Topic 20 Organic Chemistry Answers

Student note:
In the suggested answers that follow some formulas are given as a line-bond formula. These show
only the bonds between the carbon atoms, not the hydrogen atoms. Where these lines meet, and at
the ends of these lines, there is a C atom. The H required for the bonds present is assumed,
e.g. C4H10 is shown as , which equates to 4C plus the tetrahedrally arranged 10 H.

The functional groups present are shown with the atoms, e.g. C4H9OH is shown as: OH

Other formulas are given in their condensed form, e.g. C4H10 is CH3CH2CH2CH3.
An expanded structural formula shows all the bonds and all the atoms present, e.g. C4H10 is written
as:
H H H
H
C C H
H C C
H
H H H

Here are some more examples:

C5H12
O

butan-2-one
OH

propan-2-ol
Br
1-bromopropane

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20.1 Exercises

1. Give the structural formula for the following functional groups:

(a) Amine
H R R

H N R H N R R N R
Primary Secondary Tertiary
(b) Amide
R
N
C
R
R
O
(c) Ester
O

R C
O R

(d) Nitrile
R C N

2. The amines have three types – primary, secondary and tertiary. Name the type and write a
structural formula for the following amines:
(a) Methylamine
CH3NH2, primary

H3C N H

(b) Ethylamine
C2H5NH2, primary

H3C CH2 N H

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(c) Di-ethylamine
(C2H5)2NH, secondary

H3C CH2 N CH2 CH3

(d) Tri-methylamine
(CH3)3N, tertiary

CH3 N CH3

CH3

3. What does the italic letter N imply when used in naming amines and amides?
Used for secondary and tertiary amines. It is used to indicate that the second and/or third
substituent is attached to the nitrogen atom. For example in N,N-dimethylbutylamine the two
methyl groups are attached to the nitrogen.

4. Write structural formula for the following compounds:

(a) N,N-dimethylethanamine
CH3

H3C N
C CH3
H2

(b) dipropylamine
H2 H H2
C N C
H3C C C CH3
H2 H2

(c) 1,3-diaminobutane
CH3
H2
C CH
H2N C NH2
H2

3
(d) phenylamine

NH2

(e) N-methylethylamine
H2
H3C C
N CH3
H
(f) 1,1-dichloro-4,4-dimethyl-1-pentanamine
H3C
Cl H2 CH3
C C
C C
H2 CH3
Cl
NH2

(g) 5-aminohexan-1-ol
CH3
H2 H2
C C CH
HO C C NH2
H2 H2

(h) 2-methylpropanamine
CH3

H2N CH
C CH3
H2

(i) N-methylethanamine
H2
H3C C
N CH3
H

5. The smell associated with decaying flesh is due to the formation of the diamines, 1,4-
butanediamine (common name putrescine) and 1,5-pentanediamine (common name
cadaverine).
Draw structures for:

4
(a) 1,4-butanediamine
H2 H2
C C NH2
H2N C C
H2 H2

(b) 1,5-pentanediamine
H2 H2 H2
C C C
H2N C C NH2
H2 H2

6. By applying IUPAC rules, name the following amines and label them as primary,
secondary or tertiary:
(a) CH3(CH2)2NH2
Primary amine, 1-aminopropane or 1-propanamine or 1-propylamine
(b) CH3NHCH3
Secondary amine, N-methylmethanamine or di-methylamine
(c) CH3NHCH2(CH2)2CH3
Secondary amine, N-methylbutanamine
(d) HOCH2CH2NH2 (an ethanolamine used as an emulsifying agent)
Primary amine, 1-hydroxyethanamine
(e) C6H5NH2 (trivial name analine)
Primary amine, phenylamine
(f) (CH3CH2)2NH
Secondary amine, diethylamine
(g) (CH3CH2)3N
Tertiary amine, triethylamine
(h)

Tertiary amine, N,N-ethyl-methyl-propanamine

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7. Deduce structural formula for the following amides:
(a) Ethanamide
O

C NH2

H3C

(b) A repeating unit in a polyamide

C
N
H
n
(c) 2-methylpropanamide
O

C NH2

H3C CH

CH3

(d) N-methylbutanamide
O

HN C CH3

H3C H2C CH2

(e) N,N-diethylmethanamide
O

CH

H2C N

H3C H2C CH3

8. By applying IUPAC rules, name the following amides:

(a) Ethanamide
(b) N,N-dimethylpropanamide
(c) heptanamide

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(d) N,N-dimethyl-2-methylpropanamide
(e) 3-methylbutanamide

9. The legal, but very addictive, health damaging drug, nicotine is an amide. Use the IB data
book to name another amide that is a drug, or is used in medicine.
Examples illustrated in the IB data book include lidocaine and acyclovir.

Chilli peppers belong to the Capsicum family of plants. They contain amides and are extensively
used in preparing ‘hot’ tasting foods.

10. Deduce structural formula for the following esters:

(a) Methyl butanoate
O

O C CH3

H3C H2C CH2

(b) Ethyl propanoate

O

H2C C CH3

H3C O CH2

(c) 2-propyl ethanoate

CH3 O

CH C
H3C O CH3

(d) 1-hexyl ethanoate

H3C O
C
H2 H2
H3C C C O
C C C
H2 H2 H2

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11. By applying IUPAC rules, name the following esters:
(a) ethylbutanoate
(b) l-pentylethanoate
(c) l-propylethanoate
(d) 3-methylbutanepropanoate

12. Deduce structural formulas for the following nitriles:

(a) Butanenitrile
H2C CH3

N C CH2

(b) Propenenitrile
CH2

N C CH
(c) 2-methylpropanenitrile
N

CH CH3

H3C

(d) 3-hydroxybutanenitrile
CH3
N
C CH
C OH
H2

13. By applying IUPAC rules, name the following:

(a) pentanenitrile
(b) pentanamine
(c) N-ethylmethylamide
(d) ethylbutanoate

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20.2 Exercises

1. Define, with an example, the following terms;

(a) Halogenoalkane
Compounds where one or more halogen atoms replace one or more hydrogen atoms in alkanes,
e.g. C2H5Cl, chloroethane.
(b) Nucleophile
Molecules or ions that can form a covalent bond with another molecule because they have a lone
pair of electrons, e.g. NH3. They are electron rich species which are attracted to partial positive
charges, δ+, i.e. nuclei. Nucleophile means nucleus-loving.
(c) Substitution reactions
Reactions where atom(s) in molecules are replaced by other atoms or molecules, e.g. in this
reaction the OH group is replaced by a Br:
C3H7OH + HBr → C3H7Br + H2O
(d) Nucleophilic substitution
Is a reaction where a nucleophile, e.g. OH‾, replaces another atom or group of atoms, e.g. a Br in
an alkane.
C3H7Br + OH‾ → C3H7OH + Br‾
(e) Leaving group
That which leaves a compound during substitution, e.g. Br is the leaving group in (d) above.
(f) Best leaving group
If two leaving groups could be involved, e.g. Cl or I from a compound, the more favoured is labelled
the best, i.e. iodine. The C—Cl bond is shorter than the C—I bond, hence stronger.
(g) Worst leaving group
Fluorine is a bad leaving group because of its strong covalent bonding to a C atom (smaller atom,
therefore bond distance shorter, therefore stronger bond).
(h) Substrate
The molecule onto which substitution occurs, e.g. C3H7Br is the substrate when reacting with OH‾.

The term substrate is more common in biochemistry.

Substrates are the molecules on which enzymes react to catalyse the reaction.
Enzymes are remarkably effective in catalysing bio-chemical reactions.

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2. Some common nucleophiles are listed. Write Lewis structures for each.
(a) hydroxide ion (b) water molecule

O O
H H H
(c) cyanide ion (d) ammonia molecule

N
H
H
C N H

(e) bromide ion (g) ethoxide ion

Br O

As their names show nucleophiles are involved in both nucleophilic substitution and nucleophilic
addition reactions.

3. Supply the missing word.

All of the above nucleophiles have a common property; they are Lewis bases.

