Chapter–2

Causes of solubility: The following types of forces of attraction are operated when a solute is mixed
with a solvent:

Solutions
(i) Inter-ionic attraction in the solute molecules: Ions are held together in the lattice due to
electrostatic forces. Due to these forces molecules are stabilised and the energy released is called
lattice energy. This is defined as the energy released when 1 g mole of the compound is formed
due to electrostatic attraction between the ions.
(ii) Inter-molecular attraction between solvent molecules: Water is a polar solvent because of the
difference in electronegativity between hydrogen and oxygen atoms constituting water molecule.
This difference gives rise to the development of a slight negative charge on oxygen and equal
positive charge on hydrogen. A dipole is thus created giving rise to dipole–dipole attraction
between water molecules.
(iii) Solvation: It represents force of attraction between solute and solvent molecules. If the solvent is
water then the energy released is called hydration energy.
If hydration energy > lattice energy, then solution is easily formed. Both the ions of the solute get
hydrated to overcome the lattice energy of the solute.
1. Solution: A solution is a homogeneous mixture of two or more pure substances, the relative ratio of which
can be changed within certain limits. (iv) Temperature: Saturated solution represents equilibrium between undissolved solute and dissolved
solute.
When the constituents of the solution are two it is called binary, if three then ternary, if four then quaternary
and so on. Undissolved solute + Solvent Solution Dsol H = ! x
The two constituents of the solution are solvent and solute. If Dsol H < 0, i.e., (–ve), the dissolution is exothermic. In this case, as the temperature increases,
Solvent (A): It is the component of the solution: solubility decreases (Le Chatelier’s principle).
(i) which is present in a relatively large proportion in the solution, and If Dsol H > 0, i.e., (+ve), there is endothermic dissolution. In this case, increase in temperature
increases the solubility (Le Chatelier’s principle).
(ii) whose physical state is same as that of the resulting solution.
(b) Liquid–liquid solutions: When two liquids are mixed, three different situations result:
Solute (B): It is the component of a solution which is present in relatively small proportion.
(i) Miscible liquids: The two components are completely soluble. They are miscible only when they
2. Types of Solutions have similar nature or belong to the same homologous series. Example: water and alcohol (both
Table 2.1 polar), benzene–toluene (both belong to the same homologous series). There is a rule:
Type of Solution Solute Solvent Examples Like dissolves like – Polar solute is soluble in polar solvent and a non-polar one in a non-polar
solvent.
Gas Gas Mixture of oxygen and nitrogen gases
(ii) Partially miscible liquids: This happens only when the intermolecular forces of one liquid
Gaseous Solutions Liquid Gas Chloroform mixed with nitrogen gas is greater than that of the other is. Solubility, however, increases with increasing temperature.
Solid Gas Camphor in nitrogen gas Examples: aniline-water, phenol-water.
Gas Liquid Oxygen dissolved in water (iii) Immiscible liquids: Two components are completely immiscible. This happens when one liquid
is polar and the other is non-polar. Examples: Carbon tetrachloride-water; chloroform-water.
Liquid Solutions Liquid Liquid Ethanol dissolved in water
(c) Gas–liquid solutions: The gases are generally soluble in water and to a limited extent in other solvents
Solid Liquid Glucose dissolved in water too. Solubility, however, depends on the following factors:
Gas Solid Solution of hydrogen in palladium (i) Nature of gas: Easily liquefiable gases are generally more soluble in common solvents.
Solid Solutions Liquid Solid Amalgam of mercury with sodium (ii) Nature of liquid: Those gases which easily form ions in solution are more soluble in water than
Solid Solid Copper dissolved in gold
in other solvents. Ion formation in other solvents is not an easy process.
HCl(g) + H2O(l) H3O+(aq) + Cl–(aq)
Amongst the nine types of solutions, the widely studied ones are: (iii) Pressure: Pressure is an important factor affecting the solubility of gas in liquids. This is governed
(a) Solid–liquid (b) Liquid–liquid and (c) Gas–liquid solutions. by Henry’s law.
(a) Solid–liquid solutions: A small amount of solute (usually ionic solids) is dissolved in a large quantity (iv) Temperature: With rise in temperature, the solubility generally decreases because gas is expelled.
of solvent. If the amount of solvent is large as compared to the solute, the solution is referred to as a Some gases, however, find their solubility increased at a higher temperature.
dilute solution. °° Henry’s law: It states that at a constant temperature, the solubility of a gas in a liquid is directly
Saturated solution: A solution is said to be saturated if it holds the maximum amount of solute at a proportional to the pressure of the gas.
given temperature in a given quantity of the solvent. The most commonly used form of Henry’s law states that the partial pressure (p) of a gas in vapour
Solubility: It may be defined as the maximum amount of solute that can be dissolved in 100 g of phase is proportional to the mole fraction of the gas (x) in the solution and is expressed as
solvent at a specified temperature. The solubility of solid into liquid depends upon the following p = KH x
factors: Here KH is the Henry’s law constant and x is the mole fraction of the gas.
(i) Nature of solute (ii) Nature of solvent (iii) Temperature Note: Mole fraction is discussed in detail further in this chapter.

