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Reasoning Questions
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All reasoning questions can be classified in three classes:
(i) Physical Properties
(ii) Acidic & Basic Nature
(iii) Preparation & Chemical Properties of compounds
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Physical Properties
1. Dipolar Nature:
The dipolemoment order is: R – Cl > R – F > R – Br > R – I
Though fluorine is more electronegative than chlorine yet the dipolemoment of R – Cl is greater
than that of R – F because the dipole moment vector is a product of charge and distance
μD = q × d
and bond length of C – Cl bond is greater than C – F bond.
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CH3Cl

In CH3Cl the polarity vectors of 3 H atoms and Cl atoms add up and give it a large dipole moment
In CH2Cl2, all bond moments are in the same direction. so they are additive and the net resultant μ
is more than CHCl3.
In CHCl3, the bond moment of one of the Cl atoms opposes the net moment of the other two, so
the net resultant μ is less than that of CH2Cl2.
Dipole moment for symmetrical Molecules CCl4 is zero
∴ Order CCl4 < CHCl3 < CH2Cl2 < CH3Cl
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In Chlorobenzene, the Cl-atom is linked to a sp2 hybridized carbon atom ∴ has more s-character &
more electronegative & thus density of electrons of C−Cl bond is less near the Cl-atom in
chlorobenzene Also −R effect of the benzene ring decreases the electron density of the C−Cl bond
near the Cl-atom & less dipole.
In Cyclohexylchloride, the Cl-atom is linked to a sp3 hybridized carbon atom ∴ has less s-
character & less electronegative & thus density of electrons of C−Cl bond is more near the Cl-
atom in cyclohexyl chloride & more dipole.
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Amongst isomeric di chloro benzenes, the p-isomer being symmetrical has zero dipole moment
because here the two equal and opposite dipoles cancel each other. The dipole moments of the o-
and m-isomer decreases as the angle between the two halogen atoms increases. Thus, o-isomer
with a bond angle of 60° between the two chlorine atoms has the highest dipole moment (2·54 D)
while the m-isomer with a bond angle of 120° between the two chlorine atoms has a dipole
moment of 1·72 D which is approximately equal to that of the chlorobenzene (1·69 D).
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Q. 1. Arrange each set of compounds in order of Property indicated & give reasons:
(i) CH2Cl2, CHCl3, CCl4 (Dipole moment) [NCERT][SP 15]
(ii) Chlorobenzene & cyclohexyl chloride (Dipole moment) [NCERT][DB 10C,
11C][AI 10C][F 12]
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3. Melting & Boiling Points:
a. Melting & boiling points ∝ Number of C - atom
CH3Cl < CH3CH2Cl
b. Melting & boiling points ∝ Molecular mass of the Compounds
CH3Cl < CH2Cl2 < CHCl3 < CCl4
CH3Cl < CH3Br
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c. In isomeric compounds:
(i) Branching increases molecule will tend to become spherical & surface area decreases ∴
vonderwaal force decreases ∴ boiling point decreases.
1
Boiling points ∝
Branching in Parent Chain

n – Pentane > iso - pentane > neo – pentane


(ii) Branching increases molecule assumes a spherical form that leads to a much more
closed packing (i.e. compactness increases) ∴ melting point increases
Melting points ∝ Branching in Parent Chain
n – Pentane < iso - pentane < neo - pentane
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(iii) Boiling points:
Cis compounds (more dipolar nature) > Trans compounds (less Polar nature)
(iv) Melting points:
Trans compounds (more compactness) > Cis compounds (less compactness)
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(d) Melting & boiling points:
Compounds having H - bonding > which cannot form H - bonding.
(e) Melting & boiling points ∝ Strength of H - bonding
(i) Amine < Alcohol < Acid
(ii) 1o Alcohol > 2o Alcohol > 3o Alcohol
(iii) 1o Amines > 2o Amines > 3o Amines
(f) In Aromatic compounds Melting & boiling points of Para compounds are more than that of
ortho & meta due to symmetry
Due to inter molecular hydrogen bonding Melting & boiling points increases (i.e. volatile
nature decreases) wile due to intra molecular hydrogen bonding Melting & boiling points
decreases (i.e. volatile nature increases)
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Non Polar Dipolar Compounds Hydrogen bonding

