Peter Williams

ChemistryUnit4
pH(definition)
(pH=)log[H+]
OR
(pH=)log[H3O+]
CalculatingpHfrompKa
Ka=104.28(convertpKaintoKa)
Ka=[H+]2/0.050(molesofcompoundintoequation)
[H+]=(0.05x104.28)=1.61988x103(moldm3)(rearrangement)
pH=log1.61988x103=2.7905=2.8(calculatepHfrom[H+])
Calculation(strongacid)
(pH=log0.0100)=2(.00)
Calculation(weakacid)
[H+]=Ka[CH3COOH]/[CH3COO]
OR
[H+]2=Ka[CH3COOH]
[H+]=1.75x107
pH=3.38/3.4
Weakaciddefinition
(Weak)dissociates/ionizestoasmallextent
(Acid)protondonor
Assumptions(weakacid)
assumesthatdegreeofionisationoftheacidisverysmall/negligible
[CH3COOH]eqm=[CH3COOH]initial
allofthehydrogenionscomefromtheacid/ignorehydrogenionsfromthewater
Ka(expression+calculation)
(Ka=)[H+][A]/[HA](notamarkunlessstates,butproducts/reactants)
1.3x105=[H+][5x102]/[7.5x102](valuesaddedintoexpression)
[H+]=1.95x105(rearranged+answer)
Kc(expression)
(Kc=)[X][B]/[Y][A](notamarkunlessstates,butproducts/reactants)
Explainwhynounits
Unitscancel
OR
samenumberofmoles/samenumberofmoleculesoneachside
1

Peter Williams

Kw(expression)
Kw=[H+]x[OH]
OR
Kw=[H3O+]x[OH]

Reject:Inclusionof[H2O]

Kw(calculatingpHfromconc.ofNaOH(strongalkali))
[H+]=Kw/[OH]=1.00x1014/0.00750=1.33x1012(moldm3)
pH=log10[H+]=11.875=11.88/11.9
Sodiumhydroxide+propanoicacid
CH3CH2COOH+NaOHCH3CH2COO()Na(+)+H2O
Ethanoylchloride+ethanol=ethylethanoate(ester)
CH3COCl+CH3CH2OHCH3COOCH2CH3+HCl(reversible)
Ethylethanoate(ester)+NaOH(alkali)
(CH3COOCH2CH3+NaOH)CH3COONa+CH3CH2OH/C2H5OH
(Reactionwithsodiumhydroxideis)notanequilibrium/notreversible/goesto
completion
DilutionFactor(weakacidvsstrongacid)
(Dilution/additionofwater)shiftstheequilibrium
CH3COOHCH3COO+H+/
CH3COOH+H2OCH3COO+H3O+
totheright
OR
degreeofdissociationincreases
sothe[H+]isgreaterthanexpected
Titrationcalculation(findingconcentrationofX/(Methanoicacid)fromneutralization)
MolesNaOH/X=(0.00750x20.0)/1000=1.50x104(mol)(molesofNaOH)
(SinceHCOOH:NaOHratiois1:1)
[HCOOH(aq)]=1.50x104/0.0250(conc.=moles/vol.)
TitrationpHchanges(drawingongraph)

