CHAPTER - SOLUTIONS

TYPES OF SOLUTIONS: Table 2.1 (Page no. 34, NCERT Text Book)

Expressing Concentration of Solution

1. Mass percentage (w/w): Mass of component in the solution X 100
Total mass of solution

2. Volume percentage (V/V): Volume of the component X 100

Total volume of solution

3. Mass by volume percentage (w/V) = Mass of solute dissolved in

100ml solution

4. Parts per million = Number of parts of the component X 106

Total number of parts of all components of the solution

5. Mole Fraction = Number of moles of the component

Total number of moles of all the components

Mole fraction is a very important unit in relating some physical properties of

solutions, say vapour pressure with the concentration of solution.

SOLUBILITY: Solubility of a solid in a liquid, effect of temperature and pressure on

solubility. Pressure does not have any significant effect but for temperature, if the
dissolution process is endothermic, solubility should increase with increase in
temperature and vice versa.

➢ Solubility of a gas in a liquid.

1. Henry’s Law:
The law states that at a constant temperature the solubility of a gas in a
liquid is directly proportional to the partial pressure of the gas present
above the surface of the liquid or solution.

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 It can also be said that the mole fraction of gas in the solution is proportional
to the partial pressure of the gas over the solution.
Most commonly used form of Henrys law states that the partial pressure of
the gas in the vapour phase is proportional to the mole fraction of the gas in
the solution.

p = KH x, KH is Henry’s law constant.

Application - Bends, anoxia.

Vapour Pressure of Liquid-liquid solution

• Raoult’s Law
The law states that for a solution of volatile liquids the partial vapour pressure
of each component of the solution is directly proportional to its mole fraction
present in solution.
P1 ∝x1
And, p1 = p1o x1
Similarly, p2 = p2o x2 (where symbols have their usual meanings)
According to Dalton’s Law of Partial pressures
Ptotal = p1 + p2
Substituting p1 and p2
Ptotal= x1p1o + x2p2o
= (1-x2) p1o + x2p2o

Raoult’s Law as a special case of Henry’s Law

Raoult’s law becomes a special case of Henry’s law when KH becomes equal to
p1o
IDEAL SOLUTION:-
The solution which obeys Raoult’s law over the entire range of concentration when
enthalpy of mixing and vol. of mixing of pure component to form solution is zero.
CONDITIONS
I. PA=P0AXA PB = P0BXB
II.ΔHMIX=0
Ill. ΔVMIX=0
This is only possible if A-B interaction is nearly equal to those between A-A and B-B
interactions. e.g. :- solution of n-hexane and n-heptane.

NON IDEAL SOLUTION:-

The solution which does not obey Raoult’s law over the entire range of
concentrations.

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CONDITIONS
I. PA ≠ P°A XA PB ≠ PB0XB
II. ΔHMIX≠ 0
III. ΔVMIX≠ 0
The vapour pressure of such solutions is either higher or lower than that predicted
for Raoult’s law.
I. If vapour pressure is higher, the solution shows positive deviation (A-B interaction
are weaker than those between A-A and B-B).
Ex: mixture of ethanol and acetone.
PA> P°AXA; PB>P°BXB
ΔHMIX= Positive; ΔVMIX= Positive
II. If vapour pressure is lower, the solution shows negative deviation (A-B
interaction are stronger than those between A-A and B-B).
Ex: mixture of chloroform and acetone.
PA<P°A XA; PB<P0BXB
ΔH MIX = negative; ΔVMIX= negative

AZEOTROPE:
Mixture of liquids having the same composition in liquid and vapour phase and boil
at constant temperature. Azeotropes are of two types: -
a) Minimum boiling azeotrope:- The solution which shows a large positive
deviation from Raoult’s law. ex- ethanol —water mixture.
b) Maximum boiling azeotrope: -The solution which shows large negative deviation
from Raoult’s law. Ex- nitric acid — water mixture.

COLLIGATIVE PROPERTIES: -
Properties of ideal solution which depends upon no. of particles of solute but
independent of the nature of the particles are called colligative properties.

1. RELATIVE LOWERING OF VAPOUR PRESSURE:-

P0A -PA/P0A= XB
XB= nB/ nA+nB
For dilute solution, nB<<nA, hence nB is neglected in the denominator.
0
𝑃𝐴− 𝑛𝐵
=
𝑃 𝐴
𝑃𝐴0 𝑛𝐴
P0 A-PA/P A=
0 WB X MA/MB X WA

2. ELEVATION OF BOILING POINT

ΔTb= Kbm Where, ∆Tb= ΔTb—T°b
Kb= molal elevation constant / Ebullioscopic constant
m = molality

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 𝐾𝑏 ×1000×𝑊𝐵
M= ∆𝑇𝑏 ×𝑊𝐴

3. DEPRESSION IN FREEZING POINT:-

ΔTf= Kf m where , ΔTf = T0f - Tf
Kf= molal depression constant/ Cryoscopic constant
m = molality
𝐾 ×1000×𝑊𝐵
M= 𝑓 ∆𝑇 ×𝑊
𝑓 𝐴

OSMOSIS AND OSMOTIC PRESSURE

When separated by a semi permeable membrane the solvent molecules will
flow through the membrane from pure solvent to the solution. This process of
flow of the solvent is called osmosis.

