Solutions

Introduction
 In normal life we rarely come across pure substances.
 Most of these are mixtures containing two or more pure substances.
 Their utility or importance in life depends on their composition and concentration.
 For example, the properties of brass (mixture of copper and zinc) are quite
different from those of German silver (mixture of copper, zinc and nickel) or
bronze (mixture of copper and tin);
 1 part per million (ppm) of fluoride ions in water prevents tooth decay, while 1.5
ppm causes the tooth to become mottled (covered with patches of different
colours) and high concentrations of fluoride ions can be poisonous (for example,
sodium fluoride is used in rat poison);
 Intravenous (IV) injections are always dissolved in water containing salts at
particular ionic concentrations (eg: 0.9 (w/V)% of NaCl solution) that match with
blood plasma concentrations and so on.
 In this Unit, we will consider mostly liquid solutions and their formation.
 This will be followed by studying the properties of the solutions, like vapour
pressure and colligative properties.
 We will begin with types of solutions and then various alternatives in which
concentrations of a solute can be expressed in liquid solution.
Solution
 A homogeneous mixture of two or more components or substances is called True
solution.
 Homogeneous means uniform appearance, composition and properties (density,
refractive index, colour etc) throughout the solution.
 Based on the number of components, solutions may be binary (consisting of two
components), ternary (consisting of three components), quaternary (consisting of
four components) etc.
 In this Unit we shall consider only binary solutions
 Component which is dissolved in solution is known as solute
 Component in which dissolution takesplace is known as solvent
 The substance present in larger proportion is called as the solvent. (NCERT)
 One or more components other than solvent is/are called solute(s).
i.e; For binary solution, Solute + Solvent = Solution
 Solvent determines the physical state in which solution exists. i.e; physical state of
solvent and solution is same.

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 Solutions
 In any solution, solvent is always one component but solute may be one or more.
Type of Total
Example Solvent Solute(s)
sol’n components
Binary 2 Glucose water 1 (water) 1 (Glucose)
Ternary 3 Glucose salt water 1 (water) 2 (Glucose & salt)
Quaternary 4 Glucose+NaCl+NaHCO3 1 (water) 3 (Glucose, NaCl & NaHCO3)
in water
Ex.1: In a syrup containing 70 g sugar (a solid) and 45 g water (a liquid) as solution,
water is acts as the solvent and sugar is solute.
Ex.2: In a solution of alcohol and water; having 10 mL alcohol and 20 mL water, water
is solvent and alcohol will be solute.
Note:
 A solution of water and sugar is called syrup.
 A high concentrated solution of sodium chloride in water is known as Brine
solution.
 A sterilized specific concentration (0.1538M or 0.9 (w/V)%) of NaCl in water is
called saline.
 A solution of CO2 in water is called soda water or seltzer (mineral water with
bubbles)
Properties of solution
 A solution consists of a single phase. i.e. it is a monophasic system
 Formation of solution is a physical change only. i.e., chemical composition of solvent
and solute does not change during formation of a solution and individual molecules
or ions will exist in solution.
 Solute may lose its physical state, but solvent retains its physical state. Therefore
physical state of solution depends on physical state of solvent only.
 Solutions have same composition and properties (density, refractive index, colour
etc) throughout the solution. i.e; homogeneous
 Homogeneous mixture is formed by existence of uniform intermolecular attractions
between solvent and solute molecules or ions.
 The components of a solution cannot easily separated by physical methods
[filtration, decantation (pour from one vessel to another), kept long standing etc].
 Certain properties of a solution like density, viscosity, surface tension, boiling point,
Freezing point etc vary with change in composition as well as change in
concentration.

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Types of solutions
I. Based on concentration of solution (amount of solute)
 A solution in which relatively a small amount of solute is dissolved in large amount
of solvent is called a dilute solution. Ex: dil HCl, dil H2SO4, dil NaOH
 A solution in which relatively a large amount of the solute is present is called a
concentrated solution. Ex: Conc.HCl, Conc.HNO3, Conc, H2SO4, Conc. alkali
II. Based on nature of saturation and Unsaturation (based on solubility)
 1) Unsaturated solutions: The solution in which some more amount of solute can
be dissolved is called unsaturated solution.
o In these solutions, concentration is less than the solubility of solute in solvent.
o In these solutions undissolved solute does not exists. Hence there is No dynamic
equilibrium exists between dissolved solute and undissolved solute.
 2) Saturated solutions: The solution in which no more amount of solute can be
dissolved is called saturated solution.
o In these solutions, concentration is equal to the solubility of solute in solvent.
o Usually some amount of undissolved solute is present in it. Therefore, a dynamic
equilibrium exists between dissolved solute and undissolved solute.
Ex: Urea (s) ⇌ Urea (aq) NaCl (s) ⇌ NaCl (aq)
 3) Super saturated solutions: The solution which contains excess of dissolved
solute than its solubility under special conditions is known as super saturated
solution.
o In these solutions, concentration is more than the solubility of solute in solvent.
o These solutions are unstable and try to attain saturated condition by
crystallisation of excess dissolved solute.
o There is no existence of equilibrium at super saturated condition.
III. Based on nature of solvent used
 A solution containing water as a solvent is called aqueous solution.
Ex: aq NaCl, aq NaOH, aqNH3.
 A solution containing alcohol as a solvent is called alcoholic solution.
Ex: alc KOH, alc NaOH, alc DMG.
 A solution containing organic liquids like benzene, chloroform, ether, carbon
tetrachloride, etc., as a solvent is called Non-aqueous or organic solution.
Ex: Br2 in CCl4, Naphthalene in Benzene

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 Solutions
IV. Based on the physical state of solvent and solute
Type of solution Solute Solvent Common Examples
Gas Gas Mixture of Oxygen and nitrogen gas
Gaseous
Liquid Gas Chloroform mixed with nitrogen gas
Solutions
Solid Gas Camphor in nitrogen gas
Gas Liquid Oxygen dissolved in water
Liquid solutions Liquid Liquid Ethanol dissolved in water
Solid Liquid Glucose dissolved in water
Gas Solid Solution of hydrogen in palladium
(absorption of H2 gas on pd)
Solid solutions
Liquid Solid Amalgam of mercury with sodium
Solid Solid Copper dissolved in gold
Note: Almost all processes in body occur in some kind of liquid solutions
Methods of expressing conc. of solution
 The amount of solute dissolved in the given solution is called concentration of that
solution.
 The solution whose concentration is known accurately is called standard solution.
 The solution which maintains concentration equal to
calculated value is known as primary standard solution.
Ex: Oxalic acid sol’n, EDTA sol’n, Na2CO3 sol’n…etc.
 The flask or container used to prepare a primary standard
solution is known as standard flask or volumetric flask.
 The solution which donot maintains concentration equal to calculated value is
known as secondary standard solution. It is mainly due to presence of impurity in
solute or interaction of solute with atmosphere.
Ex: NaOH sol’n, KOH sol’n, FeSO4 sol’n…etc.
 The exact concentration of secondary standard solutions can be determined by
titration with primary standard solution.
 Composition of a solution can be described by expressing its concentration.
 Concentration of a solution can be expressed either qualitatively or quantitatively.
 For example, qualitatively we can say that the solution is dilute (i.e., relatively very
small quantity of solute) or it is concentrated (i.e., relatively very large quantity of
solute). But in real life these kinds of description can add to lot of confusion and thus
quantitative description of the solution must be needed.

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 Solutions
 The concentration of solution can be expressed quantitatively either in physical
methods or in chemical methods by several ways.
 Physical methods: Mass %, Volume %, Mass by volume %, Strength of a Solution (S)
and parts per million.
 Chemical methods: Molarity, Formality, Normality, molality and mole fraction
1. Mass percentage (w/w)
 The Mass of solute in gms dissolved in 100gms of solution is called Mass percentage.
Mass of the component in the solution
 Mass % of a component = ×100
Total mass of the solution
w Masssolute w Wsolute
( )% = ×100 or ( )% = ×100
w Total Masssolution w Wsolute +Wsolvent
 x % (w/w) solution means x gms of solute is present in 100gms of solution (or)
x gms of solute is mixed with (100-x) gms of solvent.
For example, if a solution is described by 10% glucose in water by mass, it means
that 10 g of glucose is mixed with 90 g of water resulting in a 100 g solution.
Ex: 5% (w/w) NaOH solution means 5gms of NaOH is present in 100gms of solution
(or) 5gms of NaOH is mixed with 95gms of water.
 Concentration described by mass percentage is commonly used in industrial
chemical applications.
For example, commercial bleaching solution contains 3.62 mass percentage of
sodium hypochlorite (NaOCl) in water. i.e; 3.62 gms of NaOCl + 96.38 g of water.
Industrial sulphuric acid is 98% by mass
Industrial nitric acid is 68% by mass
2. Volume percentage (V/V)
 The volume of solute (in ml) dissolved in 100ml of solution is called volume
percentage. It is mainly used for solutions containing liquids (liquid-liquid sol’s)
Volume of the component in the solution
 Volume % of a component = ×100
Total volume of the solution
v Vsolute v Vsolute
 ( )% = ×100 (or) ( )% = ×100
v Vsolution v Vsolute +Vsolvent
 x % (v/v) solution means x ml of solute is present in 100ml of solution. (or) x ml of
solute is mixed with (100-x)ml of solvent.
 For example, 10% ethanol solution in water means that 10 mL of ethanol is
dissolved in 90mL of water such that the total volume of the solution is 100 mL.
 A 35% (v/v) solution of ethylene glycol is an antifreeze used in cars for cooling the
engine. At this concentration the antifreeze lowers the freezing point of water to
255.4K (–17.6°C).