Peter Williams

Whyph=pka/[H+]=Kaatequivalencepoint
pH=pKa/[H+]=Ka(whenacidishalfneutralized)
workoutKatofindpHatequivalencepoint
pHafteradditionofexcessNaOHtoweakacid
MolesofexcessNaOH=10/1000x0.50=5x103(convert10cm3todm3andinto
moles(volxconc.))
So[NaOH/OH]=5x103x1000/50=0.10moldm3
EITHER:
Kwroute:
[H+]x0.1=1x1014
SopH=log1x1014/0.1=13
OR
pOHroute:
pOH=1
SopH=(141)=13
Buffersolution(definition)
MaintainsanalmostconstantpH/resistschange(s)inpH
forsmalladditionsofacidoralkali/
(fromtext)namedbuffersolutioninfruit(acid):Citricacid
Buffersolution(explanation)
(buffercontains)largeconcentrationsof[HA]and[A]
(Additionofalkali/base):description/equationstoshowthatH+reactswithOH(to
formH2O)andmoreaciddissociates(toreplaceH+)
(Additionofacid):AreactingwithH+inanycontextdescribedinwords(e.g.by
referencetoweakacidequilibrium)
theratioof[A][HA]hardlychanges/theratioof[HA][A]hardlychanges
Buffersolution(explanationfromtext)(ethanoicacid+NaOH)
Bufferhaslargeamount/excess/reservoirofCH3COOH(andCH3COO)
OHionsaddedreactwithCH3COOH
Ratio/valuesof[CH3COOH]to[CH3COO]remains(almost)unchanged
IGNOREconcentrationofhydrogenionsremainsconstant
ALLOWanswersintermsofHAandA
Howtocreatebuffersolution
addSodiumethanoate/CH3COONaORPotassiumethanoate/CH3COOKtoethanoic
acid
Buffersolution(calculation)(methanoicacid+sodiummethanoatefromtext,pH4.9)
(pH=4.9)so[H+]=(1.2589254x105)=1.259x105([H+]=10pH)
Ka/[H+]=[HCOO]/[HCOOH]=1.6x104/1.259x105(rearrangement)
12.7(:1)(ratiotextaskedforratio)

Peter Williams

Makingabuffersolution(sodiumethanoate+ethanoicacid)
Scenario:

[base]=Ka[acid]/[H+](expression)
[H+]=(10pH4.70)=1.995x105(calculate[H+]frompHtoputintoKaequation)
[base]=1.7x105x1/(1.995x105)=0.852
molesbase=0.852x0.5=0.426(mol)
massbase=0.426x82=34.9g
Indicatorcolourchanges(bathscenariofromtext)
(pH)range(ofindicator)3.8to5.4
Bubblebathis(initiallyyellowsince)pHlessthan3.8/is3.4
Addingofwater/dilution(ofacid)causespHtorise/means[H+]decreases
HencepHrisesto5.4soblue/changescolour
BoilingTemperatures(ethanal<ethanol<ethanoicacid)
hydrogenbondsinbothethanoicacidandethanolORnohydrogenbondsinethanal
hydrogenbondsarestrongerthanvanderWaals
ethanoicacidhasmoreelectrons/ethanoicacidhasthemostelectrons
Testforcarbonylgroup
(Test):2,4dinitrophenylhydrazine/Bradysreagent
(Result):yellowprecipitate/orangeprecipitate
Testforcarbonylgroup(aldehyde)
(Warmwith)Fehlings(solution)/Benedicts(solution)
redprecipitate/brownprecipitate/brickredprecipitate
OR
(Warmwith)Tollens(reagent)
silver(mirror)/black(solid)
PCl5
reactswithalcohol(OH)/acidgroups(COOH)
onemoleofadi/tricarboxylicacidreactswith2/3molesofPCl5
sodiumcarbonate
reactswithcarboxylicacid(COOH)
CH3COOH+Na2CO3>CH3COONa+NaHCO3

effervescenceseen

Iodineinsodiumhydroxide
Iodoformproduced
musthaveCH3CH(OH)
Hydroxideions(wateretc.)+haloalkane(drawingmechanismfromrateequation)(3)
Choiceofbromoalkanemustbeconsistentwithrateequationin(a)(iii)
If[OH]isnotinrateequation,secondary/tertiarybromoalkane
If[OH]isinrateequation,primary/secondarybromoalkane
EitherSN1orSN2mechanismcanscore2marksregardlessofchoiceofbromoalkane
4

Peter Williams

CurlyarrowfromCBrbondtoBr(makingBr)
CurlyarrowfromanywhereonOH/HOtoC+incorrectintermediate(making
alcohol)

Ratetransitionstep(haloalkane+hydroxideion)(2)

