ISOMERISM

( same ________________, different arrangement of ______ in the molecule )

STRUCTURA ISOMERISM
( ________ structural and s!ace formulae ) C"AI# ISOMERISM Molecules are of the _____ t$!e, %ut ha&e different _________________' E(am!les ) *OSITIO#A ISOMERISM Molecules ha&e _____ car%on s+eleton, %ut differ in the ________ of !articular atoms or grou!s' E(am!les ) ,U#CTIO#A ISOMERISM Isomers contain different __________ grou!s and %elong to different homologous series' E(am!les )

STEREOISOMERISM
( _______ structural formulae, ________ s!ace formulae)

O*TICA ISOMERISM

Caused %$ !resence of _____ or ______ _____________ car%on atoms in the molecule' E(am!les)

2EOMETRICA ISOMERISM

Caused %$ a%sence of _________ _____________ a%out an al+ene, or similar dou%le %ond' E(am!les )

STRUCTURAL ISOMERISM
-' Structural isomerism occurs .hen com!ounds ha&e the same molecular formula %ut different structural formulae' /' It can %e su%di&ided into three different categories) Chain isomerism *ositional isomerism ,unctional grou! isomerism Chain Isomerism 0 Occurs .hen there are different arrangements of the car%on chain' 0 That is a straight chain or %ranched chain' 0 Chain isomers !osses the same __________ grou!, and %elong to the same homologous series' 0 The$ ha&e different ___________ !ro!erties, %ut same _________ !ro!erties' E(am!les) %utane /0 meth$l!ro!ane

1utan0-0ol

/0meth$l!ro!an0-0ol

;/) An aldeh$de has the molecular formula, C 9":O' <rite the structural formulae of the aldeh$de .hich sho.s chain isomerism'

*ositional isomerism 0 0 Occurs .hen the same functional grou! can %e !laced at different !ositions' The$ ha&e similar chemical !ro!erties %ut different in !h$sical !ro!erties' E(am!les) (a) 1romoal+anes .ith the molecular formula, C3"41r

(%) Alcohols .ith the molecular formula, C3"4O"

(c) Al+enes .ith the molecular formula, C5"-6 *ositional isomerism is im!ortant in aromatic com!ounds' E(am!les) The molecular formula of %en7ene is C 8"8' If t.o %romine atoms re!lace t.o h$drogen atoms to form disu%stituted %en7ene, C8"91r/,

,unctional Isomerism' 0 0 Occurs .hen structural isomers ha&e same molecular formula %ut contain different functional grou!' So that, the$ ha&e different chemical and !h$sical !ro!erties' E(am!les) (a) Al+ene and c$cloal+ane ,or e(am!le, !ent0-0ene and c$clo!entane ha&e the molecular formula, C 5"-6 (%) Alcohol and ether ,or e(am!le, !ro!an0-0ol and metho($ethane ha&e the molecular formula C 3":O' (c) Aldeh$des and +etones ,or e(am!le, !ro!anal and !ro!anone ha&e the molecular formula C 3"8O'

(d) Car%o($lic acid and ester

,or e(am!le, an organic com!ound .ith the molecular formula of C 3"8O/ ma$ %e !ro!anoic acid, meth$l ethanoate or eth$l methanoate'

;3) Structural Isomerism -' The structural formulas of eight !airs of organic com!ounds are sho.n %elo.' =etermine .hether the organic com!ounds in each of these !airs are (i) the same com!ounds, (ii) different com!ounds or (iii) Isomers' " > (a) Cl ?C?Cl > " (%) 1r?C"/ > C"/?C"/ > 1r (c) "OC"/C"/C"3 (d) C"/ClC"/C"/C"/C"/Cl (e) C"3C"/C"/C"O (f) C"3C"/C"/O" (g) C"3C"/C"@C"C"3 "/C "/ C (h) C"3C"/COO" Cl > " ?C?Cl > " C"/C"/?Cl > C"/ 1r C"3C"(O")C"/O" ClC"/C"/C"/C"/C"/Cl C"3COC"/C"3 C"3C"(O")C"3 C"/ C"/ C"/

C"3COOC"3

/' <rite structural formulae to sho. structural isomerism in each of the follo.ing molecules' (a) C/"9Cl/ (%) C3"8O (c) C3"8 (d) ClC8"9O"

STEREOISOMERISM
Stereoisomerism occurs .hen the com!ounds .ith the same molecular and structural formulae ha&e different arrangement of atoms in s!ace' There are / t$!es of stereoisomerism' O!tical Isomerism

a) O!tical acti&it$ O!tical acti&it$ is the a%ilit$ of certain cr$stal or solutions of certain su%stances to rotate the !lane of !lane0 !olarised light' Such su%stances are said to %e ______________' O!tical isomers !ossess the same structural formula %ut differ in their effect on !lane0!olarised light' Sim!le su%stances .hich sho. o!tical isomerism e(ist as t.o isomers +no.n as enantiomers' The isomer .hich rotates the !lane of !olarisation to the right ( that is in cloc+.ise direction ) is +no.n as the _________________ isomer or the __________ or the _____ isomer' The isomer that rotates the !lane !olarisation to the left ( that is in anti0cloc+.ise ) is called _____________ isomer or _______________ or the _____ isomer' The degrees of rotation of the t.o isomers are eAual %ut of o!!osite sign' <hen o!ticall$ acti&e su%stances are made in the la%, the$ often occur as a 56B56 mi(ture of the t.o enantiomers' This is +no.n as a racemic mixture or racemate' It has no effect on !lane !olarised light'

b) Chiral molecules

T.o enantiomers of a generic amino acid

(L)0Alanine (left) and (D)0alanine (right) in 7.itterionic form at neutral !"

