Suggested Solutions to Discussion Questions (Tutorial 17)

1. (a)
Ethyl ethanoate Ethanol
<
Phenol
<
<
Consider a weak acid, HA
HA
H+
+
A
More stable A, greater dissociation, stronger acid.
No acidic proton electron donating benzene
ring
present.
ethyl group
present
allows
intensifies
delocalisation of of
cannot act as
negative charge
negative charge on
an acid!
and destabilizes
Oalkoxide anion
O of
into
benzene
ring
stabilizing
the
phenoxide ion

ethanoic acid <

negative charge is
dispersed over 2
electronegative
oxygen atoms in 2
equivalent
resonance
structures causing
the anion to be
greatly stabilised

benzoic acid [1]

Presence
of
benzene
enables
delocalisation of
negative charge in
the anion into the
benzene
ring,
stabilising the anion

(b) CH3CH2CH2CH2COOH < CH3COOH < HOCH2COOH < CCl3COOH

HA
H+
+
A
More stable A, greater dissociation, stronger acid.
Compare stability of A, taking CH3COO as reference:
alkyl groups are elctron donating by inductive effect. It intensifies the negative
charge & destabilises the anion. CH3CH2CH2CH2COO is only slightly less stable
than CH3COO due to longer alkyl chain (effect of alkyl chain length is minimal)
OH is electron withdrawing by inductive effect. It helps to disperse the negative
charge & stabilises the anion. HOCH2COOH is more acidic than CH3COOH.
the presence of 3 Cl atoms (electron withdrawing by inductive effect) disperses the
negative charge extensively. CCl3COO is greatly stabilised & CCl3COOH is the
strongest acid among the 4.
2.

All three compounds react with Na(s) to give effervescence of H2(g) and the
corresponding Na+ salts which are soluble in water.
E

CH2OH

H3C

OH

Na (s)

COOH

Na(s)

CH2O Na + 1/2 H2

H3C

O Na + 1/2 H2

Na (s)

COO Na + 1/2 H2

G
Both E and F have no reaction with aqueous Na2CO3. G reacts with aq. Na2CO3 to
give effervescence of CO2(g) and Na+ salt which is soluble in water.

COOH

+ Na2CO3 (aq)

COO Na + CO2

G
1

E has no reaction with aqueous NaOH. Both F and G react with NaOH to give the
corresponding Na+ salts which are soluble in water.

H3C

OH

+ NaOH (aq)

H3C

O Na + H2O

+ NaOH (aq)

COOH

COO Na + H2O

G
Add aqueous Na2CO3 to the sample. If effervescence of CO2 is detected, then the
sample is G. If not, then the sample is either E or F, which can be differentiated by
adding aqueous NaOH. Only F is soluble in aqueous NaOH.
3. C6H5COOH
and
C6H5OH
[acid strength]
Test:
Add Na2CO3 (aq)
[or NaHCO3 (aq)]
Observations: Effervescence observed.
No effervescence observed
Colourless gas (CO2) evolved
formed white ppt with aq. Ca(OH)2
Equation:
2 CH3COOH + Na2CO3 2 CH3COONa+ + CO2 + H2O
(b) HOCH2CH2COCl
and
ClCH2CH2COOH [acyl chloride vs acid]
Test:
Add AgNO3(aq)
Observations: White fumes
No white fumes
White ppt (AgCl)
No ppt observed
Equation:
HOCH2CH2COCl + H2O HOCH2CH2COOH + HCl
Cl(aq) + Ag+(aq) AgCl (s)
(c)C6H5COCl and C6H5COBr and C6H5CH2Cl [acyl chloride vs acyl bromide vs alkyl halide]
Test:
Add AgNO3(aq)
Observations: White fumes
White fumes
White fumes
White ppt (AgCl) Off-white ppt (AgBr)
White ppt (AgCl) only when
heated
Equation:
C6H5COX + H2O C6H5COOH + HX
C6H5CH2Cl + H2O
C6H5CH2OH + HCl
X(aq) + Ag+(aq) AgX (s)
X= Cl, Br
Cl(aq) + Ag+(aq) AgCl (s)
(d) CH3COOCH2CH2CH3
and
CH3COOCH(CH3)2
Test:
1) Heat with NaOH (aq)
2) Add aq. I2
Observations: No yellow ppt formed
yellow ppt formed