4. Both OH‾ and H2O are nucleophiles. Which of these is the better nucleophile? Give the
reasons for your choice.
OH‾ is an ion and has the stronger overall negative charge; it has three lone electron pairs; water,
a polar molecule, only two. Therefore, OH‾ is the better nucleophile.

5. The factors affecting the rate of nucleophilic substitution are: the nucleophile involved,
the halogen present and the type of halogenoalkane reacting.
(a) Explain how the rate of nucleophilic substitution is dependent on which nucleophile is
used.
Rate is dependent on the strength of the negative charge on the nucleophile e.g. OH ‾, is a faster
reactant than a polar molecule, e.g. H2O or NH3. This is because the strength of electrostatic
attraction depends on the magnitude of the charge.
(b) Explain how the rate of nucleophilic substitution in the halogenoalkanes is dependent
on which halogen is present.
The rate is dependent on the ease of breaking the C—X bond. The strongest bond is C—F
(because the F atom is small). The weakest C—I (because the I is the largest halogen atom). The

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bond distance in C—I is the largest, making it the least strong. Therefore, the reaction is the
fastest.
(c) Explain how the rate of nucleophilic substitution in the halogenoalkanes is dependent
on the type of halogenoalkane reacting, i.e. primary, secondary or tertiary.
The rate is determined by the mechanism. Primary halogenoalkanes proceed by a SN2 mechanism
which is slower than the SN1 mechanism. Tertiary halogenoalkanes proceed by SN1 mechanism.
The activation energy hurdles are lower for SN1 than they are for SN2 m echanisms.

6. (a) Complete these equations and label the nucleophile, the substrate and the leaving
group.
substrate leaving group nucleophile

(i) CH3C(CH3)HCH2 ―I + OH‾  CH3C(CH3)HCH2OH + I‾

(ii) CH3CH2C(Cl)HCH3 + NH3  CH3CH2(NH2)HCH3 + HCl
Substrate with Cl the leaving group nucleophile

(b) Rewrite the above completed equations using structural formulas, adding electron lone
pair electrons where appropriate, δ+ and δ- symbols to show bond polarity and curly arrows
in order to show the mechanism.
(i)

(ii)

7. Write balanced equations to show the formation of

(a) An alcohol from 2-bromo-2-methylbutane
CH3C(Br)(CH3)CH2CH3 + OHˉ → CH3C(OH)(CH3)CH2CH3 + Brˉ
(b) pentan-1-ol from an iodoalkane
CH3CH2CH2CH2CH2—I + NaOH → CH3CH2CH2CH2CH2—OH + NaI

11
 If a halogen atom is directly attached to an aromatic ring, such as in bromobenzene, nucleophilic
substitution will not occur unless extreme conditions are used.

8. Draw a structural formula for each of the following and then classify as a primary,
secondary or tertiary halogenoalkane.
(a) Ethyl bromide
H2
C
Br CH3

primary halogenoalkane.
(b) 1-chloro-2-methylpropane
CH3

Cl CH
C CH3
H2

primary halogenoalkane.

(c) 1-chloro-2-methylbutane
Cl

H2C CH2 CH2 CH3

CH3

primary halogenoalkane.
(e) 2-bromo-2-methylbutane
CH3
H2C

Br C CH3

CH3

tertiary halogenoalkane.

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(f) 3-iodo-2,3-dimethylpentane
H3C CH3
CH

I C CH2

CH3 CH3

tertiary halogenoalkane.
(g) 2-bromopentane
Br
H2
C CH
H3C C CH3
H2

secondary halogenoalkane.

9. Consider the following equation: OH- + (CH3)3C—Br  (CH3)3C—OH + Br-

(a) Identify the nucleophile OHˉ, the substrate (CH3)3C-Br, and the leaving group Brˉ.
(b) Rewrite the above equation, using structural formulas. Now add electron lone pairs, δ+
and δ- to show bond polarity and curly arrows to the equation to show the mechanism.

(c) Is this reaction an example of heterolysis or homolysis?

No free radicals formed, no breaking of a bond into two equal parts, therefore heterolysis.

10. Explain what is meant by SN1 and SN2 mechanisms.

SN1 (substitution nucleophilic uni-molecular) is a two step mechanism which involves only one
reacting species in the rate determining step. SN2 (substitution nucleophilic bimolecular) involves
two reactants in it rate determining step.

The symbols SN1 and SN2 represent Substitution Nucleophilic 1st order and 2nd order reactions
respectively. Order describes the number of reactants involved in determining the rate of the
reaction.

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11. Substituting reactions
(a) Describe, with equations and curly arrows, the substitution reaction between a primary
bromoalkane and ammonia.

(b) Describe, with equations and curly arrows, the substitution reaction between a primary
bromoalkane and potassium cyanide.

12. Consider the reactions given in question 11. Explain these reactions in terms of the SN2
mechanism.
The nucleophile (NH3 or CNˉ) is attracted to the carbon atom and begins to bond to it as the Br
atom begins to leave.
This situation is the transition state. Because experiment shows rate is determined by the
concentration of both the nucleophile, e.g. [CN–] and the halogenoalkane,[R—Br], it is a
bimolecular mechanism, hence SN2.

13. The nitriles are important intermediates in organic syntheses. They are readily
hydrolysed and can be reduced using hydrogen and a catalyst, usually nickel. Using
equations, describe the reduction of nitriles using hydrogen.
Using propanenitrile and a nickel catalyst the reaction is:
Ni catalyst / pressure

CH3CH2CN + 2H2(g) → CH3CH2CH2NH2

propanamine

14. Consider the following reactions:

A. CH3CH2Br + H2O  CH3CH2OH + HBr
B. CH3CH2Br + OH-  CH3CH2OH + Br‾
(a) Rewrite these two equations, using full structural formulas.

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(b) Place curly arrows, δ charges and lone pair electrons in the equations to show the
mechanisms in the above reactions.
(c) Identify each as SN1 or SN2 mechanisms. Give your reason.
Both A and B are SN2 as both are primary halogenoalkanes.
(d) Circle the carbocation in A. No carbocation formed since it is an SN2 mechanism!
(e) What is the hybridization of the central C atom in A?
sp3 because the bonding is tetrahedral.
(f) Name the products formed in the reactions above.
In A ethanol and hydrogen bromide; in B ethanol and the bromide ion.
(g) Why does the nucleophile in B attack the substrate on the opposite side to the leaving
group?
Because the δ– on the Br repels the nucleophile into the opposite position making this the only
place from where the nucleophile can attack.
(g) Why is B described as a one-step or concerted process?
Because the leaving group leaves as the nucleophile takes its place.

15. Refer to the energy diagrams shown below.

(a) Mark on each the ∆H of reaction and activation energy, EA.

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(b) Classify each reaction as either SN1 or SN2 and explain your choice.
The first shows an activated complex the (transition state) at the EA hurdle and is characteristic for
primary haloalkanes, e.g. OHˉ + C3H7Br, therefore SN2 mechanism.
The second shows the formation of an intermediate (at dip after the top for EA) and this suggests
the SN1 mechanism.
(c) What is the difference between an intermediate in a reaction and a transition state (also
called an activated complex)?
Transition states cannot be detected, it is a theory; intermediates (e.g. free radicals) can be
detected.
(d) Mark any transition states and/or intermediates on the diagrams above.

Discuss with your teacher whether or not this question is appropriate as a knowledge extension
question.

16. (a) Write an equation, using structural formulas, to show the transition state (or the
intermediate) in the reaction between sodium hydroxide solution and 1-bromobutane.

Br
H H2 H2
H2 H2 C C
C C H3C CH2 CH2 C
H3C C OH + Br
H3C C Br H H2
H2
OH
OH

(b) Now put in curly arrows.

(c) Which would act the fastest: 1-iodo, 1-bromo or 1-chlorobutane? Why?
1-iodo because the I—C bond, being the longest (I largest atom) makes this bond the weakest,
hence the reaction is the fastest.
(d) Label the functional group carbons in the substrate, product and transition
state/intermediate as sp, sp2, or sp3 hybridised.
Substrate and product C has 4 covalent bonds, therefore sp3 hybridisation. Transition state 3
covalent + 2 ½ bonds = 4 bonds, therefore sp3.

