So|ub|||ty of a|coho|s |n water

1he small alcohols are compleLely soluble ln waLer WhaLever proporLlons you mlx Lhem ln you wlll geL
a slngle soluLlon

Powever solublllLy falls as Lhe lengLh of Lhe hydrocarbon chaln ln Lhe alcohol lncreases Cnce you geL Lo
four carbons and beyond Lhe fall ln solublllLy ls noLlceable and you may well end up wlLh Lwo layers ln
your LesL Lube

1he so|ub|||ty of the sma|| a|coho|s |n water

Conslder eLhanol as a Lyplcal small alcohol ln boLh pure waLer and pure eLhanol Lhe maln
lnLermolecular aLLracLlons are hydrogen bonds



ln order Lo mlx Lhe Lwo you would have Lo break Lhe hydrogen bonds beLween Lhe waLer molecules and
Lhe hydrogen bonds beLween Lhe eLhanol molecules lL needs energy Lo do boLh of Lhese Lhlngs

Powever when Lhe molecules are mlxed new hydrogen bonds are made beLween waLer molecules and
eLhanol molecules



1he energy released when Lhese new hydrogen bonds are made more or less compensaLes for LhaL
needed Lo break Lhe orlglnal ones

ln addlLlon Lhere ls an lncrease ln Lhe dlsorder of Lhe sysLem an lncrease ln enLropy 1haL ls anoLher
facLor ln decldlng wheLher Lhlngs happen or noL

noLe lf you havenL come across enLropy before donL worry abouL lL l menLlon lL because Lhe energy
released when Lhe new bonds are made lsnL qulLe enough Lo compensaLe for breaklng Lhe old ones
meanlng LhaL Lhe mlxlng process ls endoLhermlc lf lL werenL for Lhe lncrease ln enLropy Lhe soluLlon
wouldnL be formed


1o really undersLand Lhls you need Lo have sLudled enLropy and free energy lf you should know abouL
Lhls buL arenL happy abouL Lhe calculaLlons lnvolved you mlghL llke Lo have a look aL chapLer 11 of my
chemlsLry calculaLlons book

1he |ower so|ub|||ty of b|gger a|coho|s

lmaglne whaL happens when you have goL say 3 carbon aLoms ln each alcohol molecule



1he hydrocarbon chalns are forclng Lhelr way beLween waLer molecules and so breaklng hydrogen
bonds beLween Lhose waLer molecules

1he CP end of Lhe alcohol molecules can form new hydrogen bonds wlLh waLer molecules buL Lhe
hydrocarbon Lall doesnL form hydrogen bonds

1haL means LhaL qulLe a loL of Lhe orlglnal hydrogen bonds belng broken arenL replaced by new ones

All you geL ln place of Lhose orlglnal hydrogen bonds are van der Waals dlsperslon forces beLween Lhe
waLer and Lhe hydrocarbon Lalls 1hese aLLracLlons are much weaker 1haL means LhaL you donL geL
enough energy back Lo compensaLe for Lhe hydrogen bonds belng broken Lven allowlng for Lhe
lncrease ln dlsorder Lhe process becomes less feaslble

As Lhe lengLh of Lhe alcohol lncreases Lhls slLuaLlon [usL geLs worse and so Lhe solublllLy falls


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ucas 1est
1he Lucas 1esL for alcohols does noL examlne how many carbons are presenL ln an alcohol 1he Lucas
1esL examlnes whaL degree of alcohol prlmary secondary or LerLlary an unknown alcohol could be
1he behavlor of Lhe Lucas 8eagenL causes LerLlary alcohols Lo replace Lhelr CP wlLh a Cl almosL
lnsLanLly secondary alcohols a blL longer and prlmary alcohols vlrLually do noL chlorlnaLe aL all