Equation:
CH3COOCH2CH2CH3 +OH CH3COO + HOCH2CH2CH3
CH3COOCH(CH3)2 +OH CH3COO + HOCH(CH3)2
HOCH(CH3)2 + 4I2 + 6OH CH3COO + CHI3 + 5I + 5H2O

4.

(a)

2
4
CH3COOH + H2O
CH3CH2OH + [O]
heat

dilH SO , aq.KMnO

2
CH3COOH
CH3COCl + SO2 + HCl
room temperature

SOCl

O=

(b)

(c)

room temperature
CH3CH2OH + CH3CH2COCl
CH3C-O-CH2CH3
(from a)

CH3CH2OH + [O]

K2Cr2O7(aq), dil H2SO4, heat

with immediate distillation

CH3CHO + H2O

O
CH3

C H

OH

KCN

HCN

CH3

C CN
H

OH
CH3

C CN

OH

dil HCl
+ 2H2O + H+

H
(d)
CH3CH2CH2OH + 2 [O]

CH3

C COOH

heat

+ NH4+

KMnO4 (aq), dil H2SO4,

heat

CH3CH2COOH + H2O

room temperature

CH3CH2COOH + SOCl2

CH3CH2COCl + SO2 + HCl

O

+CH3CH2COCl + Na O

5.

C O

+ NaCl

COCl

COOH

room temperature
SOCl2

COCl

+
6.

CH3CH2

NH2CH2COOH

HCl

room temperature
CONHCH 2COOH

SO2

HCl

F undergoes neutralization with NaOH(aq)

F contains an acidic fn gp
F is either a phenol or a carboxylic acid
F undergoes condensation reaction with 2,4-DNPH but does not undergo oxidation with
Fehlings solution
F is a carbonyl compound that is not an aliphatic aldehyde
F is either an aromatic aldehyde or a ketone
F undergoes electrophilic substitution with Br2 water to give G.

 F contains a strongly activated benzene ring

F is a phenol
Since G has 2 H atoms substituted with 2Br atoms
G is a 2- or 4-substituted phenol
F gives a positive iodoform test to yield H
F is a methyl ketone
H is a carboxylic acid with 1 C less
H undergoes neutralization with both NaOH(aq) and Na2CO3(aq).
H is a carboxylic acid (confirmed)
H is obtained by alkaline hydrolysis of J followed by acidification.
H is 1,2-disubstituted.
OH

O
C

OH

H is
OH

OH

Br

O
C

OH
CH3

O
C

CH3

OH

Br

[1] per correct structure

Equations:
[F + NaOH]
OH

O-Na+ O

O
C

CH3

+ NaOH

CH3

+ H 2O

[F + 2,4-DNPH]
OH

OH

O2N

CH3

CH3
C

H2NNH

NO2

O2N

NNH

NO2 + H2O

[F + Br2(aq)]
OH

O
C

OH
CH3

Br

O
C

+ 2Br2

CH3

+ 2HBr

Br

[F + aq. alkaline I2]

OH

O-

O
C

O
C

CH3 + 3I2 + 5OH-

O-

+ CHI3 + 3I- + 4H2O

[acidification after iodoform test]

[acidification after J + NaOH]
O-

OH

O
C

O-

O
C

+ 2H

OH

[J + NaOH]
OH

O-

O
C

OCH3

O
C

+ 2OH-

O-

+ H2O

+ CH3OH

[J + Na2CO3]
OH
2

OH

O
C

OH

+ Na2CO3

O
C

O-Na+

+ CO2 + H2O