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Chemistry3
1
Fundamentals
Answerstoworkedexamples
WE1.1
Derivedunits
WorkouttheSIderivedunitformolarmass(themassofonemoleofasubstance).
Strategy
WriteanequationforthemolarmassandsubstitutetheSIunitsforthevarious
quantities.
Solution
Molarmassisthemassofsubstancepermole
/
wheremisthemassofsubstance,whichintheSIsystemhastheunitkg,andnthe
amountofsubstance,whichhastheunitmol.Theunitsofmolarmassaretherefore
kg
mol
kgmol
Molarmassesareoftenquotedinunitsofgmol1anditisimportanttobecarefulto
remembertoconvertthemtokgmol1beforesubstitutingintoanequationor
calculation.
WE1.3
Relativeatomicmassofmagnesium
Naturallyoccurringbrominecontains79Br(abundance50.69%)and81Br
(abundance49.31%).Calculatetherelativeatomicmassofnaturallyoccurring
bromine.
OXFORD H i g h e r E d u c a t i o n
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Strategy
Usetherelativeabundancestocalculateaweightedaveragerelativeatomicmass.
Solution
Theaveragerelativeatomicmassisgivenbytheweightedaverageofthemassesof
theindividualisotopes
wherexiindicatestherelativeabundanceofisotopei,andAr,iistherelativeatomic
massofisotopei.Apercentageof50.69indicatesarelativeabundanceof
50.69%
50.69/100
0.5069
so,usingthepreciserelativeatomicmassesfortheisotopesinTable1.5,then
0.5069
78.9183
0.4931
80.9163
79.90
wherethesolutionhasbeenquotedtofoursignificantfiguresbecausethisisthe
samelevelofprecisionasfortherelativeabundances.
WE1.5
Empiricalformulaeandmolecularformulae
Acompoundwasfoundtocontain1.18%hydrogen,42.00%chlorine,and56.82%
oxygenbymass.Whatisitsempiricalformula?
Strategy
Determinetherelativeamounts,i.e.numberofmoles,ofeachelementin100gofthe
compoundfromtherelativecompositionbymass,usingEquation1.2.Findthe
simplestratio,andhencetheempiricalformula,bydividingbythesmallestrelative
amount.
Solution
Thecompoundcontains56.82%oxygenbymass.Thus,100gofthecompoundmust
contain56.82gofoxygen.AccordingtoEquation1.2,thisisequivalenttoarelative
amountof
O
O/
56.82g/16.00gmol
3.551mol
OXFORD H i g h e r E d u c a t i o n
Settingthecalculationsfortheotherelementsasatable,
H
Cl
%mass
1.18%
42.00%
56.82%
mass,m
1.18g
42.00g
56.82g
amount,n
1.18g
1.01gmol
ratio
42.00 g
35.45 g mol
1.17mol
1.17mol
1.17mol
1.00
56.82g
16.00gmol
1.18 mol
1.17 mol
1.17 mol
3.55mol
1.01
3.55mol
1.17mol
3.00
ThesimplestratiooftheamountsoftheelementsisthusH:Cl:O=1:1:3,sothatthe
empiricalformulaisHClO3.
WE1.7
Percentageyieldofareaction
IntheHaberprocess,nitrogenreactswithhydrogentoformammonia:
N2(g)+3H2(g)2NH3(g)
Thereactiondoesnotgotocompletionandanequilibriummixtureofreactantsand
productsisformed.Toinvestigatetheequilibrium,1.00molofnitrogenand3.00mol
ofhydrogenaresealedinacontainerat100atmpressureand400C.The
equilibriummixturecontains8.57gofammonia.Whatisthepercentageyieldofthe
reaction?
Strategy
Determinethemaximumtheoreticalyieldofammoniafromthestoichiometryofthe
reactionandtheamountsofstartingmaterials.Calculatethepercentageyieldfrom
theratiooftheactualtothetheoreticalyield.
