Solutions 29

3 Solutions
QUICK LOOK An alloy is a mixture or metallic solid solution composed of
two or more elements and the properties of alloys are usually
A solution is a mixture in which substances are intermixed so different from those of its component elements. Alloy
intimately that they cannot be observed as separate constituents are usually measured by mass. Some well-known
components. The dispersed phase or the substance which is to alloys include bronze (three-quarters copper, one-quarter tin);
be dissolved is called solute, while the dispersion medium in brass (two-thirds copper, one-third zinc); pewter (a mixture of
which the solute is dispersed to get a homogenous mixture is tin and copper with traces of antimony); and numerous alloys
called the solvent. And the Solubility of a substance may be of iron-particularly steel-as well as alloys involving other
defined as the amount of solute dissolved in 100 g of a solvent metals.
to form a saturated solution at a given temperature as with Kinds of Solutions: Gas, liquid and solid, these three states of
change in temperature solubility changes. matter either behave as solvent or solute Depending on the
A saturated solution is a solution which contains at a given state of solute or solvent, mainly there may be following nine
temperature as much solute as it can hold in presence of types of binary solutions. Among these solutions the most
dissolve ding solvent. Any solution may contain less solute significant type of solutions are those which are in liquid phase
than would be necessary to saturate it. Such a solution is and may be categorised as:
known as unsaturated solution. When the solution contains  Solid in liquid solutions,
more solute than would be necessary to saturate it then it is  Liquid in liquid solutions
termed as supersaturated solution.  Gas in liquid solutions.

An aqueous solution is a solution in which the solvent is water. Table 3.1: Solvent, Solute and Example
Example of an aqueous solution: acetic acid as solute and Solvent Solute Example
water as solvent and nonaqueous solvents are ethyl acetate, Gas Gas Mixture of gases, air.
Gas Liquid Water vapours in air, mist.
used in nail polish removers, and turpentine, used to clean paint
Gas Solid Sublimation of a solid into a gas, smoke.
brushes. Aqueous-solution reactions can lead to the formation Liquid Gas CO2 gas dissolved in water .
of a solid, as when a solution of potassium chromate (K 2CrO4)
Liquid Liquid Mixture of miscible liquids, e.g., alcohol in water.
is added to an aqueous solution of barium nitrate Ba[NO 3]2 to
Liquid Solid Salt in water, sugar in water.
form solid barium chromate (BaCrO 4) and a solution of Solid Gas Adsorption of gases over metals; hydrogen over
potassium nitrate (KNO3). palladium.
We have primarily discussed liquid solutions, and in particular Solid Liquid Mercury in zinc, mercury in gold, CuSO4.5H 2O
aqueous solutions. It should be stressed, however, that Solid Solid Homogeneous mixture of two or more metals
solutions can also exist in the gaseous or solid phases. The air (alloys), e.g., copper in gold.
we breathe is a solution, not a compound; there is no such thing
Water and oil and immiscible due to their respective molecule
as an “air molecule” in its place, it is made up of diatomic
structures, and hence their inherent characteristics of
elements; monatomic elements; one element in a triatomic
intermolecular bonding. Water molecules are polar, meaning
molecule; and two compounds
that the positive electric charge is at one end of the molecule,
The “solvent” in air is nitrogen, a diatomic element that while the negative charge is at the other end. Oil, on the other
accounts for 78% of Earth's atmosphere. Oxygen, also hand, is non-polar-charges are more evenly distributed
diatomic, constitutes an additional 21%. Argon, which like all throughout the molecule. The immiscible quality of oil and
noble gases is monatomic, ranks a distant third, with 0.93%. water in relation to one another explains a number of
The remaining 0.07% is made up of traces of other noble gases; phenomena from the everyday world.
the two compounds mentioned, carbon dioxide and water (in The dispersion of two substances in an emulsion is achieved
vapour form); and, high in the atmosphere, the triatomic form through the use of an emulsifier or surfactant. Made up of
of oxygen known as ozone (O3). molecules that are both water-and oil-soluble, an emulsifier or
30 JEE-Main and Advanced Chapter-wise Solved Papers: Chemistry
surfactant acts as an agent for joining other substances in an Raoult’s Law: When a non-volatile substance is dissolved
emulsion. The two words are virtually synonymous, but in a liquid, the vapour pressure of the liquid (solvent) is
“emulsifier” is used typically in reference to foods, whereas lowered. According to Raoult’s law (1887), at any given
“surfactant” most often refers to an ingredient in detergents and temperature the partial vapour pressure (p A) of any
related products. component of a solution is equal to its mole fraction (X A)
multiplied by the vapour pressure of this component in the
In an emulsion, millions of surfactants surround the dispersed
droplets of solute, known as the internal phase, shielding them pure state (pA ). That is, p A  pA  XA
from the solvent or external phase. Surfactants themselves are
often used in laundry or dish detergent, because most stains on The vapour pressure of the solution (P total) is the sum of the
plates or clothes are oil-based, whereas the detergent itself is partial pressures of the components, i.e., for the solution of two
applied to the clothes in a water-based external phase. The volatile liquids with vapour pressures p A and p B .
emulsifiers in milk help to bond oily particles of milk fat Ptotal  p A  p B  (p A X A) (p B X B)
(cream) and protein to the external phase of water that
comprises the majority of milk's volume. Relative lowering of vapour pressure is defined as the ratio of
Colligative Properties: Certain properties of dilute solutions lowering of vapour pressure to the vapour pressure of the pure
containing non-volatile solute do not depend upon the nature of solvent. It is determined by Ostwald-Walker method.
the solute dissolved but depend only upon the concentration w
i.e., the number of particles of the solute present in the p  p n m
Thus according to Raoult’s law,  
solution. Such properties are called colligative properties. p nN w  W
 Lowering of vapour pressure of the solvent. m M
 Osmotic pressure of the solution. Where, p  Vapour pressure of the solution
 Elevation in boiling point of the solvent. p  Vapour pressure of the pure solvent
 Depression in freezing point of the solvent. n  Number of moles of the solute
N  Number of moles of the solvent
Since colligative properties depend upon the number of solute
particles present in the solution, the simple case will be that w and m  weight and mol. wt. of solute
when the solute is a non-electrolyte. In case the solute is an W and M  weight and mol. wt. of the solvent.
electrolyte, it may split to a number of ions each of which acts Limitations of Raoult’s Law
as a particle and thus will affect the value of the colligative  Raoult’s law is applicable only to very dilute solutions.
property. Each colligative property is exactly related to other,  Raoult’s law is applicable to solutions containing non-
Relative lowering of vapour pressure, elevation in boiling point volatile solute only.
and depression in freezing point are directly proportional to  Raoult’s law is not applicable to solutes which dissociate or
osmotic pressure. associate in the particular solution.
Vapour Pressure: The pressure exerted by the vapours above
Table 3.2: Ideal and Non-ideal Solutions
the liquid surface in equilibrium with the liquid at a given
Ideal solutions Non-ideal solutions
temperature is called vapour pressure of the liquid. The vapour Positive deviation Negative deviation from
pressure of a liquid depends on: po pB from Raoult's law Raoult's law
A P  pA p B
 Nature of Liquid: Liquids, which have weak Total vapour o
PA  p Ao A poA poB p A poB
Vapour pressure

