Topic 4: Introductory Organic Chemistry AS and Alkanes

Syllabus
2017
Topic
Level
AS

Learning objectives

4.1The difference between hazard and riskUnderstand the difference between hazard and risk4.2The hazards associated with organic compounds and why it is necessary to carry out risk assessments when dealingUnderstand the hazards associated with organic compounds and why it is necessary to carry out risk assessments when dealing with potentially hazardous materials4.3Suggest ways in which risks can be reduced and reactions carried out safely, for example: i working on a smaller scale iiBe able to suggest ways in which risks can be reduced and reactions carried out safely, for example: i working on a smaller scale ii taking precautions specific to the hazard iii using an alternative method that involves less hazardous substances4.4The concepts of homologous series and functional groupUnderstand the concepts of homologous series and functional group4.5Apply the rules of International Union of Pure and Applied Chemistry (IUPAC) nomenclature to: i name compounds relevantBe able to apply the rules of International Union of Pure and Applied Chemistry (IUPAC) nomenclature to: i name compounds relevant to this specification ii draw these compounds, as they are encountered in the specification, using structural, displayed and skeletal formulae Students will be expected to know prefixes for compounds up to C104.6Classify reactions as addition, substitution, oxidation, reduction or polymerisationBe able to classify reactions as addition, substitution, oxidation, reduction or polymerisation4.7Bond breaking can be: i homolytic, to produce free radicals ii heterolytic, to produce ionsUnderstand that bond breaking can be: i homolytic, to produce free radicals ii heterolytic, to produce ions4.8Definitions of the terms ‘free radical’ and ‘electrophile’ 4B: Alkanes Students will be assessed on their ability to:Know definitions of the terms ‘free radical’ and ‘electrophile’ 4B: Alkanes Students will be assessed on their ability to:4.9The general formula of alkanes and cycloalkanes, and understand that they are hydrocarbons (compounds of carbon and hydrogenKnow the general formula of alkanes and cycloalkanes, and understand that they are hydrocarbons (compounds of carbon and hydrogen only) which are saturated (contain single bonds only)4.10The term ‘structural isomerism’Understand the term ‘structural isomerism’ and be able to draw the structural isomers of organic molecules, given their molecular formula4.11Draw and name the structural isomers of alkanes and cycloalkanes with up to six carbon atomsBe able to draw and name the structural isomers of alkanes and cycloalkanes with up to six carbon atoms4.12Alkanes are used as fuels and obtained from the fractional distillation, cracking and reforming of crude oilKnow that alkanes are used as fuels and obtained from the fractional distillation, cracking and reforming of crude oil, and be able to write equations for these reactions4.13PollutantsKnow that pollutants, including carbon monoxide, oxides of nitrogen and sulfur, carbon particulates and unburned hydrocarbons, are emitted during the combustion of alkane fuels4.14The problems arising from pollutants from the combustion of alkane fuelsUnderstand the problems arising from pollutants from the combustion of alkane fuels, limited to the toxicity of carbon monoxide and why it is toxic, and the acidity of oxides of nitrogen and sulfur4.15Discuss the reasons for developing alternative fuels in terms of sustainability and reducing emissionsBe able to discuss the reasons for developing alternative fuels in terms of sustainability and reducing emissions, including the emission of CO2 and its relationship to climate change4.16Apply the concept of carbon neutrality to different fuels, such as petrol, bioethanol and hydrogenBe able to apply the concept of carbon neutrality to different fuels, such as petrol, bioethanol and hydrogen4.17The reactions of alkanes with: i oxygen in the air (combustion) ii halogensUnderstand the reactions of alkanes with: i oxygen in the air (combustion) ii halogens4.18The mechanism of the free radical substitution reaction between an alkane and a halogen: i using free radicals, which areUnderstand the mechanism of the free radical substitution reaction between an alkane and a halogen: i using free radicals, which are species with an unpaired electron, represented by a single dot ii showing the initiation step of the mechanism, with curly half-arrows for free radical formation iii showing the propagation and termination steps of the mechanism iv having limited use in synthesis because of further substitution reactions

A hazard is inherent; risk depends on exposure

Term Meaning What can change?
hazard the inherent potential of a substance or procedure to cause harm the hazard classification normally remains fixed for that substance and use
risk the likelihood and possible severity of harm under particular conditions amount, concentration, exposure route, duration and controls can all change it

Concentrated hydrochloric acid is corrosive: that is its hazard. Using a large open beaker near eye level creates a higher risk than handling a few drops in a tray while wearing eye protection, because exposure is more likely or consequential.

