (c) At specific composition methanol-acetone mixture will
(b) Solution (i) will follow Raoult's law form maximum boiling azeotrope and will show negative
(c) Solution (ii) will show negative deviation from Raoult's deviation from Raoult's law
law (d) At specific composition methanol-acetone mixture will
(d) Solution (iii) will show positive deviation from Raoult's form minimum boiling azeotrope and will show negative
law deviation from Raoult's law
 Solutions 389

26. KH value for Ar (g), CO2 (g), HCHO (g) and CH4 (g) are (b) Molecular mass of X is less than the molecular mass of
40.39, 1.67, 1.83 × 10–5 and 0.413 respectively. Y.
Arrange these gases in the order of their increasing solubility. (c) Y is undergoing dissociation in water while X undergoes
(a) HCHO < CH4 < CO2 < Ar no change.
(b) HCHO < CO2 < CH4 < Ar (d) X is undergoing dissociation in water.
(c) Ar < CO2 < CH4 < HCHO 32. Which one is not equal to zero for an ideal solution: [2015]
(d) Ar < CH4 < CO2 < HCHO (a) DSmix (b) DVmix
NEET/AIPMT (2013-2017) Questions (c) DP = Pobserved - PRaoult (d) DHmix
27. How many grams of concentrated nitric acid solution should 33. What is the mole fraction of the solute in a 1.00 m aqueous
be used to prepare 250 mL of 2.0M HNO3 ? The concentrated solution ? [2015 RS]
acid is 70% HNO3 [2013] (a) 0.177 (b) 1.770
(a) 90.0 g conc. HNO3 (c) 0.0354 (d) 0.0177
(b) 70.0 g conc. HNO3 34. At 100°C the vapour pressure of a solution of 6.5g of a solute
(c) 54.0 g conc. HNO3 in 100 g water is 732 mm. If Kb = 0.52, the boiling point of this
(d) 45.0 g conc. HNO3 solution will be [2016]
28. Which condition is not satisfied by an ideal solution? (a) 101°C (b) 100°C
(a) Dmix H = 0 [NEET Kar. 2013] (c) 102°C (d) 103°C
(b) Dmix V = 0 35. If molality of the dilute solutions is doubled, the value of
(c) Dmix S = 0 molal depression constant (Kf ) will be:- [2017]
(d) Obeyance to Raoult’s Law (a) halved (b) tripled
29. Of the following 0.10 m aqueous solutions, which one will (c) unchanged (d) doubled
exhibit the largest freezing point depression? [2014] 36. Which of the following is dependent on temperature? [2017]
(a) KCl (b) C6H12O6 (a) Molarity (b) Mole fraction
(c) Weight percentage (d) Molality
(c) Al2(SO4)3 (d) K2SO4
37. Which of the following statement about the composition of
30. Which one of the following electrolytes has the same value the vapour over an ideal 1 : 1 molar mixture of benzene and
of van't Hoff's factor (i) as that of the Al2(SO4)3 (if all are toluene is correct? Assume that the temperature is constant
100% ionised) ? [2015] at 25°C. (Given : Vapour Pressure Data at 25°C, benzene
(a) K3[Fe(CN)6] (b) Al(NO3)3 = 12.8 kPa, toluene = 3.85 kPa) [2016]
(a) The vapour will contain a higher percentage of benzene
(c) K4[Fe(CN)6] (d) K2SO4 (b) The vapour will contain a higher percentage of toluene
31. The boiling point of 0.2 mol kg–1 solution of X in water is (c) The vapour will contain equal amounts of benezene
greater than equimolal solution of Y in water. Which one of and toluene
the following statements is true in this case ? [2015] (d) Not enough information is given to make a predication
(a) Molecular mass of X is greater than the molecular mass
of Y.
 EBD_7753
390 CHEMISTRY

Hints & Solutions

EXERCISE - 1 9. (b) Relation between molality and mole fraction is
1000 ´ x2 1000 ´ .2
1. (b) Lowering in vapour pressure is the highest for that m= = = 3.2
x1M1 .8 ´ 78
molecules for which Vont-Hoff factor is maximum be-
cause. Now, Von’t Hoff factor is maximum for BaCl2 [As Thus, X (m) = 3.2
number of ions formed here after dissociation in water Wt ´ 1000 7.1 ´ 1000
10. (b) M = ; M= = 0. 5M
is zero], this will have the highest lowering of vapour M.Wt . ´ V 142 ´ 100
pressure. Dp n2 n2 640 - 630 0.0156
2. (b) For an ideal solution, DHmixing = 0 11. (a) = or = =
p ° n1 + n2 n1 + n2 640 1
DH = DH1 + DH2 + DH3 (According to Hess's law)
i.e., for ideal solutions there is no change in magnitude or 1 mole i.e., 78g benzene contains solute = 0.0156 mol
of the attractive forces in the two components present. 0.0156 ´ 103
\ Molality of solution = = 0.2 m
m 1000 78
3. (a) DT = K b . ´
M W Number of moles
12. (c) Molarity =
Volume of solution (L)
1 1000 1 1000
0.25 = K b . ´ = Kb ´ ´
M W 60 W Mass 1000
Moles of water = = = 55.6
Molar mass 18
0.3 1000
DT = K b ´ ´ 55.6
180 W Molarity = = 55
1
DT 3 13. (c)
= ´ 60 = 1 Þ DT = 0.25 °C pV = nRT
0.25 180
nRT 1.75 ´ 0.0821 ´ (273 + 17)
New boiling point of glucose solution = 100.25 °C. p= =
4. (d) V 342 ´150 /1000
5. (b) The molality involves weights of the solute and the [M.W. of sucrose = 342]
solvent. Since weight does not change with the 1.75 1000
temperature, therefore molality does not depend upon =p= ´ ´ 0.0821 ´ 290 = 0.8 atm.
342 150
the temperature.
14. (b) Q 10 g glucose is dissolved in = 100 ml solution.
6. (b) Density = 1.17 gm/cc (Given) \ 180 g (g mole) is dissolved in
Mass
As d < 100
Volume = ´ 180 = 1800 ml = 1.8 L
10
volume = 1cc \ mass = d = 1.17g
No. of moles 1.17 ≥1000 Mass of solute
Molarity < < 15. (d) ppm = ´ 106
Mass of solution
Volume in litre 36.5 ≥1
10
<
1170
=32.05M
\ ppm = ´ 106 = 10 ppm
36.5 106
mole 5 / 40 p° - p
7. (a) Molarity = = 16. (a) = xsolute
litre 250 /1000 p°
Given, p° = 0.8 atm, p = 0.6 atm, xsolute = ?
5 1000
= ´ = 0.5 M 0.8 - 0.6 0.2
40 250 = xsolute or = xsolute ,
0.8 0.8
mole 37 / 36.5 or xsolute = 0.25
8. (b) Molarity = =
litre 100 / 1.18 ´1000
m ´ 1000
[37 gm HCl in 100 gm of solution 17. (c) DT = K b
MW
100 100 ù
= C.C = lú 0.44 ´ 1000
1.18 1.18 ´ 1000 û Þ 0.567 = 5.12 ´
M ´ 22.2
37 1.18 ´ 1000 512 ´ 0.44 ´ 1000
= ´ = 11.96 » 12. ÞM = = 178.9
36.5 100 0.567 ´ 22.2
 Solutions 391