Hydrocarbons < Halogen < Ethers < Aldehyde < Ketone < Amine < Alcohol < Acid

H - bonding H - bonding is Strong due to


Single Bonded Compounds Multiple Bonded Compounds
is weak due More E.N. “O” atom
∴ Dipole is less ∴ Dipole is more
1R group ∴ 2R groups 1R group ∴ 2R groups ∴ to less E.N. (O-H) bonds in acids are
“N” atom more strongly polarized due
Dipole is less ∴ Dipole is Dipole is less Dipole is
to the adjacent e-
more more
withdrawing (C=O) group.
Hence acids form
stronger H-bonds.
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Note: Difference in melting point of Hydrocarbon & ether is very less.
Due to weak dipole-dipole interactions, the boiling points of lower ethers such as dimethyl ether
and ethyl methyl ether are only slightly higher than those of the n-alkanes having comparable
molecular masses. So much so, the boiling point of diethyl ether is about the same (307·6 K) as
that of n-alkane having comparable molecular mass (n-pentane, b.p. 309·1 K). However, as the
hydrocarbon part increases beyond four carbon atoms, the boiling points of ethers are even
slightly lower than n-alkanes of comparable molecular masses. This is mainly because the
presence of oxygen atom which makes ether molecules less symmetrical as compared to n-alkanes
having comparable molecular masses. As a result, the van der Waals forces of attraction between
ether molecules are slightly lower than those in little more symmetrical n-alkanes having
comparable molecular masses. For example,
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Ethers CH3OCH3 CH3OC2H5 C2H5OC2H5 C2H5OCH2CH2CH3 C2H5OCH2(CH2)2CH3
Mol. mass 46 60 74 88 102
b.p. (K) 250 283 307·6 336·6 366
n-Alkanes Propane n-Butane n-Pentane n-Hexane n-Heptane
Mol. mass 44 58 72 86 100
b.p. (K) 231 273 309·1 342 371
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Q. 2. Arrange each set of compounds in order of boiling points & give reasons:
(i) Bromomethane, Bromoform, Chloromethane, Dibromomethane. [NCERT]
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(ii) 1-Chloropropane, Isopropyl chloride, 1-Chlorobutane. [NCERT]


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(iii) Pentan-1-ol, butan-1-ol, butan-2-ol, ethanol, propan-1-ol, methanol. [NCERT][


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(iv) Pentan-1-ol, n-butane, pentanal, ethoxyethane. [NCERT][


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(v) CH3CH2CH2CHO, CH3CH2CH2CH2OH, H5C2-O-C2H5, CH3CH2CH2CH2CH3 [NCERT]


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(vi) CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3 [NCERT][AI 13]


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(vii) C2H5OH, (CH3)2NH, C2H5NH2 [NCERT]


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(viii) 1 - Chloro enthane or - 2 methyl -2- chlorobutane [SP 09]


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Q. 3. Explain why:
(i) p-dichlorobenzene has higher melting point than those of o & m isomers. [AI 09C][SP
15][DB 13][NCERT]
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(ii) Propanol has higher boiling point than that of the hydrocarbon, butane? [NCERT]
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(iii) While separating mixture of ortho & para nitrophenols by distillation, Which isomer will
be volatile. [NCERT][DB 14]
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(iv) Boiling point of ethanol is higher in comparison to methoxymethane. [NCERT][AI 09]


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(v) Why do primary amines have higher boiling point than tertiary amines? [NCERT][AI
14][F 10]
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(vi) Carboxylic acids have higher boiling point than alcohols. [SP 09][F 13]
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(vii) The boiling points of aldehydes and ketones are lower than of the corresponding acids.
[DB 08]
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3. Solubility:
All organic compounds are soluble in organic solvents (like: Alcohol, phenol, ether,
benzene…….etc) as like dissolves like
All organic compounds which are soluble in water is only due to formation of hydrogen bonding
(eg: Alcohol, phenol, ether, amines, …….etc) and which are insoluble is due to inability to form
hydrogen bond as like dissolves like
Solubility ∝ Extant of Hydrogen bonding
1
Solubility ∝
Sterric Hindrance

(thus as R group increases solubility decreases also Aromatic compounds are less soluble in
water)
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Q. 4. Explain why
(i) Alkyl halides, though polar, are immiscible with water? [NCERT][AI 10C][F 12]
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(ii) Haloalkanes easily dissolve in organic solvents, why? [NCERT][DB 11]


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(iii) Alcohols are comparatively more soluble in water than hydrocarbons of comparable
molecular masses. [NCERT][AI 12]
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(iv) Acetone is highly soluble in water but benzophenone is not. [SP 13]
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(v) Miscibility of ethoxyethane with water [SP 11]


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(vi) Ethylamine is freely soluble in water whereas aniline is only slightly soluble. [AI 08, 11][F
13]
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(vii) Ethanol is soluble in water. Why? [AI 13]


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Q. 5. Arrange the following in order of solubility in water: C6H5NH2, (C2H5)2NH, C2H5NH2.