The combination of reacting atoms, molecules or ions in the transition state is also called the
activated complex.

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17. For the equation: Nu- + R—X  R—Nu + X‾ where Nu‾ is a nucleophile,
(a) Write a rate equation for an SN1 pathway
Rate = k[R – X]
(b) and an SN2 pathway.
Rate = k[Nuˉ][R – X]

18. Which of the following is NOT a good nucleophile?

A. OH‾
B. H‾
C. NO2+
D. NH3‾
E. CN‾
Option C is correct, because of its + charge the NO2+ is not a nucleophile.

19. When 1-chloropentane is refluxed with KOH(aq) a nucleophilic substitution reaction

occurs.
(a) Write a balanced equation for this reaction and name the products.
C5H11Cl + KOH(aq)  C4H9CH2OH + KCl(aq)
(b) Explain why this reaction is described as nucleophilic substitution.
The reaction mechanism involves the OHˉ seeking out the δ+ carbon attached to the
δ– Cl.
(c) Draw a structure for the attacking nucleophile and show the charge and the lone pair
electrons.

OH
(d) The reverse reaction is possible. Name the nucleophile in this reaction and give its
structure.

Br
Bromide ion from hydrobromic acid, HBr (aq). Structure

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(e) Sketch and then label the apparatus used for reflux.

A condenser used to condense and so run back the reactants and products into the
reacting flask is called a reflux condenser. Reflux means to flow or run back.

20. Nitriles and synthesis

(a) Why are nitriles useful compounds for an organic synthesis?
They add a carbon atom to a molecule which is useful to build up a chain or to react to give amines
or acids.
(b) Nitriles can be reduced to amines. Using butanenitrile as your example, give an equation
for the catalytic reduction of a nitrile using hydrogen. Name the catalyst.
Nickel is the catalyst.
C3H7CN + 2H2(g) → C3H7CH2NH2
(c) Hydrolysis of a nitrile produces a carboxylic acid. Give an equation for the reaction of
propanenitrile when refluxed with an aqueous acid.
C2H5CN + H+(aq) + 2H2O → C2H5COOH + NH4+(aq)
(d) Why is reflux required for reaction (c) above?
Volatile reactants can escape from a reaction mixture when heated and heating is required in the
breaking of the covalent bonds in order to form new bonds. Covalent bonds are strong.

18
20.3 Exercises

1. What is the difference between a condensation and elimination reaction, when both can
split off water molecules?
Both involve the splitting off a small molecule, but condensation gives a joining of molecules;
elimination gives a double bond.

2. Write an equation to show the elimination of HBr from 2-bromobutane.

CH3CH(Br)CH2CH3 + OH–(al) → CH3CH=CHCH3 + H2O + Br–

Note: alcoholic NaOH is used. The OH–(al) in ethanol is reacting as a Lewis base. This must be
shown in the equation. Aqueous NaOH gives OH–(aq) which acts as a nucleophile.

3. Describe, and explain the mechanism, for the elimination of HBr from
2-bromopropane.
The atoms removed are H and Br; their elimination producing propene. The mechanism involves
attack by a strongly basic nucleophile, e.g. :OH–, in alcoholic solution, with EN2 mechanism
favoured for primary and secondary halogenoalkanes and EN1 favoured for tertiary
halogenoalkanes.

The mechanism shown is EN2 because the rate determining step involves two reactants: [:OH–]
and [C3H7Br].

An EN1 mechanism involves only the one reactant, e.g. rate = k[C3H7Br], and the formation of an
intermediate carbocation.

4. Why are elimination reactions so useful in synthesis?

It is useful because it gives a reactive double bond into a molecule and double bonds are reactive.

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5. The conditions present will determine main product from the reaction between a
halogenoalkane and an alkali, e.g. NaOH.
(a) What conditions are needed for an elimination reaction?
The alkali is in an ethanol solution, e.g. NaOH(al), and reflux is required.

Nucleophilic substitution, not elimination, occurs with aqueous alkali, NaOH(aq).

(b) Complete this sentence.

Elimination is more likely with a secondary or tertiary halogenoalkane.

Elimination is favoured when the halogen is in the middle of the C chain.

(c) Write the equation for NaOH(al) reacting with 2-bromobutane.

CH3CH(Br)CH2CH3 + OHˉ(al) → CH2=CHCH2CH3 + H2O + Brˉ
(d) What conditions favour nucleophilic substitution?
Using OHˉ(aq), refluxing, and a primary halogenoalkane.
(e) Write the equation NaOH(aq) reacting with 1-bromopropane.
C3H7Br + OHˉ(aq) → C3H7OH + Brˉ(aq)
(f) Outline the mechanism for the reaction in (e) above.
The mechanism involves the C – Br bond breaking as the nucleophile forms a new bond with this
C. It is an SN2 mechanism because the rate determining step is
rate = k[OHˉ(aq)][ C3H7Br].

H3C H3C
HO
CH Br CH OH + Br

H3C H3C

6. Just as nucleophilic substitution reactions can be classified a SN1 or SN2 reaction, so

elimination reactions can be classified as EN1 or EN2
(a) Explain, with an example, what is meant by a reaction having an EN1 mechanism.
The EN1 mechanism is similar to SN1.
The rate is determined only by the concentration of the reactant. A carbocation, i.e. +C, forms as
an intermediate when the C – Br bond breaks.

20
(b) Explain, with an example, what is meant by a reaction having an EN2 mechanism.
This is a bimolecular reaction, i.e. rate determined by both the [OH ˉ] and the [halogenoalkane].
(c) In the worked example 2 above is the mechanism suggested EN1 or EN2? Give reasons
for your answer.
EN2 because the mechanism involves both [OHˉ] and [2-bromopropane] in the rate determining
step. It is a bimolecular reaction, with the rate = k[OHˉ][2-bromopropane].

7. Altering the reaction conditions may cause the same reactant to produce different
products. The reaction of a haloalkane with sodium hydroxide is an example.
(a) A haloalkane reacting with dilute aqueous sodium hydroxide, NaOH (aq).
(i) Write an equation for the reaction of 2-bromopropane with dilute NaOH.
C3H7Br + OHˉ(aq)  C3H7OH + Br–
(ii) Using structural formula and curly arrows show the mechanism for the
reaction.
H3C H3C
HO
CH Br CH OH + Br

H3C H3C

(iii) What is the name given to this type of reaction?

Substitution-nucleophilic-bimolecular, i.e. SN2
(iv) Complete this sentence:
In this reaction the OH– is acting as a nucleophile
(b) A haloalkane reacting with hot alcoholic sodium hydroxide under reflux.
(i) Write an equation for the reaction of 2-bromopropane with hot NaOH(al).
CH3CH(Br)CH3 + OHˉ(al)  H2C = CHCH3 + H2O + Br–

(ii) Using structural formula and curly arrows show the mechanism for the
reaction.

(iii) What is the name given to this type of reaction?

21
Elimination, as H and Br have been eliminated from the molecule to leave a double bond.
(iv) Complete this sentence:
In this reaction the OH– is acting as a base.

22
20.4 Exercises

1. Define, with an example, these terms:

(a) Carboxylic acid
Are organic compounds and weak acids with the general formula R – COOH, e.g. ethanoic acid,
CH3COOH.
(b) Ester

Are the organic smells and flavours in nature. Formed from the reaction between and acid and
alcohol and have the general formula RCOOR2, e.g. ethylethanoate CH3COOC2H5.

The ester functional group is a combination of the functional groups from an alcohol and a
carboxylic acid.

(c) Esterification
The reaction between an organic acid and an alcohol, with a catalyst (concentrated H2SO4) to give
an ester, e.g.
C2H5OH + CH3COOH → CH3COOC2H5 + H2O
(d) Condensation reaction
A reaction where molecules bond together by splitting off a small molecule, e.g. H2O or HBr.
Esterification is an example of a condensation reaction.
(e) Amide
Are nitrogen organic compounds containing the amide functional group, e.g. ethanamide
CH3CONH2.

Polyamides contain many amide groups. Proteins are natural polyamides.

