Topic 15 Organic chemistry: carbonyls, carboxylic

acids and chirality

15A Chirality

15A.1 Chirality and enantiomers

1 Two optical isomers or two geometric isomers both have the same molecular and
structural formulae but with their atoms and groups arranged differently in three
dimensions. With optical isomers, the difference is that the atoms and groups are
arranged to form an object and its mirror image. With geometrical isomers, the
difference is that the atoms and groups are arranged differently on opposite sides of a
C=C double bond.

2 (a) None, because all of the carbon atoms are joined to two or more identical
atoms.
(b) One. The first carbon atom is joined to three hydrogen atoms so is not chiral.
The third carbon atom is joined by a double bond to oxygen so has only three
different groups attached. The second carbon atom is chiral because it is
joined to four different atoms or groups (methyl, hydrogen, hydroxyl and
carboxylic acid).
(c) Two. The first and last carbon atoms are part of methyl groups so are not
chiral. The second carbon atom is chiral (it is joined to CH2Cl, C, H and
CHFCH3). The third carbon atom is also chiral because it is joined to H, F,
CH3 and CH2ClCHCl.

15A.2 Optical activity

1 When monochromatic light passes through the polariser it absorbs all oscillations
except those in one plane.

2 If the mixture had no optical activity, this would indicate that it contained equal
amounts of both enantiomers. The fact that the mixture has a rotation with a negative
value indicates that it contains more of the laevorotatory enantiomer than the
dextrorotatory enantiomer.

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15A.3 Optical activity and reaction mechanisms

2 2-Bromopropane is not a chiral compound and even though the attacking CN− ion can
approach the carbocation from both sides, the resulting products are not chiral. So,
neither the reactant nor the product has any optical activity.

15B Carbonyl compounds

15B.1 Carbonyl compounds and their physical properties
1 (a)

(b)

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2

15B.2 Redox reactions of carbonyl compounds

1 (a) Butan-1-ol.
(b) Pentanoic acid.

2 (a) No change – ketones are not oxidised.

(b) A colourless solution forms a silver mirror.

15B.3 Nucleophilic addition reactions

1 (a) Hydroxyethanenitrile.
(b) 2-hydroxy-2-methylpropanenitrile.

2 Propan-1-ol and propan-2-ol are not carbonyl compounds so do not give coloured
precipitates with 2,4-dinitrophenylhydrazine. Propanal does not react with iodine and
alkali because it does not contain the CH3CO group. Only propanone reacts with both
reagents because it is a carbonyl compound and contains the CH3CO group.

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15C Carboxylic acids
15C.1 Carboxylic acids and their physical properties
1 (a)

(b)

2 Both acids are soluble in water because they form hydrogen bonds with water
molecules. The solubility of hexanoic acid is lower than that of ethanoic acid because
there are more extensive London forces between the hydrocarbon chains in hexanoic
acid, and these interfere with the formation of the hydrogen bonds.

15C.2 Preparations and reactions of carboxylic acids

1 (a) (CH3)2CHCH2OH + 2[O] → (CH3)2CHCOOH + H2O
(b) (CH3 ) 2 CHCN  H   2H 2O  (CH 3 ) 2 CHCOOH  NH 4 

2 (a) (CH3)2CHCOOH + PCl5 → (CH3)2CHCOCl + POCl3 + HCl

(b) (CH3)2CHCOOH + CH3OH → (CH3)2CHCOOCH3 + H2O

15D Carboxylic acid derivatives

15D.1 Carboxylic acid derivatives: acyl chlorides
1 (With water) propanoic acid
(With methanol) methyl propanoate
(With ammonia) propanamide
(With methylamine) N-methylpropanamide

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2 (a) CH3CH2CH2COCl + CH3CH2CH2OH → CH3CH2CH2COOCH2CH2CH3 +
HCl
(b) CH3CH2CH2COCl + CH3CH2NH2 → CH3CH2CH2CONHCH2CH3 + HCl

15D.2 Carboxylic acid derivatives: esters

1 (a) Propyl propanoate.

(b) Methyl 2-methylpropanoate.

