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Chapter2

AqueousSolutionsandSolubility

Chapter 2 Problems -- Solutions--Gamma Version


Section2.1.
SubstancesinSolutions
2.1.

Tastingsamplesisunsafeandforbiddeninthelaboratory.Ifyouhadasolutionofa
sugar,howcouldyoudetermineifthesoluteisuniformlydistributedthroughoutthe
solutionwithouttastingsamples?Explainyourplan.
Answerto2.1:Studentsanswerwillvary.Anexampleofananswerfollows.
Usingapipette,collectsamplesfromvariousplacesthroughoutthemixture.Each
samplecouldthenbeanalyzedforpropertieslikedensity,boilingpoint,freezing
point,orspecificgravity.Theresultscouldbecomparedtoeachotherandtoan
analysisoftheentiresolution.

2.2.

Mixturesinvolvingsolidsandliquidscanbeclassifiedintotwogroups:homogeneous
solutionsandheterogeneousmixturesinwhich,afteratime,thesolidsettlesoutofthe
mixture.Whenasoliddoesnottrulydissolveintheliquidbutformsaheterogeneous
mixture,itiscalledasuspension.Asuspensionisusuallyshakentoredistributethesolid
priortouse.Gotoyourlocalgroceryand/ordrugstoreandidentify5productsthatare
solutionsand5productsthataresuspensions.
Answerto2.2:Someexamplesofsolutionsmightbe:softdrinks,salinesolutions
forcontactlenses,rubbingalcohol,liquidbleach,liquidsoaps.Someexamplesof
suspensionsmightbe:MilkofMagnesia,Peptobismol,oralantibioticslike
Amoxycilin,calaminelotion,paint.

2.3.

Drawenergydiagramsfortheseprocesses.Labeleachenergychangeasendothermicor
exothermicandexplainwhyyoudrawitthisway.
(a) Asolventchangingfromtheliquidstatetothegaseousstate.
(b) Gaseoussolventmoleculessolvatingasolutetoformaliquidsolution.
Answerto2.3:
(a)

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(b)
(b)

2.4.

(a) Whenacertainliquidmolecularsubstancedissolvesinwater,thesolutionfeelscool.
Sketchanenergydiagramthatshowstherelationshipsamongenergytheoretically
neededtoseparatethemoleculesintheliquidstate,energyreleasedwhenthemolecules
dissolveinwater,andthenetenergychangeinthissolutionprocess.
(b) Whenacertainliquidmolecularsubstancedissolvesinwater,thesolutionfeels
warm.Sketchanenergydiagramthatshowstherelationshipsamongenergytheoretically
neededtoseparatethemolecules,theenergyreleasedwhenthemoleculesdissolve,and
thenetenergychangeinthissolutionprocess.
Answer2.4:
(a)Thesolutionfeelscooltothetouchbecausetheprocessisdrawing
neededheatenergyfromyourhand,providingtheenergyneededforthe
overallsolutionprocess.Thisisasketchoftheenergydiagramshowing
thisendothermicsolutionprocess.

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SeparatedMolecules
Energyadded

Energyreleased
Solution
NetEnergyChange

Liquid
(b) The solution feels warm to the touch because the process is
releasing heat energy to your hand, releasing some of the energy
from the overall solution process as heat energy. This is a sketch
of the energy diagram showing this exothermic solution process.

SeparatedMolecules
Energyadded

Energyreleased

Liquid
Solution

2.5.

NetEnergy
Change

Theoverallsolutionprocessforsolutionofcalciumchloride,CaCl2,inwateris
exothermic.Drawanenergydiagramforthisprocess.
Answer2.5:

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Section2.2.
SolutionsofPolarMoleculesinWater
2.6.

Canyoupredictwhetherasubstancewillbesolubleinwaterbylookingatitsline
formula?Canyoupredictwhetherasubstancewillbesolubleinwaterbylookingatits
structuralformula?Explainyourresponses.
Answer2.6:No,youcannotpredictwhetherasubstancewillbesolubleinwater
bylookingitslineformula.However,bylookingatitsstructuralformula,youcan
tellwhetherasubstancewilldissolveinwaterornot.Astructuralformulawillhave
regionsofpolarandnonpolargroupsthatwillallowyoutopredictwhetherthe
substancewilldissolveinwaterornot.

