Account for the following:
(i) pKb of aniline is more than that of methylamine.
(ii) Ethylamine is soluble in water whereas aniline is not.
(iii) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide.
(iv) Although amino group is o, p- directing in aromatic electrophilic substitution reactions, aniline on nitration gives a substantial amount of m-nitroaniline.
(v) Aniline does not undergo Friedel-Crafts reaction.
(vi) Diazonium salts of aromatic amines are more stable than those of aliphatic amines.
(vii) Gabriel phthalimide synthesis is preferred for synthesising primary amines.
(i) pKb of aniline is more than that of methylamine:
Aniline undergoes resonance and as a result, the electrons on the N-atom are delocalized over the benzene ring. Therefore, the electrons on the N-atom are less available to donate.
On the other hand, in case of methylamine (due to the +I effect of methyl group), the electron density on the N-atom is increased. As a result, aniline is less basic than methylamine. Thus, pKb of aniline is more than that of methylamine.
(ii) Ethylamine is soluble in water whereas aniline is not:
Ethylamine when added to water forms intermolecular H - bonds with water. Hence, it is soluble in water.
But aniline does not undergo H - bonding with water to a very large extent due to the presence of a large hydrophobic - C6H5 group. Hence, aniline is insoluble in water.
(iii) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide:
Due to the +I effect of - CH3 group, methylamine is more basic than water. Therefore, in water, methylamine produces OH - ions by accepting H+ ions from water.
Ferric chloride (FeCl3) dissociates in water to form Fe3+ and Cl - ions.
Then, OH - ion reacts with Fe3+ ion to form a precipitate of hydrated ferric oxide.
(iv) Although amino group is o,p - directing in aromatic electrophilic substitution reactions, aniline on nitration gives a substantial amount of m-nitroaniline:
Nitration is carried out in an acidic medium. In an acidic medium, aniline is protonated to give anilinium ion (which is meta-directing).
For this reason, aniline on nitration gives a substantial amount of m-nitroaniline.
(v) Aniline does not undergo Friedel-Crafts reaction:
A Friedel-Crafts reaction is carried out in the presence of AlCl3. But AlCl3 is acidic in nature, while aniline is a strong base. Thus, aniline reacts with AlCl3 to form a salt (as shown in the following equation).
Due to the positive charge on the N-atom, electrophilic substitution in the benzene ring is deactivated. Hence, aniline does not undergo the Friedel-Crafts reaction.
(vi) Diazonium salts of aromatic amines are more stable than those of aliphatic amines:
The diazonium ion undergoes resonance as shown below:
This resonance accounts for the stability of the diazonium ion. Hence, diazonium salts of aromatic amines are more stable than those of aliphatic amines.
(vii) Gabriel phthalimide synthesis is preferred for synthesising primary amines:
Gabriel phthalimide synthesis results in the formation of 1° amine only. 2° or 3° amines are not formed in this synthesis. Thus, a pure 1° amine can be obtained. Therefore, Gabriel phthalimide synthesis is preferred for synthesizing primary amines.
Give simple chemical tests to distinguish between the following pairs of compounds.
(i) Propanal and Propanone
(ii) Acetophenone and Benzophenone
(iii) Phenol and Benzoic acid
(iv) Benzoic acid and Ethyl benzoate
(v) Pentan-2-one and Pentan-3-one
(vi) Benzaldehyde and Acetophenone
(vii) Ethanal and Propanal
A 5% solution (by mass) of cane sugar in water has freezing point of 271 K. Calculate the freezing point of 5% glucose in water if freezing point of pure water is 273.15 K.
How the following conversions can be carried out?
(i) Propene to propan-1-ol
(ii) Ethanol to but-1-yne
(iii) 1-Bromopropane to 2-bromopropane
(iv) Toluene to benzyl alcohol
(v) Benzene to 4-bromonitrobenzene
(vi) Benzyl alcohol to 2-phenylethanoic acid
(vii) Ethanol to propanenitrile
(viii) Aniline to chlorobenzene
(ix) 2-Chlorobutane to 3, 4-dimethylhexane
(x) 2-Methyl-1-propene to 2-chloro-2-methylpropane
(xi) Ethyl chloride to propanoic acid
(xii) But-1-ene to n-butyliodide
(xiii) 2-Chloropropane to 1-propanol
(xiv) Isopropyl alcohol to iodoform
(xv) Chlorobenzene to p-nitrophenol
(xvi) 2-Bromopropane to 1-bromopropane
(xvii) Chloroethane to butane
(xviii) Benzene to diphenyl
(xix) tert-Butyl bromide to isobutyl bromide
(xx) Aniline to phenylisocyanide
A solution of glucose in water is labelled as 10% w/w, what would be the molality and mole fraction of each component in the solution? If the density of solution is 1.2 g mL-1, then what shall be the molarity of the solution?