Solution
Thestoichiometryofthereactionshowsthatwhen1.00molofnitrogenismixed
with3.00molofhydrogen,themaximumtheoreticalyieldofammoniais2.00mol.
Themolarmassofammoniais
14.00
1.01 gmol
17.03gmol
OXFORD H i g h e r E d u c a t i o n
Thus,themaximumtheoreticalyieldis
2.00mol
17.03gmol
34.06g
Then,usingEquation1.4,
percentageyield
actualyield
theoreticalyield
100
8.57g
34.06g
100
25.2%
WE1.9
Naminginorganiccompounds
Whatarethesystematicnamesfor(a)SeF4and(b)Fe(ClO4)3?
Strategy
FollowtherulesfornaminginorganiccompoundsonP.3031.
Solution
(a)Seleniumandfluorinecancombineinmorethanoneway,sothenumbersof
atomsintheformulaneedtobeidentified.Fluorineismoreelectronegative,sothe
compoundisseleniumtetrafluoride.
(b)Ironformsmorethanonetypeofion,sotheoxidationstateneedstobe
indicated.Theanionisperchlorate,ClO4,sothecompoundisiron(III)perchlorate
oriron(III)chlorate(VII).UsingIUPACnomenclature,itisiron(III)
tetraoxidochlorate(1).
WE1.11 Constructingandbalancingaredoxequationfromhalfequations
Fe2+ionsareoxidizedtoFe3+byMnO4ionsinacidicsolution.TheMnO4ionsare
reducedtoMn2+ions.Constructhalfequationsandabalancedoverallequationfor
thereaction.
Strategy
Writeunbalancedhalfequations.Thenbalancetheprimaryelementsandthen
balancethesecondaryelementssuchasHandO.Balancethechargebyadding
electronswhereappropriate.Finally,combinethetwohalfequations,multiplying
theequationsasappropriateinordertoensurethatthenumberofelectrons
balances.Cancelanycomponentsthatappearonbothsidesoftheequation.
OXFORD H i g h e r E d u c a t i o n
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Solution
Steps1and2:Writingtheunbalancedhalfequations
Fe2+(aq) Fe3+(aq)
oxidation
MnO4(aq) Mn2+(aq)
reduction
Step3:BalanceOandHbyaddingH2OandH+ions(inacidicsolution)
Fe2+(aq) Fe3+(aq)
oxidation
MnO4(aq)+8H+(aq) Mn2+(aq)+4H2O
reduction
Step4:Balanceelectricchargebyaddingelectrons
Fe2+(aq) Fe3+(aq)+e
MnO4(aq)+8H+(aq)+5e Mn2+(aq)+4H2O
oxidation
reduction
Step5:Multiplyoxidationhalfequation5,sonumberofelectronstransferredis
sameinbothhalfequations.
5Fe2+(aq) 5Fe3+(aq)+5e
MnO4(aq)+8H+(aq)+5e Mn2+(aq)+4H2O
oxidation
reduction
Step6:Addthetwohalfequationsandcancelouttheelectrons
5Fe2+(aq) 5Fe3+(aq)+5e
MnO4(aq)+8H+(aq)+5e Mn2+(aq)+4H2O
MnO4(aq)+8H+(aq)+5Fe2+(aq) 5Fe3+(aq)+Mn2+(aq)+4H2O
oxidation
reduction
overall
Steps7and8Nofurthersimplificationisnecessaryasatomsandchargesbalance.
WE1.13 Findingouthowmuchsoluteisinagivenvolumeofsolution
Asolutionofsodiumcarbonatehasaconcentrationof0.157moldm3.Whatvolume
ofsolutioncontainsexactly1.00gofsodiumcarbonate?
Strategy
Determinetheamountofsodiumcarbonatethecorrespondsto1.00gbycalculating
themolarmassandapplyingEquation1.2.Usethedefinitionofconcentrationto
determinethevolumeofsolution.