5 é ù
18. (b) Molarity = No. of moles of solute = =2M
600
Volume in litres 2.5 ê 600mm = 760 atmosphere ú
ë û
19. (a) Mole fraction of any component A in solution
38 ´ 20 ´ 1000 ´ 0.083 ´ 288
x=
No. of moles of A ÞM =
Total No. of moles of solution
30 ´ 500
As total no. of moles of solution > No. of moles of A = 1211 » 1200
Thus x can never be equal to one or zero. 27. (c) These two components A and B follows the condition of
Raoult’s law if the force of attraction between A and B is
m 1000
20. (d) DT = k b ´ equal to the force of attraction between A and A or B and
M W B.
10 1000 28. (a) Given V.PP = 80 torr
Þ 1 = 2.53 ´ ´ V.PQ = 60 torr
M 100
Ptotal = V·PP × xp + V·Pq × xq
Þ M = 2.53 ´ 100 = 253 g é 3 2ù
1 = ê80 ´ + 60 ´ ú = 16 × 3 + 12 × 2
ë 5 5û
21. (b) One molal solution means one mole of solute is present
Ptotal = 48 + 24 = 72 torr
in 1 kg (1000 g) solvent
29. (d) A solution containing A and B components shows
i.e., mole of solute = 1
negative deviation when A–A and B–B interactions
1000g 1000 are weaker than that of A–B interactions. For such
Mole of solvent (H2O) = =
18g 18 solutions.
DH = –ve and DV = –ve
1 18 30. (b) Chloroform and acetone form a non-ideal solution in
Mole fraction of solute = = = 0.018. which A......B type of interactions are readily seen due
æ 1000 ö 1008
ç1 + ÷ to intensive H-bonding instead of A......A and B......B
è 18 ø
type. Therefore, the solution shows negative deviation
22. (d) from Raoult's law i.e.
23. (d) NV = N1V1 + N2V2 + N3V3
DVmix = - ve ; DH mix = - ve
1 1 1 \ Total volume of solution is less than 80 ml.
or, 1000N = 1 ´ 5 + ´ 20 + ´ 30 or N = .
2 3 40 31. (c) Here, DV = 500 - 300 = 200 cc = 0.2 L
m 1000 p = 0.6 atm
24. (d) DT = k f ´ ´
M W q = 10 J
W = p D v = (0.2 ´ 0.6) = 0.12 Latm
0.1 ´ 1000
= 1.86 ´ = 0.186 Also, 1 L atm = 101.3 J
1000
\ W = 0.12 × 101.3 = 12.156 J
Since NaCl is 100% ionised so Vant Hoff factor = 2 But q = –ve, when heat is liberated
So, DT ' = i ´ DT = 2 ´ 0.186 = – 0.372°C \ DE = q + W = -10 + 12.16 = 2.16 J
25. (a) Given vapour pressure of pure solvent
32. (b) Positive deviations are shown by such solutions in
(P°) = 121.8 mm Hg; Weight of solute (w) = 15 g
which solvent-solvent and solute-solute interactions
Weight of solvent (W) = 250 g; Vapour pressure of
are stronger than the solute-solvent interactions. In
solution (P) = 120.2 mm Hg and Molecular weight of
such solution, the interactions among molecules
solvent (M) = 78
becomes weaker. Therefore their escaping tendency
From Raoult’s law
increases which results in the increase in their partial
Po - P
w M vapour pressures.
= = ´
Po m W In pure methanol th ere exists intermolecular
121.8 - 120.2 15 78 H–bonding.
= ´
121.8 m 250 ---O – H--- O—H --- O—H---
15 ´ 78 121.8 | | |
or m= ´ = 356.2 CH3 CH3 CH3
250 1.6
26. (b) p = CRT On adding benzene, its molecules come between
ethanol molecules there by breaking H-bonds which
600 20 ´ 1000 ´ 0.083 ´ (273 + 15) weaken intermolecular forces. This results in increase
=
760 M ´ 500 in vapour pressure.
 EBD_7753
392 CHEMISTRY

43. (a) Freezing point of water is, T = 0°C

33. (b) Moles of glucose = 18 = 0.1 When 342 g of cane sugar (C12H22O11) is dissolved in
180 1000 g of water, the freezing point of water is depressed
by DTf which is given by,
Moles of water = 178.2 = 9.9
18 w sol 1000
DTf = Kfm = K f ´
Total moles = 0.1 + 9.9 = 10 M.W w solvent

