1

Acyl Chlorides WS 1
7
7
1 2016 JUN P41 Q05
5
5 Dicarboxylic
Dicarboxylic acids
acids dissociate
dissociate in
in stages.
stages.
stage 1 stage 2
stage 1 stage 2
HO
HO22C(CH
C(CH22))nnCO
CO22H
H HO
HO22C(CH
C(CH22))nnCO
CO22– +
–
+ H
+
H+
–
– O
O22C(CH
C(CH22))nnCO
CO22– +
–
+ 2H
+
2H+
(a)
(a) The
The pK
pKaa values
values for
for stage
stage 1
1 and
and stage
stage 2
2 for
for some
some dicarboxylic
dicarboxylic acids
acids are
are listed
listed below.
below.

pKaa(1)
pK (1) pK
pKaa(2)
(2)
n
n in
in HO
HO22C(CH
C(CH22))nnCO
CO22H
H for
for stage
stage 11 for
for stage
stage 22
1
1 2.83
2.83 5.69
5.69
2
2 4.16
4.16 5.61
5.61
3 4.31 5.41
"
" For
3 4.31 5.41

For comparison,
comparison, the pKaa of
the pK of ethanoic
ethanoic acid,
acid, CH
CH33CO
CO22H,
H, is
is 4.76.
4.76.
(i)
(i) State
State the
the mathematical
mathematical relationship
relationship between pKaa and
between pK and the
the acid
acid dissociation
dissociation constant
constant K
Kaa..
.......................................................................................................................................
....................................................................................................................................... [1]
[1]
(ii)
(ii) With
With reference
reference to
to the
the table
table above,
above, suggest
suggest why
why the pKaa(1)
the pK (1) values
values
are
are all
all smaller
smaller than
than the pKaa of
the pK of ethanoic
ethanoic acid,
acid,
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
become
become larger
larger as
as n
n increases.
increases.
.............................................................................................................................................
.............................................................................................................................................
[3]
[3]
(iii)
(iii) Suggest
Suggest why
why all
all the pKaa(2)
the pK (2) values
values in
in the
the table
table above
above are
are larger
larger than
than the
the pK
pKaa of
of ethanoic
ethanoic
acid.
acid.
.............................................................................................................................................
.............................................................................................................................................
.......................................................................................................................................
....................................................................................................................................... [1]
[1]

(b)
(b) The
The monosodium
monosodium salts
salts of
of edible
edible dicarboxylic
dicarboxylic acids
acids are
are added
added to
to some
some foodstuffs
foodstuffs as
as buffers.
buffers.
(i)
(i) Explain
Explain what
what is
is meant
meant by
by the
the term
term buffer
buffer solution.
solution.
.............................................................................................................................................
.............................................................................................................................................
.......................................................................................................................................
....................................................................................................................................... [2]
[2]
(ii)
(ii) Write
Write two
two equations
equations to
to show
show how
how monosodium
monosodium butanedioate, HO22CCH
butanedioate, HO CCH22CH
CH22CO
CO22Na,
Na, acts
acts
as a buffer.
as a buffer.
.............................................................................................................................................
.............................................................................................................................................
.......................................................................................................................................
....................................................................................................................................... [2]
[2]
[Total:
[Total: 9]
9]
Bilal Hameed
© UCLES 2016 9701/41/M/J/16
Acyl Chlorides
[Turn over 1
© UCLES 2016 9701/41/M/J/16 [Turn over
 2
4
2 2016 JUN P42 Q02
2 Ethanoic acid is a weak acid.

(a) Explain what is meant by the term weak acid.

....................................................................................................................................................

.............................................................................................................................................. [1]

(b) The pKa values of four acids are listed below.

"
acid structural formula pKa
1 CH3CO2H 4.8
2 CH3CH2CO2H 4.9
3 CH3CHCl CO2H 2.8
4 CH2Cl CH2CO2H 4.0

(i) State the mathematical relationship between pKa and the acid dissociation constant Ka.

....................................................................................................................................... [1]

(ii) With reference to acidity, explain the difference in pKa values between

acid 1 and acid 2,

.............................................................................................................................................

.............................................................................................................................................

acid 2 and acid 3,

.............................................................................................................................................