Total vapour
Vapour pressure
Vapour pressure

intermolecular forces, are volatile and have greater vapour PB  p oB X B

pressure. For example, dimethyl ether has greater vapour
Ideal
pressure than ethyl alcohol. Mole fraction
A  1 A  0 Ideal
 Temperature: Vapour pressure increases with increase in Mole fraction
Mole fraction
B  0 B  1 A  1 B  1 A  1 A  0
temperature. This is due to the reason that with increase in
B  0 A  0 B  0 B  1
temperature more molecules of the liquid can go into
vapour phase. Obey Raoult's law at Do not obey Raoult's Do not obey Raoult's
every range of law. law.
 Purity of Liquid: Pure liquid always has a vapour pressure
concentration.
greater than its solution.
 Solutions 31
H mix  0; neither H mix  0. Endotherm H mix  0. Exothermic n = number of moles of solute
heat is evolved nor ic dissolution; heat is dissolution; heat is V = volume of solution
absorbed during absorbed. evolved. m = molecular weight of solute
dissolution.
w = weight of solute
Vmix  0; total Vmix  0. Volume is Vmix  0. Volume is
volume of solution is increased after decreased during Relation of Osmotic Pressure with Different Colligative
equal to sum of dissolution. dissolution. Properties: Osmotic pressure is related to relative lowering of
volumes of the vapour pressure, elevation of boiling point and depression of
components.
freezing point according to the following relations,
P = pA + pB p A  p oA X A p A  p oAX A; p B  p oB XB
P  p A  pB  poA XA  pBo XB  Po  P  dRT
p B  p oB XB  pA  p B  (a)    A o A 

i.e., pA  p XA :pB pA X A  p AX B
 PA  M
A
 p A  p B  pA
 p B X B dRT
XA  pBX B (b)   Tb 
1000  K b
A–A, A–B, B–B A–B attractive force A–B attractive force
interactions should be should be weaker than should be greater than dRT
(c)   Tf 
same, i.e., 'A' and 'B' are A–A and B–B A–A and B–B attractive 1000  K f
identical in shape, size attractive forces. 'A' forces. 'A' and 'B' have
and character. and 'B' have different different shape, size and In the above relations,
shape, size and character.
character.
 = Osmotic pressure
Escaping tendency of 'A' and 'B' escape Escaping tendency of d = Density of solution at temperature T
'A' and 'B' should be easily showing higher both components 'A' and R = Universal gas constant
same in pure liquids vapour pressure than 'B' is lowered showing M = Mol. Mass of solute
and in the solution. the expected value. lower vapour pressure
than expected ideally.
K b = Molal elevation constant of solvent
Examples: Dilute Examples: Acetone + Examples: Acetone + K f = Molal depression constant of solvent
solutions; benzene + ethanol acetone + CS2: aniline; acetone +
toluene: n-hexane + n- water + methanol; chloroform; CH3OH + Isotonic, Hypertonic and Hypotonic Solutions
heptane; water + ethanol; CCl4+ CH3COOH; H2O +  Isotonic or iso-osmotic solutions: Two solutions of
chlorobenzene + toluene; CCl4+CHCl3 ; HNO3 chloroform + different substances having same osmotic pressure at same
bromobenzene; ethyl acetone + benzene; diethyl ether; water +
temperature are known as isotonic solutions.
bromide+ ethyl iodide; CCl4+CH3OH; HCl; acetic acid +
n-butyl chloride + n- cyclohexane + ethanol pyridine; chloroform + For isotonic solutions,  1   2 Primary Condition . . .(i)
butyl bromide benzene Also, C1  C 2

