Solutions

1. A solution is a homogeneous mixture of two or 9.

more chemically non-reacting substances.
The components of a solution generally cannot be separated by filtration, settling or
centrifuging.
2. A solution may be classified as solid, liquid or a gaseous solution.
3. Solubility is defined as the amount of solute in a saturated solution per 100g of a
solvent.
4. The solubility of a gas in a liquid depends upon
(a) the nature of the gas and the nature of the liquid,
(b) the temperature of the system, and
(c) the pressure of the gas.
5. The effect of pressure on the solubility of a gas in a liquid is governed by Henry’s
Law. It states that the solubility of a gas in a liquid at a given temperature in directly
proportional to the partial pressure of the gas Mathematically, P = KHX where P is the
partial pressure of the gas; and X is the mole fraction of the gas in the solution and KH
is Henry’s Law constant.
6. The vapour pressure of a liquid is the pressure exerted by its vapour when it is in
dynamic equilibrium with its liquid, in a closed container.
7. According to Raoults Law, the vapour pressure of a solution containing a non-volatile
solute is directly proportional to the mole fraction of the solvent ( X A). The proportionality
constant being the vapour pressure of the pure solvent, i.e., P× X A or P = P° XA.
8. A solution which obeys Raoult’s Law at all concentrations and temperatures is known
as an ideal solution.
9. Characteristics of an ideal solution:
(a) ∆sol V = 0, i.e., there is no change in volume when an ideal solution is formed.
(b) ∆sol H= 0; i.e., heat is neither evolved nor absorbed during the formation of an ideal
solution.
10. (a) The solution shows positive deviation from Raoult’s Law if its vapour pressure is
higher than that predicted by Raoult’s Law.
(b) The solution shows negative deviation if its vapour pressure is lower than that
predicted by Raoult’s Law.
11. Colligative properties of solutions are those properties which depend only upon the
number of solute particles in the solution and not on their nature. Such properties are
(a) Relative lowering in vapour pressure,
(b) Elevation of boiling point,
(c) Depression of freezing point and
(d) Osmotic pressure.
12.
Thus, according to Raoult’s Law, the relative lowering of vapour pressure of a solution is
equal to the mole fraction of the solute.
13. For a dilute solution, the elevation in boiling point is found to be proportional to the
molality of the

where ∆Tb is the elevation in boiling point, ‘m’ is the molality and K b is the Molal
elevation constant
14. The depression in freezing point (∆Tf) is proportional to the molality of the solution.

where Kf is molal depression constant (freezing point depression constant).

15. The spontaneous flow of solvent molecules from a dilute solution into a
concentrated solution when the two are separated by a perfect sernipermeable
membrane is called osmosis.
16. Osmotic pressure (π) is the pressure which must be applied to the solution side
(more concentrated solution) to just prevent the passage of pure solvent into it through
a sernipermeable membrane.
Mathematically, π = CRT= nB/V- RT
where n is the osmotic pressure of the solution,
C is the concentration of solution
nB is the number of moles of solute,
V is the volume of the solution in litres,
R is the gas constant, and T is the temperature on the Kelvin scale.
17. Isotonic solutions are those solutions which have the same osmotic pressure. Also
they have same molar concentration.
For isotonic solutions, π1 = π2 Also, C1 = C2
18. Van’t Hoff factor, ‘ i’ is used to express the extent of association or dissociation of
solutes in solution. It is die ratio of the normal and observed molar masses of the solute,
i. e.,

19. In case of association, observed molar mass being more than the normal, the factor
‘T has a value less than one. But in case of dissociation, the van’t Hoff factor is more
than one because the observed molar mass has a less value.
20. In case of solutes which do not undergo any association or dissociation in a solvent,
the Vant Hoff factor, ‘i’, will be equal to one because the observed and normal molar
masses will be same.
21. Inclusion of van’t Hoff factor, ‘F, modifies the equations for colligative properties as
follows:

Chemical Kinetics
1. Chemical kinetics is the branch of chemistry which deals with the study of rates (or
fastness) of chemical reactions, the factors affecting it and the mechanism by which the
reactions proceed.
2. Rate of reaction is the change in concentration of reactants or products per unit
time.
For a general reaction, A+B –> C
The rate of reaction

The negative sign indicates that the concentration is decreasing with time.
Unit for reaction rate is mol L-1s-1.
3. The rate of reaction is not a constant quantity (except for zero order reactions). It
decreases as the reaction proceeds in the forward direction.
4. A rate law expresses a mathematical relationship between the reaction rate and the
molar concentration of one or more reactants.