2.7.

Explainwhattheexpressionlikedissolveslikemeans.Illustrateyourexplanationwith
appropriateexamples.
Answer2.7:Thelikedissolveslikeexpressionreflectsthefactthatattractions
betweensolutemoleculesandsomeattractionsbetweensolventmoleculesmustbe
replacedbyasolutesolventattractionswhenasolutionforms.Ifthenewattractions
aresimilartothosereplaced,verylittleenergyisrequiredforthesolutiontoform.
Apolarliquid,suchaswater,isgenerallythebestsolventforionicandpolar
compounds.Nonpolarliquids,suchashexanearebettersolventsfornonpolar
compoundslikeforexamplewax.

2.8.

Foreachofthefollowingcompounds,writeoutthestructuralformula,usingareference
handbooktofindthestructuresyoudontknow.Circleallthepolarbondsfoundineach
structure.Showthedirectionofthebondpolarityforeachone.DonotconsidertheCH
bondtobepolar.
(a) testosterone
(b) acetylsalicylicacid
(c) methylsalicylate
Answer2.8:
(a)testosteronestructure

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H2
C

OH

H 2C

H2
C

C
H

CH 3

H 2C
C
CH 3
CH
CH
C
CH
C

C
H2

OH
CH
CH 2
C
H2

CH 2

and with dipoles shown

O H
testosterone
(with polar bonds circled and
direction of dipoles shown)
O
(b)

O
O

CH 3
O

acetyl salicylic acid


(aspirin)
(c)

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H3C

O
O

methyl salicylate
(oil of wintergreen)

2.9.

(a) UseLewisstructurestohelpexplainwhyethanol,CH3CH2OH,ismisciblewith
water.
(b) Howdoyoupredictthesolubilityof1pentanol,CH3(CH2)4OH,inwaterwill
comparetothatofethanolinwater?Explain.
Answer2.9:(a)Thedashedlinesrepresentthenetworkofhydrogen
bondsthatformbetweenethanolandwater.
H H
H C H
H C
H
O H
O H

H
O H

H
O H

Note that there are two hydrogen bonds between nonbonded


electron pairs on the oxygen of ethanol, and another hydrogen bond
between the OH groups hydrogen and the covalently bonded
oxygen in water. The water molecules have other nonbonded pairs
on oxygen and covalently bonded hydrogen, all of which are
capable of extending the network of hydrogen bonds. This
opportunity for maximum hydrogen bonding accounts for the
miscibility of ethanol in water.

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(b)Pentanolislikelytobesolubleinwater,becauseitsalcoholgroupcanalso
hydrogenbondwithwater.Thesolubilityofpentanolisexpectedtobelessthanthat
ofethanolbecausethenonpolarhydrocarbonfragmentislarger.

2.10.

Explainintermsofintermolecularattractionseachofthefollowinglikedissolveslike
observations.
(a) Methanol(CH3OH)isnotmisciblewithcyclohexane(C6H12).
(b) Naphthalene(C10H8)isinsolubleinwater.
(c) Naphthaleneissolubleinbenzene(C6H6).
(d) 1Propanol(CH3CH2CH2OH)ismisciblewithwater.
Answer2.10:(a)Cyclohexaneisanonpolarsolventwhilemethanolisa
polarone.Theinteractionbetweenwaterandcyclohexanemoleculesare
veryweak.Inthemixedstate,withoutinteractionbetweenmethanoland
cyclohexanemolecules,bothwaterandcyclohexanemoleculeslosesome
oftheirfreedomofmovementtomakewayforeachother.Thistypeof
reorganizationofunlikemoleculesisunfavorable.
(b)Naphthalenedoesnotcontainanypolargroups.Watermoleculesform
hydrogenbondingwitheachotherandreorganizationofwatermoleculein
ordertoaccommodatenaphthalenemoleculeswouldbeunfavorable.In
thiscasewatermoleculeswouldlosesomeoftheirfreedomofmovement
whilemakingwayfornaphthalenemolecules.
(c)Bothnaphthaleneandbenzenedonotcontainanypolargroups.The
reorganizationinvolvedinmixingtwononpolarcompoundsfavorsthe
mixedstate.
(d)Moleculesofwatercanformahydrogenbondswithacteone,whichfavorsthe
mixedstate.