Risk assessment therefore asks: what harm can occur, who or what could be exposed, how likely and severe is it, and which controls reduce that risk to an acceptable level?

A control measure reduces risk; it does not usually remove the chemical's inherent hazard. Do not use 'hazard' and 'risk' as synonyms.

Organic-chemistry hazards require a risk assessment

Common organic-chemistry hazard Possible source Potential harm
flammable volatile solvents and fuels ignition, fire and burns
harmful or toxic vapours, products or reagents harm by inhalation, ingestion or skin exposure
corrosive strong acids or alkalis used with organic substances tissue and eye damage
irritant some vapours and liquids skin, eye or respiratory irritation
environmental hazard persistent or toxic releases harm to organisms and ecosystems

A risk assessment identifies the substances, quantities, concentrations, temperatures, apparatus, exposure routes and people involved. It then selects controls, records emergency action and considers disposal before work begins.

Organic compounds are often volatile and flammable, so vapour can spread beyond the vessel and meet an ignition source. The same chemical can present very different risks at microscale and at bulk scale.

A hazard pictogram identifies a class of harm; it does not by itself state the risk of the planned procedure. Conditions and controls must also be assessed.

Reduce risk by changing scale, controls or method

Risk-reduction route Example Why risk falls
work on a smaller scale use millilitres rather than tens of millilitres less material and energy are available if something goes wrong
take hazard-specific precautions use a fume cupboard for toxic vapour; exclude flames for a flammable solvent; wear eye protection for splashes the control blocks the relevant exposure or ignition route
use a less hazardous method replace a toxic or highly flammable reagent where a suitable safer alternative exists the initiating hazard is reduced or removed

Prefer controls that remove or contain the hazard before relying only on personal protective equipment. Check ventilation, heating method, secure apparatus, spill response and waste route for the actual procedure.

For carbon monoxide, improve containment and ventilation, use a fume cupboard or suitable extraction, monitor where necessary, and limit exposure time. Gloves alone do not control an inhalation hazard.

A generic precaution is not enough: the control must match the hazard and exposure route. A smaller scale reduces consequences but does not make unsafe technique acceptable.

A homologous series shares a functional group

A homologous series is a family of organic compounds with the same functional group and general formula, similar chemical reactions, and a gradual trend in physical properties. Successive members differ by CH2_2.

A functional group is the atom or group of atoms responsible for the characteristic reactions of an organic compound. Examples include C=C in alkenes, –OH in alcohols and –COOH in carboxylic acids.

Series Functional feature General formula for the relevant acyclic series
alkanes C–C and C–H single bonds only CnH2n+2\mathrm{C_nH_{2n+2}}
alkenes C=C CnH2n\mathrm{C_nH_{2n}}
alcohols –OH CnH2n+1OH\mathrm{C_nH_{2n+1}OH}

Members of a homologous series do not have identical physical properties: boiling temperature usually changes gradually with chain length. Similar chemistry comes from the shared functional group.

IUPAC names encode the longest chain and substituents

Carbon atoms 1 2 3 4 5 6 7 8 9 10
stem meth- eth- prop- but- pent- hex- hept- oct- non- dec-

Choose the longest parent chain containing the principal functional group and any required multiple bond. Number from the end giving the lowest relevant locants. Name and alphabetise substituents, use di-, tri- or tetra- for repeats, then add the suffix and locant for the functional group.

CH3_3C(CH3_3)2_2CH2_2CH(CH3_3)CH3_3 has a five-carbon parent chain and methyl groups at 2, 2 and 4, so its name is 2,2,4-trimethylpentane. Commas separate numbers and hyphens separate numbers from words.

Representation What must be shown
structural/condensed connectivity in grouped form, such as CH3_3CH2_2OH
displayed every atom and every bond
skeletal carbon-chain lines and vertices; C and attached H atoms are omitted, but heteroatoms and their H atoms are shown

The visually straightest line is not necessarily the longest carbon chain. Trace all connected carbon routes before selecting and numbering the parent.

