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HALOALKANES & HALOARENES

Physical
state
Colour: - Halo alkanes are colourless in nature in their pure state.
Bromo alkanes and iodoalkanes develop colour on exposure to light because of their decomposition.
Polarity: - The polarity of carbon –halogen bond is as follows:-
 (D):- C-Cl > C-F > C-Br > C-I
 C-F <  C-Cl: - even though F is more electronegative because of the extremely small size of Fluorine atom
Boiling  If the alkyl group is same then the boiling points of haloalkanes increases with increase in the size of
Point:- halogen i.e. the order is :- RCl < RBr < RI.
Reason: - with the increase in the size and mass of the halogen the magnitude of van der Waal’s forces of
attraction increases due to increase in the surface area.
 In case of isomeric alkyl halides the b.pt. decreases with increase in branching in the hydrocarbon part
(alkyl group) due do decrease in the magnitude of van der Waal’s forces of attraction because of decrease in
the surface area. i.e. In case of isomeric alkyl halides the b.pt. decreases as 1 > 2 > 3
 In case of alkyl halides containing the same halogen the b.pt increases with increase in the size & molecular
mass of the hydrocarbon part (alkyl group)
 The boiling points of various halogen compounds increase with increase in number of halogen atoms.
For example:-
The b.pt. of haloalkanes is higher as compared to that of corresponding parent alkanes because
haloalkanes are comparatively more polar than alkanes and thus there exist strong dipole-dipole attractive
interactions between haloalkane molecules whereas in case of alkanes only weak Van der Wall’s forces exist
between their molecules.
 For monohalo derivatives of benzene the b.pt. follows the order :-Iodo > Bromo > Chloro

Boiling & Melting point of isomeric dihalo derivatives of benzene:-

Their boiling points do not differ by a large extent
But their melting points do differ by a large extent. The m.pt. of p- isomer is much higher than the m.pt. of o-
and m- isomer because of its symmetrical structure which cause an effective close packing of its molecules in
the crystal lattice and thus has strong interparticle attractive forces.
Density  Alkyl chlorides are generally lighter than water.
 Alkyl bromides and iodides are heavier than water.
 The densities follow the order R-I > R-Br > R-Cl.
 In general, the density of halogen derivatives increases with increase in number and atomic mass of the
halogen atoms.
 All Haloarenes are heavier than water. The order of their densities is Iodoarene > Bromoarene>
Chloroarene.
Solubility  Alkyl halides are usually insoluble in water.
in Water  Reason: - Alkyl halides though polar in nature, are insoluble in water because of their incapability to form
hydrogen bond with water molecules because of which the amount of energy required in overcoming the
forces of attraction between the haloalkane molecules and that required to break the hydrogen bonds
already existing between the water molecules is much more than the energy released when new attractions
are set up between haloalkane and water molecules.
 Alkyl halides are soluble in non polar organic solvents such as ether and benzene.
 Haloarenes are insoluble in water because of their incapability to form hydrogen bonds with water
molecules but are soluble in organic solvents.

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ALCOHOLS & PHENOL
Physical  Liquids
state
Colour: -  Colourless
Polarity: -  Alcohol molecules are polar in nature
Boiling  Alcohols have high b.pt. because of the presence of intermolecular hydrogen bonding among the
Point:- molecules
intermolecular
H- bonding
R R

+ - + + - +
H O H O H O H O
- -

R R

 Similarly the intermolecular H- bonding in phenols can be represented as:-

intermolecular
H- bonding

+ - + - + - + -
H O H O H O H O

 Their boiling point of alcohols is comparatively higher than that of the comparable molecular mass
hydrocarbons, ethers and alkyl halides.
 The boiling points of alcohols and phenols increases with increase in the length of the C-chain because of
increase in van der Waal’s forces.
 The boiling points of alcohols, decrease with increase of branching of the C-chain due to reduction in
surface area as a result of which the VdW forces decrease in magnitude
For example, ethanol and propane have comparable molecular masses but their boiling points differ widely.
The boiling point of methoxy methane is intermediate of the two boiling points.
Solubility  Alcohols and phenols are soluble in water because to their ability to form hydrogen bonds with
in Water water molecules.
intermolecular
H- bonding

+ - + - + - + -
H O H O H O H O

H R H R

 Lower alcohols (such as methanol, ethanol) are miscible with water in all proportions.
With the increase in the size of alkyl/aryl part i.e. the hydrocarbon chain the length of the hydrophobic part
also increases and thus the solubility decreases .