.............................................................................................................................................

acid 3 and acid 4.

.............................................................................................................................................

.............................................................................................................................................
[3]

© UCLES 2016 9701/42/M/J/16

Acyl Chlorides 1 Bilal Hameed

 3
14
3 2017 JUN P42 Q06
6 The table lists some organic acids and their pKa values.

acid formula pKa

ethanoic acid CH3CO2H 4.76
chloroethanoic acid Cl CH2CO2H 2.86
aminoethanoic acid (glycine) H2NCH2CO2H 9.87

(a) (i) State the relationship between pKa and the strength of an acid.

....................................................................................................................................... [1]

(ii) State the mathematical relationship between pKa and the acidity constant Ka.

" ....................................................................................................................................... [1]

(iii) Give reasons for why the pKa value for chloroethanoic acid is smaller than that for ethanoic
acid.

.............................................................................................................................................

.............................................................................................................................................

....................................................................................................................................... [2]

(b) (i) Use the zwitterionic structure for aminoethanoic acid (glycine) in aqueous solution to write
an equation for its dissociation giving H+(aq) ions.

....................................................................................................................................... [1]

(ii) Calculate the pH of a 0.100 mol dm–3 solution of aminoethanoic acid.

pH = .............................. [2]

© UCLES 2017 9701/42/M/J/17

Bilal Hameed Acyl Chlorides 1

 16
4
16
7 1616
Compounds W, X, Y and Z are isomers of each other with the molecular formula C8H7Cl O.
4 2017
All JUN P42contain
Q07 a benzene ring.
77 four isomers
Compounds
Compounds W,
W, X,
X, Y
Y and
and ZZ are
are isomers
isomers of
of each
each other
other with
with the
the molecular formula C
molecular formula C8H
H7Cl
Cl O.
O.
7 Compounds
OnlyAll W, X,
one of isomers
the Ycontain
isomers andcontains
Zaare isomers
a chiral ofcentre.
each other with the molecular formula C88H77Cl O.
The All four
All four four of
isomers
results isomers
contain
six contain
tests a a benzene
benzene
benzene
carried out
ring.
ring.
on ring.
W, X, Ycentre.
and Z are shown in the table.
Only
Only one
one of the
the isomers
ofisomersisomers contains
contains aa chiral
chiral centre.
OnlyTheoneresults
of the of six contains a chiral centre.
The results
The results six tests
of sixoftests tests carried
carried
carried
out on
out out
on on
W, X,
W, W,
X, X,
Y
Y and
Y andand Z
Z are
are
Z are
shown
showninin
shown
the table.
inthe
the table.
table.
observations with each isomer
test observations with each isomer
isomer
W observations
X with each
test
test observations with each Y isomer Z
W X Y Z
1 add coldtest AgNO3(aq) white ppt. W
W forms none X
X white ppt.Y
Y forms none Z
Z
11 addadd cold
cold AgNO
AgNO33(aq) white
white ppt.
(aq) immediately ppt. forms
forms none
none white
very
white ppt. forms
slowly
ppt. forms none
none
1 add cold AgNO3(aq) immediately
white ppt. forms none
immediately very
white slowly
very ppt. forms none
slowly
2 heat with NaOH(aq), immediately very slowly
22 heat
then add with
heat with NaOH(aq),
dilute NaOH(aq), white ppt. none white ppt. none
2 heat then
HNO with
3 +
then add
AgNO
add dilute
NaOH(aq),
3 (aq)
dilute white
white ppt.
ppt. none
none white
white ppt.
ppt. none
none
HNO
then HNO +
add 3dilute AgNO (aq) white ppt. none white ppt. none
3 + AgNO3(aq)
3
+ I2(aq) none
" ""
3 add
HNO NaOH(aq)
+ AgNO (aq) pale yellow ppt. none none
3 add NaOH(aq) + I (aq) none
3 3
add NaOH(aq) + I22(aq)
3
none pale yellow ppt. none
pale yellow ppt. none none none
4
44 NaOH(aq) + I2(aq)
"
3 add none pale yellow ppt. red
none noneppt. none
solution none
none none
none red ppt.
red ppt. none
none
solution
solution
4
5 add none none red ppt. none
55 cold,
solution
add dilute,
add cold,
cold, dilute,
dilute,
no change
no change
no change
nono
change
change
no change
no
nochange
change
no change
decolourises
decolourises
decolourises
4(aq)(aq)
5 add cold, dilute, 44(aq) no change no change no change
decolourises
6 add
66 Br 2(aq)
add
add Br22(aq)
Br (aq)4(aq)
no change
no
no change
change
nono
change
no change
change
no
decolourises
no
decolourises change
change
no change
decolourises
and
and forms
and white
forms white
forms white
6 add Br2(aq) no change no change no change decolourises
ppt.
ppt.
ppt.
and forms white
(a) Use the ppt.
Use experimental
(a) Use
(a) the
the experimental
experimental results in the
results
results in table
in the
the above
table
table above
abovetoto
todetermine
determinethe
determine thegroup(s),
the group(s), in
group(s), in
in addition to the
addition to
addition to the
the
benzene
benzene ring,
ring,ring,
benzene present
present in
in the
present the four
fourfour
in the isomers
isomers
isomers W,
W,W, X,
X,X,
YYY
andand Z.
andZ.Z.
(a) Use the experimental results in the table above to determine the group(s), in addition to the
Complete
benzene
Complete ring, the
the table
present
the table
Complete below,
in
below,
table the identifying
four thethe
isomers
identifying
below, identifying W,group(s)
X, Y and
group(s) present
Z. inineach
present eachisomer.
isomer.

