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1 Strength of an acid depends on the stability of its conjugate base. The more stable the D
conjugate base is, the more likely the acid ionises (Position of equilibrium lies to the
right.)
The acid strength of the 2 carboxylic acids in this question will be the greater than that of
phenol (narrow to options B and D) due to the greater dispersal of the negative charge
between the highly electronegative two O atoms of the carboxylate anion as compared
to that of the phenoxide ion.
Chloroethanoic acid is a stronger acid than ethanoic acid due to the electron withdrawing
Cl atom which disperses the negative charge on its conjugate base and stabilising it to
a greater extent, favouring the dissociation of O–H bond to form H+.
2 Chloroethanoic acid is a stronger acid than ethanoic acid due to the electron withdrawing D
Cl atom which disperses the negative charge on its conjugate base and stabilising it to
a greater extent, favouring the dissociation of O–H bond to form H+.
4 Ester can be synthesised either using carboxylic acid and alcohol or acyl halide and C
alcohol / phenol. Hence all the options except D and E will give an ester, though only one
of them will give CH3CO2CH2CH(CH3)CH2CH3.
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7 Ease of hydrolysis depends on how electrophilic the electron deficient carbon is (for A
same X) and the bond strength of the C–X bond (for different X).
A CH3CH2COCl will hydolyse the fastest due to the highly electron deficient
carbonyl carbon (bonded to 2 electronegative atoms).
CH2=CHCl will hydrolyse the slowest due to the partial double bond between C
and Cl formed from the delocalisation of lone pair of electrons on Cl into the
bond of C=C.
B CH3CH2I will hydrolyse the fastest due the C–I bond being the weakest.
C C6H5CH2Br will hydrolyse the fastest due to absence of partial C–X double bond.
D C6H5CH2l will hydrolyse the fastest due to absence of partial C–X double bond.
8 A It is the opposite. If indeed the lone pair of electrons (lp) on the Cl atom is more C
readily delocalised, the carbonyl carbon will be less electron deficient and less
susceptible to nucleophilic attack (lower ease of hydrolysis).
The lp on Cl resides in the 3p orbital while the bond of C=O is formed from
side–on overlap of the 2p orbitals of C and O. Hence the delocalisation of lp on
Cl into >C=O is less effective.
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9 V has a more electron deficient C and reacts with water, phenol and ethanol (all are D
nucleophiles) more readily than U.
Both do not react with 2,4–DNPH (not aldehyde nor ketone).
OH OH OH
CH2 CH2 CH2 CH2 CH2 CHO
OH OH
12 The 1st step is nucleophilic (acyl) substitution while the 2nd step follows the nucleophilic A
addition mechanism. The 3rd step can be an acid–base reaction or hydrolysis reaction.
OH
H C H
O
H C H + OH- hydrolysis
O
H H
O H
H C H
+ OH- acid–base
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ether is not
ester O CN nitrile hydrolysed
H 3C O
O
H3 C
H 3 C CH 3
Cyphenothr in
NaOH (aq)
ref lux
O [+ NH3 (g)]
CO2 Na
H 3C
O Na + HO O
H3 C
H 3C CH 3
15 Refer to Q4. C
16 “reacts with hot, NaOH” reacts with phenol and/or carboxylic acid (circled). C
hydrolyse ester and/or amide (boxed).
17 “contains four 1o alcohol” four –CH2OH groups (accounted for C4H12O4, left with 1 C) A
CH2OH
HOCH2 C CH2OH
CH2OH
Structure of pentaerythritol is .
Upon oxidation, all four 1o alcohol will be oxidised to carboxylic acid with the structural
formula C(CO2H)4 i.e. molecular formula is C5H4O8.
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19 Compound that will produce the largest mass of AgCl depends on amount of reactants B
used and how electrophilic is the electron deficient C atom.
Since 1 gram of each of the compounds is used, the compound with the smallest Mr will
form the largest mass of ppt.
Though options A and D are acid chlorides and they hydrolyse most readily, the reaction
mixture was heated before addition of AgNO3(aq) so both C–Cl bonds in option B will
also hydrolyse to give Cl–. Hence, B will give a larger amount of AgCl ppt and produce
the largest mass of AgCl(s).