Where m and n are determined experimentally and represent the order of reaction with
respect to A and B respectively, m + n represents the overall order of reaction.
5. Rate constant is the rate of reaction when the concentration of each of reacting
species is unity. It is represented by ‘k’ It is also called specific reaction rate or velocity
constant of reaction.
6. Order of reaction is defined as the sum of the exponents to which the concentration
terms are raised in the rate equation (or rate law) of the reaction. It can be fraction, zero
or any whole number.
7. Modularity of reaction is defined as the number of reacting particles (atoms or
molecules or any other species), which collides simultaneously to bring about the
chemical change.
It is a theoretical concept. Its value is always a whole number. It is never more than
three. It cannot be zero.
8. First order reaction: A reaction is said to be first order if its reaction rate is
determined by the variation of one concentration term only.
9. The integrated rate equation expresses the concentration of reactants as a function
of time.
10. The integrated rate equation for a first order reaction is given as
11. Second order reaction: The reaction in which sum of powers of concentration terms
in rate law equation is two.

12. Zero order reaction: Those reactions in which rate of reaction does not change
with concentration of the reactants.
Rate law for such a reaction is expressed as. Rate = k [A]°[B]°
13. Half life period: It is the time required for the initial concentration of the reactant to
be reduced to half its value.

14. It has been found that for a chemical reaction with rise in temperature by 10 °C, the
rate constant gets nearly doubled.
15. The temperature coefficient of a reaction is the ratio of the rate constants of the
reaction at two temperatures differing from one another by 10°C. The two temperatures
usually taken are 35 °C and 25 °C.
16. The variation of rate constants with temperature can be represented by the
Arrhenius equation,
K=Ae-Ea/Rt
 
where A is a constant known as frequency factor, and Ea is-called the energy of
activation.
From the above equation, the rate constants at two different temperatures are related
as
17. There are two important theories of reaction rates:
(i) Collision theory and,
(ii) Transition state theory.

Haloalkanes and Haloarenes

1. Haloalkanes are classified as fluoro, chloro, bromo or iodo compounds according to
the type of halogen present and as mono-, di- tri-, tetra- haloalkanes, etc., according to
the one, two, three, four, etc., halogen atoms respectively present in their molecule.
2. Alkyl halides are further classified as primary (1°), secondary (2°) and tertiary (3°)
according to the halogen atom attached to primary, secondary and tertiary carbon
atoms, respectively.
3. Due to electronegativity difference between the carbon and the halogen, the shared
pair of electron lies closer to the halogen atom. As a result, the halogen carries a small
negative charge, while the carbon carries a small positive charge. Consequently, C-X
bond is a polar covalent bond.
4. Methods of Preparation of Haloalkabes: Haloalkanes can be prepared from
displacement of alcoholic group in alkyl alcohol by halogen acid, PCl 5 or PCl3.
Haloalkanes can also be prepared by addition of halogen acids or halogens on alkene
and alkyne. Alkyl halides can also be prepared by free radical halogenation of alkane.
5. Methods of preparation of Haloarenes. Haloarenes can be prepared by side chain
halogenation or nuclear halogenation of aromatic hydrocarbons.
6. From diazonium salts:
(i) By Sandmeyer reaction:
(ii) By Gattermann reaction:
7. Chemical reactions of haloalkanes
(a) Nucleophilic substitution reactions:
(i) C-X bond in alkyl halide is more polar due to electron repelling nature of alkyl group
(-) and thus readily undergo nucleophilic substitution reaction. These are of two types:
(1) SN1(Substitution, nucleophilic, unimolecuiar): In such type of reactions, rate = k
[RX], i.e., rate, is independent of concentration of nucleophile and occurs in two steps.
Such reactions are favoured by polar solvents.
(2) SN2(Substitution, nucleophilic, bimolecular): In such type of reactions, rate = k
[RX] [ Nu ]–, i.e., rate of reaction depends on concentration of nucleophile and take place
in one step.
(ii) A SN2 reaction proceeds with complete stereochemical inversion while a S N1 reaction
proceeds with racemisation.
(b) Elimination reaction: When a haloalkane with β-halogen atom is heated with
alcoholic solution of potassium hydroxide, there is elimination of hydrogen atom from α-
carbon and a halogen atom from the a-carbon atom. An alkene is formed as a product,
also called β-elimination.
(c) Reaction with metals:
8. Aryl halides are extremely less reactive towards nucleophilic substitution reaction due
to following reasons:
(a) In haloarenes, the lone pair of electrons on the halogen atom are delocalized on the
benzene ring due to resonance.
(b) In haloalkanes, the halogen atom is attached to sp 3-hybridized carbon while in
haloarenes the halogen atom is attached to sp 2– hybridized carbon.
9. Electrophilic substitution reaction: Haloarenes undergo the usual electrophilic
substitution reactions of the benzene ring such as halogenation, nitration, sulphonation
and Friedel crafts reactions. Halogen atom is slightly deactivating and o, p-directing.
10. Trichloromethane (Chloroform):
The major use of chloroform today is in the production of the freon refrigerant R-22.
Chloroform is stored in closed dark coloured bottles completely filled so that air is kept
out Because it is slowly oxidised by air in the presence of light to an extremely
poisonous gas, carbonyl chloride (Phosgene).