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(f) Monomer
The small molecule that is able to form with other molecules to form a polymer, e.g. ethene, is the
monomer for polyethene.
(g) Polymer
Large (i.e. very long chained) molecules made by joining monomers, e.g. polyethene (CH2CH2)n
where n is large.
(h) Polyester
Polymers made from ester monomers, e.g. PET, polyethyleneterephthalate, is a polyester. PET is
used to make bottles for soft drinks.
(i) Polyamide
Polymers made by the linking of amide functional groups, e.g. the very strong kevlar (used in bullet
proof vests and in constructions) is a synthetic polyamide; nylon is another. Proteins are examples
of natural polyamides.
(k) Repeating unit
The basic unit in a polymer that repeats itself thorough out the polymer chain,
e.g. [–R1–NH–CO–R2–CO–NH–] is the repeating unit for polyamides. Nylon is a polyamide.
(l) Natural polymer
Found in nature. Proteins are an example, cellulose another.

Some examples of proteins:

keratins – used to make hair, hooves, claws, feathers, beaks and fingernails,
enzymes – nature’s so efficient biochemical catalysts,
hormones – the compounds that stimulate organs into action,
fibres – e.g. wool and silk fibres, and
elastin – the structural protein of skin.

(m) Synthetic polymer

Man made polymer, e.g. the very useful nylons.
(n) Plastics
A polymer that can be easily moulded into shape, e.g. polythene.
Thermoplastics become ‘plastic’ i.e. can be moulded when hot and harden on cooling.
Thermosetting plastics become hard when heated, because cross linking occurs. Once set they do
not melt.

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 Esters are named from the alcohol and acid from which they are made. Thus an ester is given a
two word name: the first word describing the alcohol, the second the acid. However, in writing the
formulas it is usual give the acid component first, then the alcohol.

2. Some revision. Here are some esters:

Methyl butanoate (apple flavour)
Ethyl butanoate (pineapple flavour)
Ethyl methanoate (raspberries)
Ethyl ethanoate (nail polish remover)
(a) Give the names of the alcohols and the acids from which they are derived.
Methanol and butanoic acid.
Ethanol and butanoic acid.
Ethanol and methanoic acid.
Ethanol and ethanoic acid.
(b) Write structural formulas for these alcohols, acids and esters.

OH HO HO O O O
Methanol Ethanol methanoic acid Ethyl methanoate

O O O

OH

OH O
butanoic acid ethanoic acid. Ethyl ethanoate

O O

O
Methyl butanoate Ethyl butanoate
(c) How are 3-methyl-1-butyl-ethanoate and 2-methyl-1-propyl-butanoate related?
They are isomers.

3. Physical properties and uses

(a) Outline the physical properties associated with esters.

25
Sweet smelling, slightly soluble, have distinct flavours. Fats are solid esters (triesters made from
triols and long chained saturated fatty acids) while vegetable oils are liquid esters (triesters made
from triols and long chained unsaturated fatty acids).
(b) Outline the uses of esters.
In artificial flavours, making solvents (e.g. ethyl ethanoate is a solvent for nail polish), in making a
wide variety of polyesters used in clothing, and in pharmaceuticals.

4. Chemical reactions of esters

(a) The main chemical reaction of esters is hydrolysis. This can be acid or alkaline
hydrolysis. Give, with equations, an example of each.
H+

CH3COOC2H5 + H2O  CH3COOH + C2H5OH

OH–

CH3COOC2H5 + NaOH → CH3COONa + C2H5OH + H2O

(b) Why is alkaline hydrolysis the preferred method?
The acid hydrolysis is reversible. The second produces a salt, e.g. CH3COONa, and gives a better
yield. The acid CH3COOH can be made by adding HCl(aq).
CH3COONa(aq) + HCl(aq)  CH3COOH(aq) + NaCl(aq)

5. Ethanol and acetic acid were heated with a little concentrated sulfuric acid in the flask of
the apparatus shown.

(a) Name the organic product expected from the reaction.

Ethyl ethanoate
(b) Write the equation for the reaction.
C2H5OH + CH3COOH → CH3COOC2H5 + H2O
(c) State the function of the sulfuric acid.
Provides the catalyst (H+).

26
(d) Explain why the condenser is used as shown in the diagram.
Heat is required for this reaction and the condenser prevents volatile reactants and products
escaping.
(e) Explain why the reactants must be heated for some time to obtain a satisfactory
yield of the product.
Covalent bonds are strong are strong bonds. To break them requires considerable energy, hence
longer heating.

6. This question concerns ethyl butanoate.

(a) Describe the expected odour of ethyl butanoate.
Pineapple odour.
(b) Write an equation for its preparation.
C3H7COOH + C2H5OH → C3H7COOC2H5 + H2O
(c) What is the catalyst used?
Sulfuric acid, H2SO4, concentrated.
(d) Compare the water solubility of the reactants with that of ethyl butanoate and hence
explain which components of the reaction mixture are mainly in the ‘organic’ layer, and
which are mainly in the aqueous layer, when isolating the ester from the reactions in
the separating funnel.
The acid and alcohol are water soluble; hydrogen bonding possible. Ethyl butanoate, a larger
organic molecule, is more soluble in organic layer.

7. Consider the instructions below (1-9) and then answer the questions.
AIM
To hydrolyse the ester, ethyl benzoate, under alkaline conditions, and then do
qualitative tests for the products.

PROCEDURE
1. Place about 5 cm3 of ethyl benzoate, 1 r.g. (rice grain equivalent) of pumice (or boiling
chips) and 25 cm3 of 10% sodium hydroxide solution (bench strength) in a flask and reflux for 30-
40 minutes.
2.Set the condenser for distillation and collect the first 5-10 cm3 of distillate. Allow the residue to
cool.

27
 3. Add anhydrous magnesium sulfate, MgSO4, to the distillate – enough to cover the
bottom of the container. Stopper and shake. Leave for 5 minutes and then cool.
4. Test some of the liquid with acidified dichromate solution (warm). Note colour
changes.
5. Test some for flammability. A drop on a spatula in the Bunsen flame should ignite.
6. If time permits determine boiling point.
7. Acidify the cooled residue with concentrated sulfuric acid (CARE).
8. If time permits, filter, wash and dry the acidified residue.
9. Determine its melting point, if time permits.
(a) Write a balanced equation for the reaction.
C6H5COOC2H5 + H2O → C6H5COOH + C2H5OH
(b) Explain what reflux is and why it is necessary.
Organic bonds, being covalent are strong, and these organic compounds are volatile. Therefore,
reflux is used to contain reactants and products while heating and heating is required to break the
strong covalent bonds present in the reactants.
(c) Explain the purpose of the distillation.
To separate the alcohol, the product, from unreacted reactants.
(d) Explain the purpose of the anhydrous magnesium sulfate, MgSO4.
It is a drying agent. It absorbs water.
(e) Explain the colour changes observed in step 4 with the help of an annotated
equation.
The alcohol is oxidised to an acid
C2H5OH + (O) → CH3COOH + H2O
The oxidant Cr2O72ˉ(aq) / H+(aq) gives Cr3+, so changing from orange-red Cr2O72ˉ(aq) to green
Cr3+(aq).
(f) Write an equation for the combustion.
C2H5OH + 3O2 → 2CO2 + 3H2O
(g) Write an equation for the acidification step. Explain why the residue does not distil.
2C6H5COONa + H2SO4 → 2C6H5COOH + Na2SO4
Na2SO4 is a non-volatile ionic compound.
(h) Explain why filtration of the acidified product is possible.
Benzoic acid is not very soluble in cold water.
(i) Why is the determination of a melting point much used in organic chemistry?
A sharp melting point indicates a pure substance. Impurities lower the melting point of a substance.

28
8. Ethyl ethanoate is an example of an ester.
(a) State three important commercial uses of esters.
Polymers, flavourings, solvents.
(b) Fats and vegetable oils contain naturally occurring esters. Give the general formula
of these esters and explain why they are important commercially.

Where R1, R2 and R3 are C11 to C19 carbon chains in saturated and unsaturated fatty acids.