2.11.

Predicttherelativesolubilityofgasoline,C8H18inwater.Explainthereasoningforyour
prediction.
Answer2.11:Sincegasolineisanonpolarmolecule,itwillbeinsolubleinwater.
Itwillnotinteractwithwatermolecules.

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2.12.

AqueousSolutionsandSolubility

(a) WritetheLewisstructuresfor1hexanol,CH3(CH2)5OH,and1,6hexanediol,
HO(CH2)6OH,and,ineachmolecule,identifytheregionorregionswherehydrogen
bondingwithwatercanoccur.
(b) Whichcompoundin(a)doyoupredictismoresolubleinwater?Explain.
Answer2.12:(a)ThesearethetwoLewisstructureswithregionsfor
hydrogenbondingidentified.
hexanol

H H H H H H
H C C C C C C O
H H H H H H H

Hydrogenbonding
withwatercouldtake
placeinthisregion.

1,6hexanediol, HO(CH2)6OH

H H H H H H
O C C C C C C O
H
H H H H H H H

Hydrogenbonding
withwatercouldtake
placeintheseregions.

(b)1,6hexanediolispredictedtobemoresoluble.Compoundswithmultiplepolar
groupspresentmoreopportunityforhydrogenbondingwithwatermolecules.
2.13.

Predicttherelativewatersolubilities(frommostsolubletoleastsoluble)foreachsetof
structures.Makemodelstohelpvisualizethestructures.
(a) CH3CH2CH2CH2OH

(b) CH3CH2CH2CH2NH2

CH3CH2CH2CH2CH2OH

(CH3)2CHCH2CH2NH2

HOCH2CH2CH2CH2OH

(CH3)3CCH2CH2NH2

HOCH2CH2CH2OH

(CH3CH2)3CCH2NH2

Answer2.13:Recall(Section2.2)thatasthehydrocarbonportionofanalcohol
increasesinsize,thesolubilizingandhydrogenbondingeffectofthepolarhydroxy(
OH)groupbecomesincreasinglylessimportant.Toafirstapproximation,thesolubility
isrelateddirectlytotheratioofcarbonatomstopolargroups.Inpart(a),thepolar
functionalgroupisanalcoholandinpart(b),thepolarfunctionalgroupisanamine.The
ratiosandrankordersofsolubilitiesareshown(#1ismostsolubleineachpart):

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Carbon/functgrpratio
(a) CH3CH2CH2CH2OH

4/1

5/1

HOCH2CH2CH2CH2OH 2/1

HOCH2CH2CH2OH

1.5/1

4/1

(CH3)2CHCH2CH2NH2

5/1

(CH3)3CCH2CH2NH2

6/1

(CH3CH2)3CCH2NH2

8/1

CH3CH2CH2CH2CH2OH

(b) CH3CH2CH2CH2NH2

2.14.

solubilityrank

Sugarsarenaturalproductsthataregenerallyquitesolubleinwater.Sucrose,tablesugar,
isacommonsourceofsugarinfood.Fructoseandlactosearetwoothersugarsthatare
importantinlivingsystems.Uselibraryresourcesortheinternettofindthestructural
formulasforthesethreesugars.Onthebasisoftheirstructures,explaintheirhigh
solubilityinwater.(Yourresponseshouldincludethereference(s)towhereyoufound
thestructures.)
Answer2.14:

Therearemanywebresourcesthathavethestructuresofthesesugars.Students
shouldhavethefollowingstructures:

H
C

H
H

OH
H
O
C

HOH 2C
CH2 OH

OH

HO
HO

HO

HO

CH2 OH

Fructose
(furanose form = minor isomer)

Fructose
(pyranose form = major isomer)

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H
CH2 OH
C

HO

CH2 OH

OH

OH

H
C

OH

OH

OH

Lactose

H
CH2 OH
C

HO
H

OH

CH2 OH

OH
C
O

C
Sucrose

C
H

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OH

HO

C
CH2 OH

10

Chapter2
2.15.

