VARIOUSENTHALPYCHANGE

DEFINITIONS
Thispageexplainswhatanenthalpychangeis,andthengives
adefinitionandbriefcommentforthreeofthevariouskindsof
enthalpychangethatyouwillcomeacross.Youwillfindsome
moredefinitionsonotherpagesinthissection.
Itisessentialthatyoulearnthedefinitions.Youaren'tgoingto
beabletodoanycalculationssuccessfullyifyoudon'tknow
exactlywhatallthetermsmean.

Enthalpychanges
Enthalpychangeisthenamegiventotheamountofheat
evolvedorabsorbedinareactioncarriedoutatconstant
pressure.ItisgiventhesymbolH,readas"deltaH".
Note:Theterm"enthalpychange"onlyappliestoreactions
doneatconstantpressure.Thatisactuallyhowmostlab
reactionsaredoneintubesorflasks(orwhatever)opento
theatmosphere,sothatthepressureisconstantat
atmosphericpressure.
Thephrase"atconstantpressure"isanessentialpartofthe
definitionbut,apartfromthat,youareunlikelytoneedto
worryaboutitifyouaredoingaUKbasedexamatthe
equivalentofAlevel.

Standardenthalpychanges
Standardenthalpychangesrefertoreactionsdoneunder
standardconditions,andwitheverythingpresentintheir
standardstates.Standardstatesaresometimesreferredtoas
"referencestates".
Standardconditions
Standardconditionsare:
298K(25C)
apressureof1bar(100kPa).
wheresolutionsareinvolved,aconcentrationof1moldm
3

Warning!Standardpressurewasoriginallydefinedas1
atmosphere(101.325kPa),andyouwillstillfindthatinolder
books(includingmycalculationsbook).Atthetimeofwriting
(August2010)therewasatleastoneUKbasedsyllabusthat
wasstilltalkingintermsof"1atmosphere".Itisessentialto
checkyoursyllabustofindoutexactlywhatyouneedto
learn.

Standardstates
Forastandardenthalpychangeeverythinghastobepresentin
itsstandardstate.Thatisthephysicalandchemicalstatethat
youwouldexpecttofinditinunderstandardconditions.
Thatmeansthatthestandardstateforwater,forexample,is
liquidwater,H2O(l)notsteamorwatervapourorice.
Oxygen'sstandardstateisthegas,O2(g)notliquidoxygenor
oxygenatoms.
Forelementswhichhaveallotropes(twodifferentformsofthe
elementinthesamephysicalstate),thestandardstateisthe
mostenergeticallystableoftheallotropes.
Forexample,carbonexistsinthesolidstateasbothdiamond
andgraphite.Graphiteisenergeticallyslightlymorestablethan
diamond,andsographiteistakenasthestandardstateof
carbon.
Similarly,understandardconditions,oxygencanexistasO2
(simplycalledoxygen)orasO3(calledozonebutitisjustan
allotropeofoxygen).TheO2formisfarmoreenergetically
stablethanO3,sothestandardstateforoxygenisthecommon
O2(g).

Thesymbolforstandardenthalpychanges
ThesymbolforastandardenthalpychangeisH,readas
"deltaHstandard"or,perhapsmorecommonly,as"deltaH
nought".
Note:Technically,the"o"inthesymbolshouldhavea
horizontallinethroughit,extendingoutateachside.Thisis
suchabothertoproduceconvincinglywithouttheriskof
differentcomputersproducingunreliableresults,thatIshall
usethecommonpracticeofsimplifyingitto"o".

Standardenthalpychangeofreaction,Hr

Rememberthatanenthalpychangeistheheatevolvedor
absorbedwhenareactiontakesplaceatconstantpressure.
Thestandardenthalpychangeofareactionisthe
enthalpychangewhichoccurswhenequationquantities
ofmaterialsreactunderstandardconditions,andwith
everythinginitsstandardstate.
Thatneedsexploringabit.
Hereisasimplereactionbetweenhydrogenandoxygento
makewater:

First,noticethatthesymbolforastandardenthalpy
changeofreactionisHr.Forenthalpychangesof
reaction,the"r"(forreaction)isoftenmissedoffitisjust
assumed.
The"kJmol1"(kilojoulespermole)doesn'trefertoany
particularsubstanceintheequation.Insteaditreferstothe
quantitiesofallthesubstancesgivenintheequation.In
thiscase,572kJofheatisevolvedwhen2molesof
hydrogengasreactwith1moleofoxygengastoform2
molesofliquidwater.
Noticethateverythingisinitsstandardstate.Inparticular,
thewaterhastobeformedasaliquid.
Andthereisahiddenproblem!Thefigurequotedisforthe
reactionunderstandardconditions,buthydrogenand
oxygendon'treactunderstandardconditions.
Wheneverastandardenthalpychangeisquoted,standard
conditionsareassumed.Ifthereactionhastobedone
underdifferentconditions,adifferententhalpychange
wouldberecorded.Thathastobecalculatedbacktowhat
itwouldbeunderstandardconditions.Fortunately,you
don'thavetoknowhowtodothatatthislevel.