ETHERS
Physical  Volatile liquids
state
Colour: -  Colourless
Polarity: -  Slightly polar
Boiling  The C-O bond in ethers is polar and because of it ethers have a net dipole moment.
Point:-  Boiling point of ethers are comparable to the alkanes of comparable molecular mass since the ethers are
weakly polar and this weak polarity of ethers does not affect their boiling point significantly
 Boiling point of ethers are much lower than alcohols since the ethers are weakly polar and thus have
weak dipole - dipole interactions whereas in alcohols strong intermolecular H- bonding is present.

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Solubility  The solubility of lower ethers in water is almost comparable to that of alcohols of the same
in Water molecular mass because like alcohols ether can also form hydrogen bonds with water molecule from the
more electronegative oxygen centre

ALDEHYDES & KETONES

Physical  Methanal is a gas at room temperature while Ethanal is a volatile liquid.
state
Colour: -  Colourless
Polarity: -  The double bond is polar in nature because of electronegativity difference between oxygen & carbon. The
carbonyl carbon acts as an electrophilic centre and carbonyl oxygen, a nucleophilic (Lewis base) centre.
Carbonyl compounds have substantial dipole moments and are polar than ethers.
Boiling C O
Point:- group is slightly polar in nature and thus weak molecular association is present in aldehydes and
ketones due to the dipole-dipole interactions. Because of this the b.pt. of aldehydes and ketones are
comparatively higher than the hydrocarbons and ethers of comparable molecular masses.
 But their b.pt. are lower than the alcohols of similar molecular masses due to absence of intermolecular
hydrogen bonding
Solubility  Lower members such as methanal, ethanal and propanone are soluble in water in all proportions, since
in Water they form H-bond with water.
 But the solubility of aldehydes and ketones decreases rapidly on increasing the length of alkyl
chain since on increasing the length of the hydrocarbon part the hydrophobic interactions increases.

AMINES
Physical  The lower aliphatic amines are gaseous
state  They are bad smelling compounds [have obnoxious smell].
Aniline & other aryl amines are otherwise colourless compounds but usually appear coloured due to aerial
oxidation. [It is because of this reason that Aniline appears yellow in colour]
Boiling  1°& 2°amines form intermolecular hydrogen bonding between N- atom of one amine molecule & H- atom
Point:- of other molecule.
 Since 1°amines contains more H- atoms the extent of intermolecular H- bonding is greater in 1° amines
than 2° amines
 Also 3° amines do not contain any H- atom thus they do not form intermolecular hydrogen bond and there
molecules are weakly held together by weak Van der Waal’s forces of attraction
The order of b.pt. of isomeric amines follows the order:1°>2°>3°
Solubility  Lower aliphatic amines are soluble in water because of their tendency to form hydrogen bond with water
in Water molecules but the solubility decreases with increase in the length of the Carbon chain because of increase
in size of the hydrophobic hydrocarbon alkyl part.
 Higher amines are insoluble in water.
 Amines are soluble in organic solvents like alcohol, ether and benzene.
 For the nearly same value of molar masses; alcohols are more soluble in water than amines because of the
fact that alcohols are more polar than amines because of the greater electronegativity of O- as compared
to that of N- & thus alcohols form comparatively stronger intermolecular hydrogen bonds than amines.

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CARBOXYLIC ACIDS
Physical  Aliphatic carboxylic acids upto nine carbon atoms are colourless liquids at room temperature with
state unpleasant odours.
 The higher acids are wax like solids
 Higher carboxylic acids are practically odourless due to their low volatility.
Boiling  Carboxylic acids have higher point than that of the aldehydes & ketones and even that of alcohols of
Point:- comparable molecular masse
 It is because of the fact that the molecules of the carboxylic acid are strongly associated with each other
through intermolecular hydrogen bonding
 Most of the carboxylic acids exist in the dimeric form in the vapour phase & even in non polar solvents or
in the aprotic solvents.
 [The existence of such cyclic dimers is supported by the fact that the molecular mass of acetic acid in
solvents like benzene as determined by measurement of colligative properties such as depression in
freezing point is 120 instead of 60.
 Propionic acid (b.p.141°C) boils more than 20°C higher than the alcohol of comparable molecular weight,
n-butyl alcohol (b.p. 118°C). These very high boiling points are due to the fact that a pair of carboxylic acid
molecules are held together not by one but by two hydrogen bonds.
Melting  The melting points of aliphatic carboxylic acids do not show a regular pattern. The first ten members show
point:- oscillation or alternation effect, i.e., the melting point of an acid containing even /lumber of carbon atoms
is higher than the next lower and next higher homologues containing odd number of carbon atoms.
 Acids containing even number of carbon atoms have carboxyl and terminal methyl groups on the opposite
sides of the zig-zag carbon chain because of this they fit closely in the crystal lattice thereby increasing
intermolecular forces of attraction which results in higher melting points , whereas the carboxylic acids
with odd number of carbon atoms , have the carboxyl and terminal methyl groups on the same side of the
zig-zag carbon chain and thus fit poorly in the lattice and therefore have lower melting points.
 The m. pt. of aliphatic acids having more than ten carbon atoms do not show the oscillation effect. The m.
pt. & b. pt. of the aromatic acids are usually higher than that of aliphatic acids of comparable molecular
masses since the planar benzene ring packs more effectively in the lattice than zig-zag structure of
aliphatic acids.
Solubility  The first four aliphatic carboxylic acids are soluble in water because of their tendency to form H-bonds
in Water with water molecules.
 As the number of carbon atoms in the chain increases the solubility decreases because of increase in the
hydrophobic part
 Higher carboxylic acids are practically insoluble in water due to the increased hydrophobic interaction of
hydrocarbon part.
 Carboxylic acids are also soluble to certain extent in less polar organic solvents like that of
benzene,chloroform etc.
 Benzoic acid is practically insoluble in cold water because of the presence of large hydrophobic phenyl
group
 Aliphatic carboxylic acids have nearly the same solubility as that of the alcohols.