Solutions 49 50 Xam idea Chemistry–XII

 Limitations of Henry’s Law: (g) Molality (m): It is defined as the number of moles of the solute dissolved in one kilogram (kg) of the
Henry’s law is applicable only when solvent and is expressed as:
OO The pressure of the gas is not too high and temperature is not too low. Moles of solute Number of moles of solute
Molality = = # 1000
OO The gas should not undergo any chemical change. Mass of solvent (in kg) Mass of solvent (in grams)
–1
OO The gas should not undergo association or dissociation in the solution. Unit of molality is mol kg or molal (m).
Applications of Henry’s Law: Molality is independent of temperature.
OO To increase the solubility of CO2 in soda water and soft drinks, the bottle is sealed under high pressure. 4. Vapour Pressure of Pure Liquid and Solution
OO To avoid the toxic effects of high concentration of nitrogen in the blood, the tanks used by scuba divers Vapour pressure: When a liquid is taken in a closed vessel, a part of the liquid evaporates and its vapours
are filled with air diluted with helium (11.7% helium, 56.2% nitrogen and 32.1% oxygen). occupy the available empty space. These vapours cannot escape as the vessel is closed. They would rather
OO At high altitudes, low blood oxygen causes climbers to become weak and make them unable to think have a tendency to condense into liquid form. In fact an equilibrium is established between vapour phase
clearly, which are symptoms of a condition known as anoxia. and liquid phase and the pressure that its vapour exert is termed as vapour pressure. Thus, vapour pressure
of a liquid may be defined as the pressure exerted by the vapours above the liquid surface in equilibrium
3. Methods of Expressing Concentration of Solutions: with the liquid phase at a given temperature.
The concentration of solution is the amount of the solute present in the given quantity of solution or solvent.
The vapour pressure of a liquid depends on the following factors:
It can be expressed in any of the following ways:
Nature of the liquid: Liquids having weak intermolecular forces are volatile and therefore have greater
(a) Mass percentage (w/w): It may be defined as mass of solute per 100 g of solution.
vapour pressure.
Mass of solute
Mass% of solute = × 100 Temperature: Vapour pressure of a liquid increases with increase in temperature. This is because with
Total mass of the solution increase in temperature, the kinetic energy of the molecules increases and therefore large number of
(b) Volume percentage (V/V): It may be defined as volume of solute per 100 mL of solution. molecules are available for escaping from the surface of the liquid.
Volume of solute (a) Vapour pressure of liquid–liquid solution:
Volume % of solute = × 100 Raoult’s Law for solutions of volatile liquids: It states that for a solution of volatile liquids the
Total volume of solution
partial pressure of each component of the solution is directly proportional to its mole fraction present
(c) Mass by volume percentage (w/V): It may be defined as the mass of solute per 100 mL of the in a solution. Mathematically,
solution. pA ∝ xA pB ∝ xB
Mass of solute pA = poA xA pB = poB xB
Mass by volume % = × 100
Volume of solution where pA and pB are partial vapour pressures, xA and xB are mole fractions, poA and poB are the vapour
(d) Parts per million (ppm): It is the parts of a component per million (106) parts of the solution. pressure of pure components A and B respectively.
Number of parts of the component If p is total vapour pressure then according to Dalton’s law of partial pressure,
ppm = × 106 p = pA + pB
Total number of parts of all components of the solution
= poA xA + poB xB
It is convenient to express concentration in ppm when a solute is present in trace quantities. = poA (1 – xB) + poB xB
(e) Mole fraction (x): It may be defined as the ratio of the number of moles of one component (solute or = poA + (poB – poA) xB
solvent) to the total number of moles of all the components present in the solution.
As poA and poB are constants at a given temperature, it is evident from the above equations that the total
If in a solution, nA and nB are the number of moles of solvent and solute, respectively, then vapour pressure varies linearly with the mole fraction xB (or xA since xA = 1 – xB).
Mole fraction of solvent in the solution, The composition of the vapour phase in equilibrium with the solution can be determined from the
nA partial pressure of the two components. If yA and yB are the mole fractions of components A and B
xA =
n A + nB respectively in the vapour phase, then
Mole fraction of solute in the solution, pA = yA ptotal
nB pB = yB ptotal
xB =
n A + nB In general, pi = yi ptotal
In a solution, sum of the mole fractions of all the components is unity. For example, in a binary °° Raoult’s law as a special case of Henry’s law.
solution (having two components), xA + xB = 1. In the solution of a gas in a liquid, if one of the components is so volatile that it exists as a gas, then it
(f) Molarity (M): It is defined as number of moles of solute dissolved in one litre of solution. can be said that Raoult’s law becomes a special case of Henry’s law in which KH becomes equal to poA.
Moles of solute (b) Vapour pressure of solutions of solids in liquids
Molarity = Raoult’s law for a solution containing a non-volatile solute and volatile solvent: It states that the
Volume of solution (in litre)
relative lowering of vapour pressure is equal to mole fractions of solute which is non-volatile.
Unit of molarity is mol L–1 or M (molar). Molarity changes with change in temperature as volume Mathematically, p = pA + pB
changes with change in temperature.
or, p = pA (Since solute B is non-volatile)
p = poA xA

