CHAPTER -2 (PREPARED BY MR.V K SUMAN ,PGT(CHEM.

),PH-9694422913
SOLUTIONS

1. Solution: A homogenous mixture whose composition can be varies within certain limits is termed a true
solution. 2.
Concentration of solutions
(i) Percentage of solution: It is defined as number of parts of the solute present in 100 parts of the solution.
𝒎𝒂𝒔𝒔 𝒐𝒇 𝒕𝒉𝒆 𝒄𝒐𝒎𝒑𝒐𝒏𝒆𝒏𝒕 𝒊𝒏 𝒕𝒉𝒆 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏
(a) Mass Percentage (w/w ) = 𝒙 𝟏𝟎𝟎
𝑻𝒐𝒕𝒂𝒍 𝒎𝒂𝒔𝒔 𝒐𝒇 𝒕𝒉𝒆 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏
W/W [5 % aq. sol of urea by mass] → 5 g Urea + 95 g water
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒕𝒉𝒆 𝒄𝒐𝒎𝒑𝒐𝒏𝒆𝒏𝒕
(b) Volume Percentage (V/V) = 𝒙 𝟏𝟎𝟎
𝑻𝒐𝒕𝒂𝒍 𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏

V/V [ 10 % aq.alcohol by volume] → 10 ml alcohol + 90 ml water

𝒎𝒂𝒔𝒔 𝒐𝒇 𝒕𝒉𝒆 𝒄𝒐𝒎𝒑𝒐𝒏𝒆𝒏𝒕
(c) Mass by volume percentage (w/v)= 𝑽𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒕𝒉𝒆 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏
𝑿 𝟏𝟎𝟎
W/V [ 10 % aq. sugar solution] → 10 gm sugar + 100 ml water( 10 g sugar in 100 ml solution )

(ii) Mole fraction (x):- Ratio of moles of the component to total moles of components in the solution.
𝐍𝐮𝐦𝐛𝐞𝐫 𝐨𝐟 𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐭𝐡𝐞 𝐜𝐨𝐦𝐩𝐨𝐧𝐞𝐧𝐭
Mole fraction of a component = X100
𝐓𝐨𝐭𝐚𝐥 𝐧𝐮𝐦𝐛𝐞𝐫 𝐨𝐟 𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐚𝐥𝐥 𝐭𝐡𝐞 𝐜𝐨𝐦𝐩𝐨𝐧𝐞𝐧𝐭𝐬

(For binary mixture) : xA = nA /nA +nB xA =mole fraction of comp. A, nA =moles of component A

XB = nB /nA +nB nA +nB =total no. of moles present in soln.

xA + xB =1; xA =1-xB; xB =1-xA [ A = solvent ;B=solute] nA = WA / MA ; nB = WB / MB

(iii) Molarity (M) = Number of moles of solute per litre of solution.

(iv) Molality (m) =Number of moles of solute per kg of solvent.

(v) Molality does not changes with temp. while molarity is inversely proportional

M α 1/V But V α T (According to Charle’s law)

Therefore M α 1/T

(3) Solubility:Solubility represent the maximum amount of a substance that can be dissolved in a specified
amount of solvent at a particular temperature. It depends upon

(a) Nature of solute and solvent : Like dissolves like i.e Polar solute dissolves in polar solvent and non- polar
solute in non-polar solvent.

(b) Temperature:

For Solute + Solvent ⇌ Solution ,SH = -ve

Increase of temperature decreases the solubility.
 For Solute + Solvent ⇌ Solution ,SH = +ve
Increase of temperature increases the solubility
(c) Pressure:

Pressure does not have any significant effect on solubility of solids in liquids,
because solid and liquids are highly incompressible and remain unaffected by change in
pressure.

(4) Henry’s law of gas solubility

Statement:-It states that the partial pressure (p) of the gas in vapour phase is proportional to the mole fraction
(x) of the gas in the solution.

p∝x => p = KH x

p: Partial pressure of the gas in vapour phase

x : Mole fraction of the gas in the solution

KH : Henry’s law constant

The value of KH is a function of nature and temperature of the gas.

Higher the value of KH at a given pressure, lower is the solubility of the gas in the liquid.

With increase of temperature, solubility of gas decreases i.e. KH value increases.

Application of Heny’s law-

➢ To increase the solubility of CO2 in soft drinks and soda water.

➢ Oxygen cylinders used by scuba divers are filled with diluted helium to avoid toxic effects of high
concentration of N2 In blood.

(5) Raoult’s law

FOR BOTH SOLUTE AND SOLVENT ARE VOLATILE:

Raoult’s Law states that at given temperature, the partial vapour pressure of any component of the solution is
equal to the product of the vapour pressure of pure component and its mole fraction in the solution.