pH2O = Mole fraction × Total pressure = 9.9 ´ 760 342 g 1000

= (1.86 °C /mol)× ´
10 (342g / mol) 1000
= 752.4 Torr = 1.86°C.
34. (d) Antifreeze is a water based liquid coolant used in So, freezing point of solution
gasoline and diesel engines. Compounds like methanol, = T – DTf
ethanol, glycol, glycerol are added to the water to = (0 – 1.86) °C
reduce the freezing point of the mixture below the lowest = – 1.86 °C
temperature that the engine is likely to be exposed and 44. (a) The solutions (liquid mixture) which boils at constant
to inhibit corrosion in cooling systems which often temperature and can distil as such without any change
contain a range of electrochemically incompatible in composition are called azeotropes.
metals. If all the mentioned compounds are available at Solution of HNO3 and H2O will form maximum boiling
same price then the compound having lowest molecular point azeotrope. Maximum boiling azeotropes show
weight will be the choice because negative deviation from Raoult’s law.
w 1000 Composition (%) Boiling Point
DTf = iK f ´ HNO3 68.0 359 K
M.W. w solvent H2O 32.0 373 K
So, less quantity of the compound will result in large Boiling point of the azeotrope of these two solutions is
depression in freezing point of antifreeze solution. 393.5 K.
P° - P n2 45. (c) According to Raoult's law
35. (d) =
P° n1 + n2 p° - p
= xB
640 - 600 2.5 x p°
=
640 39 78 é .2 1ù
ê xB = Mole fraction of solute = .2 + .8 = 5 ú
640 ´ 78 ´ 2.5 ê ú
x= = 80 ë p = 60 mm of Hg û
39 ´ 40
36. (c) For ideal solution,
p° - p 1
DVmixing = 0 and DH mixing = 0 . = or 4 p° = ( p) ´ 5
p° 5
37. (d) C2H5I and C2H5OH form non-ideal solution.
38. (d) Gaseous densities of ethanol and dimethyl ether would 60≥5
Þ p° < < 75mm of Hg
be same at same temperature and pressure. The heat 4
of vaporisation, V.P. and b.pts will differ due to 46. (a) When hard boiled egg after shelling is immersed in
H-bonding in ethanol. saturated brine, its size remains same because of the
39. (c) The given vapour pressure graph shows that on mixing cagulation of inner liquid there is no flow of solvent
two components having vapour pressures pA and pB molecules across the membrane.
in any ratio, the total vapour pressure of the solution, 47. (b) According to Raoult's law
shown by the line CD, does not show any deviation
from ideal behaviour. Lines AD and CB are also do not Dp n
= (mole fraction of solute)
show any deviation from their expected behaviour but p° n + N
these lines show the individual beheviour of 10
components A and B. = 0.2 \ p° = 50 mm of Hg
p°
40. (d)
For other solution of same solvent
41. (a) Molal elevation constant is given by the formula,
20 n
DTb = (Mole fraction of solute)
Kb = , where m is molality and DTb is elevation in p° n + N
m
boiling point. 20
Þ = Mole fraction of solute
42. (d) Azeotropic mixture is constant boiling mixture, it is not 50
possible to separate the components of azeotropic Þ Mole fraction of solute = 0.4
mixture by boiling. As mole fraction of solute + mole fraction of solvent = 1
Hence, mole fraction of solvent = 1 – 0.4 = 0.6
 Solutions 393

48. (a) A solution of acetone in ethanol shows positive 58. (a) Depression in freezing point µ No. of particles.
deviation from Raoult's law. It is because ethanol (when concentration of different solutions is equal)
molecules are strongly hydrogen bonded. When Al 2 (SO4 )3 provides five ions on ionisation
acetone is added, these molecules break the hydrogen
bonds and ethanol becomes more volatile. Therefore ¾® 2 Al 3+ + 3SO 42 –
Al 2 (SO 4 ) 3 ¾
its vapour pressure is increased. while KCl provides two ions
49. (a) Liquid mixture having a definite composition and boil KCl ¾¾ ↑ K ∗ ∗ Cl,
like a pure liquid is called an azeotrope. C6H12O6 and C12H22O11 are not ionised so they have
Þ Mixture showing +ive deviation from Raoult's Law single particle in solution.
forms minimum boiling azeotrope while mixture showing Hence, Al2(SO4)3 have maximum value of depression
–ive deviation from Raoult's law forms maximum boiling in freezing point or lowest freezing point.
azeotrope. 59. (a) Molecular masses of polymers are best determined by
50. (a) DTf = i × Kf × m osmotic pressure method. Firstly because other
Van't Hoff factor, i = 2 for NaCl, m = 0.01 colligative properties give so low values that they
hence DTf = 0.02 Kf which is maximum in the present cannot be measured accurately and secondly, osmotic
case. pressure measurements can be made at room
Hence DTf is maximum or freezing point is minimum.
temperature and do not require heating which may
51. (c) We know that
change the nature of the polymer.
100 ´ Kf ´ w \ m = 100 ´ Kf ´ w 60. (b) Solvent having high cryoscopic constant (camphor)
DTf =
m´ W DTf ´ W can be used in determination of molecular masses of
Now, Kf = molecular depression constant organic compounds like naphthalene, anthracene etc.,
= 50.2°C per 100 gm by cryoscopic method.
DTf = 0.502°C
61. (c) DTA = Kf mA , DTB = Kf MB
W = 25 gm
100 ´ 50.2 ´ 0.750 DTA = DTB , mA = m B
m= = 300
0.502 ´ 25 Mass of solute A Mass of B
52. (b) density of ethanol = 0.789 gm/ml. =
Molecular mass of A Molecular mass of B
wt. of 1000 ml = volume × density = 789g
Mass of CH3COOH 1000 3 9
\ Molality = Mol. mass of CH COOH ´ wt. of ethanol =
3 60 Molecular mass of B
5 1000 Molecular mass of B = 180.
= ´ = 0.1056 mol/g
60 789
K f ´ W2 ´1000 1 1000
53. (c) Osmotic pressure is a colligative property. 62. (c) DT = K f m = = 5.12 ´ ´ = 0.4K
54. (a) As both the solutions are isotonic hence there is no M 2W1 250 51.2
net movement of the solvent occurs through the 63. (b) Total no. of milli equivalents of acids
semipermeable membrane between two solutions. = (100 × 0.4 + 200 × 0.2) meq.
55. (a) Total wt. of solution = 800 gm. = 40 + 40 = 80 meq.
40 Total volume of mixture = 300
Wt. of solute = ´ 800 = 320 g.
100 \ N × 300 = 80
So, 100 gm solute precipitated 80
Remining total wt. of solute = 320 – 100 g N= = 0.2670 N.
300
= 220 g
Remining total wt. of solution = 800 – 100 64. (c) Colloidal particles exhibit ceaseless chaotic and random
= 700 g motions, such motions of the particles are called
Brownian motion.
220
\ % composition = ´ 100 = 31.43% 65. (d) V1 = 250ml; N1 = 0.4N
700
56. (a) Concentration of particles in CaCl2 solution will be V2 = 1250 ml; N 2 = ?
maximum as i = 3 for CaCl2 and i = 2 for KCl.
Applying the law of equivalence :–
Glucose and Urea do not dissociate into ions, as they
No. of equivalents before dilution = No. of equivalents
are nonelectrolytes.
after dilution
57. (a) K 4 [Fe(CN) 6 ] and Al 2(SO 4 )3 both dissociates to
\ N1V1 = N 2 V2
give 5 ions or i = 5
(0.25) ´ (0.4) = (1.25) ´ N 2
ˆˆ† 4K+ + [Fe(CN)6]4–
K4 [Fe(CN)6] ‡ˆˆ
N 2 = 0.080 N .
ˆˆ† 2Al3∗ ∗ 3SO 4,,
and Al2 (SO4 )3 ‡ˆˆ
 EBD_7753
394 CHEMISTRY