Complete the table below, identifying the group(s)

group(s) present in each isomer.
group(s) in in compound
compound
W W
W X
X
X group(s) in compound Y
Y Z
Z

W
......................................
X Y Z
...................................... ......................................
...................................... ...................................... ......................................
......................................
...................................... ...................................... ...................................... ......................................
......................................
...................................... ......................................
...................................... ...................................... ......................................
......................................
...................................... ...................................... ...................................... ......................................
......................................
...................................... ......................................
...................................... ...................................... ......................................
......................................
...................................... ...................................... ...................................... ......................................
[5]
[5]
...................................... ...................................... ...................................... ......................................
[5]

[5]

©©UCLES
UCLES2017
2017 9701/42/M/J/17
9701/42/M/J/17

© UCLES 2017 9701/42/M/J/17

© UCLES 2017 9701/42/M/J/17

Acyl Chlorides 1 Bilal Hameed

 5
17

(b) W, X, Y and Z all have the molecular formula C8H7Cl O.

(i) Use the information in (a) to suggest a structure for each of these isomers and draw these
in the boxes.

W X

Y Z

[4]

(ii) Draw a circle around the chiral centre in one of the above structures. [1]

[Total: 10]

© UCLES 2017 9701/42/M/J/17 [Turn over

Bilal Hameed Acyl Chlorides 1

 19

(vi) State the type of reaction that G undergoes when heated with dilute sulfuric acid.
6
....................................................................................................................................... [1]

5 2018 MAR P42 Q09

(b) Describe and explain the relative acidities of benzoic acid, phenylmethanol and 4-methylphenol.

CO2H CH2OH H 3C OH

benzoic acid phenylmethanol 4-methylphenol

....................................................................................................................................................

....................................................................................................................................................

....................................................................................................................................................

" ....................................................................................................................................................

....................................................................................................................................................

.............................................................................................................................................. [3]

(c) The ester 4-methylphenyl benzoate is used in the manufacture of perfumes.

H3C O

4-methylphenyl benzoate

Suggest a two-step route for the synthesis of 4-methylphenyl benzoate from 4-methylphenol
and benzoic acid.
Include reagents and conditions for each step, and the structure of the intermediate compound.

[3]

[Total: 14]

© UCLES 2018 9701/42/F/M/18 [Turn over

Acyl Chlorides 1 Bilal Hameed

 7
15
6 2018 JUN P41 Q07
7 The three substances shown all have some acidic properties.

O H
H H O H H H

H C C C H C C C O H

H H O H H H H

propanoic acid propan-1-ol phenol

(a) Write an equation for the reaction between propan-1-ol and sodium metal.