Solutions 51 52 Xam idea Chemistry–XII

 p = poA (1 – xB) = poA – poA xB Characteristics of a Solution Showing Positive Deviation
poA xB = poA – p l pA > poA xA ; pB > poB xB
p oA – p l Dmix H > 0, i.e., + ve,
or = xB
p oA l Dmix V > 0, i.e., + ve,
or Relative lowering of vapour pressure = Mole fraction of solute Some examples of the solution exhibiting positive deviations are:
5. Ideal and Non-Ideal Solutions (i) Ethyl alcohol and water
(a) Ideal solution: A solution is called an ideal solution if poB (ii) Acetone and carbon disulphide
it obeys Raoult’s law over a wide range of concentration ) (iii) Carbon tetrachloride and benzene
+pB
(Fig. 2.1) at a specified temperature. l
= pA (iv) Acetone and benzene
(p To ta poB
For an ideal solution,

xB
Vapour pressure
(B) Negative Deviation: The deviation is called

=p o
B
   p = pA + pB = poA xA + poB xB poA negative deviation, if the partial pressure of each + pB
p = pA

B
p
p oA
Liquids having similar nature and structure are likely to component (A and B) and resultant total vapour

Vapour pressure
form ideal solutions. Examples are: pressure are less than the pressure expected on the
p basis of Raoult’s law. (Fig. 2.3)
OO Mixture of methanol and ethanol A= o
p
OO Mixture of n-hexane and n-heptane
A x
A
This type of deviation is shown by the solutions in pB
pA
which
OO Mixture of benzene and toluene.
     FA – B > FA – A and FB – B
Reasons for formation of ideal solutions: A solution xA = 1 Mole fraction xA = 0
of two miscible liquids A and B will be ideal if two xB = 0 xB = 1 Due to this, there is decrease in the escaping
xB
essential conditions are fulfilled. xA tendency of A or B molecules from the surface of
solution.
(i) If FA – A is the force of attraction between molecules Fig. 2.1: Vapour pressure diagram for xA = 1 Mole fraction xA = 0
of A and FB – B is that of molecules of B, then A and an ideal solution Consequently, the vapour pressure of the solution xB = 0 xB = 1
xB
B will form an ideal solution only if, will be lower. xA
FA – B = FA – A = FB – B Characteristics of a Solution Showing Negative Fig. 2.3: Vapour pressure diagram showing
negative deviation
(ii) The solution of A and B liquids will be ideal if A and B have similar structures and polarity. Deviation
Methanol and ethanol have the same functional group and almost same polarity and therefore, l pA < poA xA ; pB < poB xB
form ideal solutions. l  Dmix H < 0, i.e., –ve, because weak A–A and B–B bonds are broken and strong A–B bond is
For an ideal solution formed. Heat is consequently released.
(i) Raoult’s law is obeyed, i.e., pA = poA xA and pB = poB xB l Dmix V < 0, i.e., –ve,
(ii) Dmix H = 0 and Vapour pressure of solution Some examples of the solution showing negative deviations are
(iii) Dmix V = 0. (i) HNO3 and water
pB poB
A+ (ii) Chloroform and acetone
(b) Non-ideal solution: A solution which does not obey p =p
Raoult’s law for all concentrations is called a non-ideal (iii) Acetic acid and pyridine
solution. poA
(iv) Hydrochloric acid and water
Vapour pressure