These esters are called triglycerides. The alcohol in glycerol is a triol; it has three –OH groups per
molecule. They are present in foods, used in cooking, and can be converted into biofuels.

This question (c) has been included as part of your general chemical knowledge; it is not part of
the examination syllabus.

(c) Describe, giving an outline of the practical details, reaction conditions and
equations, how you could produce a sample of ethyl ethanoate using ethanol as the
only organic starting material.
Separate the C2H5OH into two equal parts.
Oxidised one part using excess Cr2O72ˉ/H+ to ethanoic acid. Distill off the acid. Set up apparatus for
reflux. Add alcohol + acid + drop H2SO4(conc) + boiling chips.
Reflux for 30 minutes. Distil off the ester at its boiling range (77°C)
C2H5OH + (O) → CH3COOH + H2O
C2H5OH + CH3COOH → CH3COOC2H5 + H2O

29
9. Describe, with equations, the following reactions:
(a) diethylamine and propanoic acid
An acid-base reaction; the product, ionic, is soluble.
(C2H5)2NH + C2H4COOH → (C2H5)NH2+ C2H5COOˉ
(b) 1-propylamine and hexanoic acid
Again an acid-base reaction,
C3H7NH2 + C5H11COOH → C3H7NH3+C5H11COOˉ

An amine plus an acid gives a salt. These salts are generally soluble and medicinal amines must
be soluble to be effective. Usually HCl is used. The anti-histamine drug cetirizine dihydrochloride is
an example. Ecstasy, a hallucinogenic drug, is the hydrochloride of a secondary amine.

10. Synthetic polymers can be classed as addition or condensation polymers. Explain,

briefly, the difference.
Addition polymers involve unsaturated monomers linking to form saturated C – C chains; these are
the addition reactions. Condensation polymers form from condensation reactions, where in small
molecules, e.g. H2O, are split off as the polymer chain forms.

11. What is a co-polymer?

A polymer formed from 2 or more different monomers, e.g. an alternating co-polymer made from A
and B would be …ABABAB…. A block co-polymer …AAABBBAAA….

Co-polymerization is used to prepare a polymer with specific properties, e.g. very hard.

12. About polyesters

(a) What are the polyesters?
Are polymers formed by condensation polymerisation between acids with two or more carboxylic
functional groups and alcohols with two or more hydroxyl groups.
(b) Give the structural formula for ethane-1,2-diol. Why is it used as a monomer in
condensation polymerisation?
HO
OH
It has two –OH functional groups and can act as a monomer with its co-polymer, an acid with two
carboxylic groups.

30
 (c) Give the structural formula for benzene-1,4-dicarboxylic acid. Why is it used as a
monomer in condensation polymerisation?
HO OH

O O
It has two carboxylic acid groups per molecule and these can link via condensation reactions.

These numbers are used to show where the functional groups are to be found on
the benzene ring, just as they are in non-aromatic compounds.
2 3
HO OH
1 4

O O
6 5

(d) Now write the equation for the polymerisation reaction between the above two
monomers.
HO OH

+ HO
OH
O O

O
O O

O O
O

O
REPEATING UNIT

(e) Indicate the repeating unit in the polymer formed in (d).

(f) What is the commercial name for this polymer?
Terylene

31
 An early name for benzene-1,4-dicarboxylic acid was terephthalic acid, and for the
ethane -1,2-diol, ethylene glycol. The polymer, when spun into fibres, was called
Terylene. The ter– and –lene giving the name Terylene.
When made into a film it is called Mylar. Mylar, which is very light and strong, was
used on the Albertross – the aeroplane of enormous wing span which was pedalled
across the English Channel in March 1979. Mylar is also used in the sails of yachts.

13. (a) What are the polyamides?

Polymers in which the monomers are linked by amide bonds. They are condensation polymers.
(b) Give the structural formula for 1,6-diaminehexane. Why is it used as a monomer in
condensation polymerisation?
NH2
H2N

It has two amine groups. One at each end of the chain.

(c) Give the structural formula for hexanedioic acid. Why is it used as a monomer in
condensation polymerisation?
O

HO
OH

O
It has two carboxylic acid groups; one at each end of the chain.

(d) Now write the equation for the polymerisation reaction between the above two
monomers.

32
 O
+
HO NH2
OH H2N

H H
N N
* N
H

O O

REPEATING UNIT

H2O

(e) Indicate the repeating unit in the polymer formed in (d).

(f) What is the commercial name for this polymer?
Nylon-6,6

The first nylon prepared was called nylon 6.6 because there were two C6 monomers used, namely
hexanedioic acid and 1,6-hexanediamine.
Its uses are many and varied. Here are some: hosiery, rope, fishing lines. Parachutes and artificial
blood vessels.
Nylon, when mixed with other fibres such as wool, is both warm and very hard wearing. Stretch
fabrics have a nylon base.

33
14. The polymer shown has the trade name Nomex and is used to make fire-proof clothing:

O O O O

N N N
H H H

REPEATING UNIT
(a) Show in the diagram above the repeating unit
(b) Supply the missing words.
Nomex is a poly amide and the type of polymerisation used to make it is termed
condensation polymerisation.
(c) Draw the structural formulas of the monomers used in the manufacture of Nomex.
O O

HO OH
H2N NH2

15. Explain why the preparation and use of condensation polymers is of significant
economic importance.
Because of their so varied and hence so useful products, vast quantities of these polymers are
made and used. Paints, ropes, clothing, carpets, are but a few of the many 1000’s of products
made.

34
16. Shown is the repeating unit for a condensation polymer.

Write structural formulas for the monomers used to make this polymer.
O

OH
HO

O
NH2
H2N

35
20.5 Exercises

 Questions 1 (a) and 1 (d) involve more than two steps with chemistry beyond that which is
required at this level. Less demanding and more suitable questions to introduce in this exercise
would have been:
(a) but-2-one from but-2-ene, and
(d) butan-1-ol from butane
Do these questions before checking your answer with that given below in (a) and (d)

1. Deduce reaction pathways given the following reactants and products. Include the
conditions required and an equation for each step.
(a) butan-2-one from but-2-ene

______________________________________________________________________________

______________________________________________________________________________
OH O

H2O/ H2SO4 Cr2O72-/ H+

reflux reflux
(b) propanoic acid from propene

H2O/ H2SO4 Cr2O72-/ H+

OH OH
reflux reflux

Note that this reaction also gives propanone. A mixture of both propanone and propanoic acid is
formed.
OH O
[O]

The mixture can be separated by fractional distillation.

 Conclusion: This question has not been well thought through!

36
(c) propanal from 1-bromopropane

Cr2O72- / H+ H
Br NaOH(aq) OH
[O]
reflux
reflux O

Note: The oxidation in the final step must NOT be complete. This would produce a carboxylic acid.
Limited oxidation occurs when the Cr2O72- / H+ is added to the alcohol as the aldehyde is distilled
off. There is more alcohol than oxidant. To produce an acid the alcohol is added to excess oxidant.

(d) butan-1-ol from butane

______________________________________________________________________________

______________________________________________________________________________
Br2 NaOH(aq)
Br OH
UV reflux
(e) propanone from propene
Br OH O
HBr NaOH Cr2O72- / H+
[O]
reflux
(f) butylamine from 1-chloropropane
Cl KCN (al) H2 / Ni
CN
NH2
reflux

(g) N-ethylethanamine from ethanol

The steps are:
1. Elimination of H2O from the alcohol using concentrated H2SO4.
2. Add HBr.
3. React with NH3.
Br
conc. H2SO4 HBr NH3 N
H2C CH2 H3C CH2 + 2HBr
OH H C2H5
reflux warm
C2H5

37
(h) ethyl ethanoate from ethanol
O
H OH
Cr2O72- / H+
OH
[O] O
H2SO4
reflux O

2. (a) The aim in any synthesis is to produce a reaction pathway with the minimum number
of steps. Why is this?
Firstly, for economic reasons. For example if each step has a 1 hour reflux, then if there are 10
steps then the synthesis will take at least 10 hours. Remember that in business time is money
(staff, overheads, energy used). Secondly, not all steps result in 100% conversion of the reactant
into the desired product and as the next question will show, the more the steps the less the final
yield.
(b) In a four step synthesis each step gives a 50% yield. What is the percentage yield for the
final product?
Multiply the number of steps, 4, by the % yield in turn. First step gives 50% yield, second step
gives 50% of 50% = 25%, third step gives 50% of 25% = 12.5%, final step gives 50% of 12.5%. In
this case it is a 6.25% yield. Quite a loss!