1hus lf you use Lhe Lucas 1esL for an unknown alcohol and you see no resulL no change aL all ln your
soluLlon Lhen you have evldence suggesLlng lL ls a prlmary alcohol llke eLhyl alcohol (eLhanol C2P3CP)
lf you have a larger say 6carbon alcohol and Lhe alcohol ls also on elLher end carbon (Carbon 1 or 6)
Lhen lL wlll llkewlse be unreacLlve 8uL say Lhe CP ls on any lnner carbon (carbons 2 3 4 or 3) Lhen Lhe
Lucas LesL wlll be reacLlve buL slower Lhan on a LerLlary alcohol (such as 2meLhyl2propanol) ln whlch
lL wlll be almosL lnsLanLaneous

A|coho| ox|dat|on

Alcohol oxldaLlon ls an lmporLanL organlc reacLlon rlmary alcohols (8CP2CP) can be oxldlzed elLher
Lo aldehydes (8CPC) or Lo carboxyllc aclds (8CC2P) whlle Lhe oxldaLlon of secondary alcohols
(8182CPCP) normally LermlnaLes aL Lhe keLone (8182CC) sLage 1erLlary alcohols (818283CCP) are
reslsLanL Lo oxldaLlon 1

Mechanlsm of oxldaLlon of prlmary alcohols Lo carboxyllc aclds vla aldehydes and aldehyde hydraLes

1he dlrecL oxldaLlon of prlmary alcohols Lo carboxyllc aclds normally proceeds vla Lhe correspondlng
aldehyde whlch ls Lransformed vla an aldehyde hydraLe (8CP(CP)2) by reacLlon wlLh waLer before lL
can be furLher oxldlzed Lo Lhe carboxyllc acld

CfLen lL ls posslble Lo lnLerrupL Lhe oxldaLlon of a prlmary alcohol aL Lhe aldehyde level by performlng
Lhe reacLlon ln absence of waLer so LhaL no aldehyde hydraLe can be formed

Cx|dat|on to a|dehydes

CxldaLlon of alcohols Lo aldehydes and keLones

8eagenLs useful for Lhe LransformaLlon of prlmary alcohols Lo aldehydes are normally also sulLable for
Lhe oxldaLlon of secondary alcohols Lo keLones 1hese lnclude
Chromlumbased reagenLs such as Colllns reagenL (CrC3y2) uC or CC
AcLlvaLed uMSC resulLlng from reacLlon of uMSC wlLh elecLrophlles such as oxalyl chlorlde (Swern
oxldaLlon) a carbodllmlde (flLznerMoffaLL oxldaLlon) or Lhe complex SC3y (arlkhuoerlng
oxldaLlon)
PypervalenL lodlne compounds such as uessMarLln perlodlnane or 2lodoxybenzolc acld
CaLalyLlc 1A ln presence of excess of nMC (Ley oxldaLlon)
CaLalyLlc 1LMC ln presence of excess bleach (naCCl) (Anellls oxldaLlon)

Allyllc and benzyllc alcohols can be oxldlzed ln presence of oLher alcohols uslng cerLaln selecLlve
oxldanLs such as manganese dloxlde (MnC2)

Cx|dat|on to ketones
8eagenLs useful for Lhe oxldaLlon of secondary alcohols Lo keLones buL normally lnefflclenL for oxldaLlon
of prlmary alcohols Lo aldehydes lnclude chromlum Lrloxlde (CrC3) ln a mlxLure of sulfurlc acld and
aceLone (!ones oxldaLlon) and cerLaln keLones such as cyclohexanone ln Lhe presence of alumlnlum
lsopropoxlde (Cppenauer oxldaLlon) AnoLher meLhod ls oxoammonlumcaLalyzed oxldaLlon