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3. Mass by Volume percentage (w/v)
 The mass of solute (in gms) dissolved in 100ml of solution is called mass by volume
percentage. It is commonly used in medicine and pharmacy.
w mass of the solute
( )%= × 100
v Total volume of the solution
 x % (w/v) solution means x gms of solute is present in 100 ml of solution.
Ex: 4% (w/v) NaCl solution means 4gms of NaCl is present in 100ml of solution.
4. Strength of a Solution (S)
 The mass of solute (in gms) dissolved in one litre solution is called strength of a
solution (S). Units : gms Lit–1
mass of the solute in gms mass of the solute in gms
 S= = × 1000
Total volume of the solution in Lit Total volume of the solution in mL
Note: S = (w/V)% ×10 S = M×GMW S = N×GEW
5. Parts per million (ppm)
 The number of parts of a component dissolved in 106 parts of all components of
solution is called parts per million.
Number of parts of the component
Parts per million = × 106
Total number of parts of all components of the solution

 Concentration in parts per million can also be expressed as mass to mass, volume to
volume and mass to volume.
mass of the solute (g)
Ppm by mass = × 106
Total mass of the solution (g)
volume of the solute (mL)
Ppm by volume = × 106
Total volume of the solution (mL)
mass of the solute (g)
Ppm by mass per volume = × 106
Total volume of the solution (mL)
 When a solute is present in trace quantities, it is convenient to express
concentration in parts per million (ppm). Ex: Hardness of water is expressed in ppm
 A litre of sea water (which weighs 1030 g) contains about 6 × 10 –3 g of dissolved
oxygen (O2). Such a small concentration is also expressed as 5.8 g per 106 g of sea
water (5.8 ppm). The concentration of pollutants in water or atmosphere is often
expressed in terms of μg mL–1 or mg L–1 or ppm.
 Degree of hardness of water can be determined as follows
WCaCO3 nCaCO3
DOH = ×106 ppm ⇒ DOH = ×108 ppm
WHard water WHard water
nT(all salts)
⇒ DOH = ×108 ppm
WHard water

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6. Molarity (M)
 Molarity: The number of gram moles of the solute present in one litre of solution is
known as the Molarity. It is represented by ‘M’. Units: moles/litre or mole L–1
number of moles of the solute n n×1000
M= ⇒M = ⇒M=
volume of the solution in litres v (lit) v (ml)
W 1 W 1000
M= × ⇒ M= ×
GMW V ( in litres) GMW V ( in ml)
 The molarity is the most convenient and commonly used method of expressing the
concentration of solution.
 The molarity of a solution slightly decreases with increase in temperature of the
solution, due to increase in volume.
 Molar ⇒ 1M semi molar ⇒ 0.5M Pentimolar ⇒ 0.2M
Decimolar ⇒ 0.1M centimolar ⇒ 0.01M millimolar ⇒ 0.001M
Decamolar ⇒ 10M
Important formulae related to Molarity
w
10 × ( v )%
 When mass/volume (w/v) % is given, the molarity is M =
GMW
w
10 × d × (w)%
 When mass (w/w) % and specific gravity (density) are given M =
GMW
W d×1000
 If density and weight of solution is given, then M = ×
GMW Wsol′n ( in gms)
 Dilution law: when a solution is diluted its molarity is decreases M 1V1 = M2V2
Where M1 and V1 are Molarity and Volume of the sol’n before dilution
M2 and V2 are Molarity and Volume of the sol’n after dilution
In case of dilution, the volume of water or solvent added = V2–V1
 Molarity of mixing of two unreacting solutions
In unreacted solutions i.e; (Two sol’s have same nature either acidic or basic)
M1 V1+M2 V2
For mixing of solutions only M =
V1 +V2
M1 V1+M2 V2
For mixing followed by dilution M =
V1+V2 +V𝑤𝑎𝑡𝑒𝑟 𝑎𝑑𝑑𝑒𝑑 (Vtotal )
 Molarity of two reacting solutions in a chemical reaction
Two solutions are titrated against each other for neutralization (acid-base or
oxidant-reductant) according to the equation naA + nbB → mcC + mdD
The relation between molarities of two reacting solutions is given by
M a Va M b Vb
= ……(1)
na nb

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Where Ma = Molarity of the solution-A
Va = Volume of the solution –A consumed for neutralization reaction
na = stoichiometric coefficient of A in reaction
Mb = Molarity of the solution -B
Vb = Volume of the solution -B consumed for neutralization reaction
nb = stoichiometric coefficient of B in reaction
Wa 1000 Wa ×1000
We know that Ma = × ⇒ Ma Va = ……(2)
GMWa Va ( in ml) GMWa
Wb ×1000
Similarly Mb Vb = ……(3)
GMWb
Wa 1000 Mb Vb
From above eq (1) and (2) ⇒ × =
GMWa na nb
Ma Va Wb 1000
From above eq (1) and (3) ⇒ = ×
na GMWb nb
Wa 1 Wb 1
From above eq (1), (2) and (3) ⇒ × = ×
GMWa na GMWb nb
7. Formality (F)
 The number of formula weights of solute present in one litre of solution is called
Formality. Ionic compounds and polymers do not contain molecules and molecular
weights. Instead of molecular weight, the formula weight to be taken for Ionic
compounds and polymers.
 So instead of molarity the formality to be considered.
 For any given solution, molarity and formality are same.
Weight of the solute 1000 W 1000
𝐹= × ⇒ 𝐹= ×
Formla Wt. of the solute volume of the solution in ml FW V ( in ml)
8. Normality (N)
 The number of gram equivalents of the solute dissolved in one litre of solution is
known as its normality. It is represented by ‘N’. Units: gr. eq L–1
The normality of a solution is also slightly decreases with increase in temperature of
the solution.
number of gram equalents of the solute
N=
volume of the solution in litres
Weight of the solute 1
N= ×
GEW of the solute volume of the solution in litres
W 1 W 1000
⇒ N= × ⇒ N= ×
GEW V ( in litres) GEW V ( in ml)
 Normal ⇒ 1N seminormal⇒ 0.5N pentinormal ⇒ 0.2N
Decinormal ⇒ 0.1N centinormal⇒ 0.01N millinormal ⇒ 0.001N
Decanormal ⇒ 10N
By A. Baleswara Reddy Page 8
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w
10 × ( )%
 When mass/volume (w/v) % is given, the Normality is N = v
GEW
w
10 × d × (w)%
 When mass (w/w) % and specific gravity (density) are given ⇒N =
GEW
W d×1000
 If density and weight of solution is given, then N = ×
GEW Wsol′n ( in gms)
 Dilution law: when a solution is diluted its normality is decreases N1V1 = N2V2
In case of dilution, the volume of water or solvent added = V 2–V1
 Normality of resulting solution after mixing of two solutions
i. In unreacted solutions (Two sol’s have same nature either acidic or basic)
N1 V1 +N2 V2
N=
V1 +V2 +V𝑤𝑎𝑡𝑒𝑟 𝑎𝑑𝑑𝑒𝑑 (Vtotal )
ii. In reacted solutions as n1 A + n2B → m1C + m2D
i.e; (one sol’n have acidic nature and other sol’n have basic nature) or
(one sol’n is reducing agent or other sol’n is oxidizing agent)
a) If NAVA > NBVB , the resultant normality is corresponding to solution-A and it is
NA VA −NB VB
given by N =
VA +VB or Vtotal
b) If NBVB > NAVA, the resultant normality is corresponding to solution-B and it is
NB VB −NA VA
given by N =
VA +VB or Vtotal
 Normality in a chemical reaction, two solutions are titrated against each other for
neutralization according to following equation n1 A + n2B → m1C + m2D then the
relation between Normality’s of two reacting solutions is given by
NaVa = NbVb …..(1)
Where Na = Normality of the solution-A
Va = Volume of the solution -A consumed for neutralization
Nb = Normality of the solution -B
Vb = Volume of the solution -B consumed for neutralization
Wa ×1000 Wb ×1000
We know that Na Va = ……(2) and Nb Vb = ……(3)
GEWa GEWb
Wa ×1000
From above eq (1) and (2) ⇒ = Nb Vb
GEWa
Wb ×1000
From above eq (1) and (3) ⇒ Na Va =
GEWb
Wa Wb
From above eq (1), (2) and (3) ⇒ =
GEWa GEWb