AqueousSolutionsandSolubility

Thefatsinourbodiesarecomposedofrelativelynonpolarmoleculesthatarealmost
insolubleinwater.Vitaminsmaybeclassifiedasfatsolubleorwatersoluble.Consider
thestructuresofvitaminsAandCshownhere.Whichofthesevitaminsdoyouexpectto
bemoresolubleinaqueoussystemsandwhichinfattytissuesofthebody?Usethe
structurestoexplainyourreasoning.
H H
H
H
H H H
H
H
H
H
H C
H
C H H
H C
C
H
H
C
C
C
C
C
C
C
C
C
C
C
C
O
H
H C
C
H
H
H
H
H
C
H
H H
vitaminA

O
H
C
C
H H
C O
C
H
C
O
O
C
H
H
O
H

vitaminC

Answer2.15:Given:StructuresofvitaminsAandC.
AskedFor:Toexplainwhichofthesevitaminsshouldbemoresolubleinaqueous
systemsandwhichinfattytissuesinthebody.
Recall:Themorepolargroupspresentinthemoleculethemoresolubleitwillbein
water.
Plan:Wewillinspectthestructurestofigureoutwhichonehasthemostpolar
groups.
Explanation:VitaminChasthemostpolargroups.Thus,itwillbethemostsoluble
inaqueoussystems.
2.16.

(a) VitaminBiswatersolubleandvitaminsD,E,andKarefatsoluble.(SeeProblem
2.15.)Basedonthisinformation,explainwhichvitaminscouldbestoredinyourbody
andwhichshouldbeincludedinyourdailydiet.
(b) FromyouranswersforProblem2.15,wouldvitaminsAandCbestoredinyour
bodyorshouldtheybeincludedinyourdailydiet?
(c) Withthereadyavailabilityofvitaminsupplements,casesofhypervitaminosis,an
illnesscausedbyanexcessiveamountofvitamins,arenowbeingdiagnosedbymedical
doctors.Explainforwhichvitaminshypervitaminosisislikelytooccur?
Answer2.16:(a)VitaminsD,E,andKcanbestoredinyourbody.VitaminB
shouldbeincludedinyourdailydiet.
(b)VitaminAcanbestoredinyourbodywhilevitaminCshouldbeincludedin
yourdailydiet.
(c)Sinceonlyfatsolublevitamins(vitaminsA,D,E,andK)canbestoredinyour
body,truehypervitaminosishasbeenobservedonlyforthesevitamins.

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Chapter2

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Section2.3.
CharacteristicsofSolutionsofIonicCompoundsinWater
2.17.

InInvestigateThis2.10,whathadtobepresentinthesolutioninorderforthelightbulb
toglow?
Answer2.17:Ionsmustbepresent.

2.18.

3+
(WEB)Chap2,Sect2.3.1hasmoviesrepresentingtheFe
(aq)andNO3(aq)ions.How
WEB
manywatermoleculesareshowninthehydrationlayerforeachion?Whatarethe

similaritiesanddifferencesinthearrangementandorientationofthewatermolecules
aroundeachoftheions?Howdoyouexplainthesimilaritiesanddifferences?
Answer2.18:Bothionshavesixwatermoleculesaroundthem.However,Fe3+(aq)
isattractedtothenegative(oxygen)endsofthewatermolecules.NO3(aq)isattractedto
thepositive(hydrogen)endsofthewatermolecules.
2.19.