.............................................................................................................................................. [1]

(b) (i) Give the order of the relative acidities of propanoic acid, propan-1-ol and phenol, stating

"
....................................................................................................................................... [1]

(ii) Explain your answer to (i).

.............................................................................................................................................

.............................................................................................................................................

.............................................................................................................................................

.............................................................................................................................................

.............................................................................................................................................

....................................................................................................................................... [2]

(c) Methanoic acid, HCO2H, has a similar acid strength to propanoic acid.

Describe a chemical test to distinguish between these two acids. Name the acid which gives a
positive result in this test and describe the observations that would be made.

....................................................................................................................................................

....................................................................................................................................................

....................................................................................................................................................

.............................................................................................................................................. [2]

© UCLES 2018 9701/41/M/J/18 [Turn over

Bilal Hameed Acyl Chlorides 1

 8
16

(d) The ester phenyl propanoate, C2H5CO2C6H5, can be made from phenol and propanoic acid in
a two-step

For this two-step synthesis,

....................................................................................................................................................

....................................................................................................................................................

....................................................................................................................................................

.............................................................................................................................................. [3]

(e) An unknown compound, Z, is propan-1-ol, propanal or propanoic acid. The proton NMR
spectrum of Z dissolved in CDCl 3 is shown.

12 10 8 6 4 2 0 –2
δ / ppm

(i) From the proton NMR spectrum, identify Z.

....................................................................................................................................... [1]

(ii) State one feature that would be seen, and why, in the proton NMR spectra of each of the
two compounds that are not Z.

.............................................................................................................................................

.............................................................................................................................................

.............................................................................................................................................

....................................................................................................................................... [2]

[Total: 12]

© UCLES 2018 9701/41/M/J/18

Acyl Chlorides 1 Bilal Hameed

 9
15
7 2019 NOV P42 Q08
8 Butanedioic acid can be made in a three-step synthesis using ethane as the starting material.

ethane A
H H H H
step 1 step 2
H C C H Br C C Br B

H H H H
step 3

butanedioic acid
H H
O O
C C C C
HO OH
H H

(a) Describe the reagents and conditions needed for step 1.

" .............................................................................................................................................. [1]

(b) Name the other product also formed in step 1 which is an isomer of A.

.............................................................................................................................................. [1]

(c) Give the structural formula of B.

[1]

(d) State the reagents and conditions needed for step 2.

.............................................................................................................................................. [2]

(e) Butanedioic acid cannot be oxidised by a warm, aqueous solution of any commonly used
oxidising agents but ethanedioic acid can.

(i) Identify the oxidising agent that could be used to oxidise ethanedioic acid.

....................................................................................................................................... [1]

(ii) State the product(s) of the reaction in (e)(i).

....................................................................................................................................... [1]

© UCLES 2019 9701/42/O/N/19 [Turn over

Bilal Hameed Acyl Chlorides 1

 (i) Identify the oxidising agent that could be used to oxidise ethanedioic acid.

10
....................................................................................................................................... [1]

(ii) State the product(s) of the reaction in (e)(i).

16
....................................................................................................................................... [1]
(f) Compare and explain the relative acidities of hexanoic acid, hexan-1-ol and phenol.

....................................................................................................................................................

....................................................................................................................................................

....................................................................................................................................................
© UCLES 2019 9701/42/O/N/19 [Turn over
....................................................................................................................................................

....................................................................................................................................................

.............................................................................................................................................. [3]
16
8 2020 MAR P42 Q05
5 (g) Methylpropanedioic
Gallic acid is anoccurring
acid, C7H6O5, is a naturally isomer ofaromatic
butanedioic acid.
molecule.

methylpropanedioic
gallic acid acid
HO CH3
O O
C C C O
HOHO OH
H
OH
HO
The proton NMR spectrum of methylpropanedioic acid in CCl 4 is shown.

(a) Gallic acid contains the carboxylic acid and phenol functional groups.
δ 1.1

State and explain the relative acid strength of these two functional groups.

....................................................................................................................................................
δ 12.7
" ....................................................................................................................................................
δ 3.3
....................................................................................................................................................