ALLOWstructurewithoutwedgedbondsDottedbondsmustbeshownandOHandBr
mustbeonoppositesideswithaCCorCHbondbetweenthem
Chargemarkcanbeawardedforanearmisswithasingleerrorinthestructure(e.g.one
hydrogenatommissing)
Whyprimaryandtertiaryhaloalkanesarehydrolysedviadifferentmechanisms
(Primaryandtertiary)carbocationintermediateshavedifferentstabilities
as(inductiveeffectsof)alkylgroupsstabilisetertiarycarbocation
Transesterification

longcarbonchains
watermustnotbepresent:Topreventhydrolysis

Peter Williams

Effectsonesterificationif(weak)acidconcentrationincreased
Noeffecton(positionof)equilibrium
Rate(ofattainmentofequilibrium)isfaster/equilibriumreachedsooner
Bondsbroken/madeinesterification
BondsBroken:COandOH
BondsMade:COandOH
Whyenthalpychangeisnot0inesterification
(COandOH)bondenthalpiesdifferin:differentenvironments/differentmolecules
/differentcompounds
MechanismofHCN+Ethanal(3marks)

NecessityforKCN(AND)HCN(weakacid)inreaction
WithHCNalone,insufficientCN
OR
KCNprovides(sufficient)CN
Whyproductshowsnoopticalactivity
Racemicmixture/equalamountsofthetwoenantiomers/racemateformed
CHO/aldehydegroupis(trigonal)planar
Cyanide(ion)/CN/nucleophileattacks(equally)fromaboveorbelow/eitherside(of
themolecule)
Chiral(explanation)
Achiralmoleculeisnonsuperimposableonitsmirrorimage/3Dmoleculewithnoplane
ofsymmetry
(e.g)2hydroxypropanoicacidhasacarbonatomwhichisasymmetric/hasfour
differentgroupsattached

Explanationfornonopticallyactivereactionmixture
attackfrombothsides
OR
6

Peter Williams

attackfromaboveandbelow
(gives)racemicmixture/(gives)equalamountsofeachisomer
Opticalactivityinproductandwhatittellsusaboutards
Aracemicmixtureisnotformed
OR
Moreofoneenantiomer/(optical)isomerisformed
(Someofthe)reactionisSN2
Nucleophile/OHonlyattacksfromonesideofthemolecule/fromtheoppositesideto
leavinggroup
Ratecalculation(3)
i)
rate=k[CH3CH2Br][OH]
k=(1.54x106)(0.1x0.15)(rearrangement)
(=1.0267x104)(answer)
dm3mol1s1(units)
ii)(differentconc.usingpreviousvaluefork)
If1.03x104usedthen4.12x108=4.1x108(moldm3s1)
Arrheniusactivationenergygraph+calculation(tableintext)

Appropriatescale:Plottedpointsmustcoveratleasthalfof
thegraphpaperoneachaxis
Pointsplottedcorrectlyandstraightlinedrawnthroughall
points
Gradient=10230500
Example:Ea=10230x8.31
allowTEfromincorrectgradientEa=(+)85.0
kJ(mol1)/(+)85000J(mol1)3sf

*Equationusedfrompaper:

PropanoneandIodine(whypropanoneandhydrogenarein
excess)
sothatthe[H+]and[propanone]donotaffecttherate
otherwiseacurve(graph)isobtained
Purposeofthiosulfateion
(Sodiumthiosulfate)(rapidly)reactswith/reducestheiodine(asitisformed)
Sopreventsthestarchiodinecolourappearinguntilafixedamountofreactionhas
occurred
7