SolutionAwaspreparedbymixing0.5gofethanoylchloride(acetylchloride),
CH3C(O)Cl,with100mLofwater.SolutionBwaspreparedbymixing0.5gof2
chloroethanol,ClCH2CH2OH,with100mLofwater.SolutionAconductsanelectric
currentbutsolutionBdoesnot.Whatcanyouconcludeaboutthecontentsofeach
solution?Explainthereasoningforyouranswer.
Answer2.19:SolutionAcontainsionswhileSolutionBdoesnot.

2.20.

Whationsarepresentinsolutionwhenthesesolidsdissolve?Identifyeachtypeofionas
eitheracationorananion.
(a) BaCl2

(e) NH4Cl

(b) KCl

(f) Na2S

(c) Na3PO4

(g) MgSO4

Answer2.20:(a)Ba2+(cation)Cl(anion);(b)K+(cation))Cl(anion);(c)Na+
(cation)PO43(anion);(e)NH4+(cation)Cl(anion);(f))Na+(cation)S2(anion);
(g)Mg2+(cation)SO42(anion)
2.21.

(a) Imaginethatoneofyourfriendswhoisnottakingthischemistrycoursesaysthat
saltsolutionsmustconductelectrons,justlikewires,becauseyoucanreplacepartofan
electriccircuit(asshowninthepicturesinInvestigateThis2.10)withasaltsolutionand
thecurrentwillstillflow.Howwillyouansweryourfriendandexplainhowelectric
chargecontinuestoflowwithoutaflowofelectronsthroughthesolution?
(b) (WEB)Chap2,Sect2.3.2.Wouldthisinteractivemolecularlevelrepresentationof
WEB
electricalconductivityinionicsolutionhelpyourexplanation?Whyorwhynot?

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Answer2.21:Electronsdonothavetoflowthroughthesolution.Cationsare

attractedtothenegativelychargedcathodewire,whiletheanionsareattractedtothe
positivelychargeanodewire,asshowninWEBChap2,Sect2.3.2.
2.22.

Solidsodiumchloride,NaCl,doesnotconductelectricitybutanaqueoussolutionof
sodiumchlorideisagoodconductor.Solidmercuricchloride,HgCl2,doesnotconduct
electricityandneitherwillitsaqueoussolutioneventhoughthesolidissoluble.Offera
possibleexplanationforthedifferenceinbehavioroftheaqueoussolutions.
Answer2.22:Neithersolidwillconductelectricitybecauseanyionspresentarenot
freetomoveandtransportthecharge.Sodiumchloride(aq)isagoodconductor
becausethepolarwatermoleculessurroundtheionsandpullthemapart,releasing
Na+(aq)andCl(aq)intosolution.HgCl2issolubleinwater,buttheaqueoussolution
doesnotconductelectricity.Evidentlynoionsarereleasedwhenthiscompound
goesintosolution.Themoleculeitselfstaystogetherinsolution.Thisisnotthe
usualcircumstanceforwhatappearstobeasalt,butmercury(II)chloridemolecules
staybondedtogetherevenwhilegoingintoaqueoussolution.

2.23.

Imaginethatyouareapositivelychargedionsurroundedbylargenumbersofpolar
moleculeslikeoursimpleellipsoidswithpositiveandnegativeendsChapter1Figures
1.15and1.16.Whywouldyouhaveaproblemfeelingtheattractionofanegatively
chargedionortherepulsionofanotherpositivelychargedion?Explainyourreasoning.
Usedrawings,iftheyhelpclarifyyourexplanation.
Answer2.23:Given:Imaginethatyouareapositivelychargedion
surroundedbylargenumbersofpolarmoleculeslikeoursimpleellipsoids
withpositiveandnegativeendsinChapter1.
AskedFor:Explanationofwhyyouwouldnotfeeltheattractionofanegatively
chargedionortherepulsionofanotherpositivelychargedion.
Explanation:Eachionwillbesurroundbyseveralwatermoleculeswhichcreatea
hydrationlayer.Thislayershieldstheionfromtheattractionofanoppositely
chargedionortherepulsionofasimilarlychargedion.
Picture:

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AqueousSolutionsandSolubility

+
+
+

The solvent molecules in


the "hydration sphrere" are
constantly exchanching
with the bullk solvent.