20 A Both alcohol and carboxylic acid react with PCl5(s), hence 1 mol of citric acid will C
react with 4 mol of PCl5(s).
B Only alcohol will react with HCl(g) in the presence of ZnCl2, hence 1 mol of citric
acid will react with 1 mol of HCl(g).
C Both alcohol and carboxylic acid react with Na(s), hence 1 mol of citric acid will
react with 4 mol of Na(s).
D Only carboxylic acid react with NaOH(aq), hence 1 mol of citric acid will react with
3 mol of NaOH(aq).
21 Given that the unknown is dibasic [2 x –CO2H], you can deduce the molecular mass of C
the alkyl chain = 146 – 2(45) = 56.
23 PCl5 A
CH3CHBrCH(OH)CO2H M
The alcohol and carboxylic acid functional groups undergo nucleophilic substitution
with PCl5, to produce M (CH3CHBrCH(Cl)COCl).
24 From the functional groups in citric acid and structures of all four options, and the use of A
concentrated sulfuric acid, the question is based on ‘esterification’ reaction.
In order to determine if the alcohol or carboxylic acid groups of citric acid is involved in
the reaction, we need to see the change in molecular formula after esterification.
From C6H8O7 C9H12O8, there is an increase in 3 C, 1 O and 4 H atoms. To have a
gain in 1 O atom, it must be the alcohol group that has reacted to have an additional C=O
group from another acid. To gain 3 C atoms, the reacting acid must have 3 C atoms.
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26 1 CH2CN CH2CO2H D
product
2 CO2H CO2CH2CH3
COCl
27 For 1, ester group in X undergoes acid hydrolysis to form 3o alcohol which cannot be A
oxidised by K2Cr2O7. There is no change in the colour of solution. However, the acid
hydrolysis of Y formed 2o alcohol which can be oxidised by K2Cr2O7. The colour of
solution changes from orange to green.
For 2, both the ester groups in X and Y undergo base hydrolysis. However, only Y shows
a positive iodoform test due to presence of CH3CH(OH)– group after hydrolysis.
For 3, base hydrolysis of R–Br in X followed by excess HNO3(aq) and AgNO3(aq) results
in a cream ppt of AgBr. No cream ppt is observed for Y as the Br atom is bonded to C=C
bond where the p orbital of Br interacts with the p orbital of C in C=C, resulting in partial
double bond character in the C–Br bond.
28 1 After hydrolysis of the ester group, Br2 adds across the C=C bond (electrophilic B
addition) and substitutes onto the phenol (electrophilic substitution). With Br2(aq),
substitution occurs on the phenol at the 2– and 4–positions (the 6–position is blocked
by the alkyl side–chain). Hence the reaction is with 3 moles of Br2.
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2 Cold acidified KMnO4 will result in oxidative addition (mild oxidation), where –OH is
‘added’ across the C=C double bond to give the following product, which has 2 chiral
centres (marked with *):
3 The reactions are not nucleophilic, but electrophilic addition and electrophilic
substitution as the alkene and benzene rings are both electron–rich.
29 Option 1 (Correct) D
CH3CO2H + NaOH CH3CO2–Na+ + H2O
CH3CO2– is the conjugate base (pH > 7 at 25 oC) of the weak acid, CH3CO2H.
Option 2 (Incorrect)
CH3CO2H reacts with ethylamine (CH3CH2NH2) to form a salt, [CH3CO2–][CH3CH2NH3+],
instead (via acid–base reaction).
Option 3 (Incorrect)
Cannot work. Phenol will undergo oxidation by conc H2SO4. To form ester in this case,
use CH3COCl, and react with phenol in the presence of NaOH(aq).
30 Option 1 (Correct) A
Cannot work. Bromobenzene cannot undergo nucleophilic substitution with the
carboxylate ion readily due to the partial double bond character of C–Br.
Option 2 (Correct)
Cannot work. Phenol will undergo oxidation by conc H2SO4. To form ester in this case,
use an appropriate acyl chloride, and react with phenol in the presence of NaOH(aq).
Option 3 (Correct)
Cannot work. Carboxylic acid cannot react with an acyl chloride.