Solution
Themolarmassofsodiumcarbonate,Na2CO3,is
OXFORD H i g h e r E d u c a t i o n
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CO
22.99
12.00
16.00 gmol
105.98gmol
UsingEquation1.2,theamountofsodiumcarbonatein1.00gis
N
CO
CO
1.00g/105.98gmol
CO
9.43
10 mol
Workingoutthevolumefromfirstprinciples,andthedefinitionofconcentrationas
theratiooftheamountofsubstancetothevolume,
Na CO
CO
sothat
N
CO
/ Na CO
10 mol/0.157moldm
9.43
60.1
10 dm
whichisequivalenttoavolumeof60.1cm3because1cm3=103dm3.
WE1.15 Gravimetricanalysis
A4.500gsampleofanoilcontainingthepesticideDDT(C14H9Cl5)washeatedwith
sodiuminalcoholtoliberateallthechlorinepresentasClions.Themixturewas
treatedwithsilvernitratesolutionand1.509gofAgClwererecovered.Calculatethe
percentage(bymass)ofDDTinthesample.
Strategy
Calculatethemolarmassofsilverchloride,AgCl,andhencetheamountofchloride,
Cl,ions.UsethestoichiometryofDDTtodeterminetheamountofthatcompound.
CalculatethemolarmassofDDTandthusthetotalmassofDDTpresentinthe
sampleofoil.Finally,findthepercentagebymassastheratioofthetotalmassof
DDTtothemassoftheoilsample.
Solution
Themolarmassofsilverchlorideis
A C
107.87
35.45 gmol
143.32gmol
Thus,1.509gofsilverchloridecorrespondsto
A C
A C
A C
1.509g/143.32gmol
0.01053mol
EachDDTmoleculecontainsfivechlorineatoms,sothat
OXFORD H i g h e r E d u c a t i o n
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A C
/5
0.01053mol/5
2.106
10 mol
ThemolarmassofDDTis
DDT
14
12.00
1.01
35.45 gmol
354.34gmol
sothatthemassofDDTinthesampleofoilis
DDT
DDT
DDT
2.106
10 mol
354.34gmol
0.7462g
Thepercentage,bymassofDDTinthesampleofoilisthus
DDT
100
0.7462g
4.500g
100
16.58%
WE1.17 Equilibriumconstantsintermsofconcentrations
Anequimolarmixtureofethanoicacidandethanolwasheatedat373K.At
equilibrium,theconcentrationofethanoicacidwasfoundtobe0.820moldm3.
Calculatetheconcentrationofethylethanoateintheequilibriummixture.
(Hint.Usethestoichiometricequationforthereactiontodeterminethe
concentrationofethanolintheequilibriummixture.)
Strategy
Writeabalancedchemicalequationforthereactionanduseittoproducean
expressionfortheequilibriumconstantintermsoftheconcentrationsofthe
productsandreactants.Rearrangetheexpression,usingthevalueforthe
equilibriumconstantintheWorkedExampletodeterminetheconcentrationoethyl
ethanoate.
Solution
Thebalancedequationforthereactionbetweenethanoicacidandethanolis
CH3CO2H(l)+C2H5OH(l)CH3CO2C2H5(l)+H2O(l)
sothattheequilibriumconstantis
CH CO C H l
CH CO H l
H O l
C H OH l
4.00
Ifequalamountsofethanoicacidandethanolaremixedinitially,then
OXFORD H i g h e r E d u c a t i o n
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CH CO C H l
H O l
C H OH l
and
CH CO H l
sothat
CH CO C H l
0.820moldm
4.00
Rearranging,
CH CO C H l
4.00
0.820moldm
sothat
CH CO C H l
2.00
0.820moldm
1.64moldm
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Answerstoboxes
Box1.3 TheAmesburyArcher
Howdothethreeisotopesofoxygenvaryinthenumberofprotons,neutrons,and
electronspresent?
Strategy
Deducetheatomicnumberandmassnumbersforthethreeisotopesofoxygenand
hencethenumberofprotonsandneutrons.