Osmotic Pressure (): The osmotic pressure is a colligative n1 n 2

or 
property. For a given solvent the osmotic pressure depends V1 V2
Secondary Conditions
only upon the molar concentration of solute but does not w1 w2
or  . . .( ii)
depend upon its nature. The following relation relates osmotic m1V1 m 2V 2
pressure to the number of moles of the solute, According to
E quation (ii) holds good only for those solutes which neither
Boyle Van't Hoff law (at conc. temp.)   C . . .(i)
possess the tendency to get associate nor dissociate in
According to Gay lussac Van't Hoff law (at conc. temp.)
solution, e.g.,
 T . . .(ii)
Urea and glucose are isotonic then,  1   2 and C1  C 2
From equation (i) and (ii) we get   CT,
  CRT (Van't Hoff equation) Urea a nd NaCl are isotonic then,  1   2 but C1  C 2
(dissociate)

n  n U rea and Benzoicacid are isotonic then, 1  2 but C1  C2

  RT  C   ; (associate)
V  V
 Hypertonic and Hypotonic Solution: The solution which
w RT  w
  n   has more osmotic pressure than the other solution is called
m V  m
as hypertonic solution and the solution which has lesser
Here, C  concentration of solution in moles per litre osmotic pressure than the other is called as hypotonic
R= gas constant solution. The flow of solvent is always from lower osmotic
T = temperature
32 JEE-Main and Advanced Chapter-wise Solved Papers: Chemistry
pressure to higher osmotic pressure i.e. from hypotonic to Freezing point is the temperature at which the liquid and the
hypertonic solution. solid states of a substance are in equilibrium with each other or
it may be defined as the temperature at which the liquid and the
Ebullioscopy: Elevation in boiling point is determined by solid states of a substance have the same vapour pressure. It is
Landsberger’s method and Cottrell’s method. Study of observed that the freezing point of a solution is always less
elevation in boiling point of a liquid in which a non-volatile than the freezing point of the pure solvent. Thus, the freezing
solute is dissolved is called as ebullioscopy. point of sea water is low than that of pure water. The
Boiling point of a liquid may be defined as the temperature at depression in freezing point (T or Tf ) of a solvent is the
which its vapour pressure becomes equal to atmospheric difference in the freezing point of the pure solvent (Ts ) and the
pressure, i.e., 760 mm. Since the addition of a non-volatile solution (Tsol.). Ts  Tsol  T f or T
solute lowers the vapour pressure of the solvent, solution
NaCl or CaCl 2 (anhydrous) are used to clear snow on roads.
always has lower vapour pressure than the solvent and hence it
must be heated to a higher temperature to make its vapour They depress the freezing point of water and thus reduce the
pressure equal to atmospheric pressure with the result the temperature of the formation of ice.
solution boils at a higher temperature than the pure solvent.
Thus sea water boils at a higher temperature than distilled Important Relations Concerning Depression in Freezing Point
 Depression in freezing point is directly proportional to the
water. If Tb is the boiling point of the solvent and T is the
lowering of vapour pressure. Tf  p0  p
boiling point of the solution, the difference in the boiling point
T or Tb ) is called the elevation of boiling point.  Tf  K f  m