Henry's law constant for CO2 in water is 1.67 x 108Pa at 298 K. Calculate the quantity of CO2in 500 mL of soda water when packed under 2.5 atm CO2 pressure at 298 K.
Calculate the mass of a non-volatile solute (molar mass 40 g mol-1) which should be dissolved in 114 g octane to reduce its vapour pressure to 80%.
The vapour pressure of pure liquids A and B are 450 and 700 mm Hg respectively, at 350 K. Find out the composition of the liquid mixture if total vapour pressure is 600 mm Hg. Also find the composition of the vapour phase.
Calculate the mole fraction of benzene in solution containing 30% by mass in carbon tetrachloride.
How many mL of 0.1 M HCl are required to react completely with 1 g mixture of Na2CO3 and NaHCO3 containing equimolar amounts of both?
If NaCl is doped with 10-3mol % of SrCl2, what is the concentration of cation vacancies?
Define the following terms:
(i) Mole fraction (ii) Molality (iii) Molarity (iv) Mass percentage.
What role does the molecular interaction play in a solution of alcohol and water?
How will you bring about the following conversions?
(i) Ethanol to but-1-yne
(ii) Ethane to bromoethene
(iii) Propene to 1-nitropropane
(iv) Toluene to benzyl alcohol
(v) Propene to propyne
(vi) Ethanol to ethyl fluoride
(vii) Bromomethane to propanone
(viii) But-1-ene to but-2-ene
(ix) 1-Chlorobutane to n-octane
(x) Benzene to biphenyl.
Give the IUPAC names of the following compounds:
(i) CH3CH(Cl)CH(Br)CH3
(ii) CHF2CBrClF
(iii) ClCH2C≡CCH2Br
(iv) (CCl3)3CCl
(v) CH3C(p-ClC6H4)2CH(Br)CH3
(vi) (CH3)3CCH=CClC6H4I-p
Amongst the following compounds, identify which are insoluble, partially soluble and highly soluble in water?
(i) phenol (ii) toluene (iii) formic acid (iv) ethylene glycol (v) chloroform (vi) pentanol.
What inspired N. Bartlett for carrying out reaction between Xe and PtF6?
What type of solids are electrical conductors, malleable and ductile?
From the rate expression for the following reactions, determine their order of reaction and the dimensions of the rate constants.
(i) 3 NO(g) → N2O(g) Rate = k[NO]2
(ii) H2O2 (aq) + 3 I - (aq) + 2 H+→ 2 H2O (l) + I3- Rate = k[H2O2][I - ]
(iii) CH3CHO(g) → CH4(g) + CO(g) Rate = k [CH3CHO]3/2
(iv) C2H5Cl(g) → C2H4(g) + HCl(g) Rate = k [C2H5Cl]
Arrange the following:
(i) In decreasing order of the pKbvalues:
C2H5NH2, C6H5NHCH3, (C2H5)2NH and C6H5NH2
(ii) In increasing order of basic strength:
C6H5NH2, C6H5N(CH3)2, (C2H5)2NH and CH3NH2
(iii) In increasing order of basic strength:
(a) Aniline, p-nitroaniline and p-toluidine
(b) C6H5NH2, C6H5NHCH3, C6H5CH2NH2.
(iv) In decreasing order of basic strength in gas phase:
C2H5NH2, (C2H5)2NH, (C2H5)3N and NH3
(v) In increasing order of boiling point:
C2H5OH, (CH3)2NH, C2H5NH2
(vi) In increasing order of solubility in water:
C6H5NH2, (C2H5)2NH, C2H5NH2.
Outline the principles of refining of metals by the following methods:
(i) Zone refining
(ii) Electrolytic refining
(iii) Vapour phase refining
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Why ortho product in little amount is also formed in nitration of aniline?