Classify a reaction by its structural change

Reaction class Recognising change Example pattern
addition two reactants form one main product across a multiple bond C=C becomes C–C as atoms add
substitution one atom or group is replaced by another alkane H replaced by Cl
oxidation oxygen is gained or hydrogen is lost primary alcohol to aldehyde
reduction hydrogen is gained or oxygen is lost C=O to C–OH
polymerisation many monomers join to form a long-chain molecule many alkenes form an addition polymer

Compare bonds and functional groups in reactants and products. Classify the actual transformation, not the reagent name: converting C=C to C–C by adding atoms is addition, while replacing C–H by C–Cl is substitution.

A reaction can involve more than one change in a complex molecule. Name the class for the specified position or step rather than forcing the whole scheme into one label.

Bond fission can divide an electron pair equally or unequally

Bond breaking Electron movement Products Arrow convention
homolytic fission one bonding electron goes to each atom two free radicals two curly half-arrows, each moving one electron
heterolytic fission both bonding electrons go to one atom a cation and an anion a full curly arrow, moving an electron pair

Under ultraviolet light, Cl–Cl can split homolytically: Cl22Cl\mathrm{Cl_2 \rightarrow 2Cl\boldsymbol{\cdot}}. H–Cl can be represented as breaking heterolytically to H+^+ and Cl^- when both electrons go to chlorine.

After drawing arrows, count electrons and charges in every product. A radical has an unpaired electron; heterolysis produces opposite charges whose total equals the reactant charge.

Homolytic does not mean the bond breaks into ions. Equal electron division makes radicals; unequal division makes ions.

Radicals have an unpaired electron; electrophiles accept a pair

Species Definition Typical notation/example
free radical a species with an unpaired electron Cl\boldsymbol{\cdot} or CH3_3$\boldsymbol{\cdot}$
electrophile an electron-pair acceptor H+^+ accepts a lone pair; Brδ+^{\delta+} can accept a pair during addition

The unpaired electron makes many radicals highly reactive. An electrophile is electron-deficient and is attracted to an electron-rich region such as a lone pair or a π\pi bond.

A radical is defined by an unpaired electron, not by having a charge. An electrophile accepts an electron pair; it need not carry a full positive charge.

Alkanes and cycloalkanes are saturated hydrocarbons

Family General formula Structural feature
acyclic alkane CnH2n+2\mathrm{C_nH_{2n+2}} open chain; C–C single bonds only
monocyclic cycloalkane CnH2n\mathrm{C_nH_{2n}} one carbon ring; C–C single bonds only

A hydrocarbon contains carbon and hydrogen only. Saturated means that it contains no carbon–carbon multiple bond, so each carbon has the maximum number of hydrogen atoms allowed by its C–C connectivity.

Closing an alkane chain to make one ring removes two hydrogen atoms, which explains the change from Cn_nH2n+2_{2n+2} to Cn_nH2n_{2n}. For example, propane is C3_3H8_8 and cyclopropane is C3_3H6_6.

Cn_nH2n_{2n} does not prove that a compound is a cycloalkane; an acyclic alkene can have the same general formula. Inspect the bonds and ring connectivity.

Structural isomers share a formula but differ in connectivity

Structural isomers are compounds with the same molecular formula but different structural formulae: their atoms are connected in different ways.

C4_4H10_{10} can be CH3_3CH2_2CH2_2CH3_3 (butane) or CH3_3CH(CH3_3)CH3_3 (2-methylpropane). Both contain four carbons and ten hydrogens, but the carbon skeletons differ.

To find isomers, vary the carbon skeleton, functional-group position or functional group where the formula permits it. After each drawing, recount atoms, check valencies, assign an IUPAC name and reject any structure that is just a rotated or renumbered duplicate.

Different orientations of the same connectivity are not structural isomers. A molecular formula alone also does not show which atoms are connected.