Solution
Theatomicnumberofoxygenis8,sothatallisotopeshave8protons.However,for
thethreeisotopesofoxygen,thenumberofneutronsinthenucleusdoesvary.The
numberofneutronsisgivenbythedifferencebetweenthemassnumberandthe
atomicnumber,sothatfor O,theatomicnumberis16,andthereforethereare
eightneutrons.Inthesameway,therearenineneutronsin O,andtenneutronsin
O.
Box1.5 Measuringlowconcentrations
Thelabelonabottleofmineralwatersaysitcontains27mgcalciumperlitre.
(a)WhatistheconcentrationofCa2+ionsinppm(bymass)andthepercentageby
massofCa2+ions?
(b)WhatistheconcentrationofCa2+ionsinmoldm3?
Strategy
Assumingthatthedensityofwateris1.0gdm3,calculatethemassofonelitreof
solution.CalculatetheproportionofCa2+ionsbymassasafractionofthetotalmass.
Solution
Assumingthatthedensityofmineralwateris1.0gcm3,thenonelitreofwater,
whichisequivalenttoavolumeof103cm3,has,fromWorkedExample1.1,amassof
1.0gcm
10 cm
1.0
10 g
1.0kg
Then,fromEquation1.6,theconcentrationbymassofCa2+ionsis
OXFORD H i g h e r E d u c a t i o n
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C
H O
0.027g
1000g
10 ppm
0.027g
1000g
100%
(b)Theatomicmassofcalciumis
27ppm
0.027%
40.1gmol sothat,fromEquation1.8,
/
Ca
27
10 gdm /40.1gmol
6.7
10 moldm
Box1.7 Potentialenergyandkineticenergy
(a)Calculatetheenergyneededforabungeejumperweighing65.0kgtoclimbfrom
thegroundtoaplatform35.0mhigh.
(b)Calculatethekineticenergyofanitrogenmoleculetravellingat500ms1.
Strategy
UseEquation1.16,whichdefineshowthepotentialenergyofanobjectvarieswith
itsheightabovethesurfaceoftheEarth,andEquation1.17,whichdefinesanobjects
kineticenergy.
Solution
(a)Thegravitationalpotentialenergyofthepersonstandingontheplatformis
equaltotheenergyneededforthepersontoclimbfromthegroundtotheplatform.
Thus,fromEquation1.16,
PE
65.0kg
9.81ms
35.0m
22300kgm s
22.3kJ
(b)Themolarmassofnitrogenis
2
14.00gmol
28.00gmol
sothat,themassofanindividualnitrogenmoleculemustbe
/
4.651
28.00gmol /6.022
10 mol
10
kg
4.651
10
OXFORD H i g h e r E d u c a t i o n
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fromEquation1.17,
KE
4.651
10
kg
500ms
5.81
10
Box1.9 Butanehairstylers
Thelabelonabutanerefillforahairstylerstatesthatitcontains14gofisobutane.
TheformulaofisobutaneisC4H10.
(a)Assumingthefuelburnscompletely,accordingtothethermochemicalequation
above,calculatetheheatenergysuppliedfrom14gofisobutane.
(b)Suggestastructuralformula(seeSection1.3,p.12)forisobutaneandgiveits
systematicIUPACname.
(YoucanreadaboutstructuralisomersandnaminghydrocarbonsinSection9.5,
p.415.Youwillbeabletocalculateenthalpychangesundermorerealisticconditions,
notjust25C,afterstudyingSection14.4,p.681.)
Strategy
Calculatetheamountofiosbutanethatisequivalentto14gandhenceworkoutthe
fractionofthemolarenthalpychange.
Solution
(a)Fromthethermochemicalequation,2878kJofenergyaresuppliedwhen1mol
ofbutanereactswithoxygenat298K.Themolarmassofisobuteneis
4
12.00
10
1.01 gmol
58.10gmol
sothat14.0gmustcorrespondtoanamount
/
14.0g/58.10gmol
0.241mol
0.241mol
2878kJmol
690kJ
(b)Drawingthestructureofisobuteneineitheratwoorthreedimensionalform
showsthatthesystematicIUPACnameis2methylpropane.
