ALKANES

LECTURE OUTLINE (1) Hydrocarbon (2) Basic facts of alkanes (3) Nomenclature of branched chain isomer (4) Physical properties (5) ethods of preparation

(!) "eactions (#) $ycloalkanes (%) $rude oil HYDROCARBON Hydrocarbons are compounds that contain the element carbon and hydro&en only' (he t)o important classes of hydrocarbon that )e are &oin& to study are* + + ,lkanes ,lkenes

BASIC FACTS OF ALKANES (i) (ii) , homolo&ous series of saturated aliphatic hydrocarbon )ith &eneral formula $nH2n-2' Names of alkanes end )ith .ane/' n 1 2 3 4 5 ! # % olecular formula $H4 $2H! $3H% $4H12 $5H12 $!H14 $#H1! $%H1% Name ethane 1thane Propane Butane Pentane He3ane Heptane 4ctane 0tructural formula $H4 $H3 $H3 $H3 $H2 $H3 $H3 ($H2)2 $H3 $H3 ($H2)3 $H3 $H3 ($H2)4 $H3 $H3 ($H2)5 $H3 $H3 ($H2)! $H3
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(iii)

0tructural isomerism e3ists in alkanes containin& more than 3 carbon atoms (due to chain isomerism)' 13ample* Pentane ($5H12) has 3 isomers

NOMENCLATURE OF BRANCHED CHAIN ISOMERS (here are three steps to follo) in order to name branched chain isomers' (i) Step 1* 5dentify parent chain (the lon&est continuous carbon chain) and name compound after it' (ii) Step 2* 5dentify substituents of parent chain )hich are alkyl &roups1'

(iii) Step 3* 6etermine position of alkyl &roup by numberin& the carbon atoms consecuti7ely from one end of the parent chain to the other' + + + (i7) Number such that a smaller di&it is &i7en to carbon attached to substituent' 5f some alkyl &roups occur more than once as substituents8 indicate by prefi3 di+8 tri+8 tetra+ etc' ,rran&e substituent in alphabetical order or increasin& si9e i&norin& prefi3es'

13ample* Alkane Name W !n" Name

#HYSICAL #RO#ERTIES (i) (ii) 5nsoluble in )ater but soluble in ben9ene8 ether and other non+polar sol7ents' :loats on top of )ater (that it8 less dense than )ater)'

(iii) ;iscosity of li<uid alkanes increase )ith increasin& molecular mass as lon& molecules ha7e hi&her tendency to become .tan&led up/ )ith one another' (i7) Boilin& and meltin& point a' 0trai&ht chain alkanes + + Boilin& point increases )ith number of $ atoms due to increasin& 7an der =aals/ forces' eltin& point increases in 9i&+9a& pattern because intermolecular forces in a crystal depend not only on si9e of molecules but also on ho) )ell they packed into a crystal lattice'

,t room temperature and atmospheric pressure8 first 4 alkanes ($ 1 > $4) are &ases? ne3t 13 alkanes ($5 > $1#) are li<uids? $1% or more are solids

b' Branched chain isomers + 5t has lo)er boilin& point that strai&ht chain isomer' o "eason* Branched molecules are more spherical8 hence packed less closely )ith resultant decrease in 7an der =aals/ forces + 1ffect of branchin& on packin& and on meltin& point is irre&ular'

METHODS OF #RE#ARATION (i) 6ecarbo3ylation + + + Heat sodium salt of carbo3ylic acid )ith soda lime 2' "$42+Na- - Na4H "H - Na2$43 13amples*

(ii)

Hydro&enation of alkanes + + +
"1 "3 "2 "4 H H H2 "2 "3 "4

"eact alkenes )ith hydro&en &as at 142o$ usin& Ni catalyst' No heat needed if Pt or Pd are used as catalysts'

Pd / Pt /

Ni (140oC)