[NCERT][DB 11, 14]
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1. Why is sulphuric acid not used during the reaction of alcohols with KI? [NCERT]
Ans: In the presence of sulphuric acid (H2SO4), KI produces HI
2KI + H2SO4 ⎯→ 2KHSO4 + 2HI
Since H2SO4 is an oxidizing agent, it oxidizes HI (produced in the reaction to I2).
2HI + H2SO4 ⎯→ I2 + SO2 + H2O
As a result, the reaction between alcohol and HI to produce alkyl iodide cannot occur.
Therefore, sulphuric acid is not used during the reaction of alcohols with KI. Instead, a non-
oxidizing acid such as H3PO4 is used.
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2. Haloalkanes react with KCN to form alkyl cyanides as main product while AgCN forms
isocyanides as the chief product. Explain. [NCERT][SP 09]
Ans: KCN is predominantly ionic and provides cyanide ions in solution. Although both carbon
and nitrogen atoms are in a position to donate electron pairs, the attack takes place mainly
through carbon atom and not through nitrogen atom since C—C bond is more stable than C—N
bond. However, AgCN is mainly covalent in nature and nitrogen is free to donate electron pair
forming isocyanide as the main product.
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3. Although chlorine is an electron withdrawing group, yet it is ortho-, para- directing in
electrophilic aromatic substitution reactions. Why? [NCERT]
Ans: Chlorine withdraws electrons through inductive effect and releases electrons through
resonance. Through inductive effect, chlorine destabilises the intermediate carbocation formed
during the electrophillic substitution.
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Through resonance, halogen tends to stabilize carbocation and effect is more pronounced at
ortho- and para- positions. The inductive effect is stronger than resonance & causes net electron
withdrawal & thus causes net deactivation. The resonance effect tends to oppose the inductive
effect for the attack at ortho- and para positions and hence makes the deactivation less for
ortho- and para attack. Reactivity is thus controlled by the stronger inductive effect and
orientation is controlled by resonance effect.
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4. The treatment of alkyl chlorides with aqueous KOH leads to the formation of alcohols but in
the presence of alcoholic KOH, alkenes are major products. Explain. [NCERT][DB 13]
Ans: In aqueous Solution, KOH is almost completely ionized to give OH– ions which being a
strong nucleophile brings about a substitution reaction on alkyl halides to form alcohols.
Further in the aqueous solution, OH– ions are highly solvated (hydrated). This solvation
reduces the basic character of OH – ions which, therefore, fail to abstract a hydrogen from the β
carbon of the alkyl chloride to form an alkene.
In contrast, an alcoholic solution of KOH contains alkoxide (RO –) ions which being a much
stronger base than OH – ions preferentially eliminates a molecule of HCl from an alkyl chloride
to form alkenes.
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5. Grignard’s reagents should be prepared under anhydrous conditions. [F 12][SP 11]


Ans: This is because Grignard reagent reacts with water to form Alkane
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6. Why is (±) – Butan-2-ol is optically inactive? [DB 13]


Ans: (±)-Butan-2-ol exist in two eventiomeric forms which rotate the plane of polarised light in
opposite directions in equal amounts. Therefore, cancelling each other and becoming optically
inactive.
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7. Account for the following: [DB 13] [AI 13]


(i) The C—Cl bond length in chlorobenzene is shorter than that in CH3—Cl.
(ii) Chloroform is stored in closed dark brown bottles.
Ans: (i) In CH3–X the carbon atom is sp2 hybridised while in halobenzene the carbon atom is
sp3 hybridised. The sp2 hybridised carbon is more electronegative due to greater s-character and
holds the electron pair of C–X bond more tightly than sp3 hybridised carbon with less s-
character. Thus, C–X bond length in CH3–X is bigger than C–X in halobenzene.
(ii) Because chloroform is slowly oxidised by air in the presence of light to an extremely
poisonous gas phosgene.
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8. The presence of a base is needed in the ammonolysis of alkyl halides. [SP 09]
Ans = To remove HX formed so that the reaction shifts in the forward direction.
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9. Use of DDT was banned in United States in 1973. [SP 11]


Ans Due to chemical stability of DDT and its fat solubility it is not metabolized very rapidly by
animals and hence is banned in US.
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Alcohol, Phenol
& Ethers
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1. Explain how does the −OH group attached to a carbon of benzene ring activate it towards
electrophilic substitution?
Answer: - The −OH group is an electron-donating group. Thus, it increases the electron density
in the benzene ring as shown in the given resonance structure of phenol.
As a result, the benzene ring is activated towards electrophilic substitution.
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2. Explain the fact that in aryl alkyl ethers (i) The alkoxy group activates the benzene ring
towards electrophilic substitution and (ii) It directs the incoming substituents to ortho and para
positions in benzene ring.
Answer: - (i) In aryl alkyl ethers, due to the +R effect of the alkoxy group, the electron density
in the benzene ring increases as shown in the following resonance structure.

Thus, benzene is activated towards electrophilic substitution by the alkoxy group.


(ii) It can also be observed from the resonance structures that the electron density increases
more at the ortho and para positions than at the meta position. As a result, the incoming
substituents are directed to the ortho and para positions in the benzene ring.
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3. Write the products obtained when benzyl phenyl ether is heated with HI. [Sample Paper
2011]
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4. Phenyl methyl ether reacts with HI to give phenol & methyl iodide & not iodo benzene &
methyl alcohol. Why? [Delhi Board 2010 C]
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NCERT &
NCERT Exemplar
Questions
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