T  Tb  T b or T Where K f  molal depression constant or cryoscopic

constant; m  Molality of the solution (i.e., no. of moles of
Important Relations Concerning Elevation in Boiling Point solute per 1000g of the solvent); Tf  Depression in
 The elevation of boiling point is directly proportional to the
freezing point.
lowering of vapour pressure, i.e., Tb  p0  p 1000  K f w 1000  K f  w
 Tf  or m 
 Tb  K b  m m W Tf  W
Where, Kb= m olal elevation constant or ebullioscopic Where K f is molal depression constant and defined as the
constant of the solvent; m = Molality of the solution, i.e., depression in freezing point produced when 1 mole of the
number of moles of solute per 1000 g of the solvent; solute is dissolved in 1 kg of the solvent. W and w are the
Tb  Elevation in boiling point.
weights of solute and solvent and m is the molecular weight
1000  K b  w 1000  K b  w of the solute.
 Tb  or m
m W Tb  W R(T0) 2 0.002(T 0) 2
 Kf  
W here, Kb is molal elevation constant and defined as the lf 1000 lf
elevation in b.pt. produced when 1 mole of the solute is Where, T0  Normal freezing point of the solvent;
dissolved in 1 kg of the solvent. W and w are the weights of
lf  Latent heat of fusion/g of solvent; K f for water is
solute and solvent and m is the molecular weight of the solute.
0.002(T0 ) 2 1.86deg kg mol 1
 Kb 
lV
Colligative Properties of Electrolytes: The colligative
Where T0= Normal boiling point of the pure solvent; 1 v=
properties of solutions, viz. lowering of vapour pressure,
Latent heat of evaporation in cal/g of pure solvent; K b for osmotic pressure, elevation in b.p. and depression in freezing
water is 0.52deg  kg mol 1. point, depend on the total number of solute particles present in
solution. Since the electrolytes ionise and give more than one
Cryoscopy: Depression in freezing point is determined by particle per formula unit in solution, the colligative effect of an
Beckmann’s method and Rast’s camphor method. Study of electrolyte solution is always greater than that of a non-
depression in freezing point of a liquid in which a non-volatile electrolyte of the same molar concentration. All colligative
solute is dissolved in it is called as cryoscopy. properties are used for calculating molecular masses of non-
Solutions 33
volatile solutes. However osmotic pressure is the best MULTIPLE CHOICE QUESTIONS
colligative property for determining molecular mass of a non- One and More than One Correct
volatile substance.
1. Th e Henry’s law constant for the solubility of N 2 gas in
water at 298 K is 1.0×10–5 atm. Mole fraction of N2 in air is
Van’t Hoff’s Factor (i): In 1886, Van’t Hoff introduced a
0.8. The number of moles of N 2 from air dissolved in 10
factor ‘ i’ called Van’t Hoff’s factor, to express the extent of
moles at 298 K and 5 atm pressure is: [JEE 2009 P-I]
association or dissociation of solutes in solution. It is ratio of
a. 4.0 × 10–4 b. 4.0 × 10–5
the normal and observed molecular masses of the solute, i.e.,
c. 5.0 × 10–4 d. 4.0 × 10–6
Normal molecular mass
i 2. For a dilute solution containing 2.5 g of a non-volatile
Observed molecular mass
non-electrolyte solute in 100 g of water, the elevation in
In case of association, observed molecular mass being more boiling point at 1 atm pressure is 2C.Assuming
than the normal, the factor i has a value less than 1. But in case concentration of solute is much lower than the
of dissociation, the Van’t Hoff’s factor is more than 1 because concentration of solvent, the vapour pressure (mm of Hg)
the observed molecular mass has a lesser value than the normal of the solution is: (take K b  0.76K kgmol )1
molecular mass. In case there is no dissociation the value of ‘ i’
[JEE 2012 P-II]
becomes equal to one.
a. 724 b. 740 c. 736 d. 718
Since, colligative properties are inversely proportional to
molecular masses, the Van’t Hoff’s factor may also be written 3. T he vapour pressure of acetone at 20ºC is 185 torr. When 1.2
as, g of a non-volatile substance was dissolved in 100 g of
Observed value of colligative property acetone at 20ºC, its vapour pressure was 183 torr. The molar
i= mass (g mol–1) of the substance is: [JEE Main 2015]
Calculated value of colligative property assuming no
association or dissociation a. 32 b. 64 c. 128 d. 488
No.of particles after association or dissocia tion 4. 18 g glucose (C6H I2P6) is added to 178.2 g water. The
i
No.of particles before association or dissoci ation
vapor pressure of water (in torr) for this aqueous solution
Introduction of the Van’t Hoff factor modifies the equations for is : [JEE Main 2016]
the colligative properties as follows, a. 7.6 b. 76.0 c. 752.4 d. 759.0
PAo  PA
Relative lowering of vapour pressure   iX B 5. Mix ture(s) showing positive deviation from Raoult’s law
PAo
at 35ºC is(are): [JEE Adv. 2016 P-II]
Elevation of boiling point, Tb  ik bm a. carbon, tetrahedral + methanol
Depression in freezing point, Tb  ik fm b. carbon disulphide + acetone
inRT c. benzene + toluene
Osmotic pressure,   ;  iCRT d. phenol + aniline
V
From the value of ‘i’, it is possible to calculate degree of
6. A set of solutions is prepared using 180 g of water as a
dissociation or degree of association of substance.
solvent and 10 g of different non-volatile solutes A, B and
C. The relative lowering of vapour pressure in the
Degree of Dissociation () presence of these solutes are in the order [Given, molar
It is defined as the fraction of total molecules which dissociate mass of A  100 g mol –1; B  200 g mol –1; C  10,000 g
into simpler molecules or ions. mol–1] [JEE Main 2017]
i 1 a. A > B > C b. B > C > A c. C > B > A d. A > C > B
 l m  number of particles in solution
m 1
7. The freezing point of benzene decreases by 0.45°C when
Degree of Association (): It is defined as the fraction of the
0.2 g of acetic acid is added to 20 g of benzene. If acetic
total number of molecules which associate or combine together
acid associates to form a dimer in benzene, percentage
resulting in the formation of bigger molecules.
association of acetic acid in benzene will be: (for benzene
i 1
 ; m  number of particles in solution. 5.12 K kg) [JEE Main 2017]
1/m 1
a. 94.6% b. 64.6% c. 80.4% d. 74.6%
34 JEE-Main and Advanced Chapter-wise Solved Papers: Chemistry
8. For a solution formed by mixing liquids L and M. the 12. An aqueous solution contains 0.10 M H 2Sand 0.20 M
vapour pressure of L plotted against the mole fraction of HCl. If the equilibrium constant for the formation of HS
M in solution is shown in the following figure. Here x L is 1.0  107 and that of S2 from HS ions is 1.2  1013
and xM represent mole fractions of L and M, then the concentration of S2 ions in aqueous solution is:
respectively, in the solution. The correct statement(s) [JEE Main 2018]
applicable to this system is(are): [JEE Main 2017 ] a. 5  10 19 b. 5  10 8
c. 3  10 20 d. 6  10 21
Z