"1

13amples*

REACTIONS (i) Halo&enation + @eneral e<uation* " > H - A2 +

250 400oC or uv light

" > A - H > A8 )here A B $l or Br

Proceed by free radical substitution mechanism' o Hi&h temperature or u7 li&ht needed to &enerate radical o $hain reaction in7ol7in& 3 basic steps' 5nitiation Propa&ation (ermination

o Hydro&en atom(s) of alkane substituted by halo&en' o 13ample* $hlorination of methane 5nitiation* HeatCli&ht pro7ides ener&y for homolytic clea7a&e of $l>$l bond to &enerate free radical'

Propa&ation*

1ach step consumes a radical and &enerates another' (o&ether8 these t)o propa&ation steps consume one $H 4 molecule and produces one H$l molecule and one $H 3$l molecule8 &i7in& the net reaction' (ermination*

+ +

Here8 free radicals are consumed but not &enerated' , sin&le free radical (once formed) can produce a lar&e number of molecules of product by chain reaction se<uence' "eaction does not step at monosubstitution' ore than one hydro&en atoms in alkane can be replaced by chlorine )ith elimination of H$l'

o "eaction is not clean meanin& that it does not &i7e a sin&le or&anic product' o onosubstituted alkanes8 $H3$l8 predominate if e3cess alkane is used' :ully substituted alkanes8 $$l 48 predominate if e3cess chlorine is used'

o Dnlike methane8 ethane and hi&her alkanes &i7e rise to isomeric halo&en deri7ati7es )hen more than one hydro&en atom is substituted' :or e3ample8 there are t)o dichloroethane that can be formed8 $H2$l$H2$l or $H3$H$l' (his is typical of reactions of alkanes since they tend to be indiscriminate because there is little difference bet)een the stren&th of the differently situated $>H bonds' + 5n terms of reacti7ity8 : E $l E Br E 5' o :2 reaction is too e3plosi7e and cannot be used in the laboratory' o $l2 or Br2* reaction at 252 > 422o$ or u7 li&ht' o 52 is too unreacti7e to replace hydro&en atoms in alkane' + :or monosubstituted alkanes of more than 3 carbon atoms8 halo&enation can take place at any of the carbon atoms8 leadin& to position isomerism' (o determine )hich of the product is the maFor product8 t)o factors need to be taken into consideration' o 0tability of alkyl radical in the propa&ation step ( aFor factor) "3$ E "2$H E "$H2 E $H3

o Probability factor ( inor factor)

 (he number of e<ui7alent H that can be substituted' o 13amples*

(ii)

$ombustion a' Gimited supply of o3y&en + + 5ncomplete combustion to produce $4 (or $) and H 24' 13ample*

b' Dnlimited supply of o3y&en + + $omplete combustion to produce $42 and H24' 13ample*

$omplete combustion of hydrocarbons pro7ides the basis for <ualitati7e analysis' o $3Hy - (3 - yC2)42 3$42 - (yC2)H24 o ,mount of $42 and H24 produced can be measured and composition of hydrocarbon can be calculated'

CYCLOALKANES (i) (i) (ii) (iii) 0aturated hydrocarbons that contain a rin& of $ atoms' @eneral formula is $nH2n' $hemical beha7iour of cycloalkanes is similar to that of the open chain alkanes' 13amples Name $yclopropane St $%t$ al &! m$la
H2 $ H2 $ $H2 $H2 $H2

Skeletal &! m$la

$yclobutane
H2 $ H2 $

$yclopentane
H 2$ H 2$

H2 $ $H2 $ H2 H2 $ $H 2 $H 2 $ H2 $H3 $H

$yclohe3ane
H 2$ H 2$

ethylcyclohe3ane

H 2$ H 2$

$H 2 $H 2 $ H2 $H3 $H $H3 $H $H 2 $ H2 $H 3

182+dimethylcyclohe3ane

H 2$ H 2$

181+dimethyl+3+ ethylcyclohe3ane

H2 $ $H H 2$ H 2$ $ H2 $H 2 $ $H3 $H3

CRUDE OIL (i) Petroleum or crude oil is a fossil fuel that deri7ed from once+li7in& matter' 5t is a comple3 mi3ture of hydrocarbons8 mainly alkanes8 cycloalkanes and aromatic hydrocarbons' (ii) 5n the refinin& of crude oil8 this mi3ture is partly separated by fractional distillation' :ractions collected are*