OXFORD H i g h e r E d u c a t i o n
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Box1.11 WhyisKevlarsostrong?
Intermsofintermolecularattractions,suggestwhyitispossibletomakestrong
ropesoutofKEVLARornylon,butnotfrompolythene(poly(ethene)).
Strategy
Considerthenatureoftheinteractionsbetweenthechains.
Solution
HydrogenbondingbetweenadjacentchainsinKevlarandnylonleadstoordered
structuresinwhichthealignedchainscannotmovepastoneanotherveryeasily.In
poly(ethene),theonlyintermolecularattractionsbetweenthechainsaretheweaker
Londondispersioninteractions.So,fibresmadefromnylonorKevlararestronger
thanfibresmadefrompoly(ethene).
OXFORD H i g h e r E d u c a t i o n
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Answerstoendofchapterquestions
1.
TheCCbondlengthinacrystalofdiamondis0.154nm.Whatisthisdistancein(a)
metres,(b)picometres,(c)ngstroms?
Strategy
UsetheSIprefixesinTable1.2toconvertthebondlength.Rememberthat1is
equivalentto11010m.
Solution
(a)1.541010m
(b)154pm
(c)1.54
3.
Asealedflaskholds10dm3ofgas.Whatisthisvolumein(a)cm3,(b)m3,(c)litres?
Strategy
UsetheSIprefixesinTable1.2.
Solution
Avolumeof10dm3,whichisequivalentto1L,maybewrittenas
10dm
10 dm
10
10 m
10
10 m
10 m
0.01m
But,1m3=106cm3,because
1m
10 cm
10 cm
sothat
10dm
10 m
10
10 cm
10 cm
5.
Howmanymolesofatomsarecontainedinthefollowingmasses:(a)22.0gof
magnesium;(b)43.2gofchlorine;(c)126mgofgold;(d)1.00kgofmercury?
Strategy
UseEquation1.2todeterminetheamountofeachelement,usingtheSIprefixesin
Table1.2toensurethattheunitsareconsistent.
OXFORD H i g h e r E d u c a t i o n
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Solution
Theamountofeachelementisgivenbytheratioofthemasstothemolarmass
/
(a)Thus,formagnesium,whichhasamolarmassof24.31gmol1,then
M
22.0g/24.31gmol
0.905mol
43.2g/35.45gmol
1.22mol
(b)Forchlorine,
C
(c)Forgold,
A
126
10 g/196.97gmol
6.40
10 mol
(d)Formercury,
H
10 g/200.59gmol
4.99mol
7.
Thestructureofsuccinicacidisshownbelow
(a)Writedownthemolecularformulaofsuccinicacidandworkoutitsmolarmass.
(b)Whatistheempiricalformulaofsuccinicacid?
(c)Whatisthepercentageofcarboninsuccinicacid?
(d)Calculatetheamountofsuccinicacidina0.125gsampleofthepureacid.
(e)Howmanymoleculesofsuccinicacidarepresentinthe0.125gsample?
(f)Howmanycarbonatomsarepresentinthe0.125gsample?
Strategy
Considerthemolecularformulaofsuccinicacid.UseEquation1.2todeterminethe
amountofsuccinicacid.
Solution
(a)ThemolecularformulaofsuccinicacidisC4H6O4,sothatthemolarmassis
412.01 61.01 416.00 gmol
118.1gmol
(b)Theempiricalformula,whichistheratiooftheelements,isC2H3O2.
(c)Therearefourcarbonatomsineachmoleculeofsuccinicacid.Thus,the
proportionofthemassofthemoleculethatiscarbonis
OXFORD H i g h e r E d u c a t i o n
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%C
12.01gmol
100%
/118.1gmol
40.7%
(d)Theamountofsuccinicacidis
/
0.125g/118.1gmol
1.06
10 mol
(e)Thenumberofmoleculesin0.125gsuccinicacidis
A
1.06
10
6.022
10 mol
6.38
10
(f)Everymoleculeofsuccinicacidcontainsfourcarbonatoms,sothetotalnumber
in0.125gsuccinicacid
4
6.38
10
2.55
10
9.