Peter Williams

ALLOW(forsecondmark):Sopreventsthestarchiodinecolourappearinguntil
allthethiosulfatehasreacted
Experimenttoshoworderis1(wrtpropanone)
doubletheconcentrationof(propanone)
(observe/if):slope/gradientoflinedoubles
Calculateinitialrateofreactionorformation
(Calculate)gradient(oftangent)
Att=0/atthestart/atthebeginning/whenreactionisatitsfastest/attheorigin
Reactantstepsis2
I2notinvolvedinratedeterminingstep
(so)theremustbeanotherstepwhereI2isinvolved/sotheremustbeafaststepwhere
I2isinvolved
I2notinvolveduntilaftertheratedeterminingstep
Reactantstepsis(morethanonestep)
Thenumber(s)(ofparticles)intherateequation/ratedeterminingstepdonotmatch
thoseintheequationforthereaction
Quenching(sodiumhydrogencarbonate)equation
HCO3+H+H2O+CO2
OR
HCO3+H+H2CO3
Quenching(sodiumhydrogencarbonate,NaHCO3)explanation
Quenchesreaction/stopsreaction/slowsreaction/freezesreaction
byneutralizingtheacid/removingtheacid/neutralizingthecatalyst/removingthe
catalyst
OR
Sothattheaciddoesnotreactwiththethiosulfate
ReactionBetweenpropanoneandIodine
CH3COCH3+3I2+4NaOHCHI3+CH3COONa+3NaI+3H2O(3)
Usinganalternativemethodtosamplingmixtureduringtitration
Colorimetry/Useacolorimeter
Measuretransmittance/absorbance(atvarioustimes)
(Useacalibrationcurveto)converttransmittance/absorbanceandconcentration
OR
transmittance/absorbanceproportionaltoconcentration
Kpexpression

Products/reactantsasusual
Calculatingmolarfraction(XA)

Peter Williams

Calculatingpartialpressures

Totalpressure
Totalpressureisthesumofpartialpressuresifwehave1partialpressurewecanwork
outother2iftheyareequimolar(commonexamcomplication)
EffectofpressureonKp
Noeffect(asKpdependentonlyontemperature)
Whylittleeffectofpressureoncatalystsduringreaction
Reactiontakesplaceonsurfaceofthecatalyst
(catalyst)surfaceissaturatedwithreactantmolecules/reactants(atthepressureofthe
reaction)
OR
...dependsontheavailabilityofactivesitesoncatalystsurface(2)
Heterogenousexplanationandwhycatalystspeedsupreaction
Thecatalystisinadifferentstate/phasetothereactants
Itprovidesanalternative(reaction)route/mechanism/gasesadsorbedoncatalyst
surface
Ofloweractivationenergy/weakensbondsinreactants
GreaterproportionofmoleculeshaveEEa
Industrialequilibrium
productsremoved
OR
notaclosedsystem
OR
balancebetweenrateandyield
Maximisingatomeconomy(equilibrium)
Removeproductsasmade
Benefitsofusingacatalysttoenvironment
Reactioncanoccuratlowertemperature/hasloweractivationenergy/requiresless
energy
(so)lessfuelneeded/feweremissions(fromfuels)/fewerrawmaterialsneeded/less
naturalresourcesused
Predictingentropychangesigns(positive)
Gasformed(fromsolid)
OR
Liquidformed(fromsolid)
OR
Gasandliquidformed(fromsolid)
Moremolesofproductthanreactants/moremolesformed
OR
4mol(ofreactants)to7mol(ofproducts)
9

Peter Williams

Greateryieldaslower(endothermic)temperature(regardingentropy)
(Reactionisexothermic)sothevalueofSsurroundingsbecomesmorepositive/larger
(at100Cthan250)
ThereforeStotalbecomesmorepositive(at100Cthan250)
oppositeforexothermicreactions!
Spontaneous(explanation,thermodynamics)
Stotalispositive/Stotal0
Entropychangeofthesystem
Ssys=(PRODUCTS){(REACTANTS)}
=549(Jmol1K1)
Entropychangeofthesystem(explanationforpositive)
Yes,asreactionproduces2molecules/molesfromone/moremolecules/moles
(and)allproductsaregases
OR
Yes,(asthereactionisendothermic)Ssurroundingsisnegative
Sincethereactiontakesplace/goes(spontaneously)Stotalispositiveandtherefore
Ssystemispositive
Entropychangeofthesurroundings
i)
Ssurr=H/T
=(1648x103)298(.15)(Jmol1K1)
=(+)5530(Jmol1K1)
ii)Whyreactionisfeasible(regardingpreviousanswer)
SoStotalispositive(soreactionisfeasible)
Entropychangeforreaction(total)
i)
Stotal=(549.4)+(+5530)=+4980.6/+4981Jmol1K1
(1)forvalue
(1)forcorrectsignandunits(mustincludeunitsifstatesinquestion)
ii)
Positivesofeasible/spontaneous/willoccur/reactiongoes/reacts(at298K)
ChangeintemperatureandeffectonKp(haberprocess)
AthighertemperatureSsurrislesspositive/decrease/morenegative
makingStotalmorenegative/lesspositive/decreases
(so)Kpdecreases
soequilibriumpositionfurtherleft/inendothermicdirection/inreversedirection
OR
loweryieldofammonia/reactionislessfeasible
Advantageofusingahightemperatureinequilibriaconcepts
Rate(ofreachingequilibrium)ishigher/faster
RelationshipbetweenStotalandK
Stotal=RlnK
ALLOW:StotalisproportionaltolnK
10