:raction "efinery &as @asoline Jerosine (Paraffin oil) @as oil and diesel fuel "esidue

H by mass of crude oil 1>2 15 > 25 12 > 15 15 > 25

Boilin& ran&e C o$ I 22 22 > 1#5 1#5 > 252 252 > 422

42 > 52

E 422

No' of $ atoms Dses in main components 1>4 @aseous fuels or li<uefied petroleum &as (GP@)8 petrochemicals 5 > 12 Petrol 11 > 14 :uel for tractor and Fet en&ine8 domestic heatin& 15 > 25 Heat furnaces in industry8 fuel for hi&h speed diesel en&ines in lorries and buses E 25 :uel oil in lar&e furnaces e&' po)er stations or bi& ships8 lubricatin& oil and paraffin )a38 bitumen and asphalt (road surfacin&)

(iii) :ractional distillation separates the crude oil into its component fractions but cannot chan&e the proportion of the 7arious products' + + + + 0ome fractions are in hi&her demand' ,bout K2H of the )orld/s oil supply is used as fuel' (he demand for li&hter fractions is much &reater than the more abundant hea7y fractions' Gess useful fractions are con7erted to the more useful ones by the process of crackin&'

(i7) $rackin& is the process by )hich lar&er molecules in the hi&her+boilin& fractions of crude oil are broken do)n to smaller molecules' + (he t)o important types of crackin& are*

a' (hermal crackin& or pyrolysis o Heatin& at hi&h temperature of bet)een 452 > #22 o$' o "eaction proceeds by free radical substitution mechanism' b' $atalytic crackin& o Dsa&e of catalyst8 combine )ith heatin& bet)een 422 > 522 o$' o $atalyst used is normally aluminium o3ide mi3ed )ith either silica or chromium (;5) o3ide'

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o 5onic mechanism (acidic o3ides used as catalysts promote the formation of carbocations)' + No sin&le e<uation can represent the numerous indi7idual reactions occurrin& durin& the crackin& process' 0ome e3amples are* o "($H2)5$H3 "$H2$H2$H3 - $3H! o "($H2)4$H3 "H - $2H4 - $3H! o $nH2n-2 $3H23-2 - $yH2y (n B 3 - y) (7) "eformin& is the process by )hich strai&ht chain alkanes are con7erted to branched chain alkanes8 cycloalkanes and aromatic hydrocarbons' (he formation of rin&s also produces hydro&en' + 13amples o "($H2)4$H3 "$H2$H($H3)$H2$H3 o
$H3($H2)5$H3 +H2 +3H2

(7i)

Dsefulness of crackin& and reformin& + + $rackin& increases the proportion of petrol a7ailable from a &i7en crude oil' "eformin& impro7es the <uality of petrol by pre7entin& .knockin&/' (.Jnockin&/ is the metallic rattlin& sound heard )hen a car accelerates uphill and is caused by the une7en burnin& of lon& chain hydrocarbons in petrol' 5t decreases life of en&ine throu&h )ear and tear' 0trai&ht chain alkanes are more prone to .knockin&/ than either branched chain or cyclic alkanes)

TERMS AND DEFINITION 1' ,lkyl &roup + @roups of carbon and hydro&en ha7in& the &eneral formula $ nH2n-1' + Dsually denoted by the letter R' + Name follo)s that of correspondin& alkane since it contains one less H atom (ends )ith >yl instead of >ane)'

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2' 0oda lime + 4btained by slakin& $a4 )ith Na4H solution8 thus obtainin& a dry8 caustic alkali )hich is not deli<uescent' + Beha7es chemically as Na4H' + Preferred to solid Na4H because it attacks &lass less readily'

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