Enumerate alkane and cycloalkane isomers systematically

Formula Distinct alkane names
C4_4H10_{10} butane; 2-methylpropane
C5_5H12_{12} pentane; 2-methylbutane; 2,2-dimethylpropane
C6_6H14_{14} hexane; 2-methylpentane; 3-methylpentane; 2,2-dimethylbutane; 2,3-dimethylbutane

For a cycloalkane, choose a ring size from three up to the total carbon count, then distribute the remaining carbons as substituents. Number substituted rings to give the lowest set of locants and reject rotations, reflections and alternative numbering of the same connectivity.

C4_4H8_8 gives cyclobutane and methylcyclopropane. For C5_5H10_{10}, valid connectivities include cyclopentane, methylcyclobutane, ethylcyclopropane, 1,1-dimethylcyclopropane and 1,2-dimethylcyclopropane. This same ring-size method extends to six carbons.

Use displayed, structural or skeletal formulae consistently. In a skeletal ring, every unlabelled vertex is carbon and enough hydrogens are implied to give carbon four bonds.

Cis/trans forms have the same connectivity and are stereoisomers, not additional structural isomers. Do not double-count them in a structural-isomer list.

Crude oil is separated and converted into useful alkanes

Process What happens Chemical or physical? Example/evidence
fractional distillation hydrocarbons separate by boiling range in a temperature gradient physical separation lower-boiling fractions condense higher in the column
cracking long-chain molecules split into smaller, more useful molecules chemical reaction C10H22C8H18+C2H4\mathrm{C_{10}H_{22} \rightarrow C_8H_{18}+C_2H_4}
reforming straight chains rearrange to branched, cyclic or aromatic products with improved fuel quality chemical reaction C6H14C6H12+H2\mathrm{C_6H_{14} \rightarrow C_6H_{12}+H_2} for cyclisation with dehydrogenation

Alkanes burn exothermically, so fractions containing them are used as fuels. Supply and demand rarely match crude-oil composition, so cracking increases smaller fuels and alkene feedstocks, while reforming improves combustion quality.

For every cracking or reforming equation, conserve the number of carbon and hydrogen atoms. Fractional distillation has no reaction equation because no covalent bonds change.

Cracking does not simply separate an existing mixture: it breaks covalent bonds and makes new molecules. Fractional distillation separates without changing molecular identities.

Alkane combustion can release several pollutants

Pollutant How it arises during fuel use
carbon monoxide, CO incomplete combustion when oxygen is insufficient
carbon particulates (soot) very incomplete combustion of hydrocarbon fuel
unburned hydrocarbons fuel escapes combustion or burns incompletely
nitrogen oxides, NOx_x N2_2 and O2_2 from air react at high engine temperatures
sulfur oxides, SOx_x sulfur-containing impurities in fuel are oxidised

Pollutant formation depends on fuel composition and combustion conditions. Improving oxygen mixing can reduce CO and soot, but high combustion temperature can favour nitrogen-oxide formation.

Carbon monoxide is not produced because carbon is absent; it forms when carbon-containing fuel is only partially oxidised. Nitrogen oxides come mainly from air at high temperature, not from the alkane formula.

CO is toxic; nitrogen and sulfur oxides form acids

Pollutant Specified problem Causal explanation
carbon monoxide toxicity CO binds strongly to haemoglobin, reducing the blood's ability to transport oxygen
nitrogen oxides acidity they react with oxygen and water to form acidic solutions, contributing to acid deposition
sulfur oxides acidity they dissolve and oxidise in atmospheric water to form acids, contributing to acid deposition

Acid deposition lowers the pH of soils and surface waters and can damage carbonate stone and living systems. In an enclosed space, incomplete combustion makes CO especially dangerous because it is colourless and toxic.

For this objective, keep the causal claim precise: CO toxicity is explained through haemoglobin and reduced oxygen transport; the specified issue for nitrogen and sulfur oxides is their acidity.

Alternative fuels trade sustainability against emissions

Alternative fuels are developed to reduce dependence on finite crude oil, improve long-term security of supply and reduce harmful or greenhouse-gas emissions over the fuel's life cycle.

Criterion Question for comparison
resource sustainability Is the feedstock renewable, and how quickly is it replaced?
climate effect How much net CO2_2-equivalent is emitted from production, transport and use?
air quality Are CO, particulates, sulfur oxides or nitrogen oxides reduced?
practicality What energy density, storage, infrastructure, land and cost are required?