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Relation between Molarity and Normality
N × GEW = M× GMW ⇒ N= M× n-factor
For a given solute, GMW ≥ GEW. So for any given solution M ≤ N.
Determination of Equivalent weight
Equivalent weight: The weight of the substance which combines with 1 gram of
hydrogen or 8 grams of oxygen is called equivalent weight.
𝐆𝐌𝐖 𝐀𝐭𝐨𝐦𝐢𝐜 𝐖𝐞𝐢𝐠𝐡𝐭 𝐅𝐨𝐫𝐦𝐮𝐥𝐚 𝐖𝐞𝐢𝐠𝐡𝐭
𝐆𝐄𝐖 = 𝐄𝑬𝒍𝒆𝒎𝒆𝒏𝒕 = 𝐄𝒊𝒐𝒏 =
𝐧−𝐟𝐚𝐜𝐭𝐨𝐫 𝐕𝐚𝐥𝐞𝐧𝐜𝐲 𝐜𝐡𝐚𝐫𝐠𝐞 𝐨𝐟 𝐢𝐨𝐧
𝐌𝐨𝐥𝐞𝐜𝐮𝐥𝐚𝐫 𝐖𝐞𝐢𝐠𝐡𝐭/𝐅𝐨𝐫𝐦𝐮𝐥𝐚 𝐖𝐞𝐢𝐠𝐡𝐭
 𝐄𝑨𝒄𝒊𝒅 =
𝐁𝐚𝐬𝐢𝐜𝐢𝐭𝐲
36.5 63 98
Ex: E𝐻𝐶𝑙 = =36.5 E𝐻𝑁O3 = = 63 EH2 SO4 = = 49
1 1 2
82 98 126
EH3 PO3 = = 41 EH3 PO4 = = 32.66 EH2 C2 O4 .2H2 O = =63
2 3 2
𝐌𝐨𝐥𝐞𝐜𝐮𝐥𝐚𝐫 𝐖𝐞𝐢𝐠𝐡𝐭/𝐅𝐨𝐫𝐦𝐮𝐥𝐚 𝐖𝐞𝐢𝐠𝐡𝐭
 𝐄𝑩𝒂𝒔𝒆 =
𝐀𝐜𝐢𝐝𝐢𝐭𝐲
40 74 35
Ex: E𝑁𝑎𝑂𝐻 = = 36.5 E𝐶𝑎(𝑂𝐻)2 = = 37 ENH4OH = = 35
1 2 1
𝐌𝐨𝐥𝐞𝐜𝐮𝐥𝐚𝐫 𝐖𝐞𝐢𝐠𝐡𝐭/𝐅𝐨𝐫𝐦𝐮𝐥𝐚 𝐖𝐞𝐢𝐠𝐡𝐭
 𝐄𝑺𝒂𝒍𝒕 =
𝐓𝐨𝐭𝐚𝐥 𝐩𝐨𝐬𝐢𝐭𝐢𝐯𝐞 𝐨𝐫 𝐧𝐞𝐠𝐚𝐭𝐢𝐯𝐞 𝐜𝐡𝐚𝐫𝐠𝐞
58.5 95 133.5
Ex: E𝑁𝑎𝐶𝑙 = = 58.5 E𝑀𝑔𝐶l2 = = 47.5 EAlCl3 = = 44.5
1 2 3
𝐆𝐌𝐖/𝐅𝐨𝐫𝐦𝐮𝐥𝐚 𝐖𝐞𝐢𝐠𝐡𝐭
 𝐄𝑶𝒙.𝒐𝒓 𝑹𝒆𝒅 𝒂𝒈𝒆𝒏𝒕 = Or
𝐓𝐨𝐭𝐚𝐥 𝐂𝐡𝐚𝐧𝐠𝐞 𝐢𝐧 𝐎𝐱𝐢𝐝𝐚𝐭𝐢𝐨𝐧 𝐧𝐮𝐦𝐛𝐞𝐫 𝐩𝐞𝐫 𝐦𝐨𝐥𝐞
𝐆𝐌𝐖/𝐅𝐨𝐫𝐦𝐮𝐥𝐚 𝐖𝐞𝐢𝐠𝐡𝐭
 𝐄𝑶𝒙.𝒐𝒓 𝑹𝒆𝒅 𝒂𝒈𝒆𝒏𝒕 =
𝐧𝐨. 𝐨𝐟 𝐞𝐥𝐞𝐜𝐫𝐭𝐨𝐧𝐬 𝐭𝐫𝐚𝐧𝐬𝐟𝐨𝐫𝐞𝐝 𝐩𝐞𝐫 𝐦𝐨𝐥𝐞 𝐢𝐧 𝐫𝐞𝐚𝐜𝐭𝐢𝐨𝐧
158
Ex: 1 MnO4− → Mn2+ (change in Ox. No = +7 to +2 = 5) ⇒ E𝐾𝑀𝑛O4 = = 31.6
5
158
Ex: 2 MnO4− → MnO2 (change in Ox. No = +7 to +4 = 3) ⇒ E𝐾𝑀𝑛O4 = 52.6
3
158
Ex: 3 MnO4− → MnO42− (change in Ox. No = +7 to +6 = 1)⇒ E𝐾𝑀𝑛O4 = = 158
1

Ex: 4 Cr2O72− → Cr3+

(Change in ave Ox. No = +6 to +3 = 3. For two Cr total change in Ox. No per mole=6)
294
EK2 Cr2 O7 = = 49
6

Eg: 5 Mohr's salt is Ferrous ammonium sulphate. Its formula is FeSO 4 (NH4)2 SO4. 6H2O,
in its reactions in acidic medium ferrous (Fe+2) ion gets oxidized to ferric (Fe+3);
392
Formula weight = 392. o GEW of Mohr's salt = = 392.
1

For ferrous oxalate in redox reaction, n-factor = 3.

By A. Baleswara Reddy Page 10
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9. Molality (m)
Molality: The number of gram moles of the solute present in one kg of solvent is
known as the Molality. It is represented by ‘m’. Units: moles/kg or mole Kg–1
number of moles of the solute n n×1000
𝑚= 𝑚= ⇒ 𝑚=
weight of the solvent in kgs 𝑊 0 (kg) 𝑊 0 (g)
W 1 W 1000
⇒ 𝑚= × ⇒ 𝑚= ×
GMW 𝑊 0 ( in kgs) GMW 𝑊 0 ( in gms)
 The molality of a solution does not change with temperature. i.e, molality is
independent of temperature.
 Molality is the most inconvenient method of expressing concentration of a solution
because it involves determining the weights of liquids.
10 × solubility
 The molality of a saturated solution is given by 𝑚 =
GMW
(If solubility is expressed in gms/100g of solvent)
 Relation between molality and Molarity is m × Wo = M × V
w
(w)% 1000
 When mass (w/w) % is given 𝑚 = × w
GMW 100 −( )%
w
w
( v )% 1000
 When (w/v)% and density given 𝑚 = × w
GMW 100 ×d −( v )%

 Relation between molality, Molarity and density

1000×M 1000×d×m
𝑚=
(1000×d)− M ×GMW
and M = 1000+ m ×GMW
 Relation between mole fraction and molality is
m Xsolute 1000
XSolute = 1000 and 𝑚= ×
m+ (1−Xsolute ) GMW of the solvent
GMW of solvent
Xsolute 1000
For very dilute solution we can take 𝑚= ×
1 GMW of the solvent
 Relation between Molarity, molality and density of solvent. m × dsolvent = M
(Assume volume of solvent and solution is same)
10. Mole fraction (X)
 Mole fraction: The ratio of the number of moles of one component to the total
number of moles of the all components in the solution is called mole fraction.
 It is represented by ‘X’ and it has no units. It is also independent of temperature.
 For a binary solution containing two components A and B,
n𝐴
The mole fraction of component-A is XA =
n𝐴 + n𝐵
n𝐵
The mole fraction of component-B is XB =
n𝐴 + n𝐵

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 Solutions
 For a solution containing ‘i' number of components, we have
n𝑖 n
Xi = =∑𝑖
n1 + n2 + n3+ ⋯………+ ni ni
 In any solution, the sum of mole fractions of all components is equal to unity (1)
x1 + x2 + .................. + xi = 1
 In a binary solution, XA + XB =1
X𝐴 n𝐴
 Ratio of mole fractions of two components is equal to ratio of their moles =
X𝐵 n𝐵
n𝐴
 For dilute solutions, mole fraction of solute can be taken as is X A =
n𝐵

 Relation between Molarity, density and mole fraction of solution

XA ×d×1000
M= [Here A=solute and B= solvent]
XA GMWA +XB GMWB
For gaseous Mixture
 Consider a binary gaseous system contain ‘A’ and ‘B’ gases, let partial pressure of
gas-A is PA, partial pressure of gas-B is PB and total pressure PT = PA + PB.
P𝐴 P𝐴
Mole fraction of gas-A is YA = =
P𝐴 + P𝐵 P𝑇
P𝐵 P𝐵
Mole fraction of gas-B is YB = =
P𝐴 + P𝐵 P𝑇