.............................................................................................................................................. [2]

(b) A buffer solution was prepared by dissolving 2.04 g of gallic acid in 250 cm3 of a solution
containing 0.0600 mol dm–3 of gallate ions, C7H5O5–.
14 12 10 8 6 4 2 0
C7H6O5 C7H5O5– + H+ Ka = 3.89 10–5 mol dm–3 at 298 K
δ / ppm
(i) buffer solution.
(i) Identify the protons in the methylpropanedioic acid molecule that are responsible for each
area of the proton NMR spectrum.
.............................................................................................................................................

12.7 ..................................................................................................................................
.............................................................................................................................................

3.3 ....................................................................................................................................
....................................................................................................................................... [2]

(ii) 1.1 ....................................................................................................................................

Calculate the pH of this buffer solution.
[2]

© UCLES 2019 9701/42/O/N/19

Acyl Chlorides 1 Bilal Hameed
 .............................................................................................................................................

11
....................................................................................................................................... [2]

(ii) Calculate the pH of this buffer solution.

17
pH = .............................. [3]
(iii) Write two equations to show how a solution containing gallic acid, C7H6O5, and gallate
ions, C7H5O5–, acts as a buffer.

.............................................................................................................................................

© UCLES 2020 .............................................................................................................................................

9701/42/F/M/20

.............................................................................................................................................

....................................................................................................................................... [2]

(c) Compound K is used as the starting material in a synthesis of gallic acid.

K L M

COOH concentrated HNO3 COOH concentrated HNO3 COOH

and and
concentrated H2SO4 concentrated H2SO4
step 1 step 2
NO2 O2N NO2
NH2 NH2 NH2

Nitronium ions, NO2+, are generated by the reaction between concentrated sulfuric acid and
concentrated nitric acid.

12 (i) Construct an equation for the formation of NO2+ by this method.

....................................................................................................................................... [1]

(ii) Complete the mechanism and draw the intermediate of step 1.

Include all relevant charges and curly arrows to show the movement of electron pairs.

intermediate
COOH

L + H+

NH2 +
NO2
Bilal Hameed Acyl Chlorides 1
[2]
 12
9
9 2020 JUN P41 Q06
6 (a) Compare and explain the relative acidities of 2-chloropropanoic acid, 3-chloropropanoic acid,
and propanoic acid. Explain your answer.

.................................... > .................................... > ....................................

most acidic least acidic

explanation ................................................................................................................................

....................................................................................................................................................

....................................................................................................................................................

....................................................................................................................................................

....................................................................................................................................................

....................................................................................................................................................
[3]

(b) (i) The numerical values of Ka for methanoic acid, HCO2H, and pyruvic acid, CH3COCO2H,
are given.

acid Ka
HCO2H 1.78 10–4
CH3COCO2H 4.07 10–3

An equilibrium mixture containing the two acid-base pairs is formed.

HCO2– + CH3COCO2H HCO2H + CH3COCO2–

Use the Ka values to calculate the equilibrium constant, Keq, for this equilibrium.

Keq = .............................. [1]

(ii) Use your value of Keq to predict the position of this equilibrium. Indicate this by placing a
tick ( ) in the appropriate box in the table. Explain your answer.

equilibrium lies equilibrium lies equilibrium lies

to the left in the middle to the right

.............................................................................................................................................

.............................................................................................................................................
[1]

© UCLES 2020 9701/41/M/J/20 [Turn over

Acyl Chlorides 1 Bilal Hameed

 13 Keq = .............................. [1]

(ii) Use your value of Keq to predict the position of this equilibrium. Indicate this by placing a
tick ( ) in the appropriate box in the table. Explain your answer.

equilibrium lies equilibrium lies equilibrium lies

to the left in the middle to the right

.............................................................................................................................................

.............................................................................................................................................
10
[1]
10
(iii) Ethanedioic acid, HO2CCO2H, has two dissociation constants, Ka1 and Ka2, whose
(iii) Ethanedioic
pKa values are 1.23 acid,and HO 2CCO2H, has two dissociation constants, Ka1 and Ka2, whose
4.19.
© UCLES 2020 9701/41/M/J/20 [Turn over
pKa values are 1.23 and 4.19.
Suggest equations to show the two dissociations that give rise to these pKa values.
Suggest equations to show the two dissociations that give rise to these pKa values.
pKa1 1.23 .............................................................................................................................
pKa1 1.23 .............................................................................................................................
pKa2 4.19 .............................................................................................................................
pKa2 4.19 .............................................................................................................................
[2]
[2]
(iv) (iv)
StateState
the mathematical relationship
the mathematical between
relationship between a and
pKpK the acid dissociation constant Ka.
a and the acid dissociation constant Ka.