3. (a) What is the difference between the terms reaction pathways and reaction
mechanisms?
The reaction pathway indicates the steps in the synthesis, along with all the conditions.
Reaction mechanism gives an insight into how the reaction is actually occurring.
(b) In the following reactions, circle where the curly arrows are correctly used;

The correct mechanisms are the first and third mechanism since both illustrate the movement of
electrons from the nucleophile to the electrophile.

38
20.6 Exercises

1. Explain, with an appropriate example, what is meant by:

(a) structural isomers
Compounds with the same molecular formula but have different structures, e.g. C4H10 is the
molecular formula for butane and 2-methylpropane.
(b) stereoisomers
Compounds with the same molecular formula and same structural formula but have different 3D
shapes, e.g. cis-but-2-ene and trans-but-2-ene.
(c) cis-trans (geometric) isomerism
In the cis isomer the functional groups are on the same side of the C = C. In trans they are on
opposite sides.
(d) optical isomerism
Results from the opposite effect optical isomers can have on plane polarised light. The amino acid
alanine shows optical isomerism; one isomer will rotate plane polarised light in one direction; the
other isomer will rotate plane polarised light in the opposite direction. This occurs because the
central atom is asymmetric, i.e. has four different groups attached
(e) chiral carbon atom
When the C atom in a molecule is attached to four different atoms or group it is described as chiral.
Alanine has a chiral C atom. Chiral carbon atoms are asymmetric.

Lactic acid, 2-hydroxypropanoic acid, is an example of a chiral compound. Its chiral C atom
gives isomers that can exist as mirror images, so making them optically active.
Hint: Draw a mirror as a line before drawing optical isomers. One isomer will be
a reflection of the other.

39
(f) achiral
Not attached to 4 different atoms or groups. The C in the –COOH group in amino acids is achiral. It
is attached to only three groups (four bonds, but only three groups).
(g) racemic mixture
When there are equal amounts of the optical isomers present in a mixture it is described as
racemic, e.g. lactic acid from sour milk is a racemic mixture.

Racemic mixtures are not optically active because the two optically active isomers
cancel out each other. They have an equal, but opposite effect on polarised light.

(h) enantiomers
Are compounds which react chemically the same, but differ in the way they rotate polarised light –
they are optically active. Lactic acid exists as enantiomers.

Although enantiomers have the same general chemistry and the same
physical properties, their biochemistry can differ. The tragedy of thalidomide is
an example.
Although some reactions produce a racemic mixture, nature seems to prefer
the making of one enantiomer. In biological systems if the molecule does not fit,
then it does not work or, as with thalidomide, does damage.
On a positive side research into enantiomers that do damage may help to
control or remove cancerous cells.

(i) optical activity

The ability rotate plane polarised light, shown by optical isomers. Lactic acid shows optical activity.
(j) dextrorotary (no example needed)
An optical isomer that rotates plane polarized light to the right (clockwise).
(k) restricted rotation
The inability of the carbon atoms in a carbon-carbon double or triple bond to rotate is described as
restricted rotation. The result is geometric stereoisomerism, e.g. the cis- and trans- isomers of 1,2-
dichloroethene.

40
2. Which of the following can exist as stereoisomers? Explain your choices.
(a) CH3CH2CH2CH3
No – because no chiral C atoms present.
(b) CH3CH(OH)COOH
Yes, the central atom has four different atom/groups of atoms attached, therefore, chiral.
(c) C4H9Cl
No – all C achiral
(d)
H
H3C C CHO

CH2CH3
Yes, central C is chiral.

3. In question 2 above draw and name the structural isomers for (a) and (c).
(a)

H3C H

CH CH3 C
H3C CH3
H3C H3C

isobutane 2-methylpropane
(c)
Cl Cl
Cl
H2 H2
H3C C H2C C H2C CH3 H3C CH3
CH CH3 C CH3 CH C
H2

Cl CH3 CH3

2-chlorobutane 1-chlorobutane 1-chloro-2-methylpropane 2-chloro-2-methylpropane

41
4. 1,2-dichloroethene can exist as a stereoisomer. Explain how this is possible, and draw
and name the stereoisomers.
Cl

Cl Cl
Cl
Trans 1,2-dichloroethene Cis 1,2-dichloroethene
It contains a C = C. The pi bonds restrict rotation, therefore geometric isomerism possible, giving
cis- and trans- isomers.

5. One form of stereoisomerism is called geometric isomerism. With the help of structural
formulas, show which of the following have geometric isomers, and which have not.
(a) 1,1-dichloroethene
Cl

Cl NO GEOMETRIC ISOMERS

H2C

(b) 1,2-dichloroethene
Cl

Cl Cl
Cl
Trans 1,2-dichloroethene Cis 1,2-dichloroethene
(c) but-2-ene

Trans but-2-ene Cis but-2-ene

(d) 1,2-dichlorocyclopropane

Cl Cl
Cl Cl
Trans 1,2-dichlorocyclopropane Cis 1,2-dichlorocyclopropane

42
(e) 1,2- dichlorocyclobutane

Cl Cl Cl Cl

Cis 1,2-dichlorocyclobutane Trans 1,2-dichlorocyclobutane

(f) 1,3-dichlorocyclobutane
Cl Cl

Cl Cl

Cis 1,3-dichlorocyclobutane Trans 1,3-dichlorocyclobutane

6. Restricted rotation
(a) What is meant by restricted rotation?
Rotation is not possible due to the rigidity of the structure. In alkenes and alkynes the double and
triple bonds cannot rotate; their compounds show restricted rotation.

Some inorganic complexes also show restricted rotation, which gives rise to cis- and trans-
isomers. Cisplatin, an anticancer drug, is an example.

(b) Explain, with examples, how restricted rotation forms.

The sigma and pi bond in a double bond are perpendicular to each other and hence for a rotation
to occur, the pi bond would have to break.
Pi bond

Sigma bond

43
7. Hybridisation.
(a) Using ethene as an example, explain, with a diagram, sigma (σ) bonding, pi (π) bonding
and sp2 hybridisation.
Pi bond

Sigma bond

Orbitals that overlap ‘end to end’ give sigma covalent bonds. The C – H bonds are sigma. The
‘side to side’ overlap of orbitals produce pi bonds. Carbon’s p orbitals form these π bonds. The
hybridisation involves a 2s electron being promoted to the 2p orbitals, giving an s with one electron
and 2p orbitals, each with one electron. This is designated as a sp2 hybrid. The remaining p orbital
electron forms the π bond.
(b) Which of the bonding, σ or π, is the stronger and why?
The pi bond is weaker than the sigma bond, because there is more extensive overlap, i.e. shorter
distance in the σ bond, so making it the stronger.

This means that the C = C bond (being a σ + π bond) is stronger than a C – C bond
being (σ), but not as strong as two σ bonds.

8. But-2-ene-1,4-dioic acid has stereoisomers.

(a) Draw and name these isomers.
O
HO
HO
OH
O
O O OH

Trans but-2-ene-1,4-dioic acid Cis but-2-ene-1,4-dioic acid

(b) How could you distinguish between these isomers?
Determine melting point. The trans form has the higher Tm. This is because the trans form is more
open than the cis form. This allows the molecules to come closer together and the resulting
hydrogen bonding gives the trans the higher Tm.

44
(c) When heated one of the above isomers forms a ring compound. Which reacts in this
way, the cis or trans form, and why?
The cis form because it already has more of a ring structure to it
(d) Write the equation to show the reaction in (c).
HO

heat + H2O
O
O O
O OH O
furan-2,5-dione
Cis but-2-ene-1,4-dioic acid

A beam of ordinary light consists of the electromagnetic waves that oscillate in an infinite number
of planes. When a beam of ordinary light is passed through a polariser only the lightwaves
oscillating in a single plane passed through. Hence the name ‘plane polarized light’. A polariser is
used to determine whether or not the substance is optically active. Optical isomers rotate the plane
of polarised light.