Peter Williams

Entropychangeforreaction(total)usingRlnK
Stotal=(8.31ln8.54)=(+)17.8(Jmol1K1)
R=8.31K=(8.54)
Calculatingwhattemperatureequilibriumisreached
17.8=225+((206.1x1000))/T(onemarkforStotal=Ssys+(Ssurr)
T=(206.1x1000)/207.2=995/990(K)(onemarkforrearrangement+answer)
Calculatingminimumtemperatureneededforreactiontobefeasible
Stotal=0
T=HSsurroundings
OR
T=()71900()143(1)
=502.8(K)
Effectoftemperatureonequilibriumconstant(regardstoentropy)
SsurroundingsorH/TbecomeslessnegativemakingStotalmorepositive(asT
increases)
BecauseStotalincreasesequilibriumconstantincreases
Effectoftemperatureonequilibriumconstant(regardstoentropy)enthalpy=0
H/T=0
(so)Stotaldoesnotchange
(AsStotal=RlnK)Kdoesnotalter
Spontaneous(explanation,thermodynamics)extended(3)
(Ssystemisnegative):aslossofdisorderasgassolid
OR
asdecreaseinentropyasgassolid
(Ssurrispositive):(heat)energyreleased(increaseskineticenergyandhence
movementofthesurroundingmolecules)
StotalispositivebecauseSsurris(numerically)greaterthanSsys
IRspectrumexample(IdentifyXandY)(Functionalgroup)

peakat3400(cm1)
XhasanOH(group)ORXisanalcohol
(Fromthechemicalinformation)
Xisprimaryorsecondary(alcohol)
Yisanaldehydeoraketone
11

Peter Williams

IRspectrumopticalisomers
cannotbedistinguishedbecausebothisomershaveidenticalgroups(ref.groups)
Overlappingpeaks
QisduetoCO(fromtext)
The(CO)aldehyderangeis17401720cm1and(CO)carboxylicacidrangeis
17251700cm1
Sothepeaks/absorptionscannotbeusedtodistinguishthesetwocompoundsbecause
theyoverlap
OR
The(broad)absorptionQcoversboththealdehydeandthecarboxylicacidranges
NMRHydrogen1nuclei
Radiowaves/radiofrequencyinteractwith1Hnuclei
NMRHydrogeninteraction
Protons/nuclei/theyhaveapropertycalledspin/haveamagneticmoment/havea
magneticfield
whichflips/changes
alignagainsttheexternalmagneticfield(whenradiationisabsorbed)
NMRspectrum(IdentifyXandY)(Structure)

XisCH3CH(OH)CH2CH3
YisCH3COCH2CH3
12

Peter Williams

THIRD:
hydrogenORHinfive(different)environments
OR
(somustbebutan1olorbutan2oland)not2methylpropan1olwhichhasfour
peaks/hydrogenenvironments
OR
NOTE:Candidatesmayannotateastructuralordisplayedformulatoshowthattherearefive
environments.(Forthismark,nodetailsofsplittingorchemicalshiftsareneeded.):

splittingpattern(2,6,1,5,3)consistentwithbutan2ol
FOURTH:
splittingpattern(2,6,1,5,3)consistentwithbutan2ol
OR
assignpeakscorrectlyquotingchemicalshiftsfromthespectrum
FIFTH:
(NMRspectrumofY)
hydrogenORHinthree(different)environments
NOTE:Candidatesmayannotateastructuralordisplayedformulatoshowthattherearethree
environments.(Forthismark,nodetailsofsplittingorchemicalshiftsareneeded.)