 Mole fraction is very useful in calculations involving gas mixtures and also in
relating some physical properties of solution like vapour pressure.
 One hundred times of mole fraction is called mole percentage. Mole fraction and
mole percentage have no units.
Mole percentage = Mole fraction ×100
Note
 Each method of expressing concentration of the solutions has its own merits and
demerits.
 Volume %, (w/v)%, strength of solution, Molarity, Formality and normality are
function of temperature because volume terms involved and it depends on
temperature.
 Mass %, ppm, mole fraction and molality are independent of temperature because
mass does not depends on temperature.
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑝𝑢𝑟𝑒
 % of purity = ×100
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑖𝑚𝑝𝑢𝑟𝑒
 Concentration of hydrogen peroxide can be expressed as follows
M N (w⁄V)% Strength Vol
= = = =
1 2 3.4 34 11.2
(Here strength of H2O2 depends on its units also)
By A. Baleswara Reddy Page 12
 Solutions
Solubility
 The maximum amount of solute that can dissolve in a specified amount (let 100gms)
of solvent to form a saturated solution at a given temperature is called its solubility.
 Solubility can be expressed as solute in g/100g of solvent or solute in g/1Kg of
solvent or M or m or mole fraction.
 Solubility depends on the nature of solute and solvent as well as temperature and
pressure.
 Solubility of a substance in a solvent can be predicted by using a concept of like
dissolves like. It means polar solutes dissolve in polar solvents like water, ethanol
etc and Non polar solutes dissolve in non polar solvents like benzene, ether, CCl 4 etc.
 In general, solubility can be possible to express for solid in liquid and gas in liquid
type of solutions and it is not suitable for most of the liquid in liquid solutions
because miscible liquids are always soluble at all proportions. (i.e; there is no
attainment of saturated condition for liquid in liquid solutions except few like
phenol water system)
1. Solubility of a solid in liquid
 The solution in which no more solute can be dissolved is called saturated solution.
 The solution in which some more solute can be dissolved is called unsaturated
solution.
 Saturated solution can be prepared by successive addition of solute to the given
amount of solute.
 The process of dissolving a solid solute into solvent or solution is called dissolution.
During dissolution process, solute loses its physical appearance and the
concentration of solution increases gradually.
 At high concentrations the dissolved solute particles in solution may collide with
each other and they separate from the solution in the form of solid crystals. It is
known as crystallization.
 After attainment of saturated condition the dissolution and crystallization takes
place simultaneously with equal rates. i.e a dynamic equilibrium exist between
dissolved solute and undissolved solute.
 Solute + solvent ⇌ solution or Solute (s) ⇌ Solute (aq)
 At this stage the concentration of solution remains constant and it is equal to
solubility.
By A. Baleswara Reddy Page 13
 Solutions
Factors affecting the solubility of a solid in a liquid
i) Nature of the solute and solvent
 Every solid does not dissolve in a given liquid.
 In general, polar solutes dissolve in polar solvents like water, ethanol etc and Non
polar solutes dissolve in non polar solvents like benzene, ether, CCl 4 etc.
Ex: Sodium chloride and sugar dissolve readily in water but not soluble in benzene.
On the other hand, naphthalene and anthracene dissolve readily in benzene but not
in water.
 It is observed that polar solutes dissolve in polar solvents and non polar solutes in
non-polar solvents. In general, a solute and solvent with similar intermolecular
interactions can soluble or we may say like dissolves like.
ii) Lattice energy, hydration energy and dielectric constant of solvent
 The solubility of an ionic solid in a liquid depends on Lattice energy and Hydration
energy.
 The amount of energy required to dissociate one mole of ionic crystal into its ions is
called Lattice energy.
 The amount of energy released when one mole of ions undergo hydration (combine
with water molecule through attractions) is called Hydration energy.
 If Hydration energy > Lattice energy, the solid dissolves in water.
 If Hydration energy < Lattice energy, the solid does not dissolves in water or slightly
soluble
 Lattice energy depends upon force of attraction between oppositely charged ions
q1 q2
and inversely proportional to dielectric constant of solvent. U= .
r2 ×D
 Where q1, q2 are charges, r distance between charges, D is the dielectric constant of
medium.
H.E and Di electric constant
 Solubility of ionic substance ∝ c
lattice energy

i.e; Ionic solids dissolve more in a solvent having high dielectric constant.
Solubility of NaCl Solvent Di electric constant
S1 Water 82
S2 Ethyl alcohol 33.5
S3 Benzene 2.3
The order of solubilities is S1 > S2 > S3
By A. Baleswara Reddy Page 14
 Solutions
iii) Presence of other substance
 Solubility of a substance is also depends of presence of other substance in medium
or solvent
Solubility of AgCl Medium
S1 Water
Aq. NH3 or NH4OH (Solubility increases)
S2
(AgCl + 2NH3→[Ag(NH3)2]Cl soluble complex)
S3 NaCl solution (Common ion effect decreases the solubility)
The order of solubilities is S2 > S1 > S3
iv) Temperature
 The effect of temperature on solubility of can be explained by using Le-chatelier
principle
Enthalpy of solution is given by ΔHsol’n = L.E (+ve) + H.E (–ve)
 If L.E > H.E, the dissolution process is endothermic (heat absorbing process ΔH =
+ve). Solute + solvent + Heat ⇌ solution Solubility ∝ T
The solubility should increase with increase in temperature.
Ex: Dissolution of NH4Cl, Glucose,...etc
 If L.E < H.E, the dissolution process is exothermic (heat releasing process ΔH = –ve)
𝟏
Solute + solvent ⇌ solution + Heat Solubility ∝
𝑻𝒆𝒎𝒑
The solubility should decrease with increase in temperature.
Ex: Dissolution of NaOH, KNO3...etc
v) Pressure
 There is no significant effect of pressure on solubility of solid in liquids because
solids and liquids are highly incompressible.

2. Solubility of a gas in a liquid

 Almost all gases are soluble in water to different extents. The existence of aquatic
life in lakes, rivers, sea etc. is due to dissolution of oxygen gas in water from air.
 Solubility of a gas in a liquid at a particular temperature is also expressed in terms of
molarity or molality or in terms of mole fraction (X A) of the gas.
 We know that the solution of gas in liquid in a closed vessel is always maintaining
dynamic equilibrium between dissolved gas and undissolved gas.
 Gas + solvent ⇌ solution or Gas(g) ⇌ Gas(aq)

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 Solutions
 Factors affecting the solubility of a gas in a liquid
i) Nature of the gas and solvent
 Solubility of gas is also depends on polar and non-polar nature of gas and liquid.
Oxygen, nitrogen and carbon dioxide are much more soluble in ethyl alcohol than in
water while H2S and NH3 are more soluble in water than in ethyl alcohol at the same
temperature and pressure. Here the greater solubility of these gases is due the
similar intermolecular attractions between the gas and the solvent. (like dissolves
like). Here note that, non-polar gases also can dissolve in polar solvent to small
extent. i.e; all gases can dissolve in all liquids to some extent.
 Easily liquefiable gases are more soluble and it is expressed in terms of critical
temperature also. [ Solubility ∝ Tc ]
Ex: SH2 <SCH4 < SNH3
 The greater solubility of certain gases is due to their reaction with the solvent.
Ex: hydrogen, oxygen, nitrogen, etc. dissolve in water only to a small extent whereas
gases like SO3, CO2, HCl, NH3, etc. are highly soluble in water.
SO3 + H2O → H2SO4 →2H+ + SO42– CO2 + H2O → H2CO3 →H+ + HCO3–
NH3 + H2O → NH4OH →NH4+ + OH– HCl + H2O → H3O+ +Cl–
 Therefore, generally the solubility of a gas in solvent depends on reactivity of gas
with solvent, critical temperature and also depends on polar and non-polar nature of
both gas and solvent.
ii) Presence of other substance
 Solubility of a gas is also depends on presence of other substances in medium or
solvent. For example, Solubility of CO2 in KCl solution is less than pure water but
solubility of CO2 in KOH solution is more than pure water.
iii)Temperature
 The dissolution of a gas in a liquid is always an exothermic process, i.e., it is
accompained by evolution of heat. (because here lattice energy for gases is zero)
Gas + solvent ⇌ solution + Heat
 According to Le Chatelier’s principle, increase of temperature would shift the
equilibrium in the backward direction.
𝟏
Therefore Solubility of gas ∝
𝑻𝒆𝒎𝒑
 The effect of temperature on solubility of gas in liquid is given by
C2 ∆H 1 1
log = [ − ] Where C1 and C2 are the concentrations of solution
C1 2.303R T1 T2
at T1 and T2 temperatures respectively, ΔH = Heat of solution of one mole of gas