PL 13. The vapour pressures of pure liquids A and B are 400 and
600 mmHg, respectively at 298 K. On mixing the two
liquids, the sum of their initial volumes is equal to the
volume of the final mixture. The mole fraction of liquid B
1 XM
is 0.5 in the mixture. The vapour pressure of the final
a. Attractive intermolecular interactions between L – L. in
solution, the mole fraction of components A and B in
pure liquid L and M – M in pure liquid M are stronger
vapour phase, respectively are: [JEE Main 2019]
than those between L – M when mixed in solution
a. 500 mmHg, 0.5, 0.5 b. 450 mmHg, 0.4, 0.6
b. The point Z represents vapour pressure of pure liquid
c. 450 mmHg, 0.5, 0.5 d. 500 mmHg, 0.4, 0.6
M and Raoult's law is obeyed when x L  0
14. If solubility product of Zr 3(PO4)4 is denoted by K sp and its
c. The point Z represents vapour pressure of pure liquid M
molar solubility is denoted by S, then which of the
and Raoult’s law is obeyed from x L  0 to x L  1 following relation between S and Ksp is correct.
d. The point Z represents vapour pressure of pure liquid L [JEE Main 2019]
and Raoult’s law is obeyed when x L  1 1/9 1/7
K  K 
a. S=  sp  b. S=  sp 
9. For 1 molal aqueous solution of the following  929   216 
1/6 1/7
compounds, which one will show the highest freezing K   K 
point? [JEE Main 2018] c. S=  sp  d. S=  sp 
 144   6912 
a. [Co(H 2O) 3Cl ].3H
3 O
2
15. For the solution of the gases w, x, y and z in water at
b. [Co(H 2O) 6]Cl 3 298K, the Henry’s law constants (KH) are 0.5, 2, 35 and
c. [Co(H 2O) 5Cl]Cl 2.H 2O 40 kbar, respectively. The correct plot for the given data
d. [Co(H 2O) 4Cl ]Cl.2H
2 O
2
is: [JEE Main 2019]
z
y z
10. An aqueous solution contains an unknown concentration
of Ba 2+. When 50 mL of a 1 M solution of Na 2SO4 is Partical x Partical y
w
added, BaSO 4 just begins to precipitate. The final volume a. pressure b. pressure x
is 500 mL. The solubility product of BaSO 4 is 1  10 –10. w
What is original concentration of Ba2+? [JEE Main 2018] (0,0) Mole fraction
(0,0) Mole fraction
a. 1  10–10 M of water of water