Someimportanttypesofenthalpychange
Standardenthalpychangeofformation,Hf
Thestandardenthalpychangeofformationofa
compoundistheenthalpychangewhichoccurswhenone
moleofthecompoundisformedfromitselementsunder
standardconditions,andwitheverythinginitsstandard
state.

Note:Whenyouaretryingtolearnthesedefinitions,youcan
makelifeeasierforyourselfbypickingoutthekeybit,and

addingtheotherbitsonafterwards.Thekeybitaboutthis
definitionisthatyouareforming1moleofacompoundfrom
itselements.Allthestuffaboutenthalpychangeand
standardconditionsandstandardstatesiscommontomost
ofthesedefinitions.

Theequationshowingthestandardenthalpychangeof
formationforwateris:

Whenyouarewritingoneoftheseequationsforenthalpy
changeofformation,youmustendupwith1moleofthe
compound.Ifthatneedsyoutowritefractionsonthelefthand
sideoftheequation,thatisOK.(Infact,itisnotjustOK,itis
essential,becauseotherwiseyouwillendupwithmorethan1
moleofcompound,orelsetheequationwon'tbalance!)
Theequationshowsthat286kJofheatenergyisgivenout
when1moleofliquidwaterisformedfromitselementsunder
standardconditions.

Standardenthalpychangesofformationcanbewrittenforany
compound,evenifyoucan'tmakeitdirectlyfromtheelements.
Forexample,thestandardenthalpychangeofformationfor
liquidbenzeneis+49kJmol1.Theequationis:

Ifcarbonwon'treactwithhydrogentomakebenzene,whatis
thepointofthis,andhowdoesanybodyknowwhattheenthalpy
changeis?
Whatthefigureof+49showsistherelativepositionsofbenzene
anditselementsonanenergydiagram:

Howdoweknowthisifthereactiondoesn'thappen?Itis
actuallyverysimpletocalculateitfromothervalueswhichwe
canmeasureforexample,fromenthalpychangesof
combustion(comingupnext).Wewillcomebacktothisagain
whenwelookatcalculationsonanotherpage.
Knowingtheenthalpychangesofformationofcompounds
enablesyoutocalculatetheenthalpychangesinawholehostof
reactionsand,again,wewillexplorethatinabitmoredetailon
anotherpage.

Andonefinalcommentaboutenthalpychangesofformation:
Thestandardenthalpychangeofformationofanelementinits
standardstateiszero.That'sanimportantfact.Thereasonis
obvious...
Forexample,ifyou"make"onemoleofhydrogengasstarting
fromonemoleofhydrogengasyouaren'tchangingitinany
way,soyouwouldn'texpectanyenthalpychange.Thatis
equallytrueofanyotherelement.Theenthalpychangeof
formationofanyelementhastobezerobecauseoftheway
enthalpychangeofformationisdefined.
Note:Somesourcessaythattheenthalpychangeof
formationofelementsistakenaszerobyconvention.Thatis
simplynonsense!Thestandardenthalpychangeofformation
ofelementsiszerobecauseofthewaytheenthalpychange
isdefined.
Ifthisconfusesyou,ignoreit!

Standardenthalpychangeofcombustion,Hc
Thestandardenthalpychangeofcombustionofa
compoundistheenthalpychangewhichoccurswhenone
moleofthecompoundisburnedcompletelyinoxygen
understandardconditions,andwitheverythinginits
standardstate.
Theenthalpychangeofcombustionwillalwayshaveanegative
value,ofcourse,becauseburningalwaysreleasesheat.
Twoexamples:

Notice:

Enthalpyofcombustionequationswilloftencontain
fractions,becauseyoumuststartwithonly1moleof
whateveryouareburning.
Ifyouaretalkingaboutstandardenthalpychangesof
combustion,everythingmustbeinitsstandardstate.One
importantresultofthisisthatanywateryouwriteamongst
theproductsmustbethereasliquidwater.
Similarly,ifyouareburningsomethinglikeethanol,which
isaliquidunderstandardconditions,youmustshowitasa
liquidinanyequationyouuse.
Noticealsothattheequationandamountofheatevolved
inthehydrogencaseisexactlythesameasyouhave
alreadycomeacrossfurtherupthepage.Atthattime,it
wasillustratingtheenthalpyofformationofwater.Thatcan
happeninsomesimplecases.Talkingabouttheenthalpy
changeofformationofwaterisexactlythesameastalking
abouttheenthalpychangeofcombustionofhydrogen.

Questionstotestyourunderstanding
Ifthisisthefirstsetofquestionsyouhavedone,pleasereadthe
introductorypagebeforeyoustart.YouwillneedtousetheBACKBUTTON
onyourbrowsertocomebackhereafterwards.
questionsonenthalpychangedefinitions
answers

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JimClark2010(modifiedMay2013)