2 (a) CH3CH2CH2COOCH2CH2CH3 + H2O ⇋ CH3CH2CH2COOH +

CH3CH2CH2OH
(b) CH3CH2CH2COOCH2CH2CH3 + OH− → CH3CH2CH2COO− +
CH3CH2CH2OH

15D.3 Carboxylic acid derivatives: polyesters

1 Although the first molecule has two reactive COOH groups at both ends of the
molecule, the alcohol is not a diol, so with only one OH group the polymerisation
reaction cannot proceed.

2 [−OCCOOCH(CH3)CH(CH3)O−]

15E Spectroscopy and chromatography

15E.1 Simple chromatography

1 The stationary phase is the water in the paper; as water molecules are polar, then the
non-polar hexane molecules will not be attracted to them very much and so will travel
up the paper easily.
20
2 Rf   0.27
75

15E.2 Determining structures using mass spectra

1 The two compounds both have Mr values of 73.0 using the relative atomic masses in
the Periodic Table. They have different molecular formulae and when their relative
molecular masses are calculated using Ar values to four decimal places, only one of
them is 73.0812.

2 Using Ar values to four decimal places, the Mr value of 1,2-diaminoethane is:

(2 × 12.0000) + (2 × 14.0031) + (8 × 1.0078) = 60.0686.
Using Ar values to four decimal places, the Mr value of ethanoic acid is:
(2 × 12.0000) + (2 × 15.9949) + (4 × 1.0078) = 60.0210.
This value is close to the true value of 60.0213, so the compound is ethanoic acid.

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15E.3 Chromatography – HPLC and GC

1 In traditional column chromatography, a liquid passes down a column by gravity. In

HPLC, the liquid is passed through a metal tube under high pressure.

2 The liquids may be different and the pressures of the carrier gases may be different.

15E.4 Chromatography and mass spectrometry

1 The function of HPLC is to separate a mixture of substances, and the function of MS
is to measure the relative molecular mass of each component.

2 (a) Nandrolone, as only this one has a C=C double bond.

(b) Nandrolone and 19-norandrosterone, as they both contain C=O carbonyl
groups.

15E.5 Principles of NMR spectroscopy

1 Both 16O and 32S have even numbers of protons and neutrons so are not suitable. 19F
has an odd number of protons and so is suitable.

2 TMS has a strong signal because its molecule contains 12 equivalent protons, and it
also mixes easily with organic compounds. Water has only two equivalent protons
and so has a weaker signal; it also does not mix with most organic compounds.
13
15E.6 C NMR spectroscopy

1 CH4 has only 1.

CH3–CH3 has only 1.
CH3–CH2–CH3 has 2.
CH3–CH2–CH2–CH3 has 2.
CH3–CH2–CH2–CH2–CH3 has 3.
CH3–CH2–CH2–CH2–CH2–CH3 has 3.

2 The four peaks between 110 and 160 ppm are from four carbon atoms in the aromatic
ring.
The peak at 190 ppm is from a carbon atom in the ketone group.
The peak at 23 ppm is from a carbon atom in a C−C bond.
The structure of the compound is CH3COC6H4OH.

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15E.7 1H NMR spectroscopy

1 CH3–CH2–CH2–CH2–CH3 has 3.
(CH3)2CH–CH2–CH3 has 4.
(CH3)4C has 1.

2 The integration trace shows only the ratio of numbers of hydrogen atoms. The actual
numbers may be a multiple of this ratio.