.......................................................................................................................................
....................................................................................................................................... [1]
[1]

(c) Three teststests

(c) Three werewere
carried out out
carried on separate samples
on separate of of
samples the organic
the organicacids
acidsshown
shownininthe
the table.
table.
The following results
The following were
results obtained.
were obtained.
= observed change
= observed change
= no=observed reaction
no observed reaction

reagent(s)
reagent(s)
test test HCO H
and conditions HCO2H 2 CHCH 3COCO
3COCO 2H2
H HO
HO 2CCO
2CCO 2H2H observedchange
observed change
and conditions

.........................
.........................
1 1
.........................
.........................
.........................
.........................

.........................
.........................
2
2 .........................
.........................
.........................
.........................
.........................
3
.........................
3 .........................
.........................
.........................
.........................
Complete the table with the reagent(s) and conditions and the observed change for each test.
Assume
Complete thethese
tableorganic
with theacids all haveand
reagent(s) a similar acid strength.
conditions [5]
and the observed change for each test.
Assume these organic acids all have a similar acid strength. [5]

Bilal Hameed Acyl Chlorides 1

 14
20
10 2021 JUN P42 Q08
8 (a)
aryl chlorides.

................................. > ................................. > ................................

fastest slowest
"
....................................................................................................................................................

....................................................................................................................................................

....................................................................................................................................................

....................................................................................................................................................

.............................................................................................................................................. [3]
12
11 2021 NOV P41 Q07
7 The structure of phenylethanoic acid is shown.

OH

(a) 13
C) NMR spectrum of phenylethanoic
acid.

number of peaks = .............................. [1]

:
(b) Phenylethanoic acid, ethanol and phenol can all behave as acids.

Compare and explain the relative acidities of these three compounds.

............................................ > ............................................ > ............................................

most acidic least acidic

....................................................................................................................................................

....................................................................................................................................................

....................................................................................................................................................

....................................................................................................................................................

.............................................................................................................................................. [4]

(c) Phenylethanoic acid can be synthesised using benzene as the starting material.

Al Cl 3 catalyst to form methylbenzene.

Chloromethane reacts with Al Cl 3 to form two ions. One of these is the carbocation +CH3.

(i)
© UCLES 2021 Write an equation for the reaction between chloromethane and Al Cl 3.
9701/42/M/J/21

....................................................................................................................................... [1]
Acyl Chlorides 1 Bilal Hameed
(ii) Draw the mechanism of the reaction between benzene and +CH3. Include all relevant curly
arrows, charges and the structure of the intermediate.
 15

Acyl Chlorides WS 2
8 For
1 2005 JUN P4 Q5 Examiner'
Use
5 (a) Give an expression for Ka as applied to the weak acid RCO2H.

..........................................................................................................................................

.................................................................................................................................... [1]

(b) The Ka values for three carboxylic acids are listed in the table below.

acid Ka / mol dm–3

CH3CO2H 1.8 × 10–5

ClCH2CO2H 1.4 × 10–3

Cl2CHCO2H 5.5 × 10–2

(i) Describe and explain the trend in acid strength illustrated by these values.

..................................................................................................................................

..................................................................................................................................

..................................................................................................................................

..................................................................................................................................
(ii) Calculate the pH of a 0.100 mol dm–3 solution of ClCH2CO2H.

..................................................................................................................................

..................................................................................................................................

..................................................................................................................................
(iii) Calculate the pKa value for Cl 2CHCO2H.

..................................................................................................................................

..................................................................................................................................
[5]

Bilal Hameed Acyl Chlorides 2

 16 9 For
Examiner's
Use
(c) The acid ClCH2CO2H features in the industrial synthesis of the important weedkiller
2,4-D.

OH OH OCH2CO2H

Cl Cl
I II
+ NaOH
+ ClCH2CO2H
phenol
Cl Cl
2,4-D

(i) Suggest a possible reagent for reaction I.