+ nRT
66. (d) ( HX H + X - , i = 1.3); DTf = Kf × m × i 75. (b) p= or T = pV
1- 0.3 0. 3 0.3 V nR
DTf = 1.85 × 0.2 × 1.3 = 0.481º C 10% (w/v) aqueous solution of glucose means
\ Tf = T f° - DT f = 0 – 0.481ºC = – 0.481ºC 10 g glucose is present in 100 mL of H2O

67. (c) DTb = Kb ´ m 14 ´ 100 ´ 10 -3 ´ 180

= = 307.3 K
Elevation in boiling point is a colligative property, 0.082 ´ 10
which depends upon the no. of particles (concentration 76. (c) Normality
of solution). Thus greater the number of particles,
Mass 1000
greater is the elevation in boiling point and hence = ´
greater will be its boiling point. Equivalant mass Volume of solution
Na2SO4 ƒ 2Na+ + SO42– 4 1000
Since Na2SO4 has maximum number of particles (c) = ´ =1
40 100
hence has maximum boiling point.
77. (c) Solvent molecules flow from low concentration solution
No. of equivalents to high concentration solution.
68. (b) Normality =
Volume of solution in litre 78. (d) DT f = iK f m
Þ No. of equivalents
® K + + Br -
KBr ¾¾
= Normality × Volume of solution in litre 1 0 0
= 0.1 × 0.1 = 0.01 (1-a) a a
i=1+a
Wt Here a = 0.8 (80% ionization)
Þ = 0.01
Equivalent wt. i = 1.8
DTf = (1.8) (1.86) (0.4) = 1.339
Molecular wt. Tf = – 1.339°C
Þ w t = 0.01´
basicity 79. (a) The solution which provide same number of ions are
isotonic.
200 Ca (NO3)2 ¾¾ ® Ca2+ + 2 NO3–
wt. = 0.01´ = 1gm
2 Total ions produced = 3
No. of particles after ionisation Na2SO4 ¾¾ ® 2 Na+ + SO42–
69. (a) (i) i = Total ions produced = 3
No. of particles before ionisation
\ 0.1 M Ca (NO3)2 and 0.1 M Na2SO4 are isotonic.
(ii) DTb = i × Kb × m 80. (b) KNO3 is a strong electrolyte which dissociates into
CuCl2 ¾
¾® Cu + 2Cl 2+ - two ions. Therefore, its van’t Hoff factor is 2. Acetic
1 0 0 acid (CH3COOH) is a weak electrolyte, it does not
(1-a) a 2a dissociate completely. So, its van’t Hoff factor is less
than that of KNO3
1 + 2a \ Osmotic pressure of 0.1 M KNO3 >
i= , i = 1 + 2a
1 Osmotic pressure of 0.1 M CH3COOH
Assuming 100% ionization or P1 > P2
So, i = 1 + 2 = 3 81. (a) For highest boiling point of a solution, the DTb should
be highest, Since, DTb is directly proportional to the
13.44 molality of solution.
DTb = 3 ´ 0.52 ´ 0.1 = 0.156 » 0.16 [m = = 0.1]
134.4 DTb µ m
70. (b) Benzoic acid exists as dimer in benzene. Of the given solutions urea and glucose remain
71. (b) DT f = K f ´ m = 1.86 ´ 0.5 = 0.93°C; T f = -0.93°C unionized and remain as one particle in solution. In
case of Na2SO4 (a strong electrolyte) there are three
0.1 ´180 ´100 particles for each molecule (2 Na + and one SO42–)
72. (c) Kb = =1 K / m
1.8 ´1000 whereas for KNO3 (strong electrolyte) there are 2
73. (b) Isotonic solutions are those solutions which have same particles (one K+ and one NO3–). Thus for equimolar
osmotic concentrations. solutions of these two, the number of particles is more
The solution with higher osmotic concentration is called in Na2SO4 (aq) and so is molality. Thus it will exhibit
hypertonic and lower is called hypotonic solution. highest boiling point.
74. (d) Boiling temperature is a temperature at which vapour 82. (b) Given mass of solute = 8.1 g
pressure is equal to the atmospheric pressure when Mass of solvent = 100 g
external pressure is equal to 1 atm. For HBr
 Solutions 395

