Topic 1.

7: Introductory organic chemistry

Summary
Introduction
a) Homologous series and functional groups A homologous series is a series of organic compounds exhibiting similar chemical properties and trends in their physical properties, which have the same general formula (each member differing from the previous one by one CH2 unit). Compounds may contain one or more functional groups which are atoms or groups of connected atoms (e.g. C=C, OH, Br) which convey certain chemical properties on the compound. b) Nomenclature and formulae Organic compounds are named according to IUPAC nomenclature. The longest carbon chain is identified and forms the stem of the name (e.g. prop-, hex-). Functional groups and other substituents on the chain are identified by the use of a prefix or suffix to the stem and the position of attachment, e.g. 2-chloropropane has a Cl substituent at the second carbon on a propane unit; but-2-enoic acid has a COOH functional group at the first carbon and a C=C bond between the second and third carbons. Formulae may be represented in different ways as listed below: Name Molecular formula Structural formula
(bonding implicit)

Displayed formula
(bonding explicit)

Skeletal formula
(C and connected H implicit)

H
2-chloropropane C3H7Cl CH3CH(Cl)CH3

Cl C H

H C H H

Cl

C H

H
but-2-enoic acid C4H6O2 CH3CH=CHCOOH

O
O

C H3C C H

C OH
OH

c) Hazard and risk A hazard is a source or situation with a potential for harm , whereas risk is a measure of the probability that damage will occur as a result of a given hazard. Hazard is a property of a material or procedure but risk may be minimised. d) Understanding hazard and minimising risk All organic compounds are associated with hazards such as flammability, toxicity, oxidising potential, etc. Procedures involving chemicals should be designed to minimise the risk due to these hazards. Possible strategies include: the use of small quantities of material; specialised equipment ( e.g. fume cupboard, latex gloves, water bath); consideration of alternative routes using less hazardous materials.

Alkanes
a) Alkanes are a homologous series of hydrocarbons containing only CC and CH bonds and have the general formula CnH2n+2 b) Structural isomerism Structural isomers are compounds with the same molecular formula but different structural formulae. Thus, there are three structural isomers with the molecular formula C5H12. Pentane: CH3CH2CH2CH2CH3; methylbutane: CH3CH(CH3)CH2CH3; dimethylpropane: CH3C(CH3)2CH3 c) Sources and uses of alkanes The major source of alkanes is fossil fuels such as crude oil and natural gas. As they have boiling points which depend on their relative molecular mass and the degree of branching in the chain, they may be separated by fractional distillation. Shorter chain alkanes (and alkenes) may be made from longer chain alkanes by catalytic cracking and branched chain (or cyclic) alkanes may be made from straight chain isomers by catalytic reforming. The major use of alkanes is as fuels. On complete combustion they produce carbon dioxide and water. Volatile alkanes which are liquids at room temperature are particularly useful as fuels for transport as they may be stored without the use of pressure. d) Alternative fuels Fossil fuels are a finite and non-renewable resource. Moreover, carbon dioxide is a greenhouse gas which allows through radiation from the sun to heat the earth but absorbs radiation from the earth preventing it escaping into space. Sustainable fuels such as biodiesel (produced from plant oils) or bioethanol (from plant sugars) are said to be carbon neutral as they absorb CO2 when the plants grow but release it on combustion. However, they require the appropriation of agricultural land which could otherwise be used for food production. Hydrogen gas may be produced by the electrolytic decomposition of water and produces only water vapour on combustion. Producing the electricity required may involve the burning of fossil fuels. Moreover, hydrogen is difficult to store as it is a gas even at very low temperatures and high pressures.
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Methane may be produced sustainably by the anaerobic digestion of agricultural and food waste but the transport of the waste consumes fossil fuels unless it is carried out on a small-scale and local basis. e) Reactions of alkanes Apart from combustion the only significant reaction of alkanes is the free radical substitution with halogens in the presence of ultraviolet radiation. In common with all free radical mechanisms there are three basic steps to the process: initiation (production of free radicals), propagation (in which free radicals appear as reagents and products) and termination (in which free radicals are consumed).

Alkenes
a) Alkenes are a homologous series of hydrocarbons containing one C=C bond and have the general formula CnH2n. The double bond consists of a -bond due to end-on overlap of atomic 2 sp -hybrid orbitals and a -bond due to sideways-on overlap of atomic p-orbitals. b) Steroisomerism in alkenes Stereoisomers are two or more compounds which have the same structural formulae (i.e. the same atoms connected by the same bonds) but different spatial arrangements. Geometric isomerism is a form of stereoisomerism which arises when two different groups are attached to either end of a C=C double bond about which there is restricted rotation. c) Nomenclature for geometric isomers Geometric isomers are termed cis- and trans- (or E- and Z-). The cis-isomer has the substituents on the same side of the double bond whilst the trans-isomer has them on opposite sides. If there is more than one substituent at either end of the double bond, the E-isomer has the higher priority groups on opposite sides of the double bond whilst the Z-isomer has them on the zame zide. d) Addition reactions An addition reaction occurs when two (or more) molecules react to form a single product. In the case of alkenes, a single bond in the attacking species is broken and the two halves attach themselves by single bonds to the carbon atoms at either end of the double bond breaking the -bond in the process. Chemical species which can add across a C=C bond include HH (with a Ni catalyst), XX (X=halogen), HX, H-OH (in the presence of H3PO4), HOSO3H (usually followed by acid-catalysed hydrolysis to the alcohol). Oxidative addition (with acidified potassium manganate(VII)) effectively adds HO OH across the double bond to form a diol. e) Mechanism of electrophilic addition Alkenes have a region of high electron density in the -bond. This can be attacked by electrophiles (a chemical species which seeks out negative centres from which it accepts a pair of electrons to form a covalent bond). The electrophile accepts a pair of electrons from the -bond forming a -bond to one of the C atoms and leaving a positive charge on the other. The intermediate carbocation is then attacked by a nucleophile to complete the addition process. When an asymmetric electrophile adds to an asymmetric alkene, the major product is predicted by Markovnikovs rule, which states that the hydrogen from the electrophile becomes attached to the carbon of the double bond which already has the greater number of attached hydrogen atoms. This is due to the greater stability of the intermediate carbocation which has the greater number of attached alkyl groups, due to the electron-pushing effect of alkyl groups (relative to hydrogen) stabilising the positive charge on the intermediate. f) Test for alkenes Alkenes react instantaneously (and without the need of UV) with orange aqueous bromine to form a colourless product + with Br and HO added across the double bond. The attacking electrophile is BrBr and the subsequent + nucleophilic attack on the carbocation is by H H, followed by loss of H . g) Addition polymerisation of alkenes Alkenes undergo addition polymerisation via a free radical mechanism in which many monomers combine to form a long chain polymer molecule, e.g. propene:

H CH3
CHCH3 n H2C
initiator pressure

C C H H n

poly(propene)

h) Lifecycle of polymers Polymers are largely manufactured from raw materials derived from the non-renewable resource of crude oil. Mining, transport, fractional distillation and subsequent processing (cracking, etc.) all require energy resources. After use, polymers may be placed in land-fill where most will lie indefinitely as they are non-biodegradable. Recycling preserves scarce resources but requires additional transport and energy for heating. Incineration produces useful heat and thus recovers energy but care must be taken not to release toxic combustion products into the environment.

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