The flow will continue till equilibrium is attained. This flow of the solvent from
its side to the solution side can be stopped if some extra pressure is applied
on the solution. This pressure that just stops the flow of solvent is called
osmotic pressure of the solution.

Solvent molecules always flow from lower concentration to higher

concentration of solution.
Osmotic pressure depends on concentration of the solution. It is a colligative
property as it depends on the number of solute molecules and not on their
identity.

• The osmotic pressure is proportional to the molarity, C of the solution at

a given temperature T.
Π = CRT where Π is the osmotic pressure
𝑛2 𝑅𝑇
Π= 𝑉
𝑤2 𝑅𝑇
ΠV= 𝑀2
From the above equation the molar mass of solute, M2, can be calculated.
This method is useful for proteins, polymers and other macro-molecules.
• Two solutions having same osmotic pressure at a given temperature are
called isotonic solutions.
Between two solutions the one having higher osmotic pressure is called
hypertonic solutions. And the one having lower is called hypotonic
solutions.
Examples - edema, revival of wilted flowers, shrivelling of raw mangoes
to pickle etc.
• The direction of osmosis can be reversed if pressure larger than osmotic
pressure is applied to the solution side. This phenomenon is called
reverse osmosis. This is used in desalination of sea water.

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 ABNORMAL MOLAR MASS:
• When there is dissociation or association of solute then the
experimentally determined molar mass is always lower or greater than
the true value. Such a molar mass is called abnormal molar mass.
• van’t Hoff introduced a factor i which is defined as,
i= Normal Molar Mass
Abnormal Molar Mass
= Observed colligative property .
Calculated colligative property
i= Total number of moles of particles afterassociation/dissociation .
Number of moles of particle before association/ dissociation

For association, i < 1 For dissociation, i > 1

Inclusion of van’t Hoff factor modifies the equations for colligative
properties as follows:
ΔP = i n2 .
P1o n1
𝑛2 𝑅𝑇
ΔTb = i Kb m ΔTf = i Kf m Π =i 𝑉
______________________

CHAPTER – HALOALKANES AND HALOARENES

The replacement of hydrogen atom(s) in an aliphatic or aromatic hydrocarbon by

halogen atom(s) results in the formation of alkyl halide (haloalkane) and aryl halide
(haloarene), respectively.

These may be classified as mono, di, or polyhalogen (tri,tetra-, etc.) compounds

depending on whether they contain one, two or more halogen atoms in their
structures.

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They may further be classified as compounds containing sp3C-X bond
(alkyl halides, allylic halides, benzylic halides) and compounds containing
sp2C-X bond (vinylic halides and aryl halides).

Nomenclature: The common names of alkyl halides are derived by

naming the alkyl group followed by the name of halide. In the IUPAC
system of nomenclature, alkyl halides are named as halo substituted
hydrocarbons. For mono halogen substituted derivatives of benzene,
common and IUPAC names are the same. For dihalogen derivatives, the
prefixes o-, m-, p- are used in common system but in IUPAC system the
numerals 1,2; 1,3 and 1,4 are used. Table 10.1 (NCERT textbook)

Nature of C-X bond in alkyl halides:

X is more electronegative than carbon. So, the C-X bond is polarized with
C having a partial positive charge and X having a partial negative charge.

Preparation of haloalkanes:

From alcohols:

The hydroxyl group of an alcohol is replaced by halogen on reaction with

concentrated halogen acids, phosphorus halides or thionyl chloride.
From alkanes:

Free radical chlorination or bromination of alkanes gives a complex

mixture of isomeric mono- and polyhaloalkanes.

From Alkenes:

a) Addition of hydrogen halides: An alkene is converted to corresponding

alkyl halide by reaction with hydrogen chloride, hydrogen bromide or
hydrogen iodide.
Propene yields two products, however only one predominates as per
Markovnikov’s rule.

b) Addition of halogens: In the laboratory, addition of bromine in CCl4 to

an alkene resulting in discharge of reddish-brown colour of bromine
constitutes an important method for the detection of double bond in a
molecule.

Finkelstein Reaction:

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Swarts Reaction: The synthesis of alkyl fluorides is best accomplished by
heating an alkyl chloride/bromide in the presence of a metallic fluoride
such as AgF, Hg2F2, CoF2 or SbF3. The reaction is termed as Swarts
reaction.