PA = PAXA and PB = PBXB

Psolution = PTotal = Psolute + Psolvent = Po A χ A + PoB χ B = Po A(1- χ B) + Po B χ B

In very dilute solution when non-volatile solute is mixed then (WB/MB < < < WA/MA)

∆P /POA = χsolute =WBMA/ MBWA MB = WBMAPOA / ∆PW A

PA = PAX and PB = PBXB

The total vapour pressure P of such solution containing two compounds A and B is
PA = PA + PB = PAXA = PBXB As we know that XA + XB = 1;XA = (1- XB)

P = (1-XB) PA + PBXB

P = (PB - PA) XB + PA

(6) Ideal and non-ideal solution

Ideal solution Non-ideal Solution

The solutiopn which obeys Non-ideal solutions do not obey Raoult’s law at any temperature and
Raoult's law under all conditions concentration.
of temperature, pressure and
They form azeotropes.
concentration is known as ideal
solution. They do not form Positive deviation Negative deviation
azeotropes.

Enthalpy of mixing and volume of Enthalpy of mixing and volume of Enthalpy of mixing and volume of
mixing is zero. mixing is greater than zero. mixing is less than zero.
Hmix = 0 & Vmix = 0 Hmix >0 & Vmix >0
Hmix <0 & Vmix <0
P = pA + pB P > pA + pB
P < pA + pB

In this case the intermolecular In this solution, solute-solvent In this solution, solute-solvent
attractive forces between intermolecular attraction forces intermolecular attraction forces
solvent-solute molecules are are lower than the solute-solute or are more than the solute-solute or
same with solute-solute and solvent-solvent intermolecular solvent-solvent intermolecular
solvent-solvent molecules attraction forces. attraction forces.

Examples, solutions of :- Examples, solutions of :- Examples, solutions of :-

[1] n-hexane & n-heptane [1] Acetone and CS2 [1] Acetic acid - Pyridine
[2] Chloroform -Acetone
[2] Chlorobenzene & [2] Acetone and C2H5OH
Bromobenzene [3] Methyl alcohol and water [3] Aniline -Acetone
[4]Cyclohexanal and water [4] Water - Sulphuric acid
[3] Ethyl bromide & Ethyl iodide
[5]CCI4 and CHCI3
[5] Water - Nitric acid
[4] Carbon tetra chloride & silicon
tetra chloride

[5] Benzene & Toluene

 Bezene is more volatile than
toluene so, p0 >p0
1 2

0
P1

0
P1 P2
V.P
P2

X1 = 1 X1 = 0
X2 = 0 M.F X2 = 1
Benzene Toluen e

Azeotropes

Azeotropes are defined as the mixture of liquids which boil at constant temperature like a pure liquid and
possess the same composition of the components in the liquid as well as in vapour phase.

Azeotropes are mixtures and not compounds,because both the boiling point and composition of azeotropes is
changed whereas for a chemical compound, composition remains constant over a range of pressure .

There are two types of Azeotropes :-

Minimum boiling point azeotropes Maximum boiling point azeotropes

The solution which shows positive deviation, form The solution which shows negative deviation, form
minimum boiling point azeotropes at a specific maximum boiling point azeotropes at a specific
composition composition.

95% by volume of ethanol with water boil at 351.15 68% by mass of nitric acid with water boil at 393.5K
K

Colligative Properties

The properties of solution that depends upon the number of solute particles irrespective of their nature is
known as colligative properties.

[1] Relative lowering of vapour pressure

[2] Elevation in boiling point ( Tb )

[3] Depression in freezing point ( Tf )

[4] Osmotic pressure (  )

 Elevation in boiling point ( Tb ) Depression in freezing point ( Tf )

The temperature at which the V.P of liquid is equal The temperature at which vapour pressure of solid =
with the external pressure is known as boiling point. V.P of liquid of same substance, is known as freezing
point.

1 atm Solvent
Solution
Vapour pressure

Liquid
P
Solvent

Vapour pressure
Solid
P
Solution Tb
O Tf
Tb Tb
Temperature
0
Tf T
f
Temperature

The boiling point of a solution (Tb) of non-volatile The freezing point of a solution (Tf) of non-volatile
0 0
solute is higher than that of pure solvent (Tb ). i.e. solute is lower than that of pure solvent (Tf ) i.e
Tb > T0b Tf < T0f
Tf = TfO -Tf
Tb =Tb -TbO

ΔTb= Kbm Depression in freezing point:

ΔTb =elevation in B.P.
ΔTf= Kfm
Kb =B.P. elevation constant (Ebullioscopic constant)
ΔTf =Depression in freezing point.
m =molality
Kf = freezing point depression constant or cryoscopic
M2= 1000 X W2 X Kb / ΔTb X W1
const.
M2= 1000 X W2 X Kf / ΔTf X W1

Where Kb is proportionality constant , known as Where Kf is proportionality constant , known as

Ebullioscopic constant / boiling point elevation cryoscopic constant / freezing point depression
constant / molal elevation constant, depends upon constant / molal depression constant, depends
the nature of solvent. upon the nature of solvent.