11. Freons are the chlorofluorocarbons compounds of methane and ethane. They are
extremely stable, unreactive, norttoxic, noncorrosive and easily liquefiable gases.
Freon-12 (CCl2F2) is most common freons in industrial use.

Alcohols, Phenols and Ethers

1. Alcohols and phenols may be classified as
monohydric, dihydric, trihydric or polyhydric
according to number of hydroxyl groups they
contain one, two, three or many respectively in
their molecules.
2. Primary (1°), secondary (2°) and tertiary (3°)
alcohols are those in which as the OH group is
attached to a primary, secondary and tertiary
carbon atoms respectively.
3. Ethers are classified as simple or
symmetrical ethers if the alkyl or aryl groups
attached to the oxygen atom are same, and
mixed or unsymmetrical ethers if the two
groups are different.
4. Preparation of Alcohols
(a) From alkenes:
(i) By acid catalyzed hydration: The addition
reaction takes place in accordance with
Markovnikov’s rule.
(ii) By hydroboration-oxidation
(b) From carbonyl compounds
(i) By reduction of aldehydes and ketones: On
reduction, aldehydes give 1° alcohols and
ketones give 2° alcohols.
(ii) By reduction of carboxylic acids and esters
(iii) From Grignard reagents
5. Phenols may be prepared by substitution of
halogen in
(a) Haloarenes
(b) Sulphonic acid group in benzene sulphonic
acid
(c) From hydrolysis of diazonium salts
(d) Industrially from Cumene:
6. Chemical reactions of alcohols and phenols:
(a) Reactions involving the cleavage of the  O-H
bond:
(b) Reactions involving the alcohol as a whole.

7. Reactions of phenols :
(a) Electrophilic substitution reaction: The
presence of -OH group in phenols activates the
aromatic ring towards electrophilic substitution
and directs the incoming group to the ortho and
para positions due to resonance effect.
(b) Kolbe’s reaction: In this reaction sodium
phenoxide is treated with C0  at 400K under 3-7
2

atm pressure, sodium salicylate is formed

which is acidified to get salicylic acid.
(c) Reimer-Tiemann reaction: In this reaction
phenol reacts with chloroform in presence of
NaOH and produce salicyldehyde.
8. Preparation of Ethers:

9. Physical Properties:
(a) Boiling point of ethers are much lower than
corresponding alcohols because ethers do not
form intermolecular H-bonding.
(b) Slightly soluble in water.
10. Chemical properties:
(a) Cleavage ofC-O bond in ethers:

(b) Electrophilic substitution: In this, the alkoxy

group activates the aromatic ring and directs
the incoming group to ortho and para positios