By A. Baleswara Reddy Page 16

 Solutions
iv) Pressure (Henry’s law)
 The solubility of gases increase with increase of pressure.
 For solution of gases in a solvent, consider a
system as shown in Fig. (a). The lower part is
solution and the upper part is gaseous system at
pressure ‘p’ and temperature ‘T’.
 Assume this system to be in a state of dynamic equilibrium, i.e., under these
conditions rate of gaseous particles entering and leaving the solution phase is the
same. Now increase the pressure over the solution phase by compressing the gas to
a smaller volume [Fig.(b)]. This will increase the number of gaseous particles per
unit volume over the solution and also the rate at which the gaseous particles are
striking the surface of solution to enter it. The solubility of the gas will increase until
a new equilibrium is reached resulting in an increase in the pressure of a gas above
the solution and thus its solubility increases.
 The effect of pressure on solubility of a gas in a liquid is governed by Henry’s law.
 Henry was the first to give a quantitative relation between pressure and solubility of
a gas in a solvent which is known as Henry’s law.
 At a given temperature, the solubility of a gas in a liquid is directly proportional to
the partial pressure of gas on surface of liquid or solution. i.e, the solubility of gas
increases with increase of pressure. This is called Henry’s law.
 W (mass of gas) ∝ P ⇒ W = k.P (k = proportionality constant, units=g atm–1)
Note: The exact formula related to this depends on units of ‘k’.
If units of ‘k’ = Mol Lit–1 atm–1 ⇒ M = k.P (M=molarity)
If units of ‘k’ = Mol kg–1 atm–1 ⇒ m = k.P (m=molality)
If units of ‘k’ = atm–1 ⇒ x = k.P (x=mole fraction)
 Dalton, a contemporary of Henry, also concluded independently that the solubility of
a gas in a liquid solution is a function of partial pressure of the gas. If we use the
mole fraction of a gas in the solution as a measure of its solubility, then it can be said
that the mole fraction of gas in the solution is proportional to the partial pressure of
the gas over the solution.
 The most commonly used form of Henry’s law states that “the partial pressure of
the gas in vapour phase (p) is proportional to the mole fraction of the gas (x)
dissolved in the solution”. It is concluded by Dalton and is expressed as:
p ∝ x ⇒ p = KH x Where ‘KH’ is Henry’s law constant.

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 Solutions
Note: Here also in case of numericals, the exact formula depends on units of ‘K H’.
If units of ‘KH’ = Mol–1 Lit atm ⇒ p = KH M (M=molarity)
If units of ‘KH’ = Mol–1 kg atm ⇒ p = KH m (m=molality)
If units of ‘KH’ = atm ⇒ p = KH x (x=mole fraction)
If units of KH is not given, then we can take the basic formula p = KH x
 The experimental results for the solubility of HCl gas in
cyclohexane at 293K is shown in fig. The slope of the
straight line gives Henry’s law constant K H for HCl gas.
 KH is different for different gas and it also vary with
change in temperature or change of solvent.
 This suggests that KH is a function of the nature of the
gas and also solvent and temperature for a given gas.

 From above equation (p = KH x), higher the value of KH at a given pressure, the lower
is the solubility of the gas in the liquid.
𝟏 𝟏
Solubility of gas ∝ and we know Solubility of gas ∝ ⇒ KH ∝ Temp
𝑲𝑯 𝑻𝒆𝒎𝒑
 It can be seen from Table that K H values for both N2 and O2 increase with increase of
temperature indicating that the solubility of gases increases with decrease of
temperature. It is due to this reason that aquatic species are more comfortable in
cold waters (more dissolved oxygen) rather than in warm waters (less dissolved
oxygen).
 Gases are highly (maximum) soluble in a liquid at High pressure & Low temperature
Henry’s law constants for some gases in water

Limitations of Henry’s Law

 It is not applicable at very high pressure and very low temperature
 It is not applicable if gas is highly soluble in liquid.
 It is not applicable if gas react with solvent (or) gas undergo dissociation.
 NH3 + H2O → NH4+ + OH– HCl + H2O → H3O+ + Cl–

By A. Baleswara Reddy Page 18

 Solutions
Applications of Henry’s Law
 To Increase the solubility of CO2 gas in soda water and soft drinks, the bottle is
sealed under high pressure of the gas.
 At higher altitudes the partial pressure of oxygen is less. This leads to lower
concentration of oxygen in blood and tissues of mountain climbers and people living
at higher altitudes. Persons become weak and unable to think properly, due to lower
pressure of oxygen. These symptoms are called ‘anoxia’.
 Scuba (deep sea) divers when breaths air at high pressure in underwater, the
solubility of N2 gas in blood takes place. When the divers come towards surface, the
pressure gradually decreases and the dissolved gases releases which leads to the
formation of bubbles of nitrogen in the blood. These bubbles of nitrogen can blocks
capillaries and create a medical condition known as bends, which are painful and
dangerous to life.
To avoid bends, as well as, the toxic effects of high concentrations of nitrogen in
the blood, the tanks used by scuba divers are filled with air diluted with helium
(11.7% helium, 56.2% nitrogen and 32.1% oxygen).
 Oxygen in lungs present with high partial pressure and combines with haemoglobin
to form oxohaemoglobin and in tissues where partial pressure of oxygen is low,
releases oxygen for utilization in cellular activities.
 In practice, in any solution, the solute particles behaves ideally according to Henry's
law, the solvent particles behaves ideally according to Raoult's law.
Vapourization or Evaporation
 The liquid in an open vessel gradually escapes into vapour state from its surface.
 The phenomenon of escaping of molecules from surface of liquid to convert into
vapour is called Vapourization or Evaporation.
 During vapourization, liquid is converted into vapour spontaneously.
 Vapourization is surface phenomenon and it takes place at all temperatures. (Ex:
Evaporation of water at room temperature 35oC even water has 100oC boiling point)
 The molecules at the surface of liquid possess high kinetic energy and easily
overcome the attractive forces of the neighbouring molecules. So the molecules
readily escape from surface of liquid. In an open vessel the evaporation takes place
till the all liquid disappears.
 The molecules with lower K.E remain in the bulk and molecules with higher K.E at
surface are evaporated. So, during evaporation the ave. K.E of the liquid decreases
and therefore Temperature decreases. Evaporation of a liquid is endothermic
process. (Eg: water in pot become cool)
By A. Baleswara Reddy Page 19
 Solutions
 Boiling point: The temperature at which the vapour pressure of the liquid becomes
equal to the atmospheric pressure is called boiling point of the liquid.
 Evaporation occurs at all temperatures but boiling occurs only at boiling point and
above boiling point.
 The boiling point of a liquid changes with a change in external pressure and also by
addition of volatile or nonvolatile substances. B.P ∝ external pressure
Rate of evaporation
 The number of molecules escaping from the liquid surface in one second is called
rate of evaporation. The rate of evaporation depends on
1) Nature of the liquid 2) temperature
3) Surface area of the liquid 4) flow of air over the surface.
Condensation and Rate of condensation
 In a closed vessel, the evaporated molecules cannot escape into the atmosphere. So
the vapour molecules collide with each other, with walls of vessel and surface of
liquid. Among these some of the molecules with low kinetic energy are converted to
liquid by attracting the surface of liquid.
 The capturing of the vapour molecules of liquid by the surface of liquid is called
condensation. The number of molecules condensing on the liquid surface in one
second is called rate of condensation
 At any temperature, in a closed vessel, both evaporation and condensation takes
place simultaneously. After certain time, the rate of evaporation is equal to rate of
condensation. This is called equilibrium state of liquid and vapour.
Vapour pressure
 The pressure exerted by the vapour molecule on the surface of liquid when they are
in equilibrium with liquid at a given temperature is called vapour pressure.
 The vapour pressure of a liquid depends upon
1) Nature of the liquid 2) Temperature
 Vapour pressure of a liquid at a given temperature is inversely proportional to
strength of intermolecular attractions.
 When temperature increases, the rate of evaporation increases and thus vapour
pressure increases due to production of more vapour.
 The vapour pressure of the liquid depends on the fraction of solvent molecules
present on the surface of liquid. Therefore, presence of other non-volatile particles
on surface can decreases the vapour pressure of liquid.

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 Solutions
 Variation of vapour pressures of some liquids with temperature is given graphically
in Fig.
 Boiling point ∝ attractions
1
 Boiling point ∝
V.P
Clausius- Clapeyron equation
−∆H −∆H
 p∝e RT ⇒p =𝐾e RT

−∆H
 ⇒ ln p = + 𝑙𝑛𝐾
RT
−∆H
 ⇒ log p = + 𝑙𝑜𝑔𝐾
2.303RT

 From the above equation, a plot between

‘log P’ and 1/T gives a straight line with
negative slope.
 The variation of vapour pressure of a
liquid at two different temperatures is
P2 ∆H 1 1
given by ⇒ log = [ − ]
P1 2.303R T1 T2

 Where P1 and P2 are the vapour pressures of liquid at T1 and T2 temperatures

respectively
ΔH = Heat of vaporization per mole R = Gas constant.
 This equation is called ‘Clausius- Clapeyron equation’
Volatile and non volatile liquids
 The liquids whose vapour pressures are high at room temperature are called
volatile liquids.
Ex: Ether, CCl4, Acetone...etc. In these liquids intermolecular forces are weak.
 The liquids whose vapour pressures are low at room temperature are called non
volatile liquids.
Ex: Aniline, nitrobenzene, phenol, Mercury...etc. In these liquids intermolecular
forces are Strong.