For a non-ideal solution

p

Table 2.2: Characteristics of Ideal and Non-ideal Solutions

(i) Raoult’s law is not obeyed, p
A S.No. Ideal Solutions Non-ideal Solutions
i.e., pA ≠ poA xA and pB ≠ poB xB
Positive Deviation Negative Deviation
(ii) Dmix H ≠ 0 and
(iii) Dmix V ≠ 0. (i) FA – A = FB – B = FA – B FA – B < FA – A and FB – B FA – B > FA – A and FB – B
A non-ideal solution can show either positive or negative (ii) pA = poAxA ; pB = poBxB pA > poAxA ; pB > poBxB pA < poAxA ; pB < poBxB
deviation from Raoult’s law. (iii) Dmix H = 0 Dmix H > 0, i.e., +ve Dmix H < 0, i.e., –ve
xA = 1 Mole fraction xA = 0
(A) Positive Deviation: The deviation will be called positive xB = 0 xB = 1 (iv) Dmix V = 0 Dmix V > 0, i.e., +ve Dmix V < 0, i.e., –ve
xB
when the partial pressure of each component and the xA
resultant total pressure are greater than the pressure Fig. 2.2: Vapour pressure diagram showing Azeotropes or Azeotropic mixture: Azeotropes are binary mixtures having the same composition in
expected on the basis of Raoult’s law (Fig. 2.2). positive deviation liquid and vapour phase and boil at a constant temperature.
In such cases, the intermolecular forces between solvent–solute molecules (FA – B) are weaker than Types of Azeotropes:
those between solvent–solvent (FA – A) and solute–solute (FB – B) molecules. That is, (i) Minimum boiling azeotropes: These are the binary mixtures whose boiling point is less than either
FA – B < FA – A and FB – B of the two components. The non-ideal solutions which show a large positive deviation from Raoult’s
This shows that the molecules of A or B will escape more easily from the surface of the solution, law form minimum boiling azeotrope at a specific composition, e.g., a mixture of 94.5% ethyl alcohol
i.e., the vapour pressure of solution will be higher. and 4.5% water by volume.

Solutions 53 54 Xam idea Chemistry–XII

 (ii) Maximum boiling azeotropes: These are the binary mixtures whose boiling point is more than either Kb # WB # 1000
of the two components. The solutions that show large negative deviation from Raoults’s law form Therefore, DTb =
MB # WA
maximum boiling azeotrope at a specific composition, e.g., a mixture of 68% HNO3 and 32% H2O by
mass. Kb # WB # 1000
6. Colligative Properties MB =
DTb # WA
Those properties which depend on the number of solute particles (molecules, atoms or ions) but not upon
their nature are called colligative properties. The following are the colligative properties: (c) Depression of freezing point: Freezing point is defined as t
en
(a) Relative lowering of vapour pressure of the solvent, the temperature at which the vapour pressure of a substance olv
id s
in its liquid phase is equal to its vapour pressure in the solid Liqu
(b) Elevation of boiling point of the solvent, i on
phase. A solution freezes when its vapour pressure equals lut
So

Vapour pressure (atm)

(c) Depression of freezing point of the solvent,

nt
the vapour pressure of the pure solid solvent. Whenever

ve
s

ol
(d) Osmotic pressure of the solution. a non-volatile solute is added to the volatile solvent, its n
ze
(a) Relative lowering of vapour pressure: The addition of a non-volatile solute to a volatile solvent vapour pressure decreases and it would become equal to Fro