Cx|dat|on to carboxy||c ac|ds

Cx|dat|on of pr|mary a|coho|s to carboxy||c ac|ds
1he dlrecL oxldaLlon of prlmary alcohols Lo carboxyllc aclds can be carrled ouL uslng
O oLasslum permanganaLe (kMnC4)
O !ones oxldaLlon
O uC ln uMl
O Peyns oxldaLlon
O 8uLhenlum LeLroxlde (8uC4)
O 1LMC

|o| ox|dat|on

CxldaLlve breakage of carboncarbon bond ln 12dlols

Alcohols possesslng Lwo hydroxy groups locaLed on ad[acenL carbons LhaL ls 12dlols suffer
oxldaLlve breakage aL a carboncarbon bond wlLh some oxldanLs such as sodlum perlodaLe (nalC4) or
lead LeLraaceLaLe (b(CAc)4) resulLlng ln generaLlon of Lwo carbonyl groups 1he reacLlon ls also known
as glycol cleavage
wwwwlklcom
LS1L8lllCA1lCn


1hls page looks aL esLerlflcaLlon malnly Lhe reacLlon beLween alcohols and carboxyllc aclds Lo make
esLers lL also looks brlefly aL maklng esLers from Lhe reacLlons beLween acyl chlorldes (acld chlorldes)
and alcohols and beLween acld anhydrldes and alcohols


WhaL are esLers?

LsLers are derlved from carboxyllc aclds A carboxyllc acld conLalns Lhe CCCP group and ln an esLer Lhe
hydrogen ln Lhls group ls replaced by a hydrocarbon group of some klnd We shall [usL be looklng aL
cases where lL ls replaced by an alkyl group buL lL could equally well be an aryl group (one based on a
benzene rlng)

A common esLer eLhyl eLhanoaLe

1he mosL commonly dlscussed esLer ls eLhyl eLhanoaLe ln Lhls case Lhe hydrogen ln Lhe CCCP group
has been replaced by an eLhyl group 1he formula for eLhyl eLhanoaLe ls

noLlce LhaL Lhe esLer ls named Lhe opposlLe way around from Lhe way Lhe formula ls wrlLLen 1he
eLhanoaLe blL comes from eLhanolc acld 1he eLhyl blL comes from Lhe eLhyl group on Lhe end

noLe ln my experlence sLudenLs sLarLlng organlc chemlsLry geL more confused abouL wrlLlng names
and formulae for esLers Lhan for almosL anyLhlng else parLlcularly when lL comes Lo less frequenLly meL
esLers llke Lhe ones comlng up nexL 1ake Llme and care Lo make sure you undersLand!



A few more esters

ln each case be sure LhaL you can see how Lhe names and formulae relaLe Lo each oLher

,ak|ng esters from carboxy||c ac|ds and a|coho|s

1he chemlsLry of Lhe reacLlon
LsLers are produced when carboxyllc aclds are heaLed wlLh alcohols ln Lhe presence of an acld caLalysL
1he caLalysL ls usually concenLraLed sulphurlc acld ury hydrogen chlorlde gas ls used ln some cases buL
Lhese Lend Lo lnvolve aromaLlc esLers (ones conLalnlng a benzene rlng) lf you are a uk A level sLudenL
you wonL have Lo worry abouL Lhese


1he esLerlflcaLlon reacLlon ls boLh slow and reverslble 1he equaLlon for Lhe reacLlon beLween an acld
8CCCP and an alcohol 8CP (where 8 and 8 can be Lhe same or dlfferenL) ls

So for example lf you were maklng eLhyl eLhanoaLe from eLhanolc acld and eLhanol Lhe equaLlon
would be

noLe 1he mechanlsm for Lhe esLerlflcaLlon reacLlon ls covered ln Lhe caLalysls secLlon of Lhls slLe lL ls
noL requlred for any uk A level (or equlvalenL) chemlsLry syllabus

uolng Lhe reacLlons

Cn a LesL Lube scale

Carboxyllc aclds and alcohols are ofLen warmed LogeLher ln Lhe presence of a few drops of concenLraLed
sulphurlc acld ln order Lo observe Lhe smell of Lhe esLers formed

?ou would normally use small quanLlLles of everyLhlng heaLed ln a LesL Lube sLood ln a hoL waLer baLh
for a couple of mlnuLes