b) ItDs e(tremel$ im!ortant to dra. the isomers correctl$' =ra. one of them using standard %ond notation to sho. the 30dimensional arrangement around the as$mmetric car%on atom' Then dra. the mirror to sho. the e(aminer that $ou +no. .hat $ou are doing, and then the mirror image .

2-hydroxypropanoic acid lactic acid) a) Once again the chiral centre is sho.n %$ a star

%) The t.o enantiomers are)

*ro!erties of Enantiomers' i' ii' iii' Enantiomers ha&e identical !h$sical !ro!erties ( melting !oint, %oiling !oint, solu%ilit$, acid strength, densit$, etc) e(ce!t for one &ital difference' The$ differ in their effect on the !lane of !olarised light' The$ also differ in the sha!e of their cr$stals' The cr$stals of the t.o enantiomers are mirror images of one another' Enantiomers react in the same .a$ in chemical reactions .ith achiral reagents'

;9) identif$ the chiral car%on atom and mar+ it .ith an asteris+ (C) for each of the molecules gi&en %elo.' If the molecule does not contain a chiral car%on, .rite the .ord EachiralF against the molecule' (a) C"3C"/C1r @ C"/ (%) C"3C"1rC" @ C"/ (c) "OC"/C"(#"/)COO" (d) "3C C "/C "/C 5 C"/ C"/ C" C"3 C"3

(a) 2eometric Isomerism 2eometric isomerism occurs in .hich ______ ___________ is !re&ented %$ the !resence of a car%on0 car%on _____________ or ___________ structure' 2eometric isomerism is also +no.n as ____________________' The$ ha&e same structural formula (that is the seAuences in .hich the atoms or grou!s in the molecule are %onded are the same) %ut differ onl$ in ho. atoms or grou!s are orientated in s!ace'

!"o#"tric I$o#"ri$# o% Al&"n"$ a) Single C ? C %onds can rotate' The restricted rotation a%out the C @ C dou%le %onds !re&ents grou!s from mo&ing from one side of the dou%le %ond to the other' Thus, the t.o isomers cannot %e con&erted into one another at room tem!erature' %) There must %e ) a C @ C dou%le %ond .hich restricts free rotation' A ring structure .hich hinders or o%structs the rotation of a C ? C single %ond in the ring' T.o different grou!s attached to each car%on atom !f the dou%le %ond' (if one of the C atoms of the dou%le %ond has / identical grou!s, geometrical isomerism is not !ossi%le) c) The ______ isomer has identical or similar atoms or grou!s on the same side of the dou%le %ond .hile the ______ isomer has them on o!!osite sides of the dou%le %ond' d) 1oth cis and trans isomers ha&e the same functional grou!, and thus ha&e the same chemical !ro!erties' "o.e&er, the$ ha&e different !h$sical !ro!erties as a result of the different s!atial arrangements of the grou!s' Th" "%%"ct o% '"o#"tric i$o#"ri$# on phy$ical prop"rti"$ The ta%le sho.s the melting !oint and %oiling !oint of the cis and trans isomers of -,/0dichloroethene' i$o#"r cis trans #"ltin' point (C) 0:6 056 boilin' point (C) 86 9:

Gou .ill notice that) the trans isomer has the higher melting !ointH the cis isomer has the higher %oiling !oint' This is common' Gou can see the same effect .ith the cis and trans isomers of %ut0/0ene)

i$o#"r cis0%ut0/0ene trans0%ut0/0ene

#"ltin' point (C) 0-3I 0-68

boilin' point (C) 9 -

Why is the boiling point of the cis isomers higher? There must %e stronger intermolecular forces %et.een the molecules of the cis isomers than %et.een trans isomers' Ta+ing 1,2-dichloroethene as an e(am!le)

1oth of the isomers ha&e e(actl$ the same atoms Joined u! in e(actl$ the same order' That means that the &an der <aals dis!ersion forces %et.een the molecules .ill %e identical in %oth cases' The difference %et.een the t.o is that the cis isomer is a !olar molecule .hereas the trans isomer is non0!olar' 1oth molecules contain !olar chlorine0car%on %onds, %ut in the cis isomer the$ are %oth on the same side of the molecule' That means that one side of the molecule .ill ha&e a slight negati&e charge .hile the other is slightl$ !ositi&e' The molecule is therefore polar) 1ecause of this, there .ill %e di!ole0di!ole interactions as .ell as dis!ersion forces 0 needing e(tra energ$ to %rea+' That .ill raise the %oiling !oint'