® H + + Br -
HBr ¾¾ Þ Boiling pt. of solution (2M sucrose solution)
1 0 0 = DTb + Boiling pt. of pure water
(1-a ) a a
a = 90% = 0.9 = 1.04°C + 100°C = 101.04°C
88. (d) DTf = 0 – (0.00732°C) = 0.00732
i = 1 + a = 1 + 0.9 = 1.9
DTf = i × Kf × m
DT f = Kf × m × i
DT f 0.00732
moles of solute i= = = 1.97 » 2
= 1.86 × × 1.9 K f ´m 1.86 ´ 0.002
mass of solvent in kg
89. (d) When the aqueous solution of one molal KI is diluted
8.1/ 81 with water, concentration decreases, therefore the
= 1.86 × ´ 1.9 vapour pressure of the resulting solution increases.
100 /1000
= 1.86 × 1 × 1.9 = 3.534K 1000W2 1.86×1000×68.5
90. (a) DT f = K f = = 0.372
T f = T f ° - DT f M 2W1 342×1000
or Tf = 0 – 3.534 K Tf = T °f –DTf
\ Tf = – 3.534K Tf = – 0.372°C
83. (d) Osmotic pressure is a colligative property. Hence 25.3 1000
resulting osmotic pressure of the solution is given by 91. (b) Concentration of Na 2CO3 = ´ = 0.955 M
106 250
pT = p1 + p2 + p3 ..........
pT = 1.64 + 2.46 = 4.10 atm. [Na + ] = 2 × 0.955 = 1.91 M
84. (d) Addition of solute to water decreases the freezing point
of water (pure solvent). é CO32– ù = 0.955 M
ë û
\ When 1% lead nitrate (solute) is added to water, the 92. (b) Given Kf = – 1.86ºC m–1, mass of solute = 5.00 g,
freezing point of water will be below 0°C. mass of solvent = 45.0 g and DTf = – 3.82°C
85. (b) As DTf = Kf. m DTf = i × Kf .m
DTb = Kb. m 5 ´ 1000
3.82 = i × 1.86 ×
DT f DTb 142 ´ 45
Hence, we have m = =
Kf Kb \ i = 2.62 (Molecular mass of Na2SO4 = 142 g)
93. (c) If compound dissociates in solvent i > 1 and on
Kf association i < 1.
or DT f = DTb
Kb 94. (b) 1 molal solution means 1 mole of solute dissolved in
1000 gm solvent.
Þ [DTb = 100.18 - 100 = 0.18°C] \ nsolute = 1 wsolvent = 1000 gm
1.86 1000
= 0.18 × = 0.654°C \ nsolvent = = 55.56
0.512 18
As the Freezing Point of pure water is 0°C,
1
DTf = 0 –Tf xsolute = = 0.0177
0.654 = 0 – Tf 1 + 55.56
\ Tf = – 0.654 95. (d) Given a = 30% i.e., 0.3
Thus the freezing point of solution will be – 0.654°C. HA ¾¾ ® H+ + A–
86. (c) Applying the law of equivalence, 1–a a a
1 – 0.3 0.3 0.3
N1V1 + N 2V2 + N3V3 = N RVR
i = 1 – 0.3 + 0.3 + 0.3
N N N i = 1.3
´ 50 + ´ 30 + ´ 10 = N R ´ 1000
10 3 2 DTf = 1.3 × 1.86 × 0.1 = 0.2418
5 N + 10 N + 5 N = 1000 ´ N R Tf = 0 – 0.2418 = – 0.2418 °C
N WRT 1.26 ´ 0.083 ´ 300
Þ NR = 96. (d) M = =
50 pV 2.57 ´10-3 ´ 200 ´ 10-3
87. (a) Given : Kb = 0.52, molarity = 2m
Here, molality = molarity = 2 molal 31.374 ´ 10 6
= = 61038 g
Now, using DTb = Kb × m, we get 514
DTb = 0.52 × 2 = 1.04 °C 97. (d) p = pAxA + pBxB
Now, DTb = pAxA + pB (1 – xA)
= Boiling pt. of solution – Boiling pt. of Þ pAxA + pB – pBxA
solvent (pure water) Þ pB+ xA (pA – pB)
 EBD_7753
396 CHEMISTRY

98. (b) pA° = ? , Given p B° = 200 mm of Hg , xA = 0.6, 8. (c)

Molarity
Molality (m)
xB = 1 – 0.6 = 0.4, P = 290 of Hg Molarity ´ Molecular mass
Density -
1000
P = PA + PB = PA°x A + PB°xB
18
= = 5000
Þ 290 = PA° × 0.6 + 200 × 0.4 \ p°A = 350 mm of Hg. 1.8 -
18 ´ 98
99. (b) For this solution intermolecular interactions between 1000
n-heptane and ethanol are weaker than w
9. (b) pV = RT
n-heptane-n-heptane & ethanol-ethanol interactions m
hence the solution of n-heptane and ethanol is non- 4
ideal and shows positive deviation from Raoult’s law. \ 6 ´ 10-4 ´1 = ´ 0.0821´ 300 ;m = 1.64 ´105.
m
100. (a) From molarity equation : 10. (b) pV = CRT
M1V1 + M2V2 = M × V
p1 C1T1
M V + M 2V2 =
M= 1 1 where V = total volume p 2 C2T2
V
C
750 ´ 0.5 + 250 ´ 2 p1 = P, p 2 = 2 atm. C1 = C , C2 =
= 2
1000 T1 = 600 K, T2 = 700 K
= 0.875 M
P 2 ´ C ´ 600
=
EXERCISE - 2 2 C ´ 700
24
P= .
5 5 7
1. (c) Moles of urea = ; moles of fructose = ; 11. (a) CaCl 2 acts as a non-volatile solute and results in
60 180
depression in freezing point. Thus, snow fall is reduced
5 and prevents blocking of roads in the polar region.
moles of sucrose = ;
342 12. (c) Na2SO4 ¾¾ ® 2Na+ + SO 24-
Mol. before dissociation 1 0 0
5 5
moles of KCl(effective) = 2 ´ = Mol. after dissociation 1 – a 2a 1a
74.5 37.25
i = 1 - a + 2a + a = 1 + 2a
2. (b) Using the relation,
13. (b) AlCl3 furnishes more ions than CaCl 2 and thus possess
w.R.T 6 ´ 0.080 ´ 300 higher boiling point i.e., T1 > T2.
M = , we get M = = 3.6 × 105
pV -3 14. (a) Van’t Hoff equation is
2 ´ 10 ´ 0.2
3. (d) The salt that ionises to least extent will have highest pV = inRT
freezing point. [ i.e., minimum D Tf ] For depression in freezing point.
D Tf = i × Kf × m
4. (b) Greater is the effective molarity (i × C), higher the DTf
For elevation in boiling point.
value and lower the freezing point.
D Tb = i × Kb × m
5. (c) N1V1 + N2V2 = NV
For lowering of vapour pressure,
4x + 10 (1 – x) = 6 × 1; –6x = –4 ; x = 0.67
Thus 0.67 litre of 4N HCl °
Psolvent - Psolution æ n ö
= iç .
è N + n ÷ø
1 – x = 1 – 0.67 = 0.33 litre of 10 N HCl P°
solvent
% ´ 10 ´ d 22 ´ 10 ´ 1.253 15. (b) DTf = i.Kf .m ; 0.0054 = i × 1.8 × 0.001
6. (a) Molarity = = = 0.805M.
GMM 342 i = 3 so it is [Pt(NH3)4Cl2]Cl2.
% ´ 10 ´ d 22 ´ 10 ´ 1.253 16. (c) Given, W = 500 cc = 500 g
Normality = = = 4.83N
GEM 342 / 6 (Q density of water = 1g/cc)
22 ´ 1000 Weight
Molality = = 0.825m As, Density =
342(100 - 22) Volume
80 1g
Weight = Density × Volume = ´ 500cc = 500g
68 18 cc
7. (b) Mole fraction of H2O = = .
80 20 77 w = amount of urea = ?
+
18 34 Kf = 1.86°C; DTf = 0.186°C
M = Molecular mass of urea = 60
 Solutions 397