Astreamrunningoutfromacopperminecontainsadilutesolutionofcoppersulfate.
Asitpassesoveranirongrid,coppermetaldepositsonthegrid.
(a)Writeabalancedequation,withstatesymbols,forthereactiontakingplace.
(b)Writeanionicequationforthereaction.
(c)Assignoxidationstatestotheelementsineachofthereactantsandproductsin
theequationin(b).Usethesevaluestodecidewhathasbeenoxidizedandwhat
reduced.
Strategy
FollowtheapproachusedinWorkedExample1.10.
Solution
(a)
Fe(s)+CuSO4(aq)FeSO4(aq)+Cu(s)
(b)
Fe(s)+Cu2+(aq)Fe2+(aq)+Cu(s)
(c)Theoxidationstateofironchangesfrom0to+2,astheFe(s)reactstoform
Fe2+(aq).Theoxidationstateofcopperchangesfrom+2to0astheCu2+(aq)reacts
toformCu(s).Theironisthusoxidisedandthecopperreduced.
11.
Sodiumchromate(Na2CrO4)canbepreparedbyoxidizingachromium(III)saltwith
sodiumperoxide(Na2O2)inalkalinesolution.TheCr3+ionsareoxidizedtoCrO42
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ions.TheO22ionsarereducedtoOHions.Constructhalfequationsandabalanced
overallequationforthereaction.
Strategy
FollowthestepsonP.34.
Solution
Steps1and2:Writingunbalancedhalfequations,withelementsotherthanOandH
balanced
Cr3+(aq) CrO42(aq)
oxidation
O22(aq) OH(aq)
reduction
Step3:Thereactiontakesplaceinalkalinesolution.BalancingOandHbyfirst
addingH2OtobalancetheO,thenbalancingtheHbyaddingH2Otothesideofthe
halfequationthatneedsH,whilstaddingOHtotheotherside.Cancellingoutany
surpluswater.
Cr3+(aq)+4H2O(l) CrO42(aq)
oxidation
Cr3+(aq)+4H2O(l)+8OH(aq) CrO42(aq)+8H2O(l)
Cr3+(aq)+8OH(aq) CrO42(aq)+4H2O(l)
O22(aq) 2OH(aq)
O22(aq)+2H2O(l) 4OH(aq)
reduction
Step4:Balancingelectricchargesbyaddingelectrons
Cr3+(aq)+8OH(aq) CrO42(aq)+4H2O(l)+3e
O22(aq)+2H2O(l)+2e 4OH(aq)
oxidation
reduction
Step5:Multiplyingtheoxidationequation2,andthereductionequation3,so
thatthenumberofelectronstransferredisthesameinbothhalfequations.
2Cr3+(aq)+16OH(aq) 2CrO42(aq)+8H2O(l)+6e
3O22(aq)+6H2O(l)+6e 12OH(aq)
oxidation
reduction
Step6:Addingthetwohalfequationsandcancellingouttheelectrons
2Cr3+(aq)+16OH(aq) 2CrO42(aq)+8H2O(l)+6e
3O22(aq)+6H2O(l)+6e 12OH(aq)
oxidation
reduction
2Cr3+(aq)+16OH(aq)+3O22(aq)+6H2O(l)2CrO42(aq)+8H2O(l)+12OH(aq)overall
Steps7and8:SimplifyingtheequationbycancellingoutOH(aq)ionsandH2O(l)
molecules.Theatomsandchargesoneachsideoftheequationbalance.
2Cr3+(aq)+4OH(aq)+3O22(aq) 2CrO42(aq)+2H2O(l)
overall
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13.