9. Polarisation
(a) What does optically active mean?
Plane polarised light is rotated when it is passed through an optically active molecule.
(b) Describe, in brief outline, the action of a polariser. A diagram will help you get an extra
mark.
White light, oscillating in many planes, is passed through vertical slits (the polariser) making the
light now oscillating in only one plane. It now passes through the sample. The one plane light is
changed to another plane and the observer adjusts an analyser to measure how much the light has
been rotated (clockwise or anticlockwise).

45
(c) What factors must be held constant to determine the specific rotation?
The wavelength of light, the temperature and the concentration of sample used must be kept
constant in order to measure the degree of rotation.

10. Enantiomers may differ may differ in physical properties, e.g. L-aspartame (nutrasweet)
is very sweet, while the D-enantiomer is bitter. Or is sweetness a chemical property?
(a) What do the L- and D- mean?
L is from laevorotary (Latin laevus, left) meaning rotation to the left (anticlockwise). D from
dextrorotatory (dexter, right) meaning clockwise rotation, i.e. moves to the right.
(b) Limonene exists in two enantiomer forms, as does carvone. One form of limonine is
found in oranges, and smells like oranges; the other is found in lemons and smells like
lemons. With carvone you find one form with a caraway seed smell, the other a spearmint
smell.

Chiral carbon Chiral carbon

limonene carvone
Circle the chiral atoms in the structures above.

46
 Although you are asked to identify the chiral C atom in an optically active compound, strictly
speaking it is the molecule that is chiral, not the atom. It is the lack of symmetry in the structure of
the molecule that makes it optically active.

11. Compounds with the same molecular formula as pent-3-en-2-ol, show three types of
isomerism: structural, geometric and optical.
(a) Draw and name a structural isomer of this compound that does not contain a carbon-
carbon double bond.

O
H2
C C
H3C C CH3
H2

pentan-2-one
(b) Draw and name the geometric isomers of pent-3-en-2-ol.
HO OH

cis-pent-3-en-2-ol trans-pent-3-en-2-ol
(c) Give the reason why pent-3-en-2-ol shows geometric isomerism.
The C = C show restricted rotation, hence the above (cis) and across (trans) forms are possible.
(d) Draw the optical isomers for pent-3-en-2-ol.

Chiral Carbon
OH OH

H H
CH3 H3C

(e) Indicate the chiral atom in (d) above.

(f) What is the effect these optical isomers will have on plane polarised light?
The plane polarised light will be rotated the same amount but in different directions (L, left and D,
right).

Chiral, pronounced keral, comes from the Greek, kheir, meaning hand. Chiral compounds

47
 cannot be superimposed (superimpose means to place over) on each other,
just as your right hand cannot be superimposed on your left.

An Organic Revision Exercise

1. The alkanes (the saturated hydrocarbons) are inert to acids, bases, oxidizing agents and
reducing agents. Why is this?
The C – C bonds is very strong as is the C – H bond. They are non-polar bonds and C cannot
expand its octet of electrons when combined.

2. Explain:
(a) The low bond polarity in the alkanes
The electronegativity difference between C and H is small (C = 2.5, H = 2.1) hence limited bond
polarity, limited reaction.
(b) The high bond strength of the alkanes. Include a description of hybrid orbitals in your
answer.
Because the H atom is very small and the C atom, too, is small, sigma orbital overlap is extensive,
as is the s and p orbital overlap. These sigma bonds are, therefore, strong. The sp3 hybrids are
related to the tetrahedral arrangement of the 4 covalent bonds, presenting a uniform distribution of
electron pairs, so making a non-polar molecule.

3. Reaction mechanisms
(a) Although there are many millions of organic compounds four fundamental reaction
mechanisms are generally used to account for their chemistry. These are given. Briefly
explain what is meant by each.
(i) addition

48
In addition reactions functional group atoms are joined to the C atoms at the points of un-
saturation, i.e. at the carbon-carbon double or triple bond.
(ii) elimination
Two molecules join by splitting off a small molecule, e.g. H2O or HCl.
(iii) rearrangement
The atoms in a molecule rearrange to produce a new structure. The petroleum industry rearranges
the structure of alkanes to increase the octane number of petrol.
(iv) substitution
Are reactions where an atom or a molecule is replaced by another atom or molecule.
(b) Why is it that condensation is not considered to be a fundamental reaction mechanism?
Condensation is preceded by addition, and then elimination follows. It is a combination of two
fundamental reactions.

4. Explain what is meant by the terms photochemical and substitution as used in

hydrocarbon chemistry.
Photochemical refers to reactions initiated by light, e.g. photosynthesis where plants use sunlight
to convert CO2 and H2O into carbohydrates. UV light is used to initiate the production of free
radicals. These, in turn, can substitute, i.e. replace an atom, or group of atoms, in a molecule. The
reaction between Cl2 and CH4 to produce HCl and CH3Cl combines a photochemical reaction and
substitution.

5. Methane-bromine reaction.
(a) Write an equation showing the reaction of methane with bromine.
CH4(g) + Br2(g) → CH3Br(g) + HBr(g)
(b) What are the reaction conditions required for (a) above?
UV light is required
(c) Give two observations that would show that this reaction has occurred.
The brown Br2(l) becomes colourless. The products, CH3Br(g), and HBr(g) are also colourless.
Use an indicator, e.g. moist litmus, to show an acid, HBr, present.

6. Explain, with an example and using fish-hook arrows, what is meant by homolytic
fission?

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The bond breaking (fission) reaction that produces free radicals with unpaired electrons. A Br2
molecule, under UV light, will break its covalent bond to form two free radicals, each radical taking
one electron from the previous shared pair. This electron movement is shown by fish hook arrows.

7. Explain, with an example, using arrow notation, heterolytic fission.

This bond breaking produces ion intermediates during the reaction, e.g. HBr → H+ + Brˉ
The electrons are not shared.

8. What is a free radical and what chemical property is associated with such a species?
A particle with an unpaired electron. They are formed during homolytic fission. They are very
reactive, e.g. Cl∙.

9. Draw:
(a) The Lewis structure for a chlorine atom

Cl

(b) A chlorine free radical

Cl

10. Heterolytic fission tends to occur in polar bonds. Using ethanoic acid, a structural
formula and a curly arrow, explain this statement.

O O
H
O H2O O + H3O+

NB: These arrows represent

the movement of 2 electrons

A polar solvent, e.g. water, encourages heterolytic fission; attacking the δ+ H in the –OH of the
acid. The unequal sharing of electrons producing the ion shown.

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11. Using only curly arrow notation show the heterolytic and homolytic fission of HCl.

H+ + Cl-
H Cl

HETEROLYTIC FISSION

H Cl H + Cl

HOMOLYTIC FISSION

12. Classify the following reactions as heterolysis, homolysis or neither:

Ultraviolet radiation
(a) CCl2F2 CClF2 + Cl
homolysis (no ions present)
(b) Br2  Br + Br
homolysis (no ions present)
(c) NH3 + CH3COOH  CH3COONH4
heterolysis, the acid-base reaction produces ions, CH3COO– and NH4+.

13. (a) Name the following organic compounds:

A. (CH3)3CBr
2-bromo-2-methylpropane
B. CH3CH2CH =CH2
but-1-ene
(b) Give the reagent, conditions and reaction mechanism for the hydrolysis of compound A
above.
A is a tertiary halogenoalkane. It reacts with aqueous sodium hydroxide to produce a tertiary
alcohol. The mechanism is SN1.

Br OH
OH
H3C C CH3 H3C C CH3 + Br H3C C CH3

CH3 CH3 CH3

(c) Give your observations when an alcoholic solution of bromine is added to B above.
Addition occurs. The brown alcoholic Br2 becomes colourless as the reaction proceeds.