1000 ´ K f ´ w 22. (d) At 1 atmospheric pressure the boiling point of mixture

M = is 80°C.
W ´ DT f At boiling point the vapour pressure of mixture, pT = 1
atmosphere = 760 mm Hg.
1000 ´ 1.86 ´ w
60 = Using the relation,
500 ´ 0.186
60 = 20 × w pT = p A° x A + p B° xB , we get
pT = 520 x A + 1000(1 - x A )
60
\ w = = 3g
{Q pAo = 520 mm Hg ,
20
17. (b) Among the given options, CaCl 2 solution will produce
pB° = 1000 mm Hg , x A + xB = 1 }
maximum (three) ions per molecule, so it will show
minimum freezing point. or 760 = 520 x A + 1000 - 1000 x A or 480 x A = 240
w 1000 240 1
18. (d) DTb = Kb ´ or x A = = or 50 mol. percent
M W 480 2
3 1000 i.e., the correct answer is (d)
0.52 = 0 .6 ´ ´ (W = 200 ´ 1)) 23. (a) The vapour pressure of a solution of glucose in water
M 200
can be calculated using the relation
1.8 ´ 5
M= = 17.3g mol -1 p° - ps Moles of glucose in solution
0.52 =
ps Moles of water in solution
19. (d) The value of ΧTb depends upon two factors 'i ' and
'm'. It is given that 1 mol of each compound is dissolved 17.5 - ps 18/180
in 1 L of solution. Hence molarity is same for all the or = [Q p° = 17.5 ]
ps 178.2/18
compounds. Now the van't Hoff factor depends on
number of particle i.e. on degree of ionisation which 0.1´ ps
further depends on the bond dissociation energy which or 17.5 – ps = or ps = 17.325 mm Hg.
is in the order 9.9
Hence (a) is correct answer.
HI < HBr < HCl < HF
i.e., bond dissociation energy of HI is least. Lower the 24. (b) p = pA° xA + pB° xB
total
bond dissociation energy, higher is the degree of 1 3
ionisation and hence higher the number of particles, 550 = pA° ´ + pB° ´
4 4
thus i will be maximum for HI and hence ΧTb value will pA° + 3 pB° = 550 ´ 4 ...(i)
be larger for HI. In second case
20. (d) Let the mass of methane and oxygen = m gm. 1 4
Mole fraction of O2 ptotal = pA° ´ + pB° ´
5 5
Moles of O2 pA° + 4 pB° = 560 ´ 5 ...(ii)
=
Moles of O 2 + Moles of CH 4 Subtract (i) from (ii)
m / 32 m / 32 1 \ pB° = 560 ´ 5 - 550 ´ 4 = 600
= = =
m / 32 + m /16 3m / 32 3 Q p° = 400
A
Partial pressure of O2 = Total pressure × mole fraction
25. (a) p Total = p °A x A + p °B x B
1 1
of O2 , PO2 = P × = P = p°Heptane xHeptane + p°Octane x Octane
3 3
21. (a) Osmotic pressure (p) of isotonic solutions are equal.
25 /100 35 /114
For solution of unknown substance C1(concentration). = 105 ´ 25 35 + 45 ´ 25 35
5.25 / M + +
C1 = 100 114 100 114
V
0.25 0.3
Where M represents molar mass. = 105 ´ + 45 ´
0.25 + 0.3 0.25 + 0.3
1.5 / 60
For solution of urea, C2 (concentration) = 105 ´ 0.25 45 ´ 0.3 26.25 + 13.5
V = + =
0.55 0.55 0.55
Given, p1 = p2 Q p = CRT = 72 kPa
5.25 / M 1.5 / 60 26. (b) For isotonic solutions
\ C1RT = C2RT or C1 = C2 or =
V V p1 = p 2
\ M = 210 g/mol
 EBD_7753
398 CHEMISTRY

C1 = C2 31. (a) DTf = i × Kf × m

Where m = Molality of the solution
5 / 342 1/ M (i.e. number of moles of solute per 1000 g of the solvent)
=
0.1 0.1 0.1
Here m = ´10
5 1 329
=
342 M 0.1´10
Thus DTf = 4 × 1.86 × = 2.3 × 10–2
329
342
Þ M = = 68.4 gm/mol Thus Tf = 0 – 2.3 × 10–2 = – 2.3 × 10–2 ºC
5
32. (a) From Raoult law
27. (b) DTf = i × Kf × m
Given DTf = 2.8, Kf = 1.86 K kg mol–1 i = 1 p° – p No.of moles of solute
=
(ethylene glygol is a non- electrolyte) p° No. of moles of solvent+ No. of moles of solute
wt. of solvent = 1 kg When the concentration of solute is much lower than
Let of wt of solute = x the concentration of solvent,
Mol. wt of ethylene glycol = 62
p° - p No. of moles of solute
x =
2.8 = 1 × 1.86 × p° No. of moles of solvent
62 ´ 1
DTb = Kb × m
2.8 ´ 62 Number of moles of the solute
or x = = 93 gm m= ´ 1000
1.86 Mass of solvent in grams
28. (a) Molecular weight of naphthoic acid
Number of moles of the solute
C11H8O2 = 172 g mol–1. DTb = K b ´ × 1000
The theoretical value of depression in freezing point Mass of solvent in grams
Number of moles of solute
20×1000
= Kf × molality = 1.72× = 4K DT ´ Mass of solvent in grams
172×50 = b
K b ´ 1000
Van't Hoff factor, 2 ´100
= = 0.26,
Observed value of colligative property 0.76 ´1000
i= 100
Theoretical value of colligative property Number of moles of solvent = = 5.56
18
2 From equation (i) we get, 760 - p = 0.26
= = 0.5 . 760 5.56
4 On solving, p = 724.46 » 724
29. (a) PN 2 = k H x N 2 33. (b) Sodium sulphate dissociates as
0.8 × 5 = 1 × 105 × xN Na 2SO 4 ¾¾ ® 2Na + + SO -4 -
2
hence van’t hoff factor i = 3
\ x N = 4 × 10–5
2 Now DT f = i K f .m
Solubility in 10 moles = 4 × 10–4.
= 3 × 1.86 × 0.01 = 0.0558 K
120 34. (d) Colligative properties depends upon the no. of particles.
30. (c) Number of moles of urea = =2
60 Since methanol is non electrolyte hence cannot be
Total mass of solution = 1000 + 120 = 1120 g considered.
Mass 35. (a) kH = 100 kbar = 105 bar, p = 1 bar
Total volume of solution (in L) = p = k H × xA
Density
p 1
1120 112 xA = = = 10-5
k H 100 ´ 10 3
= = L
3 115
1.15 ´ 10 1000
Moles of water = = 55.5
Number of moles 18
Molarity of the solution = Weight of water = 1000 g (Q 1000 mL = 1000 g)
Volume of solution in litre
x
2×115 Mole fraction = 10–5 =
= = 2.05 mol L–1 55.5 + x
112 As 55.5 >>> x, thus neglecting x from denominator
 Solutions 399