Themostcommontypeofkidneystoneisformedfromcalciumethanedioate
(CaC2O4)whichprecipitatesoutintheurinarytractwhenconcentrationsofCa2+ions
andC2O42ionsbecometoohigh.Magnesiumionsareknowntoinhibittheformation
ofkidneystones.ToanalysetheconcentrationsofCa2+(aq)andMg2+(aq)ina
sampleofurine,theionswereprecipitatedasethandioatesandthemixed
precipitateofCaC2O4andMgC2O4analysedbygravimetricanalysis.
ThesolidethanedioateswerefirstheatedtoformamixtureofCaCO3andMgO.The
massofthismixturewas0.0433g.Thissolidwasthenheatedmorestronglytogive
amixtureofCaOandMgO.Themassofthesolidresiduefromthisprocesswas
0.0285g.WhatwasthemassoftheCa2+ionsintheoriginalsampleofurine?
Strategy
Calculatethemass,andthereforetheamount,ofCO2releasedwhentheCaCO3is
heated.Usethestoichiometryofthedecompositionreactiontodeterminethe
amountofCaCO3,andthusthemassofCa2+ionspresentintheoriginalsample.
Solution
ThemassofCaCO3andMgOis0.0433g,butdecreasesonheatingstronglythrough
thereaction
CaCO3(s)CaO(s)+CO2(g)
to0.0285g.ThemassofCO2mustthereforebe
0.0433g
CO
0.0285g
0.0148g
ThemolarmassofCO2is
12.01
CO
16.00 gmol
44.01gmol
sothattheamountofCO2liberatedis,fromEquation1.2
CO
CO
CO
0.0148g/44.01gmol
3.36
10 mol
ThestoichiometryofthereactionissuchthattheamountofCO2producedis
equivalenttotheamountofcalciumcarbonatethatdecomposes,sothat
C CO
CO
3.36
10 mol
Themolarmassofcalciumis
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40.08gmol
sothatthemassofCa2+ionsintheoriginalsampleofurinemusthavebeen
C
3.36
10 mol
40.08gmol
0.0135g
15.
Onestageinthemanufactureofmethanolfrommethaneinvolvestheconversionof
synthesisgas(amixtureofCOandH2)tomethanol.Theconversioniscarriedout
overacatalystatatemperatureofaround500Kandapressureof100atm.
H=90.7kJmol1
CO(g)+2H2(g) CH3OH(g)
(a)WriteanexpressionforKpforthereaction.
(b)At500Kand100atmpressure,anequilibriummixturecontains42%CH3OH
and48%CO.CalculateavalueforKpatthistemperature.
(c)UseLeChateliersprincipletopredictwhatwouldhappentothepercentageof
methanolinthemixtureif:(i)thetemperatureincreases;(ii)thepressureincreases;
(iii)hydrogenisaddedatconstanttemperatureandpressure.
Strategy
Calculatethepartialpressuresofeachofthecomponentsfromtheproportionsand
thetotalpressure.RememberthattheH2makesuptheremainderofthemixture.
Solution
(a)FollowingthemethodonP.64,
CH OH
CO
(b)Thepartialpressureofthecomponentsdependsuponthefraction,x,andtotal
pressurepsothat
CH OH
CO
CH OH
0.42
0.48
CO
100atm
100atm
42atm
48atm
Thepartialpressureoftheremainingcomponent,H2,mustthereforebe
H
CH OH
CO
100atm
42atm
48atm
10atm
Sothat
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42atm
48atm
10atm
8.8
10 atm
(c)(i)Theforwardreactionisexothermic,so,ifthetemperatureincreases,the
positionofequilibriummovestotheleft.Thepercentageofmethanolinthemixture
thereforedecreases.
(ii)Theamountofgasincreaseswhenmethanolreactstoformcarbonmonoxide
andhydrogen.Thus,anincreaseinpressurecausesthepositionofequilibriumto
movetotheright.Thepercentageofmethanolinthemixtureincreases.
(iii)Anincreaseinthepartialpressureofhydrogenwillcausethepositionof
equilibriumtomovetotheleft.Thepercentageofmethanolinthemixturewill
thereforeincreases.
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