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1 (a) (i)
HO COOH
R is
(b)
+
Na-O COO-Na+
CH3OH and
(c) (i)
CH3COO CO2CH3
(ii) Ester
OH
(ii) COO-Na+
O-Na+
(iii) COOH
O2N COOH
OH
OH NO2
or
(ii) Its calcium salt is an ionic compound and hence forms ion–dipole interactions with
the water molecules while aspirin, a simple molecular compound, is insoluble
because of the formation of intramolecular hydrogen bonding present within the
molecule.
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3 (a) (i) O H
C O C
L is H and
O
CH3 O C
P is
(ii)
CH3 OH NaOH
CH3 O-Na+
N
P
(b) (i)
CH2OH < CH3 OH < CO2H
M Q N
Compare M and Q
C6H5CH2OH C6H5CH2O– + H+
In phenylmethanol, the alkyl group is electron–donating. This intensifies the
negative charge on the oxygen and makes the alkoxide ion less stable. Hence,
alcohols are less likely to dissociate into ions.
CH3 OH CH3 O- + H
+
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Compare Q and N
O O
C OH C O- + H+
For benzoic acid, the p–orbital on the C atom overlaps with the p–orbitals of
the 2 neighbouring O as well as the π orbitals of the benzene ring. Hence the
negative charge on the benzoate ion can be dispersed into the ring as well as
between the two O atoms resulting in a most stable conjugate base. Therefore
N is a stronger acid than Q.
(ii) I
CH3 OH + NaOH CH3 O-Na+ + H2O
II
2 CO2H + Na2CO3 2 COO-Na+
N + CO2 + H2O
H HCN, H
trace amt of NaOH
CH3 C O CH3 C OH
(2) CN
H
dilute HCl CH3CH(OH)
CH3 C OH
heat COOH
(3) CN
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KCN in ethanol
CH2Cl CH2CN
(2) heat
dilute HCl
CH 2CN CH2COOH
(3) heat
+
Na-O O-Na+
O-Na+
(ii) COO-Na+
HO OH
OH
(iii) COOH
O2N NO2
HO OH
OH
6 (a)
O 2N CH CH2 O 2N CH CH2 H 2N CH CH3
OH Br Br
A B C
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(b)
(c) Compound Q (or 4–nitrobenzoic acid) is more acidic than benzoic acid.
(d) No. of moles of methylbenzene used = 15.4 / 92.0 = 0.167 = no. of moles of procaine
(e) (i) Aqueous solutions of S and T turn blue litmus red => carboxylic acid present
Both S and T decolourise bromine => alkene present
Both S and T decolourise bromine => electrophilic addition
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T (is cis–isomer:)
(iii) Dehydration of T (or cis–isomer) occurs at lower temperature because the two
carboxyl groups are cis to each other / nearer to each other.
(iv)
(f) (i) Amphiprotic means amphoteric / can react with acid and base / have both acidic
and basic properties / behave as acid and base.
8 O
ClCH2 C N CH2CH2NH2
The COCl carbon is attached to two highly electronegative atoms, Cl and O, as compared to
only one electronegative Cl in the case for the CH2Cl carbon. Hence, the COCl carbon has a
higher partial positive charge than the CH2Cl carbon.
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C reacts with excess PCl 5 to Nucleophilic (acyl) HCl fumes are produced.
form D, C4H4O2Cl2 with the Substitution C contains 2 carboxylic acid
evolution of white fumes. functional groups.
D contains an acyl chloride
group.
CH3 CH3
O O O O
CH3 C CH2 CH2 C OH HO C CH2 CH2 C OH
B C
A
O
O C
O O
Cl C CH2 CH2 C Cl
O C
D E
O
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alternatively,
CH3
CH3
O CH3O O CH3O
CH3 C C C OH HO C C C OH
CH3 H C H
CH3
A B
CH3O O
O O C
Cl C C C Cl CH3
H
D E O C
O
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O CH3
CH(OH)CH3 CH2CH2OH CH2CHO
C
COOH COOH
COOH COOH
V W X Y
(c) I O CH3
COO-Na+
C
COO-Na+
COOH 3I2 5OH-
CHI3 3I- 4H2O
II CH2CHO CH2COO-
(d) CH3
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