decreases the escaping tendency of the solvent molecules from the surface of solutions as some of that of solid solvent at a lower temperature. The difference
in the freezing point of pure solvent (T of ) and that of the ∆Tf
the surface area is occupied by non-volatile solute particles. According to Raoult’s law, the relative
solution (Tf ) is known as depression of freezing point
lowering of vapour pressure is equal to mole fraction of solute.
(DTf ). Thus,
p oA – p nB Tf Tfo
Thus, = xB = Depression of freezing point = DTf = T of – Tf .
p oA n A + nB Temperature (K)
It has been found that for a dilute solution, depression in
Fig. 2.5: Vapour pressure temperature
For a dilute solution, nB << nA, hence neglecting nB in the denominator, we have freezing is directly proportional to molality of the solution. curves showing depression in
p oA – p nB WB # M A DTf ∝ m or DTf = Kf m freezing point of solution
= n =
p oA A MB # WA where Kf is a constant called molal depression constant or cryoscopic constant.
p oA WB # M A When m = 1 mol kg–1, DTf = Kf
MB = f p#
p oA – p WA Hence, molal depression constant may be defined as the depression in freezing point when one mole
of non-volatile solute is dissolved in one kilogram (1000 g) of solvent. The unit of Kf is K kg mol–1.
(b) Elevation of boiling point: Boiling point is
Boiling point of
the temperature at which the vapour pressure Solvent Solution WB # 1000
of a liquid becomes equal to the atmospheric Since, m=
1 atm MB # WA
pressure. When a non-volatile solute is added
to a volatile solvent, the vapour pressure of the K f # WB # 1000
nt
l ve

solvent decreases. In order to make this solution \

DTf =
n
So

ti o

MB # WA
Vapour pressure (atm)

boil, its vapour pressure must be increased by

lu
So

raising the temperature above the boiling point

K f # WB # 1000
of the pure solvent. The difference in the boiling
or, MB =
point of solution (Tbo) and that of pure solvent ∆Tb DTf # WA
(Tb) is called elevation of boiling point (DTb).
The values of Kb and Kf which depend upon the nature of the solvent and concentration of the solution,
Thus,
can be ascertained from the following relations:
Elevation of boiling point = DTb = Tb – Tbo
Tb0 R # M A # (Tbo) 2
(Fig. 2.4) Tb Kb =
For dilute solution, it has been found that the D vap H # 1000
Temperature (K)
elevation of boiling point is directly proportional Fig. 2.4: Vapour pressure temperature
curves showing elevation in R # M A # (T fo) 2
to the molal concentration of the solute in the Kf =
boiling point of solution
solution. Thus, D fus H # 1000
DTb ∝ m or DTb = Kb m
where Kb is a constant called molal elevation constant or ebullioscopic constant. where,     R = Universal gas constant
When m = 1 mol kg–1, DTb = Kb MA = Molecular mass of solvent
Hence, molal elevation constant may be defined as the elevation in boiling point when one mole of a Tbo = Boiling point of pure solvent
non-volatile solute is dissolved in one kilogram (1000 g) of solvent. The unit of Kb is K kg mol–1. Dvap H = Enthalpy of vapourisation of solvent
WB # 1000
As m= T of = Freezing point of pure solvent
MB # WA
Dfus H = Enthalpy of fusion of solid solvent

Solutions 55 56 Xam idea Chemistry–XII

 (d) Osmosis: When a solution is separated from its solvent by a semipermeable membrane (SPM) there For example, when ethanoic acid is dissolved in benzene it undergoes dimerisation and shows a
is a spontaneous flow of solvent molecules from solvent compartment to solution compartment. molecular mass of 120 (normal molecular mass is 60).
The phenomenon is called osmosis. This movement of solvent is only in one direction. In diffusion, O------H—O
Benzene
however, movement takes place in both the directions. 2CH3—COOH H3C—C C—CH3
°° Semipermeable membrane (SPM): A membrane through which only solvent molecules can pass but O—H------O