SIXTH:
splittingpattern(1,4,3)isconsistentwithbutanone
OR
assignpeakscorrectlyquotingchemicalshiftsfromthespectrum
13

Peter Williams

Determiningstructuralformulaanothermarkscheme

FourdifferentH/hydrogen/protonenvironments
Applicationofthe(n+1)ruletopeakJ(whichisa
quartet/splitsintofour)

OR

Applicationofthe(n+1)rulepeakM(whichisadoublet/splitsintotwo)
AnymentiontoexplainnosplittingforpeakLasthereisnoHisattachedtotheadjacent
carbon
PeakL(CH3)nexttoC=O
PeakM(CH3)nexttoCH
PeakKOH
PeakJ(CH)nexttoCH3
Advantageofameasuringcylinder/pipette
Measuringcylinderquicker/Measuringcylindercanmeasureavarietyofvolumes
Pipettemoreaccurate/(graduated)pipettemoreprecise/pipettecanbeusedtoextract
samplesfromareactionmixture(fortitration)
Washingusingsodiumbicarbonate
Tapfunnel/separatingfunnel(apparatususedforwashing)
Toneutralize/remove/reactwith(excess)acid(sodiumbicarbonate)
Suitabledryingagentafterwashing
Add(anhydrous)calciumchloride/sodiumsulfate/magnesiumsulfate/
Allowsilicagel
(Re)distillationapparatus
Roundbottomedorpearshapedflask+stillheadwithstopperorthermometer+heat
source
Thismarkcannotbegivenifapparatusiscompletelysealed/largegapsbetween
components
Downwardsslopingcondenser(withcorrectwaterflow)+collectionvessel
Thermometerincorrectpositionwithbulboppositecondenseropening

14

Peter Williams

Maximisingyieldwhenreacting(aldehyde)
(Steam)distiloffmelonal(asitforms)
Allowaddalimitedamountofoxidizingagent/excessalcohol/excess
Topreventfurtheroxidation/Topreventcarboxylicacidforming
Gaschromatographyvsliquidchromatography
Substancestobeseparatedhavedifferent(forcesof)attractiontooneorbothofthe
mobileandstationaryphases
GC:mobilephasea(inert/unreactive)gas
GC:Stationaryphasealiquid(onan(inert)solid)/asolid
HPLC:stationaryphaseasolid/silica
HPLC:mobilephasealiquid
WhynitrogenusedduringGCnotoxygen
Nitrogeninert/unreactive/lessreactive(thanoxygen)
Oxygenmightreactwithchemicalsgoingthroughcolumn/samplemightoxidise
Whatpropertiesdeterminespeedthroughgascolumns
Solubility(inliquid/stationaryphase)
OR
Interactionwithliquid/stationaryphase
OR
Interactionbetweenmobileandstationaryphase
OR
Attractionforliquid/stationaryphase
OR
Strengthof(named)intermolecularforces
OR
Adsorptiononliquid/stationaryphase
15

Peter Williams

OR
Absorptiononliquid/stationaryphase
MinimizinghazardswhendealingwithNaOH/Alcohols(anyOH)
Hazardmethanol/alcoholisflammable
Precautionuseelectricalheatingsource/waterbath/avoidnakedflames
Hazardmethanol/alcoholistoxic
PrecautionUseinwellventilatedarea/fumecupboard
HazardNaOH/reactionmixtureiscorrosive/burns(theskin)/damagestheeyes
Precautionweargloves/goggles
Minimizinghazardswhendealingwithacylchlorides(any)
Toxic(steamy/misty)fumes/toxicHCl(gas)/corrosiveHCl(gas)/toxicpropanoyl
chloride/lachrymatorypropanoylchloride
Souseinafumecupboard
Catalysingesterreactions
ReagentPropanoylchloride/CH3CH2COCl
Cl/chloride(ion)isabetterleavinggroup
(because)CClbondisweaker(thanC0)
Drawapolymer/sectionofpolymerquestions