b. 5  10–9 M
c. 2  10–9 M Partical z
z Partical y
d.1.1  10–9 M c. pressure d.
y pressure x
11. When metal ‘M’ is treated with NaOH, a white gelatinous x w w
precipitate ‘X’ is obtained, which is soluble in excess of Mole fraction (0,0)Mole fraction
NaOH. Compound ‘X’ when heated strongly gives an of water of water
oxide which is used in chromatography as an adsorbent. 16. Which one of the following statements regarding Henry’s
The metal ‘M’ is: [JEE Main 2018] law not correct? [JEE Main 2019]
a. Fe b. Zn a. The value of K H increases with function of the nature
c. Ca d. Al of the gas.
Solutions 35
b. Higher the value of K H at a given pressure, higher is 24. A t 35°C, the vapour pressure of CS2 is 512 mm. Hg and
the solubility of the gas in the liquids.
that of acetone is 344 mm Hg. A solution of CS2 in
c. The partial of the gas in vapour phase is proportional to
acetone has a total vapour pressure of 600 mm Hg. The
the mole fraction of the gas in the solution.
d. Different gases have different KH (Henry’s law false statement amongst the following is:
constant) values at the same temperature. [JEE Main P-I 2020]
a. Heat must be absorved in order to produce the solution
17. A solution of sodium sulfate contains 92 g of Na + ions per
35°C.
kilogram of water, the molality of Na + ions in that
b. Raoult’s law is not obeyed by this system.
solution in mol kg–1 is: [JEE Main 2019]
c. CS2 and acetone are less attracted to each other than to
a. 16 b. 8
themselves.
c. 4 d. 12
d. A mixture of 100 ml. CS 2 an d 100 ml. acetone has a
18. Liquids A and B form an ideal solution in the entire volume < 200 ml.
composition range. At 350 K, the vapor pressures of pure
A and pure B are 7× 10 3 Pa and 12 × 10 3 Pa, respectively. 25. An open beaker of water in quilibrium with water vapour
The composition of the vapor in equilibrium with a is in a sealed container. When a few grams of glucose are
solution containing 40 mole percent of A at this added to the beaker of water, the rate at which water
temperature is: [JEE Main 2019] molecules: [JEE Main P-II 2020]
a. xA = 0.37; xB = 0.63 b. xA = 0.28; xB = 0.72 a. leaves the vapour decreases
c. xA = 0.76; xB = 0.24 d. xA = 0.4; xB = 0.6 b. leaves the solution decreases
c. leaves the vapour increases
19. The amount of sugar (C 12H22O11) required to prepare 2L d. leaves the solution increases
of its 0.1 M aqueous solution is: [JEE Main 2019]
a. 68.4 g b. 17.1 g 26. T he size of a raw mango shrinks to a much smaller size
c. 34.2 g d. 136.8 g when kept in a concentrated salt solution. Which one of
the following process can explain this?
20. Elevation in the boiling point for 1 molal solution of [JEE Main P-II 2020]
glucose is 2 K. The depression in the freezing point of 2 a. Dialysis b. Reverse osmosis
molal solutions of glucose in the same solvent is 2 K. The c. Osmosis d. Diffusion
relation between Kb and Kf is: [JEE Main 2019]
a. Kb = 0.5 Kf b. Kb = 2 Kf 27. Henry's constant (in kbar) for four gases , ,  and  in
c. Kb = 1.5 Kf d. Kb = Kf water at 298 K is given below :
   
21. The concentration of dissolved oxygen (DO) in cold water –5
KH 50 2 2  10 0.5
can go upto: [JEE Main 2019]
3 –3
a. 10 ppm b. 14 ppm (d ensity of water = 10 kg m at 298 K) This table
c. 16 ppm d. 8 ppm implies that: [JEE Main P-II 2020]
a. Solubility of  at 308 K is lower than at 298 K
22. 8g of NaOH is dissolved in 18g of H 2O. Mole fraction of b. The pressure of a 55.5 molal solution of  is 1 bar
NaOH in solution and molality (in mol kg –1) of the c. The pressure of a 55.5 molal solution of  is 250 bar
solutions respectively are: [JEE Main 2019]
d.  has the highest solubility in water at a given pressure
a. 0.167, 11.11 b. 0.2, 22.20
c. 0.2, 11.11 d. 0.167, 22.20 28. T he presence of Soluble Fluoride ion upto 1 ppm
concentration in drinking water, is: [JEE Main P-II 2020]
23. If Ksp of Ag 2CO3 is 8×10 –12, the molar solubility of
a. harmful to bones
Ag2CO3 in 0.1M AgNO3 is : [JEE Main 2019]
–12 –10 b. harmful to skin
a. 8×10 M b. 8×10 M
–11 c. safe for teeth
c. 8×10 M d. 8×10–13 M
d. harmful for teeth
36 JEE-Main and Advanced Chapter-wise Solved Papers: Chemistry
29. Th e reaction of NO with N 2O 4 N2O4 at 250 K gives: Density of this solution at 298 K is 2.0 g
[JEE Main P-II 2020] cm–3. The ratio of the molecular weights of the solute and
a. N 2O 5 b. N 2O 3  MWsolute 
solvent,   , is: [JEE Adv. 2016 P-I]
c. NO2 d. N 2O  MWsolvent 
35. Liquids A and B form ideal solution over the entire range
30. A solution of two components containing n 1 moles of the of composition. At temperature T, equimolar binary
1st component and n 2 moles of the 2 nd component is solution of liquids A and B has vapour pressure 45 Torr. At
prepared. M 1 an d M 2 are the molecular weights of the same temperature, a new solution of A and B having
component 1 and 2 respectively. If d is the density of the mole fractions xA and xB, respectively, has vapour pressure
solution in g ml –1, C 2 i s the molarity and x 2 i s the mole of 22.5 Torr. The value of xA/xB in the new solution is ___.
fraction of the 2 nd co mponent, then C 2 can be expressed (given that the vapour pressure of pure liquid A is 20 Torr
as: [JEE Main P-II 2020] at temperature T) [JEE Adv. 2018 P-I]
dx1 1000x 2
a. C2  b. C2  36. The plot given below shows P – T curves (where P is the
M 2  x 2 (M2  M1 ) M1  x2 (M2  M 1)
pressure and T is the temperature) for two solvents X and
1000dx 2 dx 2 Y and isomolal solutions of NaCl in these solvents. NaCl
c. C2  d. C2 
M1  x2 (M2  M 1) M 2  x 2 (M 2  M1) completely dissociates in both the solvents.
[JEE Adv. 2018 P-I]
31. Select the co rrect statements. [JEE Main P-II 2021]
1 2
3