x M2 = molar mass of solute

10 -5 = Þ x = 55.5 ´ 10 -5 moles w1 = mass of the solvent
55.5
or 0.555 millimoles. 5.12 ´ 1000 ´ 1
On substituting given values, DT f =
36. (d) DTb = kb.m 51.2 ´ 250
weight of solute ´ 1000 \ DTf = 0.4K
DTb = k b ´ 41. (c) Acetone and chloroform shows negative deviation from
molecular weight of solute ´
weight of solvent Raoult's law when these are mixed, the hydrogen
bonding takes place between the two molecular species
1.5 1000
0.75 = 2.5 ´ ´ due to which escaping tendency of either liquid
M 50 molecules becomes less and boiling point of solution
2.5 ´ 1.5 ´ 1000 increases.
M= = 100
0.75 ´ 50 42. (c)
37. (b ) DTf = Kf × m 43. (d) According to Henry’s law the mass of a gas dissolved
Kf is a characteristic of a particular solvent i.e., it will be per unit volume of solvent is proportional to the
different for different solvents. pressure of the gas at constant temperature m = K p i.e.
38. (a) According to Raoult’s law, as the solubility increases, value of Henry’s law
PT = xAp°A + xBp°B constant decreases. Since CO2 is most soluble in water
Given, = PT1 500 mm Hg among the given set of gases. Therefore CO2 has the
nA = 1 and nB = 2 \ xA = 1/3 and xB = 2/3 lowest value of Henry’s law constant.
44. (a) Given w = 10 g Mol. mass = 40
1 2
Þ 500 = p° + p ° Weight of solvent = 1250 × 0.8 g = 10000 g = 1 kg
3 A 3 B
10
\ molality = = 0.25
Þ 1500 = p°A + 2p°B ... (i) 40 ´ 1
Also given Qn that one more mole of B is added to the 45. (d) Glucose is non electrolyte hence depression in freezing
solution, the pressure of the ideal solution increases point will be minimum, hence freezing point will be
by 25 mm Hg. highest.
46. (b)
\ PT2 = 500 + 25 = 525 mm Hg 47. (b) Both assertion and reason are correct but reason is not
Also, nB = 3 \ xA = 1/4 and xB = 3/4 the correct explanation of assertion.
1 3 The relationship between lowering of vapour pressure
525 = p°A = p°B ... (ii) and osmotic pressure can be derived as follows:
4 4
Van’t Hoff equation for dilute solutions is
2100 = PA° + 3PB° n
Subtract (i) and (ii), p = RT ....(i)
V
p° = 600 mm Hg In case of a dilute solution, the volume of solution can
B
p° + 2p° = 1500 Þ p° = 300 mm Hg. be taken as equal to that of solvent. If N is the number
A B A of moles of solvent of molecular weight M and density
39. (d) According to Henry’s law, r , the volume V is given by
m=k×p
given KH = 1.4 × 10–3 NM
V= ....(ii)
pO2 = 0.5 or r
n pM
p O2 = K H ´ x O2 or = ....(iii)
N r.R.T .
0.5 From Raoult’s law,
\ x O2 =
1.4 ´ 10- 3 P° – P n
= ....(iv)
m P° N
No. of moles; n = P° – P pM
M \ =
P° r RT [From (iii) and (iv)]
-4 m
0.7 ´ 10 =
32 pM
or ( P° – P ) = r RT ´ P°
m = 22.4 ´ 10-4 g = 2.24 mg
40. (d) Mass of non-volatile solute = 1g MP °
Molar mass of solute = 250g mol–1 The factor r RT is constant at constant temperature.
Mass of benzene = 51.2g, Kf = 5.12 K kg mol–1
\ ( P° – P ) µ p
K ´ 1000 ´ w 2
DTf = f or lowering of V.P. µ osmotic pressure
M 2 ´ w1 Thus assertion is correct.
where, w2= mass of the solute Osmotic pressure is a colligative property is correct.
 EBD_7753
400 CHEMISTRY