..................................................................................................................................
(ii) What type of reaction is

reaction I, .................................................................................................................

reaction II? ...............................................................................................................

(iii) Describe a test (reagents and observations) that would distinguish phenol from
compound A.

CH2OH

compound A

reagents ...................................................................................................................

observation with phenol ...........................................................................................

observation with compound A ..................................................................................

[5]
[Total: 11]

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Examiner’s
Use
Section
17 A

Answer all questions in the spaces provided.

2 2007 NOV P4 Q1
1 (a) Use the general formula of a carboxylic acid, RCO2H, to write equations to explain the
following terms.

(i) Ka .............................................................................................................................

(ii) pKa ...........................................................................................................................

[2]

(b) The pKa values of four carboxylic acids are listed in the table below.

acid formula of acid pKa

1 CH3CH2CO2H 4.9

2 CH3CHCl CO2H 2.8

3 CH3CCl2CO2H 1.4

4 CH2Cl CH2CO2H 4.1

(i) Describe and explain the trend in acid strength shown by acids 1, 2 and 3.

..................................................................................................................................

..................................................................................................................................

..................................................................................................................................

..................................................................................................................................

(ii) Suggest an explanation for the difference in the pKa values for acids 2 and 4.

..................................................................................................................................

..................................................................................................................................

(iii) Calculate the pH of a 0.010 mol dm–3 solution of propanoic acid (acid 1).

..................................................................................................................................

..................................................................................................................................

..................................................................................................................................
[6]

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10 For
10 For
Examiner’s
3 2004 NOV P4 Q5 Examiner’s
Use
(d) Draw the structural formulae of the organic products of the following reactions of Use
(d) Draw the structural formulae of the organic products of the following reactions of
compound C.
compound C.

OH in NaOH (aq)
OH in NaOH (aq)

COCl
COCl
CH3NH2

CH3NH2

H 2O

H 2O

[3]

[Total: 9]
[3]

[Total: 9]

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10 For
4 2003 JUN P4 Q5 Examiner’s
Use
5 (a) Acyl chlorides are useful intermediates for making various acid derivatives. The
following reaction scheme shows some of the reactions of ethanoyl chloride.

step I OH + NaOH(aq)
CH3CO2H CH3COCl
step II

step III NH3

J

(i) Suggest a reagent for step I.

...................................................................................................................................

(ii) Write an equation showing the reaction between phenol and NaOH(aq), the
reagents in step II.

...................................................................................................................................

(iii) Draw the structural formulae of products J and K in the boxes above.
[4]

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Section A For
20 Examiner’s
Answer all questions in the spaces provided. Use

5 2010 JUN P42 Q1

1 Phenacyl chloride has been used as a component of some tear gases. Its lachrymatory and
irritant properties are due to it reacting with water inside body tissues to produce hydrochloric
acid.

It undergoes a nucleophilic substitution reaction with NaOH(aq).

Cl

+ OH– +

phenacyl chloride

(a) Write the formulae of the products of this reaction in the two boxes above. [2]

When the rate of this reaction was measured at various concentrations of the two reagents,
the following results were obtained.

experiment number [phenacyl chloride] [NaOH] relative rate

1 0.020 0.10 1.0

2 0.030 0.10 1.5

3 0.025 0.20 2.5

(b) (i) What is meant by the term order of reaction?

..................................................................................................................................

(ii) Use the above data to deduce the order with respect to each reactant. Explain your
reasoning.

..................................................................................................................................

..................................................................................................................................

..................................................................................................................................

..................................................................................................................................

..................................................................................................................................

(iii) Write the overall rate equation for the reaction.

..................................................................................................................................

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3

(iv) Describe the mechanism for this reaction that is consistent with your overall rate For
equation. Examiner’s
You should show all intermediates and/or transition states and partial charges, and Use
you should represent the movements of electron pairs by curly arrows.

[7]

(c) (i) Describe an experiment that would show that CH3COCl reacts with water at a
much faster rate than phenacyl chloride. Include the reagents you would use, and
the observations you would make with each chloride.

..................................................................................................................................

..................................................................................................................................

..................................................................................................................................

..................................................................................................................................

..................................................................................................................................