Pressure (mmHg)
(A) Crystalline solids have long range order. 4
760
(B) Crystalline solids are isotropic.
1. solvent X
(C) Amorphous solid are sometimes called pseudo solids. 2. solution of NaCl in solvent X
(D) Amorphous solids soften over a range of 3. solvent Y
4. solution of NaCl in solvent Y
temperatures.

360
362

367
368
(E) Amorphous solids have a definite heat of fusion.
Temperature (K)
Choose the most appropriate answer from the options
given below. On addition of equal number of moles of a non-volatile
a. (A), (B), (E) only b. (B), (D) only solute S in equal amount (in kg) of these solvents, the
c. (C), (D) only d. (A), (C), (D) only elevation of boiling point of solvent X is three times that of
solvent Y. Solute S is known to undergo dimerization in
32. Tw o solutions A and B are prepared by dissolving 1 g of these solvents. If the degree of dimerization is 0.7 in
non-volatile solutes X and Y respectively in 1 kg of solvent Y, the degree of dimerization in solvent X is _____.
water. The ratio of depression in freezing points for A and
37. Mole f raction of urea in 900 gram water is 0.05. Density
B is found to be 1 : 4. The ratio of molar masses of X and
of solution is 1.2 g/cm3. Find molarity of solution.
Y is : [JEE Main P-II 2022]
[JEE Adv. 2019 P-II]
a. 1 : 4 b. 1 : 0.25
38. If 250 cm 3 of an aqueous solution containing 0.73 g of a
protein A is isotonic with one litre of another aqueous
c. 1 : 0.20 d. 1 : 5
solution containing 1.65 g of a protein B, at 298 K, the
ratio of the molecular masses of A and B is_______
Integer and Subjective × 10–2 (to the nearest integer) [JEE Main P-II 2020]

33. A compound H 2 X with molar weight of 80 g dissolved 39. At 300 K, the vapour pressure of a solution containing 1
mole of n-hexane and 3 moles of n-heptane is 550 mm of
in a solvent having density of 0.4g ml 1. Assu ming no
Hg. At the same temperature, if one more mole of n-
change in volume upon dissolution, the molality of a 3.2
heptane is added to this solution, the vapour pressure of
molar solution is: [JEE Adv. 2014 P-I]
the solution increases by 10 mm of Hg. What is the
34. Th e mole fraction of a solute in a solution is 0.1. At 298 vapour pressure in mmHg of nheptane in its pure state?
K, molarity of this solution is the same as its molality. [JEE Main P-II 2020]
Solutions 37
40. A 100 mL solution was made by adding 1.43g of Den sity of H 2 O 1.0gcm 3
[JEE Main P-II 2021]
Na2CO3.xH2O. The normality of the solution is 0.1 N.
Assume no change in volume of solution on mixing.
The value of x is. (The atomic mass of Na is 23 g/mol)
[JEE Main P-II 2020]
48. In a solvent 50% of an acid HA dimerizes and the rest
41. T he osmotic pressure of a solution of NaCl is 0.10 atm dissociates. The van't Hoff factor of the acid is _____ ×
and that of a glucose solution is 0.20 atm. The osmotic 10–2.
pressure of a solution formed by mixing 1L of the sodium (Roun d off to the nearest integer) [JEE Main P-II 2021]
chloride solution with 2L of the glucose solution is
x × 10–3 atm. X is ………….. (nearest integer) Question Stem for Question No. 49 and 50
[JEE Main P-II 2020] The boiling point of water in a 0.1 molal silver nitrate solution
(solution A) is x ºC. To this solution A, an equal volume of 0.1
42. T he elevation of boiling point of 0.10 m aqueous
molal aqueous barium chloride solution is added to make a new
CrCl3.xNH 3 solution is two times that of 0.05 m aqueous
solution B. [JEE Adv. 2021 P-I]
CaCl2 solution. The value of x is …………..
The difference in the boiling points of water in the two
[Assume 100% ionisation of the complex and CaCl 2,
solutions A and B is y × 10–2 ºC.
coordination number of Cr as 6, and that all NH 3
(Assume: Densities of the solutions A and B are the same as
molecules are present inside the coordination sphere]
that of water and the soluble salts dissociate completely.)
[JEE Main P-II 2020]
Use: Molal elevation constant (Ebullioscopic Constant), K b =
43. If the solubility product of AB 2 is 3.20 10 11M 3, then –1
0.5 K kg mol ; Boiling point of pure water as 100ºC.)
the solubility of AB2 in pure water is_____× 10 –4 mol L–1
49. T he value of x is _______.
[A ssuming that neither kind of ion reacts with water]
[JEE Main P-II 2020] 50. T he value of | y | is _____ .