Combustion of fossil alkanes transfers geologically stored carbon to atmospheric CO2_2. CO2_2 absorbs outgoing infrared radiation, so increasing its concentration strengthens the greenhouse effect and contributes to climate change.

An alternative fuel is not automatically sustainable or low-carbon. Compare the complete production-and-use pathway, not tailpipe emissions alone.

Carbon neutrality is a life-cycle balance

A fuel is carbon neutral only if the amount of CO2_2 added to the atmosphere across its life cycle is balanced by CO2_2 removed or otherwise prevented from being added. The boundary must include production, processing and transport as well as use.

Fuel Carbon-neutrality judgment
petrol not carbon neutral: combustion releases fossil carbon, with further emissions from extraction and refining
bioethanol potentially close to neutral for biogenic carbon because growing plants absorb CO2_2, but farming, fertiliser, processing, transport and land-use change create additional emissions
hydrogen produces water and no CO2_2 at point of use, but neutrality depends on how H2_2 is made; renewable electrolysis can be low-carbon, fossil-fuel production is not

State the system boundary, identify every carbon or energy input, compare atmospheric uptake with emissions, and give a conditional conclusion rather than relying on a label such as 'bio' or 'hydrogen'.

Zero carbon at the exhaust is not the same as carbon neutral. Upstream energy and feedstock can dominate the life-cycle balance.

Alkanes undergo combustion and halogen substitution

Reaction Conditions and products Example
complete combustion excess oxygen; CO2_2 and H2_2O CH4+2O2CO2+2H2O\mathrm{CH_4+2O_2 \rightarrow CO_2+2H_2O}
incomplete combustion limited oxygen; CO and/or C plus H2_2O 2CH4+3O22CO+4H2O\mathrm{2CH_4+3O_2 \rightarrow 2CO+4H_2O}
halogen substitution chlorine or bromine with ultraviolet light; an H atom is replaced by halogen CH4+Cl2CH3Cl+HCl\mathrm{CH_4+Cl_2 \rightarrow CH_3Cl+HCl}

To balance complete combustion of Cx_xHy_y, form xxCO2_2 and y/2y/2H2_2O, then balance O2_2. Include state symbols when requested.

The carbon skeleton remains while a C–H bond and X–X bond are replaced by C–X and H–X bonds. Ultraviolet radiation initiates radical formation.

Halogen reaction with an alkane is substitution, not addition, because the saturated carbon skeleton has no C=C bond for addition across.

Free-radical substitution is a chain mechanism

Stage Methane/chlorine equation Role
initiation Cl2UV2Cl\mathrm{Cl_2 \xrightarrow{UV} 2Cl\boldsymbol{\cdot}} homolytic fission creates radicals; draw two curly half-arrows from Cl–Cl
propagation 1 Cl+CH4HCl+CH3\mathrm{Cl\boldsymbol{\cdot}+CH_4 \rightarrow HCl+CH_3\boldsymbol{\cdot}} a radical is consumed and another radical formed
propagation 2 CH3+Cl2CH3Cl+Cl\mathrm{CH_3\boldsymbol{\cdot}+Cl_2 \rightarrow CH_3Cl+Cl\boldsymbol{\cdot}} regenerates Cl\boldsymbol{\cdot}, continuing the chain
termination Cl+ClCl2\mathrm{Cl\boldsymbol{\cdot}+Cl\boldsymbol{\cdot} \rightarrow Cl_2}; CH3+ClCH3Cl\mathrm{CH_3\boldsymbol{\cdot}+Cl\boldsymbol{\cdot} \rightarrow CH_3Cl}; 2CH3C2H6\mathrm{2CH_3\boldsymbol{\cdot} \rightarrow C_2H_6} two radicals combine and no radical remains

A curly half-arrow moves one electron. In each propagation step, use half-arrows so bond breaking and bond formation account for the unpaired electron without inventing charge.

The product can undergo further substitution because it still contains C–H bonds. Longer alkanes can also substitute at different carbon positions. The resulting mixture of products and isomers makes the reaction poorly selective for synthesis.

A propagation step must regenerate a radical; a termination step removes radicals. Do not label Cl2_2 homolysis as propagation—it is the initiation step.