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Q Out of butan-1-ol and butan-1-amine, which one is more soluble in water and why?
Q Out of Butan-1-amine, N-methyl ethanamine & N,N-dimethy methanamine which one will have max . b. pt.
Q The boiling point of n-pentane (309 K)having molecular mass 72gm/mol is almost same as that of ethoxy
ethane(307K)having molecular mass 74gm/mol
Q The boiling point of ethoxy ethane(307K)is quite less than that of butan-1-ol(390K).
Q The solubility of ethoxyethane and butan-1-ol are 7.5 and 9 g per 100 mL water. Explain
Q The solubility of ethoxyethane is to a much greater extent as compared to that of pentane which is
immiscible with water.
Q Arrange the following compounds in the increasing order of their boiling points:
CH3CH2CH2CHO, CH3CH2CH2CH2OH, H5C2-O-C2H5, CH3CH2CH2CH2CH3
Q Arrange the following compounds in increasing order of their boiling points.
CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3

Q Out of benzamide & Phthalimide which one is more acidic

A Out of benzamide & Phthalimide it is the phthalimide which is more acidic it is because the corresponding
Phthalimide anion is is stabilised by both -I,-R effects of the neighbouring carbonyl groups
Q The C–O–H bond angle (108.9°in alcohols is slightly less than that of normal tetrahedral angle of
109°28’.Explain
3 3
A In alcohol molecule the O–atom of the C–O–H bond is sp hybridised and in two of the sp hybrid orbitals lone pairs
are present & because of the repulsion between the two l.p. the bond angle decreases.
Q The C–O bond length (136 pm) in phenol is slightly less than that of in methanol or(142 pm) that of ethers.
A It is because of the following reasons:-
(i) The C–O bond assumes a partial double bond character because of the resonance due to conjugation
between the l.p. of oxygen with π e– of the benzene ring .
2
(ii) The –OH group in phenol is attached to sp hybridised carbon atom of the benzene ring which has greater
% of s-character & thus has more electronegativity .
Q The bond angle (108.9°)in ethers is slightly less than that of normal tetrahedral angle of 109°28’. Explain
3 3
A In ethers also the O-atom of the C–O–C bond is sp hybridised and in two of the sp hybrid orbitals l.p. are present
but the bond angle is slightly greater than normal tetrahedral angle of 109°28’ because of the repulsive interaction
between the two bulky (–R) groups.

ORBITAL OVERLAP STRUCTURES OF SOME COMPOUNDS

Orbital structure of carbonyl compounds Orbital structure of phenol
unhybrid- sp3
p- orbital
 unhybrid-
p- orbital sp3
  sp2  O
C O
O sp2sp3 sp3
C
sp2 sp2 p
109° s
nucleophilic overlap
electrophilic centre H
centre

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Orbital structure of methanol Orbital structure of dimethyl ether

sp3 sp3
sp3 sp3
H O H O
sp3 sp3
sp3 sp3 H
s s s s
108.9° 111.7°
sp3 sp3 sp3 sp3 sp3 sp3
H
C C C
sp3 sp3 sp3 sp3 sp3 sp3

s s s s s s
H H H H H H

Orbital structure of amines

108° R
R
R
where R is an alkyl group or H
depending on the nature of amine

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