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 Solutions
Vapour Pressure of Solutions of Solids in Liquids
 Solution of cane sugar or glucose or urea or a salt in water and a solution of sulphur
or iodine or naphthalene dissolved in carbon disulphide are solutions of a solid in a
liquid.
 Some physical properties of such solutions are quite different from those of pure
solvent.
 If a non-volatile solute is added to a solvent to give a solution [Fig], now the vapour
pressure of the solution is only from the solvent molecules.
 This vapour pressure of the solution at a given temperature is found to be lower
than the vapour pressure of the pure solvent at the same temperature.
 In a pure liquid (solvent) the entire surface is
occupied by the molecules of the liquid. But
in the solution, the surface is occupied with
both solute and solvent molecules.
 Therefore the fraction of the surface covered
by the solvent molecules decreased.
 Consequently, the number of solvent molecules escaping from the surface is reduced
and the vapour pressure is also reduced.
 Here the decrease in the vapour pressure depends on the quantity of non-volatile
solute present in the solution, irrespective of its nature.
Lowering of vapour pressure: The difference between the vapour pressure of the pure
solvent (po) and vapour pressure of solution (p) is called lowering of vapour pressure
(ΔP) of solvent in a solution L. V. P = Δp = p0 − p
Relative Lowering of vapour pressure: The ratio of lowering of vapour pressure (Δp) of
a solution to the vapour pressure (po) of pure solvent is called relative lowering of
p0 −p Δp
vapour pressure. It can be shown as R. L. V. P = =
p0 p0
According to Von Babo, RLVP of a solution is remains same at all temperatures.
Raoult’s law
 According to Raoult’s law, in any solution, the partial vapour pressure of each
volatile component is directly proportional to its mole fraction.
 In a binary solution of non-volatile solute (A) in solvent (B), only solvent is a volatile
component. Therefore at a given temperature, the vapour pressure of solution (p) is
directly proportional to mole fraction of solvent.

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 Solutions
 Then according to Raoult’s law p ∝ XB ⇒ p = po XB
 Here the proportionality constant is equal to the
vapour pressure of pure solvent.
 A plot between the vapour pressure and the mole
fraction of the solvent is linear (Fig).
p
o Consider the equation p = po XB ⇒ = XB
p0
o We know, XA+XB = 1 ⇒ XB = 1–XA
p p 𝑝0 −p
= 1–XA ⇒ 1– = XA ⇒ = XA
p0 0
p 𝑝0
o It is called simplified Raoult’s law and it is defined as the RLVP of a solution is equal
𝑝0 −p nA
to mole fraction of solute. RLVP = =
𝑝0 nA +nB
𝑝0 −p nA
For dilute solutions, nB >>> nA and nA+nB ≂ nB, we can write =
𝑝0 nB
wA
𝑝0 −p ⁄mA 𝑝0 −p wA MB wA ×MB 𝑝0
⇒ = WB ⇒ = × mA = ×
𝑝0 ⁄M 𝑝0 mA WB WB 𝑝0 −p
B
Where wA, WB are the weights of solute and solvent, mA, MB are the molecular
weights of solute and solvent respectively.
 The above equation represents the relation between molar mass of solute and
relative lowering of vapour pressure. So it is useful for determination molar mass of
unknown solute by substituting the above values.
Limitations of Raoult’s law
It is applicable to 1) dilute solutions only
2) Solution containing non-volatile solute and is in molecular state.
3) Solutions containing solutes, which undergo neither dissociation nor association.
4) It is applicable only for ideal solutions
Vapour pressure of liquid-liquid solution
 Take a binary solution of two volatile liquid components ‘A’ and ‘B’ in a closed
vessel. At a given temperature both the component are vaporized and after some
time equilibrium is established between liquid state and vapour state of both liquids.
 Raoult’s law states that, for a solution of two volatile liquids, the partial vapour
pressure of each component of the solution is directly proportional to its mole
fraction in solution. Consider a solution of two volatile liquids ‘A’ and ‘B’
For component ‘A’ pA ∝ xA and pA = poA xA ............. (1)
For component ‘B’ pB ∝ xB and pB = poB xB ............. (2)

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 Solutions
 Where pA and pB are the partial vapour pressures of component A and B, poA and poB
are the vapour pressures of pure component A and B & xA and xB are the mole
fractions of component A and B respectively
 According to Dalton’s law of partial pressures, the total vapour pressure over the
surface of solutions is equal to the sum of the partial vapour pressures of
components present in the solution. ptotal = pA + pB
 Substituting values of pA and pB in above equation, we get
ptotal = poA xA + poB xB
= poA xA + poB (1-xA) (since xA+xB =1)
= poA xA + poB − poB xA
ptotal = poB + (poA − poB) xA ............. (3)
Or ptotal = poA + (poB − poA) xB ............ (4)
From the above equations 3 and 4, we can say,
i. Total vapour pressure over the solution can be related to the mole fraction of any
one component
ii. Total vapour pressure over the solution varies linearly with the mole fraction of any
one of the component.
iii. Depending on vapour pressures of pure components, total vapour pressure of the
solution is lower than V.P of pure more volatile component and higher than V.P of
pure less volatile component.
 A plot of pA or pB & pT versus the mole
fractions xA and xB for solution gives a linear
plot as shown in figure.
 Let component-A is less volatile than
component-B (poA < poB) then the minimum
value of ptotal = poA the maximum value of ptotal
= poB.

 If yA and yB are the mole fractions of the component-A and B respectively in vapour
phase, according to Dalton’s law of partial pressures
𝑝𝐴 𝑝𝐵
 pA = yA . ptotal => 𝑦𝐴 = and pB = yB . ptotal => 𝑦𝐵 =
𝑝𝑡𝑜𝑡𝑎𝑙 𝑝𝑡𝑜𝑡𝑎𝑙

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 Solutions
Raoult’s Law as a special case of Henry’s Law
 According to Raoult’s law, the partial vapour pressure of a volatile component in a
given solution is given by pA = poA xA.
 In the solution of a gas in a liquid, one of the components is also volatile that it exists
as a gas and we can write equation for partial vapour pressure using Henry’s law
and it is given by pA = KH xA.
 If we compare the equations for Raoult’s law and Henry’s law, it is observed that the
partial pressure of the volatile component or gas is directly proportional to its mole
fraction in solution. Only the proportionality constants are different. K H differs from
poA. Thus, Raoult’s law becomes a special case of Henry’s law in which K H becomes
equal to poA.
Ideal and Non-ideal Solutions
Liquid in liquid solutions can be classified into ideal and non-ideal solutions on the
basis of obeying Raoult’s law.
Ideal Solutions
 The solutions which obey the Raoult’s law over the entire range of concentration are
known as ideal solutions. An ideal solution is generally formed by mixing of two
liquids have same molecular structures, similar molecular sizes and both liquids
have identical intermolecular forces.
 A perfectly ideal solution is rare but some solutions are nearly ideal in behavior.
 Ex: (n-Hexane + n- heptane), (benzene + toluene), (C6H5Cl + C6H5Br),
(bromoethane + chloroethane), (Ethylene chloride + Ethylene bromide)
(Carbon tetrachloride + silicon tetrachloride), (Ethyl bromide + ethyl iodide),
 In an ideal solutions solute-solvent (A-B) interactions are equal or nearly equal to
interactions of solute-solute (A-A) and solvent-solvent (B-B).
 In ideal solutions, there is no chemical reaction between solute and solvent and
solute don’t undergo dissociation or association.
 During formation of ideal solutions there is no change in enthalpy and volume.
i.e, ΔHMix = 0 and ΔVMix = 0
 It means no heat is absorbed or evolved when components are mixed and Volume of
solution is equal to sum of the volumes of individual liquids.
 For ideal solutions, experimentally determined vapour pressure of each component
and solution is equal to vapour pressure calculated from Raoult’s law
pA(exp) = poA xA pB(exp) = poB xB & pT(exp) = poA xA + poB xB