8ecause Lhe reacLlons are slow and reverslble you donL geL a loL of esLer produced ln Lhls Llme 1he
smell ls ofLen masked or dlsLorLed by Lhe smell of Lhe carboxyllc acld A slmple way of deLecLlng Lhe
smell of Lhe esLer ls Lo pour Lhe mlxLure lnLo some waLer ln a small beaker

AparL from Lhe very small ones esLers are falrly lnsoluble ln waLer and Lend Lo form a Lhln layer on Lhe
surface Lxcess acld and alcohol boLh dlssolve and are Lucked safely away under Lhe esLer layer

Small esLers llke eLhyl eLhanoaLe smell llke Lyplcal organlc solvenLs (eLhyl eLhanoaLe ls a common solvenL
ln for example glues)

As Lhe esLers geL blgger Lhe smells Lend Lowards arLlflclal frulL flavourlng pear drops for example

Cn a larger scale

lf you wanL Lo make a reasonably large sample of an esLer Lhe meLhod used depends Lo some exLenL on
Lhe slze of Lhe esLer Small esLers are formed fasLer Lhan blgger ones

1o make a small esLer llke eLhyl eLhanoaLe you can genLly heaL a mlxLure of eLhanolc acld and eLhanol ln
Lhe presence of concenLraLed sulphurlc acld and dlsLll off Lhe esLer as soon as lL ls formed

1hls prevenLs Lhe reverse reacLlon happenlng lL works well because Lhe esLer has Lhe lowesL bolllng
polnL of anyLhlng presenL 1he esLer ls Lhe only Lhlng ln Lhe mlxLure whlch doesnL form hydrogen bonds
and so lL has Lhe weakesL lnLermolecular forces

noLe lollow Lhls llnk lf you arenL sure abouL hydrogen bondlng


use Lhe 8ACk buLLon on your browser Lo reLurn Lo Lhls page



Larger esLers Lend Lo form more slowly ln Lhese cases lL may be necessary Lo heaL Lhe reacLlon mlxLure
under reflux for some Llme Lo produce an equlllbrlum mlxLure 1he esLer can be separaLed from Lhe
carboxyllc acld alcohol waLer and sulphurlc acld ln Lhe mlxLure by fracLlonal dlsLlllaLlon

noLe rovldlng full deLalls for organlc preparaLlons (lncludlng all Lhe sLeps necessary ln cleanlng up Lhe
producL) ls beyond Lhe scope of Lhls slLe lf you need Lhls sorL of deLall you should be looklng aL an
organlc pracLlcal book




Cther ways of mak|ng esters

LsLers can also be made from Lhe reacLlons beLween alcohols and elLher acyl chlorldes or acld
anhydrldes


Maklng esLers from alcohols and acyl chlorldes (acld chlorldes)

lf you add an acyl chlorlde Lo an alcohol you geL a vlgorous (even vlolenL) reacLlon aL room LemperaLure
produclng an esLer and clouds of sLeamy acldlc fumes of hydrogen chlorlde

lor example lf you add Lhe llquld eLhanoyl chlorlde Lo eLhanol you geL a bursL of hydrogen chlorlde
produced LogeLher wlLh Lhe llquld esLer eLhyl eLhanoaLe


,ak|ng esters from a|coho|s and ac|d anhydr|des

1he reacLlons of acld anhydrldes are slower Lhan Lhe correspondlng reacLlons wlLh acyl chlorldes and
you usually need Lo warm Lhe mlxLure

1aklng eLhanol reacLlng wlLh eLhanolc anhydrlde as a Lyplcal reacLlon lnvolvlng an alcohol

1here ls a slow reacLlon aL room LemperaLure (or fasLer on warmlng) 1here ls no vlslble change ln Lhe
colourless llqulds buL a mlxLure of eLhyl eLhanoaLe and eLhanolc acld ls formed