..................................................................................................................................

..................................................................................................................................

(ii) Suggest an explanation for this difference in reactivity.

..................................................................................................................................

..................................................................................................................................
[4]

[Total: 13]

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..........................................................................................................................................
22
..................................................................................................................................... [2]
6 2009 JUN P4 Q1
(b) The Ka values for some organic acids are listed below.

acid Ka /mol dm−3

CH3CO2H 1.7 ! 10−5

Cl CH2CO2H 1.3 ! 10−3

Cl 2CHCO2H 5.0 ! 10−2

(i) Explain the trend in Ka values in terms of the structures of these acids.

..................................................................................................................................

..................................................................................................................................

..................................................................................................................................

..................................................................................................................................

(ii) Calculate the pH of a 0.10 mol dm−3 solution of Cl CH2CO2H.

pH = ...........................................

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10
7 2014 NOV P41 Q4
4 (a) Methylbenzene undergoes electrophilic substitution with nitronium ions, NO2+.
Nitronium ions are generated by the reaction between concentrated sulfuric acid and
concentrated nitric acid.

(i) Construct an equation for the formation of nitronium ions, NO2+, by this method.

.............................................................................................................................................

(ii) Complete the scheme to show the mechanism for this reaction. Use curly arrows to show
the movement of electron pairs.

CH3

NO2+

[4]

(b) (i) Describe and explain the relative acidities of chloroethanoic acid and ethanoic acid.

.............................................................................................................................................

.............................................................................................................................................

.............................................................................................................................................

(ii) Describe and explain the relative acidities of phenol and ethanol.

.............................................................................................................................................

.............................................................................................................................................

.............................................................................................................................................
[3]

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(c) Phenyl 2-hydroxybenzoate is an antiseptic.

OH

phenyl 2-hydroxybenzoate

Complete the following table about the reactions of phenyl 2-hydroxybenzoate with the three
reagents.

reagent structure of product(s) type of reaction

Na

excess
Br2(aq)

excess hot
NaOH(aq)

[6]

[Total: 13]

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15
8 2016 JUN P41 Q10
10 (a) Ethanedioic acid, C2O4H2, occurs in many vegetables. The amount that occurs in spinach can
be estimated as follows.

40.0 g of spinach leaves are crushed and mixed with distilled water, using a mortar and
pestle.
The mixture is filtered, and the leaves are washed with a little more water.
The combined filtrate and washings are made up to 100.0 cm3 with water.
A 25.0 cm3 portion of the resulting solution is added to a conical flask, along with an excess
of dilute sulfuric acid.
The acidified solution is warmed, and then titrated with 0.0200 mol dm–3 KMnO4.

VII) ions is
shown.

2MnO4– + 6H+ + 5C2O4H2 2Mn2+ + 10CO2 + 8H2O

In the titration, 15.20 cm3 of KMnO4 was required to reach the end-point.

Calculate the percentage by mass of ethanedioic acid in the spinach leaves.

percentage of ethanedioic acid = ............................. % [3]

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16

(b) Ethanedioic acid can be converted into ethanedioyl chloride:

HO2CCO2H Cl OCCOCl

(i) State a suitable reagent for this reaction.

....................................................................................................................................... [1]

(ii) For the reactions of ethanedioyl chloride below, suggest the structures of compounds J
and K and draw them in the boxes.

CH3OH COCl H2NCH2CH2NH2

COCl

J (C4H6O4) K (C4H6N2O2)
[2]

(c) When ethanedioyl chloride is reacted with silver ethanedioate, AgO2CCO2Ag, in ethoxyethane
at –30 C, an oxide of carbon, L, is formed. The molecule of L has no overall dipole and has
molecular formula C4O6.

The carbon-13 NMR spectrum of a solution of L in ethoxyethane, CH3CH2OCH2CH3, is shown

below.

150 100 50 0
δ (ppm)

(i) Use the Data Booklet to state in the boxes below the values for the peaks in the spectrum
which are due to the carbon atoms in ethoxyethane.

CH3 CH2 O CH2 CH3

δ values

[2]

(ii) Explain what the rest of the carbon-13 NMR spectrum indicates about the structure of L.

....................................................................................................................................... [1]

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