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 Solutions
Non-ideal Solutions
 The solutions which do not obey Raoult’s law over entire range of concentrations
are called non-ideal solutions.
 In non-ideal solution, solute-solvent interactions are different than solute-solute and
solvent-solvent interactions.
 Therefore during formation of non-ideal solutions there is a change in enthalpy and
volume.
i.e, ΔH ≠ 0 and ΔV ≠ 0
 For non-ideal solutions, experimentally determined vapour pressure of each
component and solution is not equal to vapour pressure calculated from Raoult’s
law pA(exp) ≠ poA xA pB(exp) ≠ poB xB & pT(exp) ≠ poA xA + poB xB
Solutions with positive deviation
 In this type of solutions solvent-solute interactions are weaker than solvent-solvent
and solute-solute interactions. Due to this, more molecules are escape from surface
of solution than expected and it increases the vapour pressure of solution.
 During formation of these ideal solutions, ΔH Mix = +ve or ΔHMix > 0 and ΔVMix = +ve
or ΔVMix > 0
 It means heat is absorbed when components
are mixed and Volume of solution is more
than sum of the volumes of individual
liquids.
 For non-ideal solutions showing positive
deviation, experimentally determined
vapour pressure of each component and
solution is greater than vapour pressure
calculated from Raoult’s law
pA(exp) > poA xA pB(exp) > poB xB & pT(exp) > poA xA + poB xB
Eg: A mixture of ethanol and hexane shows positive deviation from Raoult’s law
 We know that in ethanol, the molecules are associated through intermolecular
hydrogen bonding and in hexane the molecules are associated through Vander
Waal’s forces.
 In a mixture of ethanol and hexane, hexane molecules are come in between ethanol
molecules which weaken intermolecular forces. This results in the increase in
vapour pressure. The molecules are loosely held in solution, due to the decrease in
the magnitude of intermolecular forces.
 This leads to an increase in volume ΔVmix = +ve.
By A. Baleswara Reddy Page 26
 Solutions
Other examples
(Acetone + Ethyl alcohol), (Water + Ethyl alcohol),
(CCl4 + CHCl3), (CCl4 + Toluene),
(Water + Methyl alcohol), (Cyclohexane + Ethyl alcohol),
(Acetone + Benzene), (Acetone + CS2)
 Solution showing positive deviation forms minimum boiling azeotropes.
Solutions with negative deviation
 In this type of solutions solvent-solute interactions are stronger than solvent-solvent
and solute-solute interactions. Due to this, less molecules are escape from surface of
solution than expected and it decreases the vapour pressure of solution.
 During formation of these ideal solutions, ΔH Mix = –ve or ΔHMix < 0 and ΔVMix = –ve or
ΔVMix < 0
 It means heat is evolved when components
are mixed and Volume of solution is less than
sum of the volumes of individual liquids.
 For non-ideal solutions showing negative
deviation, experimentally determined
vapour pressure of each component and
solution is lower than vapour pressure
calculated from Raoult’s law
pA(exp) < poA xA pB(exp) < poB xB & pT(exp) < poA xA + poB xB
Eg: A mixture of Acetone and chloroform shows negative deviation from Raoult’s law
 In a mixture of acetone and chloroform, between acetone and chloroform molecules
strong attraction will be developed due to formation of hydrogen bonding. Carbon
atom in chloroform becomes more electropositive due to the inductive effect by
three chlorine atoms.
 Thus hydrogen atom of chloroform acquires more
partial positive charge to develop hydrogen bonding
with carbonyl oxygen atom of acetone and it results in
the evolution of heat energy. ΔH (mix) is negative.
Other examples
(Chloroform + ether), (Water + Nitric acid),
(acetone and aniline), (Chloroform + Nitric acid),
(Water + HCl), (Chloroform + Benzene),
(Methanol + acetic acid), (Pyridine + acetic acid)
 Solution showing negative deviation forms maximum boiling azeotropes.
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 Solutions
Azeotropic mixtures
 A binary mixture of liquid in liquid which has same composition in liquid and vapour
phase and both liquids boil at a constant temperature is called azeotrope or
azeotropic mixture
 A binary mixture of liquid in liquid which can distills without a change in its
composition at a particular temperature is called azeotropic mixture or azeotrope.
 Separation of components from azeotropic mixture is not possible by distillation or
fractional distillation.
Azeotropic mixtures are basically non-ideal solutions. They are of two types:
(a) Minimum boiling point azeotropes and (b) Maximum boiling point azeotropes.
Minimum boiling point azeotropes
 The azeotropes whose boiling point is less than either of the B.p’s of two pure
components are called Minimum boiling point azeotropes.
 The solutions which show a large positive deviation from Raoult’s law form
minimum boiling azeotropes at a specific composition.
Eg: Rectified spirit obtained from fermented sugars contains about 95.5% ethanol
(bp=351.83K) and 4.5% water (bp=373K) by volume is an example of minimum
boiling azeotrope. It boils at 351.15K
Maximum boiling point azeotropes
 The azeotropes whose boiling point is greater than either of the B.p’s of two pure
components are called Maximum boiling point azeotropes.
 The solutions which show a large negative deviation from Raoult’s law form
maximum boiling azeotropes at a specific composition.
 Eg: This azeotrope has the approximate composition, 68% nitric acid (bp=357K) and
32% water (bp=373K) by mass, with a boiling point of 393.5 K.
Zeotropic mixtures
A binary mixture having the different composition in vapour phase and the
separation of components is possible by fractional distillation is called Zeotropic
mixture.
Note: For mixing of two components to get homogeneous mixture, always entropy
increases (ΔS = +ve) and ΔG = –ve.

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 Solutions
Colligative Properties and Determination of molar mass
 Generally the physical and chemical properties of aqueous solution depend on the
nature and structure of solutes. But there are some properties which depend on
number of solute particles but not on their nature. Such properties are called
Colligative properties.
 The properties of dilute solutions containing non-volatile solute which depends only
on number of solute particles irrespective of nature of solute are called Colligative
properties.
These are:
a) Relative lowering of vapour pressure of the solvent
b) Depression of freezing point of the solvent
c) Elevation of boiling point of the solvent and
d) Osmotic pressure of the solution.
 Colligative properties are generally used to determine molecular weights of non
volatile solutes.
Relative lowering of vapour pressure (Refer Vapour pressure of solid in liquid)
Elevation of boiling point
Boiling point: The temperature at which the vapour pressure of the liquid becomes
equal to the atmospheric pressure is called boiling point of the liquid.
 The boiling point of a solution containing non volatile solute is always greater than
that of pure solvent. This increase in boiling point is called the elevation in boiling
point.
 The elevation in boiling point of solution is due to
lowering of vapour pressure of solution. i.e. at the
boiling point of pure solvent, the vapour pressure
of solution is less than 1 atm pressure. Hence, in
order to increase the vapour pressure of solution
to 1 atm, it is heated to more temperature.
 Therefore the boiling point of a solution containing non volatile solute is always
greater than that of pure solvent.
Elevation of boiling point: The difference between the boiling point (Tb) of a dilute
solution containing non-volatile solute and boiling point (Tbo) of pure solvent is called
elevation in boiling point. Δ b = Tb − Tbo
1 1
V.P ∝ B.P ∝ B.P ∝ Conc E.B.P ∝ Conc
Conc V.P

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 Solutions
 The experimental results show that, the elevation in boiling point is directly
proportional to the molality of the solution. ΔTb ∝ m Or ΔTb = Kb m
Here Kb is called molal elevation constant or Ebullioscopic constant
 The elevation in the boiling point of one molal solution is called Ebullioscopic
constant (Kb). This is also called molal elevation constant. Units of K b = K kg mol−1
W𝐴 1000
 We know that 𝑚 = ×
M𝐴 W𝐵 ( in gms)
W𝐴 1000 Kb × WA× 1000
ΔT𝑏 = K 𝑏 × × ⇒ MA =
M𝐴 W𝐵 ( in gms) ΔTb ×WB
Where MA = molar mass of solute, WA = weight of solute, WB = weight of solvent
Calculation of molal depression constant from enthalpy of fusion
R T2o MB R T2o ∆Hvap
 Kb = = (∵ lv = )
1000×lv 1000×∆Hvap MB

Where lv = latent heat of vapourization = Enthalpy of vap’n per gram of the solvent
∆Hvap = Enthalpy of vapourization per mole of the solvent
To= Boiling point of pure solvent MB = molecular mass of the solvent
R = 8.314K–1 mol–1, if lv or ∆Hvapare in joules
R = 2 cal deg–1mol–1, if lv or ∆Hvap are in calories
Depression in freezing point
Freezing point: The temperature at which the solid and the liquid forms of the liquid
are in equilibrium with each other and vapour pressure of liquid phase become equal to
solid phase is called Freezing point. Eg. Ice and water at 0oC
 For a given liquid, Freezing capacity (or) solidification ∝ Vapour pressure
 The freezing point of a solution containing non volatile solute is always less than
that of pure solvent. This decrease is called the depression in freezing point.
 The depression in freezing point of solution
is due to lowering of vapour pressure of
solution. i.e. at the freezing point of pure
liquid, the vapour pressure of solution in
liquid phase is not equal to solid phase.
Hence, in order to equalize the vapour
pressure of solid phase and liquid phase, it
is cooled to less temperature. Therefore the
freezing point of solution containing non-
volatile solute is always less than that of
pure solvent.

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 Solutions
Depression in freezing point: The difference between the freezing point (Tfo) of pure
solvent and freezing point (Tf) of a dilute solution containing non-volatile solute is
called depression of freezing point. ΔTf = Tfo – Tf
1 1
V.P ∝ F.P ∝ V.P F.P ∝ D.F.P ∝ Conc
Conc Conc
 The experimental results show that, the depression of freezing point is directly
proportional to the molality of the solution. ΔTf ∝ m ⇒ ΔTf = Kf m
Here Kf is called molality depression constant or Cryoscopic constant
 The depression of freezing point of one molal solution is called Cryoscopic constant
(Kf). This is also called molal depression constant. Units of Kf = K kg mol−1
WA 1000 Kf × WA × 1000
ΔTf = K f × × ⇒ MA =
MA WB (in gms) ΔTf ×WB

Where MA = molar mass of solute, WA = weight of solute, WB = weight of solvent

Calculation of molal depression constant from enthalpy of fusion
R T2o MB R T2o ∆Hf
 Kf = = (∵ lf = )
1000×lf 1000×∆Hf MB