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odoform was f|rst prepared by Georges Serru|as |n 1822 and |ts mo|ecu|ar formu|a was |dent|f|ed by
Iean8apt|ste umas |n 1834 t |s synthes|zed |n the ha|oform react|on by the react|on of |od|ne and
sod|um hydrox|de w|th any one of these four k|nds of organ|c compounds (|) a methy| ketone
Cn3CCk aceta|dehyde (Cn3CnC) ethano| (Cn3Cn2Cn) and certa|n secondary a|coho|s (Cn3CnkCn
where k |s an a|ky| or ary| group)



1he react|on of |od|ne and base w|th methy| ketones |s so re||ab|e that the |odoform test (the
appearance of a ye||ow prec|p|tate) |s used to probe the presence of a methy| ketone 1h|s |s a|so the
case when test|ng for secondary a|coho|s (methy| a|coho|s)

Some reagents (eg nydrogen |od|de) convert |odoform to d||odomethane A|so convers|on to carbon
d|ox|de |s poss|b|e odoform reacts w|th aqueous s||ver n|trate to produce carbon monox|de wh|ch |s
ox|d|zed by m|xture of su|fur|c ac|d and |od|ne pentaox|de When treated w|th powdered e|ementa|
s||ver the |odoform |s reduced produc|ng acety|ene Upon heat|ng |odoform decomposes to produce
d|atom|c |od|ne hydrogen |od|de gas and carbon


All subsLances are Loxlc lf Laken ln large enough quanLlLles and alcohols are no excepLlon AlLhough
eLhanol ls less Loxlc Lhan meLhanol lL ls noneLheless a polsonous subsLance and many people dle each
year from eLhanol polsonlng When someone ls sufferlng from mlld eLhanol polsonlng Lhe person ls sald
Lo be lnLoxlcaLed 8ecause anlmals ofLen consume food LhaL has fermenLed and conLalns eLhanol Lhelr
bodles have developed meLhods Lo remove or deLoxlfy eLhanol before lL can accumulaLe and polson Lhe
braln Cne way Lhe body deLoxlfles eLhanol ls Lo oxldlze lL uslng an enzyme produced by Lhe llver

lL ls where Lhe human body oxldlzes Lhe alcohol

1he llver ls responslble for Lhe ellmlnaLlon Lhrough meLabollsm of 93 of lngesLed alcohol from Lhe
body 1he body uses several dlfferenL meLabollc paLhways ln lLs oxldaLlon of alcohol Lo aceLaldehyde
Lo aceLlc acld Lo carbon dloxlde and waLer

alcohol aceLaldehyde aceLlc acld carbon dloxlde and waLer
CP3CP2CP CP3CPC CP3CC2P CC2 P2C

hLLp//wwwlnLoxcom/physlologyasp

Many blologlcal processes lnvolve oxldaLlon of alcohols Lo carbonyl compounds or Lhe reverse process
reducLlon of carbonyl compounds Lo alcohols LLhanol for example ls meLabollzed ln Lhe llver Lo
aceLaldehyde Such processes are caLalyzed by enzymes Lhe enzyme LhaL caLalyzes Lhe oxldaLlon of
eLhanol ls called alcohol dehydrogenase


8easons why meLhanol ls Loxlc yeL eLhanol ls used for alcohollc beverages

LLhanol (whlch ls known Lo lower lnhlblLlons and cause a llghLheadedness) ls oxldlzed blochemlcally Lo
aceLaldehyde


1he physlologlcal slde effecLs of consumlng eLhanol are due Lo Lhe bulldup of aceLaldehyde (causes
nausea dlzzlness sweaLlng headaches lower blood pressure)

Some people have a nonfuncLlonlng aldehydedehydrogenase enzyme 1hese people experlence Lhe
slde effecLs of aceLaldehyde wlLh low eLhanol consumpLlon


MeLhanol also geLs oxldlzed by Lhe same enzyme
buL Lhls oxldaLlon creaLes formaldehyde nC1 aceLaldehyde

lormaldehyde ls Loxlc Lo Lhe body because lL dlsrupLs oLher essenLlal enzyme from worklng properly
eLhanol ls consumed 23 Llmes fasLer Lhan meLhanol by Lhls enzyme