A similar thing ha!!ens .here there are C" 3 grou!s attached to the car%on0car%on dou%le %ond, as in cis-but-2-ene' Al+$l grou!s li+e meth$l grou!s tend to K!ushK electrons a.a$ from themsel&es' Gou again get a !olar molecule, although .ith a re&ersed !olarit$ from the first e(am!le' 1$ contrast, although there .ill still %e !olar %onds in the trans isomers, o&erall the molecules are non-polar)

The slight charge on the to! of the molecule (as dra.n) is e(actl$ %alanced %$ an eAui&alent charge on the %ottom' The slight charge on the left of the molecule is e(actl$ %alanced %$ the same charge on the right' This lac+ of o&erall !olarit$ means that the onl$ intermolecular attractions these molecules e(!erience are &an der <aals dis!ersion forces' ess energ$ is needed to se!arate them, and so their %oiling !oints are lo.er'

Why is the melting point of the cis isomers lower? Gou might ha&e thought that the same argument .ould lead to a higher melting point for cis isomers as .ell, %ut there is another im!ortant factor o!erating' In order for the intermolecular forces to .or+ .ell, the molecules must %e a%le to !ac+ together efficientl$ in the solid'

Trans isomers !ac+ %etter than cis isomers' The KUK sha!e of the cis isomer doesnDt !ac+ as .ell as the straighter sha!e of the trans isomer' The !oorer !ac+ing in the cis isomers means that the intermolecular forces arenDt as effecti&e as the$ should %e and so less energ$ is needed to melt the molecule 0 a lo.er melting !oint'

;5) <hich of the organic com!ounds sho.n %elo. e(hi%it geometric ( cis-trans ) isomerism L (a) C"3C" @ C"C"/C"3 (%) ,C" @ C", (c) C"/ @ C ( C"3)/ (d) ,ClC @ CCl,

Cyclic Co#pound$ (a) Cis-trans isomerism can arise in saturated ring com!ounds .here rotation a%out a %ond is restricted' (%) ,or e(am!le , H H H CH3

H3C cis0 -,90dimeth$lc$clohe(ane T*+ES O, OR!A-IC REACTIO-S

CH3

H3C trans0 -,90dimeth$lc$clohe(ane

Typ"$ o% bond cl"a.a'" 0=uring the course of a chemical reaction, %onds ha&e to %e %ro+en in order that ne. com!ounds ma$ %e formed' The %rea+ing or fission of %onds can occur in t.o .a$s, de!ending essentiall$ on the electronegati&it$ &alues of the t.o atoms, A and 1 , Joining the %ond' "omol$tic ,ission 1rea+ing of a single co&alent %ond in such a .a$ that one of the t.o shared electrons goes to each atom' This results in the formation of free radicals' "eterol$tic ,ission Occurs .hen a %ond %rea+s .ith the result that %oth %onding electrons sta$ .ith one of the atoms' <here A is more electronegati&e than 1, there is a tendenc$ for %oth %onding electrons to remain .ith A after ru!ture of the %ond' The more electronegati&e atom A gains a single negati&e charge and less electronegati&e atom 1 %ecomes !ositi&el$ charged'

Reaction intermediates These are su%stances that are formed in one of the ste!s of the reaction mechanism and are consumed in later ste!s' An intermediate re!resents an energ$ !rofile of the reaction' ,ree radicals Car%ocation Car%anion

A free radical is an atom or grou! of atoms .ith a single un!aired electron'

A s!ecies containing a !ositi&el$ charged car%on' The !ositi&el$ charged car%on atom is s!/ h$%ridise, .ith a !lanar structure and a %ond angle of a%out -/6o' The car%ocation is electron __________ and _____________'

An anion in .hich a car%on atom has an unshared !air of electrons and %ears a negati&e charge' There are : electrons around the car%on atom ( three %onding !airs and one lone !air)' It is electron _______ and _______________'

T$!es of reagent #ucleo!hilic reagents or nucleo!hiles or nucleus0 see+ing reagents' A nucleo!hile is an electron rich s!ecies B a molecule B a negati&e ion that can donate a !air of electrons to another slightl$ !ositi&e, MN, car%on atom or ion to form a ne. co&alent %ondH a e.is %ase' E(am!les ) Electro!hilic reagents or electro!hiles or electron0 see+ing reagents An electro!hiles is a s!ecies that can acce!t a !air of electrons to form a ne. co&alent %ondH a e.is acid' Electro!hiles are electron deficient s!ecies or !ositi&el$ charged s!ecies' E(am!les )

Classification of organic reactions' Su%stituition reaction A reaction in .hich an atom or grou! of atoms in a com!ound is re!laced %$ another atom or grou! of atoms' Addition reaction A reaction in .hich / atoms or ions react .ith a dou%le %ond forming a com!ound .ith the t.o ne. grou!s %onded to the car%ons of the original dou%le %ond' Elimination reaction A reaction in .hich a molecule such as "Cl, "1r, "I or "O" is eliminated from adJacent car%on atoms'