Preparation of haloarenes:
From hydrocarbons by electrophilic substitution: Aryl chlorides and
bromides can be easily prepared by electrophilic substitution of arenes
with chlorine and bromine respectively in the presence of Lewis acid
catalysts like iron or iron (III) chloride.

From Amines (Sandmeyer Reaction):

Alkyl halides are colourless when pure. However, bromides and iodides
develop colour when exposed to light.

For the same alkyl group, the boiling points of alkyl halides decrease in
the order: RI>RBr>RCl> RF. This is because with the increase in size and
mass of halogen atom, the magnitude of van der Waal forces increases.

The boiling points of isomeric haloalkanes decrease with increase in

branching.

Melting point of p-dihalobenzenes are higher than ortho- and meta-

isomers. It is due to symmetry of para-isomers that fits in crystal lattice
better as compared to ortho- and meta-isomers.

The solubility of haloalkanes in water is low. However, haloalkanes tend to

dissolve in organic solvents.

The reactions of haloalkanes may be divided into the following categories:

1. Nucleophilic substitution reaction
2. Elimination reactions
3. Reaction with metals.

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Nucleophilic Substitution Reactions:

(a) Substitution nucleophilic bimolecular (SN2):

• 1º haloalkane
• Bimolecular, 2nd order
• One step

Order of reactivity: 1º > 2º > 3º

Deciding factor: Steric hindrance

(b) Substitution nucleophilic unimolecular (SN1):

1. 3º haloalkane
2. Unimolecular, 1st order
3. Two steps

Order of reactivity: 3º > 2º > 1º

Deciding factor: Stability of carbocation

Allylic and benzylic halides undergo reaction via SN1 mechanism as the
corresponding carbocations are resonance stabilized.
The polarity of carbon-halogen bond of alkyl halides is responsible for
their nucleophilic substitution, elimination and their reaction with metal
atoms to form organometallic compounds.
Nucleophilic substitution reactions are categorised into SN1 and SN2 on
the basis of their kinetic properties. Chirality has a profound role in
understanding the reaction mechanisms of SN1 and SN2 reactions. SN2

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reactions of chiral alkyl halides are characterised by the inversion of
configuration while SN1 reactions are characterised by racemisation.
Elimination reactions: When a haloalkane with β-hydrogen atom is
heated with alcoholic solution of potassium hydroxide, there is elimination
of hydrogen atom from β -carbon and a halogen atom from the a-carbon
atom. As a result, an alkene is formed as a product. Since β-hydrogen
atom is involved in elimination, it is often called β-elimination.

Saytzeff Rule:
In dehydrohalogenation reactions, the preferred product is that alkene
which has the greater number of alkyl groups attached to the doubly
bonded carbon atoms.

Grignard Reagents:
An important class of organo-metallic compounds discovered by Victor
Grignard in 1900 is alkyl magnesium halide, RMgX, referred as Grignard
Reagents. These reagents are obtained by the reaction of haloalkanes
with magnesium metal in dry ether.

Grignard reagents are highly reactive and react with any source of proton
to give hydrocarbons.
RMgX + H2O →RH + Mg(OH)X

Reactions of Haloarenes:
Nucleophilic Substitution:
Aryl halides are extremely less reactive towards nucleophilic Substitution.

Chlorobenzene can be converted into phenol by heating in aqueous

sodium hydroxide solution at a temperature of 623K and a pressure of
300 atmospheres.

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The presence of an electron withdrawing group (-NO2) at ortho- and para-
positions increases the reactivity of haloarenes.

Electrophilic substitution reactions

Haloarenes undergo the usual electrophilic reactions of the benzene ring

such as halogenation, nitration, sulphonation and Friedel-Crafts reactions.
Halogen atom besides being slightly deactivating is o, p directing:

(i) Halogenation:

(ii) Sulphonation:

Wurtz reaction:

Alkyl halides react with sodium in dry ether to give hydrocarbons

containing double the number of carbon atoms present in the halide. This
reaction is known as Wurtz reaction.

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Wurtz-Fittig reaction:

A mixture of an alkyl halide and aryl halide gives an alkylarene when

treated with sodium in dry ether and is called Wurtz-Fittig reaction.

Fittig reaction:

Aryl halides also give analogous compounds when treated with sodium in
dry ether, in which two aryl groups are joined together. It is called Fittig
reaction.

Polyhalogen compounds
A number of polyhalogen compounds e.g., dichloromethane,
chloroform, iodoform, carbon tetrachloride, freon and DDT have
many industrial applications. However, some of these compounds cannot
be easily decomposed and even cause depletion of ozone layer and are
proving environmental hazards.

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