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15. Outline the reagents, conditions and equations for the two stage conversion of 1-
bromopropane to 1-butylamine.
Ammonia, 1-bromopropane, mix with gentle heating.
NH3(g) + CH3CH2CH2Br  CH3CH2CH2(NH3)Br (intermediate or transition state) 
CH3CH2CH2NH2 + HBr

Now revise your understanding of the SN2 mechanism by using structural formulas and
curly arrows for the above reaction.

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16. Benzene is an aromatic hydrocarbon.

(a) Explain the word aromatic when it is used in organic chemistry.
It is the traditional term for compounds containing benzene rings. Now these compounds are called
the arenes.
(b) Why is the benzene molecule planar?
Each C in the ring is in a trigonal planar arrangement of atoms. The 4th electron from each C is
delocalised into the areas above and below the six C atoms.
(c) Why are all of the C—C bonds in the molecule the same length?
Again, these bonds have the same length because the delocalisation of electrons; they have a
covalent bond which is shorter than a C – C bond, but longer than a C = C bond.
(d) Each carbon in benzene is sp2 hybridised. What does this mean?
One of the two s electrons from the C atom is promoted to a p orbital. The one s and the two p
electrons form a hybrid sp2 orbital. This gives the trigonal planar structure.
(e) Why are there no alkene groups in benzene?
The extra electrons required to form a C = C bond are delocalised in a plane above and below the
ring structure.
(f) What is the evidence for benzene having no alkene groups present? Refer to both
physical and chemical properties.

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Benzene is an unsaturated hydrocarbon; it burns with a smoky flame and has low Tb and is soluble
in organic solvents. Thus is like the alkenes. But chemically the differences are significant. It does
not undergo addition reactions nor does it react with oxidising agents, e.g. acidified potassium
permanganate. This is the evidence for no C = C being present.
(g) Which of the following can be used as representing benzene?

A. C6H6 B. C. D. C6H5—
A and B are correct. C is cyclohexane, C6H12, and D is the benzyl radical.
(h) Draw a more acceptable representation of the benzene molecule than any given above.

Question 16 probably extends benzene chemistry outside of the

examination syllabus. Check with your teacher.

17. Substitution reactions

(a) Give an example of a substitution reaction using benzene.
The reaction with Cl2 or Br2 is substitution.
C6H6 + Br2 → C6H5Br + HBr.
(b) How does your reaction above show the special stability of benzene?
That a catalyst (usually AlCl3 or AlBr3) and energy, e.g. UV light, are required suggest benzene is a
stable compound. The benzene ring is not changed.
(c) Benzene undergoes substitution rather than addition reactions with bromine. Why is
this?
The stability of the benzene ring due to the delocalisation of π electrons prevents changes to its
planar structure, therefore substitution is the preferred reaction.

18. Benzene is an unsaturated hydrocarbon. What chemical evidence supports the

statement?
The C to H ratio is low and it burns with a smoky flame.

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19. Explain the mechanism for the elimination of HBr from bromoalkanes.
Reflux the bromoalkane with a concentrated alcoholic solution of KOH. In this case the OH– is
acting as base – it becomes water by adding a proton. The OH– increases the polarity of the
C(δ+)―Br(δ-) bond as it approaches an H (as can be seen in the diagram below, electrons are
pushed towards the bromine). With the higher temperature this H can break off as an H+ and then
combines with the OH– to give water, H+ + OH–  H2O. At the same time the Br breaks off as
Br–.
This is illustrated with the following mechanism

As the OH– approaches any H it can, at a high temperature, pull an H+ from the bromopropane to
form water. The pair of electrons from a C―H move to a C―C bond, making it a C=C bond. These
electrons now push the electrons from the C―Br onto Br making it Br–.

20. Monomers and polymers

(a) The monomer ethenyl ethanoate (vinyl acetate) is used to make polyvinyl acetate, part of
the polymer chain being:

H2 H2 H2 H2 H2 H2
C C C C C C

O O O O O O O

O O O O O O O

CH3 CH3 CH3 CH3 CH3 CH3 CH3

Repeating unit
(i) Circle the repeating unit in this polymer.
(ii) Define monomer.
The unit (molecule) from which a polymer may be built, either by addition is condensation
polymerisation.

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 (iii) Draw a structural formula for ethenyl ethanoate.
O

O
vinyl acetate
(b) In industry the following compound is called vinyl chloride: CH2=CHCl.
(i) Give the systematic name for CH2=CHCl.
chloroethene
(ii) Using structural formulas write an equation to show the formation of the polymer,
polyvinyl chloride.

H Cl H Cl H Cl

n C C C C C C

H H H H H H

(iii) Explain what is meant by the terms thermoplastic and thermosetting polymers.
Thermoplastic means to become plastic on heating. PVC is a thermoplastic.
Thermosetting means that the polymer is resistant to heat. It has set. Bakelite is a thermosetting
polymer.
(c) Polymers are made by addition polymerisation, or by condensation polymerisation. In (a)
and (b) above, which of the polymerisations is addition and which condensation? Give your
reasons in your answer.
Both are made by addition polymerization since you are adding the same molecule.

21. A compound has the empirical formula, CHBr. It has a relative molecular mass of
185.8.
(a) Name an instrument that could used to determine relative molecular mass.
The mass spectrometer.
(b) Show that the relative molecular mass given above agrees with the molecular
formula, C2H2Br2.
Calculate the Mr
2xC= 24.0
2xH= 2.0

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 2 x Br = 159.8
185.8

(c) This compound has two structural isomers.

(i) Define structural isomer.
Compounds with the same molecular formula but have different structural formulas.
(ii) Draw structures for and name each isomer.

1,1-dibromoethene
Br

Br

1,2-dibromoethene
Br

Br Br
Br
Trans 1,2-dibromoethene Cis 1,2-dibromoethene
(d) Halogens can react with alkenes.
(i) Name the type of reaction for an alkene combining with a halogen.
addition reaction
(ii) What would you observe during the reaction in (i) above if bromine was the halogen
used?
The loss of colour (brown → colourless) during the reaction.
(e) One of the structural isomers of the compound C2H2Br2 can also show
stereoisomerism.
(i) Define stereoisomerism.
Isomers with the same molecular formulas and structural formulas but with different spatial
(3D) arrangements of their groups of atoms.
(ii) Draw and name the stereoisomers for the isomer you have chosen.
cis-1,2-dibromoethene

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 Br

Br

trans-1,2-dibromoethene
Br
Br
(iii) Explain why stereoisomerism is possible in a haloalkene, but not in a haloalkane.
The C = C bond shows restricted rotation; but the C – C bond in haloalkanes allows for
rotation. Stereoisomerism is only possible with restricted rotation.
22. Halogenoalkanes can be hydrolysed to alcohols using hot NaOH(aq).
(a) Give the equation for the alkaline hydrolysis of 1-iodopropane.
CH3CH2CH2I + OHˉ→ CH3CH2CH2OH + Iˉ
(b) Describe, using curly arrows and relevant dipoles, the mechanism for the reaction
in (a) above.

(c) The rates of hydrolysis of 1-chloropropane, 1-bromopropane and 1-iodopropane

with hot NaOH(aq) were studied under controlled experimental conditions.
(i) Outline three of the conditions that would be require controlling if the rate
comparisons obtained can be judged to be scientifically acceptable?
The temperature is controlled, i.e. set and maintained during the experiment. The
concentration of the NaOH(aq) as well as the haloalkane used remain the same in all three
experiments.
(ii) Which of the haloalkanes listed in (c) above would show the fastest, and which would
show the slowest rate?
Fastest: 1-iodopropane
Slowest: 1-chloropropane
(iii) Explain the order you have given in (ii) above.
The C – l bond length is the longest (I being the largest atom), therefore the weakest bond,
therefore the fastest reaction.

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23. Describe a possible two-step synthesis for the making of petan-2-one starting with 2-
iodopentane.
Cr2O72- / H+
[O]
NaOH
reflux

I O
OH

Warm dilute NaOH(aq) gives a secondary alcohol; refluxing with acidified dichromate produces the
ketone.

Here is a summary of the reaction pathways you must know:

Preparing 2-methylpropan-1-amine from propene
CH3
H3C
Br OH CH
HBr NaOH CN
KCN (al) H2 / Ni
CH2
reflux
NH2

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