Where lf = latent heat of vapourization / enthalpy of Vap’n per gram of the solvent
∆Hf = latent heat of vapourization per mole of the solvent
To= Freezing point of pure solvent MB = molecular mass of the solvent
Cryoscopic and ebullioscopic constants of some solvents are listed in Table
Solvent b.p./K Kb/K kg mol-1 f.p./K Kf/K kg mol-1
Water 373.15 0.52 273.0 1.86
Ethanol 351.5 1.20 155.7 1.99
Cyclohexane 353.74 2.79 279.55 20.00
Benzene 353.3 2.53 278.6 5.12
Chloroform 334 3.63 209.6 4.79
Carbon tetrachloride 350.0 5.03 250.5 31.8
Carbon disulphide 319.4 2.34 164.2 3.83
Diethyl ether 307.8 2.02 156.9 1.79
Acetic acid 391.1 2.93 290.0 3.90

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 Solutions
Osmosis and Osmotic Pressure
Semi permeable membranes (SPM): The membrane which allows the free passage of
only solvent molecules through it, but not the solute molecules, is called a semi
permeable membrane.
Eg: Parchment paper, cellophane paper (synthetic membrane), pig’s bladder some
animal membranes and inorganic precipitate membranes (copper ferrocyanide) are
commonly used as semi permeable membrane in osmosis.
Osmosis: The spontaneous flow of solvent molecules through the semi permeable
membrane from pure solvent to solution or from dilute solution to concentrated
solution is called Osmosis. This flow will continue till the equilibrium is attained.
Osmotic pressure
The hydrostatic pressure developed on the
solution at equilibrium state due to osmosis
when the solution is separated from the pure
solvent by a semi permeable membrane is called
osmotic pressure. Or
The pressure applied on the solution to just stop
the osmosis is called Osmotic pressure.
 It is represented with ‘π’. W
When height is involved, osmotic pressure is also expressed as π = hdg
Where h = height, d = density of the solution and g = gravitational acceleration
 According to Van’t Hoff law for dilute solutions, a non volatile solute in a dilute
solution behaves like a gas and all gas laws are applicable to dilute solutions.
 Therefore, the Osmotic pressure of a solution is related as
n
π V = nRT ⇒ π = ( ) RT ⇒ π = CRT ⇒ π ∝ 𝐶 (at constant temperature)
V

 The osmotic pressure of a solution is directly proportional to the concentration of

the solution. Hence it is a colligative property.
W𝐴 𝑅𝑇 W𝐴 𝑅𝑇
 Therefore osmotic pressure is given by π = ⇒ M𝐴 =
M𝐴 V(𝑙) π V(𝑙)

 Where MA = molar mass of solute, WA = weight of solute, V = Volume of solution in lit,

T= temperature and R = molar solution constant = 0.0821lit atm K -1 mol-1
 The above equation gives the relation between molar mass and osmotic pressure.

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 Solutions
 Measurement of osmotic pressure provides another method of determining molar
masses of solutes. This method is widely used to determine molar masses of
proteins, polymers and other macromolecules.
 The osmotic pressure method has the advantage over other methods as
o Pressure measurement is around the room temperature
o Involves in the measurement of molarity instead of molality and mole fraction.
o As compared to other colligative properties, its magnitude is large even for very
dilute solutions.
o The technique of osmotic pressure for determination of molar mass of solutes is
particularly useful for biomolecules as they are generally not stable at higher
temperatures
o Polymers have poor solubility in a given solvent and other colligative properties
are not significant except osmotic pressure.
Isotonic solutions
Pair of solutions having same osmotic pressure at a given temperature are known as
isotonic solutions. (π1 = π2 )
Eg: Osmotic pressure associated with the fluid inside the blood cell is equivalent to that
of 0.9% (w/v) sodium chloride solution, called normal saline solution.
 If isotonic solutions are separated by SPM, osmosis doesn’t takes place but flow of
solvent molecules takesplace across the membrane with equal rate in opposite
direction.
 Isotonic solutions have same molar concentration. For isotonic solutions π1 = π2
W𝐴1 W𝐴2 n1 n2
Therefore C1𝑅𝑇 = C2𝑅𝑇 ⇒ C1 = C2 ⇒ = ⇒ =
M𝐴1 ×V1 M𝐴2 ×V2 V1 V2

 Solution having higher concentration and possess greater osmotic pressure is called
Hypertonic solution. Solution having less concentration and possess lesser osmotic
pressure is Hypotonic solution.
Eg: Among 1M glucose solution and 2M glucose solution, 1M glucose solution is
hypotonic w.r.t 2M glucose solution and 2M glucose solution is hypertonic w.r.t 1M
glucose solution.
 If we place cells in a solution containing more than 0.9% (w/v) sodium chloride,
water will flow out of the cells and cells would shrink. Such a solution is called
hypertonic. If the salt concentration is less than 0.9% (w/v), water will flow into the
cells and they would swell. Such a solution is called hypotonic

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 Solutions
Application of osmosis
 Plants take up water from the soil through the phenomenon of osmosis through root
hairs.
 A raw mango placed in concentrated salt solution loses water due to osmosis and
shrivel into pickle.
 A carrot become limp (looses strength) when placed in water
 Wilted flowers revive (get energy) when placed in fresh water
 People taking a lot of salt (or) salty food experience water retention in tissue cells
and intercellular spaces results puffiness (or) swelling called edema
 The preservation of meat by salting and fruits by adding sugar protects against
bacterial action because bacterium on salted meat (or) candid fruit loses water
shrivels and dies.
 If the osmotic pressure of the contents of the living cell is not equal to that of the
contents surrounding it outside, two phenomena take place. They are haemolysis
and plasmolysis.
 Haemolysis is a process of entering of contents into the cell. The cell bulges (swells)
and finally bursts. Plasmolysis is a process of losing contents from the cell. The cell
collapses.
Reverse osmosis
 If a pressure higher than osmotic pressure is applied on the solution, the solvent
molecules will flow from solution to solvent side through SPM. This phenomenon is
called reverse osmosis.
 Reverse osmosis is used in desalination of sea water to get fresh drinking water.
 A schematic set up for the process is shown in Fig.
 When pressure more than osmotic pressure
is applied, pure water is squeezed out (come
out by applying pressure) from the sea water
through the membrane.
 A variety of polymer membranes are
available for this purpose.
 Cellulose acetate allows the water but not allows the impurities and ions present in
sea water during reverse osmosis.
 These days many countries use desalination plants to meet their potable water
requirements.

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 Solutions
Abnormal molar masses
Normal Molar mass: If the calculated molar mass of solute using colligative property is
equal or nearly equal to true molar mass of solute, it is said to be normal molar mass.
Eg: Glucose, urea
Abnormal molar mass: In certain solutions, the calculated molar mass of solute using
colligative property is widely deviate from true molar mass of solute; it is said to be
abnormal molar mass. Or
Molar mass which determined using colligative property is either lower or higher than
the expected (true) value is called abnormal molar mass.
Eg: NaCl, Acetic acid in benzene.
 According to Van’t Hoff’s, abnormal molar mass of solutes is due to either
dissociation or association of solute particles when dissolved in solvent
 Eg: If we dissolve one formula weight of sodium chloride, (58.5g) in water, we
expect one mole each of Na+ and Cl– ions to be released in the solution. Therefore
there will be two moles of solute particles in the solution. If we assume that NaCl is
completely dissociated in water and increase in boiling point of water is 1.04K but
not 0.52K (expected) and we get the molar mass of NaCl as 29.25 g mol–1 but not
58.5 g mol–1.
 Therefore the experimentally determined molar mass is always lower than the true
value when dissociation of solute takes place.
 Similarly, the experimentally determined molar mass is always higher than the true
value when association of solute takes place. (Acetic acid)
Van’t Hoff factor ‘i’
Van’t Hoff introduced a factor ‘i’ to correct the abnormal molar mass into normal molar
mass and it is defined as
Normal (true) molar mass
𝑖=
Abnormal (Experimantal) molar mass
Experimantal (observed) Colligative property
𝑖=
Normal (calculated) Colligative property
total no.of moles of particals after dissociation /association
𝑖=
no.of moles of particals before dissociation /association
Therefore the equations of colligative properties are modified as follows by considering
‘i’ value to get correct molar mass of solute.
𝑝0 −p wA MB
=𝑖× × ΔTb = 𝑖 ×Kb m ΔTf = 𝑖 ×Kf m π = 𝑖 × 𝐶𝑅𝑇
𝑝0 mA WB
For isotonic solutions also i1C1 = i2C2
By A. Baleswara Reddy Page 35
 Solutions
Van’t Hoff factor ‘i’ and degree of dissociation
If a molecule of solute on dissociation gives ‘n’ ions and ′α′ is the degree of dissociation
then, An → nA
Before dissociation 1 0
After dissociation 1−α nα
1 + α(n−1) i−1
𝑖= ⇒ i = 1 + α(n − 1) ⇒ α=
1 n−1

For complete dissociation i = n

Van’t Hoff factor ‘i’ and degree of association
If ‘n’ number of molecules of solute on association gives one particle and α is the degree
of association then, nA → An
Before Association 1 0
After Association 1−α α/n
1
1+ α ( −1) 1 i−1 1−i
n
𝑖= ⇒ 𝑖 = 1 + α ( − 1) ⇒ α=1 or α = 1
1 n
n
−1 1−n

𝟏
For complete association i =
𝒏

For dissociation ⇒ i > 1 For association ⇒ i < 1

For a solute undergo neither dissociation nor association ⇒ i = 1

By A. Baleswara Reddy Page 36