not the solute ones. Cellophane, parchment paper and the wall of living cell are the examples of SPM. °° Dissociation: Dissociation leads to increase in the number of solute particles in the solution resulting
It is also made of inorganic material, copper ferrocyanide [Cu2[Fe(CN)6]]. in an increase in the value of colligative property. Since colligative property is inversely related to the
°° Osmotic pressure (p): The osmotic pressure of a molecular mass, therefore, molecular mass of such a substance as calculated from colligative property
p will be less than its normal value. For example, KCl is an electrolyte. When it is dissolved in water it
solution is the excess pressure that must be applied to
a solution to prevent osmosis, i.e., to stop the passage h dissociates into K+ and Cl– ions and there would be double the number of particles if complete
dissociation takes place. Hence, it is expected to have molecular mass 37.25 g or 
of solvent molecules into it through semipermeable 74.5 
membrane (Fig. 2.6).  g.
Solvent  2 
Osmotic pressure (p) is proportional to molarity (C) KCl K+ + Cl–
of the solution at a given temperature T. Thus, Solution °° van’t Hoff Factor (i): It may be defined as the ratio of normal molecular mass to the observed
p = CRT molecular mass of the solute.
nB WB # R # T Semipermeable
or, p= RT = membrane i=
Normal molecular mass
V MB # V Observed molecular mass
WB # R # T Fig. 2.6: The principle of measuring osmotic Observed colligative property
or, MB = pressure: The pressure in excess of atmospheric or, i=
r #V
pressure that must be applied to the solution to Calculated value of colligative property
prevent it from rising in the tube is the osmotic
°° Reverse osmosis: If a pressure larger than the Total number of moles of particles after association/dissociation
pressure. This will also be equal to hydrostatic or, i=
osmotic pressure is applied to the solution side, the pressure of the liquid column of height, h. Number of particles before association/dissociation
pure solvent (or water) flows out of the solution
through the semipermeable membrane. In this van’t Hoff factor (i) expresses the extent of association or dissociation of the solute particles in the
Piston solutions.
way the direction of osmosis is reversed and so
the process is called reverse osmosis (Fig. 2.7). In case of association, i < 1
Thus, we can say that reverse osmosis is Fresh water Salt water In case of dissociation, i > 1
just opposite to the osmosis when an extra When there is neither association nor dissociation, i = 1
pressure is applied. Reverse osmosis is used in Water 8. Modified Form of Colligative Properties
desalination to get pure water from sea water. outlet SPM
Inclusion of ‘i’ modifies the equation for colligative properties as follows:
°° Isotonic solutions: Two solutions are said to Fig. 2.7: Reverse osmosis occurs when a pressure °° Relative lowering of vapour pressure of solvent
larger than the osmotic pressure is
be isotonic when they exert the same osmotic applied to the solution p oA – p A n
pressure because they have the same molar =i B
p oA nA
concentration. All intravenous injections must be isotonic with body fluids.
°° Elevation of boiling point, DTb = i Kb m
°° Isosmotic solutions: When two isotonic solutions are separated by a semipermeable membrane, no
osmosis occurs. The solutions are called isosmotic solutions. °° Depression of freezing point, DTf = i Kf m
°° Hypotonic solutions: A solution having lower osmotic pressure than the other solution is said to be °° Osmotic pressure, p = i CRT
hypotonic with respect to the other solution.
°° Hypertonic solution: A solution having higher osmotic pressure than the other solution is said to be
hypertonic with respect to other solution. Important Formulae
°° Plasmolysis: When the cell is placed in a hypertonic solution, the fluid comes out of the cell due to In the formulae given below, A represents solvent and B represents solute, also
osmosis and as a result cell material shrinks gradually. This process is called plasmolysis. MA = Molar mass of solvent MB = Molar mass of solute
7. Abnormal Molar Masses WA = Mass of solvent WB = Mass of solute
°° Association: Association of molecules leads to decrease in the number of particles in the solution V = Volume of solution d = Density of solution
resulting in a decrease in the value of colligative property. As colligative property is inversely GEM = Gram Equivalent Mass GMM = Gram Molecular Mass
related to the molecular mass. Therefore, higher value is obtained for molecular mass than normal
values.

Solutions 57 58 Xam idea Chemistry–XII

 WB 11. Molarity of a mixture: If V1 mL of a solution of molarity M1 is mixed with another solution of same
1. Mass percentage (w/w) = × 100 substance with volume V2 and molarity M2 then molarity of the resulting mixture of solution (M) can be
WA + WB
obtained as:
VB M1 V1 + M2 V2
Volume percentage (V/V) = × 100 M =
VA + VB V1 + V2
WB # 100
Mass by volume percentage a k=
w 12. Relationship between molarity (M) and mole fraction of solute (xB)
V V (mL) M # GMMA
xB =
WB M (GMMA – GMMB ) + 1000d
6
Parts per million (ppm) = × 10
WA + WB
1000 # d # xB
nA Also, M=
2. Mole fraction of A, xA = x A # GMM A + xB # GMMB
n A + nB
nB 13. Raoult’s law for volatile solute
Mole fraction of B, xB =
n A + nB pA = pAoxA and   pB = pBoxB
where pA and pB are partial vapour pressures of component ‘A’ and component ‘B’ in the solution. pAo and
      xA + xB = 1 pBo are vapour pressures of pure components ‘A’ and ‘B’ respectively.