For water Kb = 0.52 K kg mol-1 . For water Kf = 1.86 K kg mol-1 .

 Molal elevation constant ( kb) is defined as the Molal depression constant (kf) is defined as the
elevation of boiling point of one molal solution. depression in freezing point of one molal solution.

Osmosis

The spontaneous flow of solvent molecules from low

concentrated side to high concentrated side through a
semipermeable membrane is known as osmosis.

[ In diffusion, in order to maintain equal concentration the

solute particles flow from high concentrated side to low
concentrated side.]

V.P of low concentrated side > High concentrated side, So Solvent molecules flow from low concentrated
side to high concentrated side.

Hyper :Beyond / Above => Hypertonic ( Higher Concentration)

Hypo: Under => Hypotonic ( Lower Concentration )

Osmotic pressure 

The pressure exerted at high concentrated side due to osmosis is known as osmotic pressure.

Osmotic pressure is directly proportional to the concentration of the solution i.e.   C

Osmotic pressure increases with increase in temperature .i.e.   T

So   CT
 = CRT
 If two solutions having same concentration i.e. same osmotic pressure is known as Isotonic solution.

 The low concentrated solution is known as Hypotonic solution

 The solution having high concentration i.e. higher osmotic pressure is known as Hypertonic solution.

Osmotic pressure is used for the determination of molar masses of macromolecules. Because,
[1] It is performed in room temperature with help of concentration expressed in molarity.
[2] Compared to other colligative properties, its magnitude is large even for very dilute solution.
[3] Macro molecules are unstable and poor solubility at higher temperature.
Oedema
When placed in water containing less than 0.9% (mass/ volume) salt, blood cells collapse due to loss of water by
osmosis. People taking a lot of salt or salty food experience water retention in tissue cells and intercellular spaces
because of osmosis. The resulting puffiness or swelling is called edema.
Reverse Osmosis
The phenomenon of movement of solvent molecules from high concentrated side to low concentrated side through
semi permeable membrane by applying pressure on the high concentrated side which is greater than osmotic pressure is
known as reverse osmosis.It is used in desalination of sea water.

Abnormal molar mass: In case of dissociation or association of solute molecules in solution observed molar
mass will not equal to calculated molar mass, and it is called abnormal Molar mass.

Van’t Hoff Factor ( i )

𝐍𝐨𝐫𝐦𝐚𝐥 𝐦𝐨𝐥𝐚𝐫 𝐦𝐚𝐬𝐬

Van’t Hoff factor (i) =
𝐀𝐛𝐧𝐨𝐫𝐦𝐚𝐥 𝐦𝐨𝐥𝐚𝐫 𝐦𝐚𝐬𝐬
𝐨𝐛𝐬𝐞𝐫𝐯𝐞𝐝 𝐜𝐨𝐥𝐥𝐢𝐠𝐚𝐭𝐢𝐯𝐞 𝐩𝐫𝐨𝐩𝐞𝐫𝐭𝐢𝐞𝐬
=
𝐂𝐚𝐥𝐜𝐮𝐥𝐚𝐭𝐞𝐝 𝐜𝐨𝐥𝐥𝐢𝐠𝐚𝐭𝐢𝐯𝐞 𝐩𝐫𝐨𝐩𝐞𝐫𝐭𝐢𝐞𝐬

𝐓𝐨𝐭𝐚𝐥 𝐧𝐨.𝐨𝐟 𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐩𝐚𝐫𝐭𝐢𝐜𝐥𝐞𝐬 𝐚𝐟𝐭𝐞𝐫 𝐚𝐬𝐬𝐨𝐜𝐢𝐚𝐭𝐢𝐨𝐧/𝐝𝐢𝐬𝐬𝐨𝐜𝐢𝐚𝐭𝐢𝐨𝐧

=
𝐓𝐨𝐭𝐚𝐥 𝐧𝐨.𝐨𝐟 𝐦𝐨𝐥𝐞𝐬 𝐨𝐟 𝐩𝐚𝐫𝐭𝐢𝐜𝐥𝐞𝐬 𝐛𝐞𝐟𝐨𝐫𝐞 𝐚𝐬𝐬𝐨𝐜𝐢𝐚𝐭𝐢𝐨𝐧/𝐝𝐢𝐬𝐬𝐨𝐜𝐢𝐚𝐭𝐢𝐨𝐧

Molecules C6H12O6 NaCl CH3COONa 2CH3COOH Na2SO4 K4[Fe(CN)6]

1 2 1 5
Van't Hoff Factor (i) 2
2 3

Relationship between Van't Hoff factor ( i ) and degree of dissociation (  )

𝑖−1
𝛼=
𝑛−1

Relationship between Van't Hoff factor ( i ) and degree of association (  )

nA A n No. of particles
1 0 Before association = 1
1 −   n−1
n After association = 1− + n =1−  1−
n
= 1− n

𝑖−1
𝛼=
1
𝑛−1