Aldehydes, Ketones and Carboxylic Acids

1. The classes of organic compounds containing carbonyl group (CO) as the
functional group are aldehydes, ketones, carboxylic acids and their derivates. These are
collectively called carbonyl compounds.
2. Nature of carbonyl group: Oxygen atom in carbonyl group is far more
electronegative than carbon atom. As a result, the oxygen atom tends to attract the
electron cloud of the π-bond towards itself, i. e., the π-electron cloud of >c = O is
unsymmetrical.
Hence carbonyl carbon acquires positive charge and carbonyl oxygen carries negative
charge. Thus, the carbonyl group is polar in nature.
3. Methods of preparation of Aldehydes and Ketones:
(a) By controlled oxidation of primary and secondary alcohol, aldehydes and ketones
are produced.
(b) By dehydrogenation of alcohols : Primary alcohols on dehydrogenation produce
aldehydes while secondary alcohols produce ketones.
4. Preparation of Aldehydes:
(a) Acyl chloride (acid chloride) is hydrogenated using, palladium on barium sulphate
which is partially poisoned by the addition of S or quinoline. This reaction is called
Rosenmund reduction. This method is used to prepare aldehydes.
(b) N itriles are reduced to corresponding imine with stannous chloride in the presence
of hydrochloric acid, which on hydrolysis give corresponding aldehyde. This reaction is
called Stephen’s reduction.
Chromyl chloride (CrO2ClO2) oxidises methyl group of toluene to a chromium complex,
which on hydrolysis gives corresponding benzaldehyde. This reaction is called Etard
reaction.
(d) When benzene or its derivatives is treated with CO and HCl in the presence of
anhydrous AlCl3 or CuCl, it gives benzaldehyde or substituted benzaldehyde. This
reaction is called Gatterman-Koch reaction.
5. Preparation of Ketones:
(a) Treatment of acyl chlorides with dialkyl cadmium, prepared by the reaction of
cadmium chloride with Grignard reagent, gives ketones.
(b)From nitriles:

When benzene or substituted benzene is treated with acid chloride in the presence of
anhydrous A1C13, the corresponding ketone is formed. This reaction is known
as Friedel-craft’s acylation reaction.
Properties of aldehyde and ketones
(a) Aldehydes are much more reactive than ketones in nucleophilic addition reactions.
(b) Nucleophilic addition reactions: Aldehydes and ketones undergo nucleophilic
addition reactions onto the carbonyl group with a number of nucleophiles such as HCN,
NaHSO3, alcohols, ammonia derivatives and Grignard reagents.
(c) Reduction to alcohols: Aldehydes and ketones on reduction gives primary and
secondary alcohols respectively.
(d) The carbonyl group of aldehydes and ketones is reduced to CH 2 group on treatment
with zinc amalgam and concentrated hydrochloric acid (Chemmenson reduction) or
with hydrazine followed by heating with NaOH or KOH in high boiling solvent such as
ethylene glycol (Wolff-Kishner reduction).
(e) Tollen’s reagent (ammonical silver nitrate) oxidises aldehyde and the silver ions are
reduced to silver which appear as a bright silver mirror on the side of the test tube
ketones do not give this test.
(f) Aldehydes reduce Fehling’s solution to form a red precipitate of cuprous oxide.
Fehling’s solution is obtained by mixing a solution of copper sulphate and a solution of
sodium hydroxide and sodium potassium tartrate. Ketones do not reduce Fehling’s
solution..Hence no precipitate is formed.
(g) Aldehydes and ketones having atleast one α-hydrogen atom undergoes a
condensation reaction when warmed with dilute alkali to form β -hydroxy aldehydes or
β-hydroxy ketones respectively. The reaction is known as aldol condensation.
(h) The condensation of a mixture of two different aldehydes or/and ketones each
having an a-hydrogen atom, in presence of dilute alkali gives a mixture of four products.
The reaction is known as cross aldol condensation.
6. Cannizzaro reaction: Aldehydes which do not have an a-hydrogen atom, undergo
self-oxidation and reduction (disproportionation) reaction on treatment with concentrated
alkali. In this reaction, one molecule of the aldehyde is reduced to alcohol white another
is oxidised to carboxylic acid salt.
7. Electrophilic substitution reaction: It takes place at the ring in which the carbonyl
group acts as a deactivating and meta-directing group.
8. Methods of preparation of carboxylic acids:
(a) From oxidation of primary alcohols and aldehydes.
(b) Aromatic carboxylic acids can be obtained by side chain oxidation of alkyl benzenes.
(c) From hydrolysis of nitriles and amides:
(d) From reaction of Grignard reagents with carbon dioxide:
9. Aliphatic carboxylic acids having up to four carbon atoms are miscible in water due to
the formation of hydrogen bonds with water.
10. The solubility decreases as the number of carbon atoms increases.
(i) The electron withdrawing group (Cl, NO2, CN, etc.) stabilises the carboxylate anion by
dispersing the negative charge of the carboxylate anion, RCOO –, and thus increases the
acidic strength.
(ii) The presence of electron donating substituent such as alkyl group intensifies the
negative charge on the RCOO– anion and destabilises it thereby making the carboxylic
acid less acidic.
(iii) Carboxylic acids having an α-hydrogen are halogenated at the α-position on
treatment with chlorine or bromine is the presence of small amount of red phosphorus to
give α- chloro or  α – bromo carboxylic acids. This reaction is known as Hell-Volhard
Zelinsky Reaction.