44. L iquids A and B form ideal solution for all compositions 51. A company dissolves 'X' amount of CO 2 at 298 K in 1
of A and B at 25°C. Two such solutions with 0.25 and
litre of water to prepare soda water X =____ 103 g.
0.50 mole fractions of A have the total vapor pressures of
03 and 0.4 bar, respectively. What is the vapor pressure of (nearest integer) [JEE Main P-I 2022]
pure liquid B in bar? [JEE Adv. 2020 P-II] (Given: partial pressure of CO 2 at 298 K= 0.835 bar.
Henry's law constant for CO 2 at 298 K = 1.67 kbar.
45. 4.5 gm of solute having molar mass of 90 gm/mol is
Atomic mass of H, C and O is 1, 12 and 6 g mol1 ,
dissolved in water to make 250 ml solution. Calculate
respectively)
molarity of the solution [JEE Main P-I 2021]

–3
52. T he solubility product of PbI 2 is 8.0 10 .9 The solubility
46. The density of NaOH solution is 1.2 g cm . The molality
of lead iodide in 0.1 molar solution of lead nitrate is
of this solution is ________ m. [JEE Main P-II 2021]
(Round off to the Nearest Integer) x 10 6 mol/L. The value of x is ________ (Rounded off
[Use : Atomic masses : Na : 23.0 u O : 16.0 u H : 1.0 u to the nearest integer) [JEE Main P-I 2021]
Density of H 2O : 1.0 g cm–3] Given 2  1.41
3
47. When 400 mL of 0.2M H 2SO 4 solution is mixed with 53. 1.80 g of solute A was dissolved in 62.5 cm of ethanol
and freezing point of the solution was found to be 155.1
600 mL of 0.1 M NaOH solution, the increase in
K. The molar mass of solute A is _______g mol–1.
temperature of the final solution is _____ × 10 –2 K.
[Given: Freezing point of ethanol is 156.0 K. Density of
(Round off to the nearest integer).
ethanol is 0.80 g cm –3. Freezing point depression constant
[Use : H  (aq) OH (aq)  H 2O:  y H  57.1kJmol 1 ]
of ethanol is 2.00 K kg mol–1] [JEE Main P-II 2022]
Specif ic heat of H 2 O  4.18JK g1 1
38 JEE-Main and Advanced Chapter-wise Solved Papers: Chemistry
54. If O2 gas is bubbled through water at 303 K, the number
of millimoles of O 2 gas that dissolve in 1 litre of water
is_______. (Nearest Integer) (Given: Henry's Law
constant for O 2 at 303 K is 46.82 k bar and partial
pressure of O 2 = 0.920 bar) (Assume solubility of O 2 in
water is too small, nearly negligible)
[JEE Main P-II 2022]

55. If the solubility product of PbS is 8 × 10–28, then the

–l6
solubility of PbS in pure water at 298 K is x × 10 mol
–1
L . The value of x is ________. (Nearest Integer)
[Given 2  1.41] [JEE Main P-II 2022]

56. 1. 46 g of a biopolymer dissolved in a 100 mL water at

300 K exerted an osmotic pressure of 2.42 × 10 –3 bar.
The molar mass of the biopolymer is _____ × 10 4 g mol–1.
(Round off to the Nearest Integer)
[Use : R = 0.083 L bar mol –1 K–1] [JEE Main P-II 2021]

57. The treatment of an aqueous solution of 3.74 g of

Cu(NO3)2 with excess KI results in a brown solution
along with the formation of a precipitate. Passing H2S
through this brown solution gives another precipitate X.
The amount of X (in g) is ______. [JEE Adv. P-I 2022]
[Given: Atomic mass of H = 1, N = 14, O = 16, S = 32, K
= 39, Cu = 63, I = 127]

58. 0.01 mole of each H 2 CO3,NaHCO ,Na

3 CO
2 3 and NaOH
are mixed in 100 ml of water, then final pH of resulting
solution is: (Given pKa1 and pKa2 of H2CO3 is 6.8, 10.32)
[JEE Adv. P-I 2022]

59. C oncentration of H 2SO4 and Na 2SO4 in a solution is 1M

and 1.8×10 –2 M, respectively. Molar solubility of PbSO 4
–Y
in the same solution is X×10 M (expressed in scientific
notation). The value of Y is ______. [JEE Adv. P-II 2022]
–8
[Given: Solubility product of PbSO 4 (Ksp) = 1.6 × 10 .
–2
For H2SO4, Ka1 is very large and Ka2 =1.2 × 10 ]

60. 0.1 mole of anionic solid dissolve in 1.8 kg water ionic

solid is 90% dissociated in water. Vapour pressure of
solution is 59.724 mm of Hg and vapour pressure of pur
water is 60 mm of Hg. Then calculate number of ions in
ionic solid. [JEE Adv. P-II 2022]