EsterlinkincludingC=O
Restofpolymerwithoxygensatendcorrect

AllHatomsmustbeshown.
Reactionthatwouldoccurifmixedwithacidspillonalabcoattypequestion
Hydrolysis
OR
Splits/breaksesterlink
OR
polymerbreaksdowntomonomers

Whyaremanypolymerswithesterlinkagesbiodegradable
Ester(link/bond)inXcanbehydrolysed/brokendown(byenzymes)
OR
Ester(link/bond)inXcanbebrokendown
Enthalpyofhydration(definition)
Enthalpychangewhen1molofgaseousions
16

Peter Williams

Isdissolved/hydrated/solvatedsuchthatfurtherdilutioncausesnofurtherheatchange
Predictingsolubilityusingenthalpyvalues(hydration)
Referencetoenthalpyofhydration(maybeinequationHsolution=LE+Hhydration)
Solubilitydependsonrelativesizeoflatticeenergyandenthalpyofhydration
SolubilitymorelikelyifHsolutionisnegative
OR
(IfHsolutionispositive,)may/willdissolveifStotalispositive
SolubilitymorelikelyifHsolutionisnegative
Explanationastowhythingsdissolveinwater(endothermicreactionintext)
(Thereactionisendothermicso)
Entropy(change)ofsurroundingsdecreases
OR
Ssurisnegative
OR
H/Tisnegative
Butentropy(change)ofsystemincreases(asthereisanincreaseindisorder)
OR
Ssysispositive
Increaseinentropyofsystemoutweighs/greaterthandecreaseinentropyof
surroundings/valueforentropychangeofsystemisgreaterthanentropychangeof
surroundings
Totalentropy(change)ispositive
Predictingsolubilityusingenthalpyvalues(ionisation)
Thirdionizationenergyhigh(er)forMg/Mg=7733kJmol1,(thirdionizationenergyfor
Co=3232kJmol1)
(ThirdionizationenergyforMgishigh)becausetheelectronisbeingremovedfroman
innershell/fullshell/2plevel/2porbital
OR
NotcompensatedbyhigherlatticeenergyforMg3+(andsoHformationofMgCl3would
behighlyendothermic)
Enthalpychangeofsolution
Scenario:

Nochange/nomeasurablechangeintemperature
Thermometernotsensitive/preciseenough/precisionofthermometeris+or0.5
oC/graduationstoolarge
Amountofenergytakeninissmall/Hsolissmall/massofsodiumchlorideis
small/slightlyendothermic

17

Peter Williams

Stabilityofacompound(lithiumiodidevslithiumchlorideintext)
ThedifferencebetweenBornHaberandtheoreticalLEisgreaterforLiIthanforLiCl
(845and848=)3forLiClwhereas(738and759=)21forLiI
Iodideionislargerthanchlorideion/lowerchargedensityoniodideion
Theiodideionismorelikely(thanthechlorideion)tobepolarized(bylithiumion)
LiIlikelytohavemorecovalentcharacterthanLiCl
Thermodynamicstabilityofhydrogen+oxygen
AmixtureofhydrogenandoxygenisthermodynamicallyunstablebecauseStotalis
positive
OR
ReactionbetweenhydrogenandoxygenisthermodynamicallyfeasiblebecauseStotal
ispositive
Themixtureiskineticallyinert/stableorreactionis(very)slowbecausetheactivation
energyis(very)high
OR
Mixture/reactioniskineticallyinert/stablebutthermodynamicallyunstable/feasible(1)
Hydrogenethanedioateionstability(HC2O4)

HC2O4(aq)+H2O(l)C2O42(aq)+H3O+(aq)(formingacidicsolution)
Equation
States

18