3 The spectrum of ethylamine has three peaks, while that of ethanamide has two peaks.

15E.8 Splitting patterns in 1H NMR spectra

1 The peak on the left is a singlet at  = 4.0 ppm representing two protons. This
suggests a CH2 group joined to O in an alcohol, ether or ester, so O–CH2.
The peak in the middle is a singlet at  = 3.4 ppm representing three protons. This
suggests a CH3 group joined to O in an alcohol, ether or ester, so CH3–O.
The peak in the middle is a singlet at  = 2.1 ppm representing three protons. This
suggests a CH3 group joined to CO in an aldehyde, ketone, ester or acid, so CH3–
C=O.
The structure that fits these interpretations is CH3–CO–CH2–O–CH3

2 The peak on the left is a singlet at  = 2.3 ppm representing three protons. This
suggests a CH3 group joined to CO in an aldehyde, ketone, ester or acid, so CH3–CO–
The peak in the middle is a quartet at  = 1.5 ppm representing one proton. This
suggests a CH group joined to a CH3 group in an alkyl group, so CH3–CH–
The peak on the right is a doublet at  = 1.2 ppm representing six protons. This
suggests two CH3 groups joined to CH in an alkyl group, so (CH3)2–CH–
The structure that fits these interpretations is CH3–CO–CH(CH3)2

Topic 15 Exam Practice

1 D
2 D
3 B
4 C
5 C
6 B
7 (a) A and C both have chiral carbon atoms but B does not (1).
A and C have the same four groups in different spatial arrangements (1).
(b) A and C have equal but opposite optical activities so these cancel out (1).
B has no optical activity (1).
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 (c) If compound A reacts by an SN1 mechanism, a planar carbocation intermediate
will be formed (1) which will be attacked by OH− ions in the second step to
form an alcohol (1).
This attack has equal probability of forming two different alcohol molecules
(1) giving a racemic mixture (1).
If compound A reacts by an SN2 mechanism there will be an inversion of
stereochemistry (1) so only one alcohol is formed with an optical activity
equal but opposite to that of A (1).

8 (a) They can both form strong intermolecular forces with water molecules (1).
(b) (i) Nucleophilic addition (1).
(ii) The organic products are solids whose melting temperatures can be
measured (1), the values can be compared with those in data books to
identify which one is which (1).
(c)

(2)
(d) CH3CH2CH2CH2CHO + [O]  CH3CH2CH2CH2COOH (1).
Silver mirror / black precipitate (1).

9 (a) E and F react (1).

Each is either a primary alcohol or a secondary alcohol (1).
Only these have the CHOH group needed for the loss of two hydrogen atoms
in oxidation (1).

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 (b)

(1)

(c) (i) Methanol (1).

(ii) The reagent needed to convert an alcohol into an ester must contain a
carboxyl group (1).
It must be an acyl chloride because the other product is hydrogen
chloride (1).
(iii) CH3CH2COOH (1).
(iv) CH3CH2COOCH3 + NaOH → CH3CH2COONa + CH3OH
CH3CH2COONa + H+ → CH3CH2COOH + Na+ (2).

10 (a) The spectra are very similar (1) because they both have the same numbers and
types of bond (1).
(b) 2-methypropan-2-ol has two different types of carbon atom / one central C and
three identical CH3 groups (1) so its spectrum will show two peaks due to 13C
atoms (1).
2-methypropan-1-ol has three different types of carbon atom / two identical
CH3 groups, one CH group and one CH2 group (1) so its spectrum will show
three peaks due to 13C atoms (1).
(c) 2-methylpropan-2-ol has nine identical hydrogen atoms in CH3 groups and
one hydrogen atom in an OH group so two peaks (1), which are singlets
because there are no hydrogens on the central C that can affect the CH3 or OH
groups (1).
While 2-methylpropan-1-ol has six identical hydrogen atoms in CH3 groups,
two in a CH2 group, one in a CH group and one in an OH group (1).
(d) The Mr of both compounds is 74, so the peaks at m/z = 74 are due to the
molecular ions of both compounds (1).
In the left-hand spectrum the peak at m/z = 43 is due to the loss of mass of 31
(CH2OH) so the peak at m/z = 43 is due to CH(CH) 2  (1) and the peak at m/z
= 31 is due to CH2OH+ (1).
In the right-hand spectrum the peak at m/z = 57 is due to the loss of mass of
17 (OH) so the peak at m/z = 57 is due to C(CH3 )3 (1) and the peak at m/z =
29 is due to COH+ (1), so the left-hand spectrum is that of 2-methylpropan-1-
ol and the right-hand spectrum is that of 2-methylpropan-2-ol (1).

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