nB WB Total vapour pressure, p = pA + pB = pAoxA + pBoxB

Moles of solute
3. Molarity (M) = = = 14. Raoult’s law for non-volatile solute
Volume of solution in litre V (in L) MB # V (in L)
p oA – p nB nB WB MA
Moles of solute nB WB # 1000 = xB = = = # (For a dilute solution nB <<nA).
4. Molality (m) = = or m = p oA n A + nB n A MB WA
Mass of solvent in kg WA (in kg) MB # WA (in g)
p oA WB # M A
MB = f p
Gram equivalents of solute WB
5. Normality (N) = = o
Volume of solution in litre GEM of solute × V (in L) p A – pA WA

6. Relationship between Molarity and Normality p oA – p A

where xB is mole fraction of solute and is relative lowering of vapour pressure.
The normality (N) and molarity (M) of a solution are related as follows: p oA
Normality × Equivalent mass (solute) = Molarity × Molar mass (solute) 15. Elevation in boiling point:
7. Relationship between Molarity and Normality with Mass percentage (p) DTb = Kb × m
If p is the mass percentage and d is the density of the solution then Kb # WB # 1000
p # d # 10 DTb =
MB # WA
Molarity = ;
Molecular mass (solute) Kb # WB # 1000
p # d # 10 or, MB =
DTb # WA
Normality =
Equivalent mass (solute) where, DTb = Tb – Tbo
8. Relationship between Molarity (M) and Molality (m) 16. Depression in freezing point:
DTf = Kf × m
1000 # M
m = (1000 × d) – (M # GMM ) K f # WB # 1000
B
DTf =
MB # WA
9. Relationship between Molality (m) and Mole fraction of solute (xB)
K f # WB # 1000
m # GMM A or, MB =
xB = DTf # WA
1000 + m # GMM A
17. Osmotic pressure (p)
1000xB
Also, m = pV = nBRT
x A # GMM A
WB WB # R # T
10. Dilution formula: If the solution of some substance is diluted by adding solvent from volume V1 to volume pV = # R # T, MB =
V2 then MB r #V
M1V1 = M2V2 nB
p= ×R×T or p = CRT where ‘C’ is molarity.
Similarly, N1V1 = N2V2 V

Solutions 59 60 Xam idea Chemistry–XII

 Osmotic pressure is related to the relative lowering of vapour pressure, elevation in boiling point and
depression in freezing points according to the following relations:
p oA – p A
p= f p× d
# R#T

p oA MB
DTb # d # R # T
p=
1000 # Kb
DT f # d # R # T
p=
1000 # K f
where d is the density of solution at temperature ‘T’.
18. van’t Hoff factor
Normal molecular mass
i=
Observed molecular mass
Observed colligative property
or, i=
Calculated colligative propertty
Total number of moles of particles after association/dissociation
or, i=
Number of moles of particles before association/dissociation
Modified forms of colligative properties:
p oA – p A
(a) = i xB (b) DTb = i Kb m
p oA

(c) DTf = i Kf m (d) pV = i nB RT

i –1
19. a = , where a is degree of dissociation, ‘i’ is van’t Hoff factor, ‘n’ is number of ions produced per
n –1
formula of the compound.
1– i i –1
20. a =    or a =
1 1
1– n n –1
where a is degree of association, n is the number of molecules of solute that associate to form an associated
1
molecule, n < 1.
R # M A # (Tbo) 2
21. Molal elevation constant, Kb =
1000 # D vap H

R # M A # (T fo) 2
22. Molal depression constant, Kf =
1000 # Dfus H

NCERT Textbook Questions

NCERT Intext Questions

Q. 1. Calculate the mass percentage of benzene (C6H6) and carbon tetrachloride (CCl4) if 22 g of benzene
is dissolved in 122 g of carbon tetrachloride.
Mass of benzene 22 g
Ans. Mass percentage of benzene = # 100 = # 100 = 15.28%
Mass of solution 22 g + 122 g
Mass percentage of carbon tetrachloride = 100 – Mass percentage of benzene
= 100 – 15.28 = 84.72%

Solutions 61