48. (c) Both the solute and solvent will form the vapours but unit of DTb K
vapour phase will become richer in the more volatile Unit of Kb = unit of m = molality
component.
K
49. (b) = = K mol-1 kg
-1
mol kg
50. (c) Camphor has high molal depression constant.
11. (c) DTf = iKf m i.e., depression in freezing point is directly
EXERCISE - 3 related to van't Hoff factor (i). Glucose is a non-
electrolyte hence will remain undissociated. Hence for
Exemplar Questions glucose value of i is 1 whereas for MgCl2 value of i is 3.
1. (a) According to Henry's law partial pressure of a gas in Hence, depression in freezing point of MgCl2 is about
the solution is proportional to the mole fraction of gas 3 times of glucose.
in the solution. 12. (d) When an unripe mango is placed in a concentrated salt
p = KHx ; KH = (Henry's constant) solution to prepare pickle then mango loose water due
2. (d) Dissolution of sugar in water will be most rapid when to osmosis and get shrivel.
powdered sugar is dissolved in hot water because in 13. (a) Osmotic pressure (p) = CRT.
powdered form it can easily insert in the vacancies of For concentrated solution C has higher value than
water particle. dilute solution.
Also, dissolution of sugar in water is an endothermic Hence, as concentration of solution increases osmotic
process. So it is favourable at high temperature. pressure also increase.
3. (c) 14. (a) The value of molal depression constant, Kf depends
4. (b) When solute gets precipitated in the solution, then the upon nature of solvent. Therefore two different
solution is known as supersaturated solution. solutions of sucrose of same molality prepared in
5. (c) Maximum amount of solid that can be dissolved in a different solvents will have different depression in
specified amount of a given solvent does not depend freezing point.
upon pressure. The reason is solid and liquid are highly 15. (b) Number of total ions present in the solution is known
incompressible and practically remain unaffected by as van't Hoff factors (i).
change in pressure. for KCl, i= 2
6. (b) At high altitude, the partial pressure of oxygen is less for NaCl, i= 2
than at the ground level. This decreased atmospheric for K2SO4, i= 3
pressure causes release of oxygen from blood. Hence 16. (b) In reverse osmosis, solvent molecules move through
people living at high altitude have low concentration a semipermeable membrane from a region of higher
of oxygen in the blood and tissues. concentration of solute to lower concentration.
7. (a) Mixture of methanol and acetone show a positive 17. (a) The value of Henry's constant (KH) increases with
deviation from Raoult’s law. Molecules in pure increase in temperature.
methanol are hydrogen bonded. On adding acetone, 18. (b) According to Henry's law
its molecules enters in between the host molecules and pµx
break some of the hydrogen bonds between them. Þ p = KHx
Therefore, the intermolecular attractive forces between As value of KH rises solubility of gases decreases.
the solute-solvent molecules are weaker than those 19. (b) If a pressure higher than the osmotic pressure is applied
between the solute-solute and solvent-solvent on the solution, the solvent will flow from the solution
molecules. into the pure solvent through the semi-permeable
Other three remaining options will show negative membrane. This process is called reverse osmosis.
deviation. Thus, in this case, if a pressure greater than osmotic
8. (b) Colligative properties depend upon number of solute pressure is applied on piston (B). Water will move from
particles in solution irrespective of their nature. side (B) to side (A).
9. (b) Colligative properties depends upon the number of 20. (c) As van’t hoff factor depends only on no. of dissociated
particles. As we know greater the value of van't Hoff ions. Hence, i will be independent on concentration of
factor higher will be elevation in boiling point and hence solutions.
higher will be the boiling point of solution. Among the 21. (b) A mixture of bromoethane and chloroethane is an
given solution 1.0M Na 2 SO4 have highest no. of example of ideal solution. For an ideal solution, the
particles i.e highest value of ‘i’. A — A or B — B type intermolecular interaction is
Hence, 1.0 M Na2SO4 has highest value of boiling nearly equal to A — B type interaction.
point. Chloroform and acetone mixture is an example of
10. (a) DTb = Kbm elevation in boiling point non-ideal solution having negative deviation while
ethanol-acetone mixture shows positive deviation.
DTb
Kb = 22. (a) On adding salt to water to make the salt solution the
m vapour pressure of solution gets lowered. This is due
 Solutions 401

to the decrease in surface covered by solvent molecule n

which leads to decrease in number of solvent molecule < (where n solute = W/M)
V(kg)
escaping from the surface corresponding to pure
solvent. n
1.00 m < i.e., 1 mole in 1 kg of water
Hence, vapour pressure also get reduces. V(kg)
23. (a) If two liquids A and B form minimum boiling azeotrope Moles of 1 kg H2O
at some specific composition then A — B interactions 1000g
are weaker than those of A — A and B — B. Because in < < 55.55 mole
18g / mol
case of positive deviation, we get minimum boiling
azeotropes whereas in case of negative deviation we Moles of solute = 1
get maximum boiling azeotropes. Mole fraction
24. (d) As we know, M1V1 = M2V2 nsolute 1
< <
On putting values, we get n solute ∗ n water (1 ∗ 55.55)
0.02 × 4 L = M2 × 5L
0.08 = 0.01768 = 0.0177
M2 = = 0.016 M
5 æ P°- Ps ö n W1 M 2
25. (a) At specific composition methanol-acetone mixture will 34. (a) çç ÷÷ = = ´
è P° ø N M1 W2
form minimum boiling azeotrope and will show positive
deviation. This is due to weaker A — B interaction Where, W1 = wt of solute
than A — A and B — B interaction. W2 = wt of solvent
26. (c) Value of KH depends upon nature of gases dissolved M1 = Mass of solute
in water. Higher the value of KH at a given temperature
M2 = Mass of solvent
the lower is the solubility of the gas in the liquid.
Hence, correct order is : at 100°C, P° = 760 mm
Ar < CO2 < CH4 < HCHO.
760 - 732 6.5 ´18
NEET/AIPMT (2013-2017) Questions =
760 M1 ´ 100
wt ´ 1000
27. (d) Molarity (M) = M1 = 31.75 g mol–1
mol. wt. ´ vol (ml)
wt. 1000 W1 ´1000
2= × DTb = m × Kb = M ´ W × Kb
63 250
1 2
63
wt. = gm 0.52 ´ 6.5 ´1000
2
100 DTb = = 1.06°C
wt. of 70% acid = ´ 31.5 = 45 gm 31.75 ´100
70 \ boiling point of solution
28. (c) An ideal solution is that solution in which each
= 100°C + 1.06°C = 101°C
component obeys Raoult’s law under all conditions of
temperatures and concentrations. For an ideal solution. 35. (c) Kf (molal depression constant) only depends on the
DHmix = 0 and DVmix = 0. nature of the solvent and is independent of the
concentration of the solution.
29. (c) Colligative properties µ no. of particles. Since
Al2(SO4)3 contains maximum number of particles, hence 36. (a) Molarity depends on the volume of a solution which
will have the largest value of freezing point depression. can be changed with change in temperature.
37. (a) Let us consider that A is benzene and B is toluene
30. ¾¾
(c) K4[Fe(CN)6] ¬¾
¾® 4K+ + [Fe(CN)6]– 1 : 1 molar mixture of A and B
and Al2(SO4)3 ® 2Al3+ + 3SO2– 1 1
4
\ xA = and xB =
\ van’t Hoff factor is 5 for both Al2 (SO4)3 and K4[Fe(CN)6] 2 2
31. (d) DTb = iKb m Total pressure of solution (P) = PA0 x A +PB0 x B
Given, (DTb)x > (DTb)y 1 1
\ ix Kb m > iyKb m P = 12.8 × + 3.85 × = 8.325 kPa
2 2
(Kb is same for same solvent) 1
ix > iy 0 12.8´
YA = PA x A = 2 = 0.768
So, x is undergoing dissociation in water. P 8.325
32. (a) For an ideal solution DSmix > 0 \ yB = 1 – yA = 1 – 0.768 = 0.232
W 1 so, the vapour will contain higher percentage of
33. (d) Molality < ≥
M V(kg) benzene.