Nonetheless, the surface of


the hydration sphere is
partailly positively charged.

Section2.4.
FormationofIonicCompounds
2.24.

Whichofthefollowingdoyoupredicttoconductelectricitywhendissolvedinwater?
Explainyourreasoningineachcase.
(a) MgBr2

(d) CH3OCH3

(b) CH3OH

(e) KNO3

(c) NaOH

(h) CH3CH2CH2CH3

Answer2.24:(a),(c),and(e)wouldallformsolutionsthatareelectrolytessincethese
aresolubleioniccompounds.Themoleculesin(b),(d),and(h)willnotionizetoa
degreesufficienttobedetectedbymostconductivityapparatusavailabletoourstudents.
2.25.

Predictthemostlikelychargewhenthefollowingelementsformmonatomicions.
Explaintherationaleforyourchoiceineachcase.
(a) alkalimetals

(c) alkalineearthmetals

(b) oxygenfamily

(d) halogens

Answer2.25:(a)1+(b)1(c)2+(d)2(e)3(f)3+
2.26.

Writethechemicalformulafortheioniccompoundformedbythecombinationofthe
followingions.
(a) magnesiumcation+bromideanion
(b) calciumcation+nitrateanion
(c) magnesiumcation+sulfateanion
(d) potassiumcation+oxideanion
Answer2.26:(a)MgBr2(b)Ca(NO3)2(c)MgSO4(d)K2O

2.27.

Nametheseioniccompounds.

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(a) Na2SO4

(c) (NH4)2CO3

(b) MgCl2

(d) Al2S3

Answer2.27:(a)sodiumsulfate;(b)magnesiumchloride;(c)ammoniumcarbonate;
(d)aluminumsulfide.
2.28.

Writetheformulasfortheseioniccompounds.
(a) bariumnitrate

(c) calciumoxide

(b) ammoniumphosphate

(d) potassiumsulfate

Answer2.28:(a)Ba(NO3)2;(b)(NH4)3PO4;(c)CaO;(d)K2SO4
2.29.

Nametheseioniccompounds.
(a) MgS

(c) NH4NO3

(b) Na3PO4

(d) LiOH

Answer2.29:(a)magnesiumsulfide;(b)sodiumphosphate;(c)ammonianitrate;
(d)lithiumnitrate
2.30.

Writetheformulasfortheseioniccompounds.
(a) calciumiodide

(c) potassiumcarbonate

(b) sodiumfluoride

(d) bariumhydroxide

Answer2.30:(a)CaI2;(b)NaF;(c)K2CO3;(d)Ba(OH)2
2.31.

Completethisgrid,givingboththeformulaandthenameofthecompoundformed
betweeneachpairofions.
CO32

PO43

Mg2+
NH4+
Al3+
Na+
Answer2.31:

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CO32

HCO3

PO43

Mg2+

MgCO3
magnesium
carbonate

Mg3(PO4)2
magnesium
phosphate

MgF2
magnesium
fluoride

NH4+

(NH4)2CO3
ammonium
carbonate

(NH4)3PO4
ammonium
phosphate

NH4F
ammonium
fluoride

Al3+

Al2(CO3)3
aluminum
carbonate

AlPO4
aluminum
phosphate

AlF3
aluminum
fluoride

Na+

Na2CO3
sodium
carbonate

Mg(HCO3)2
magnesium
hydrogen
carbonate
NH4HCO3
ammonium
hydrogen
carbonate
Al(HCO3) 3
aluminum
hydrogen
carbonate
NaHCO3
sodium
hydrogen
carbonate

Na3PO4
sodium
phosphate

NaF
sodium
fluoride

2.32.

Findfromsuitablereferences(orlabelsoncontainers)thechemicalformulasandwrite
chemicalnamesforthefollowingionicsubstances.
(a) MilkofMagnesia

(d) Causticsoda

(b) Epsomsalt

(e) Sodaash

(c) PlasterofParis
Answer2.32:(a)Milkofmagnesia:Mg(OH)2magnesiumhydroxide;(b)Epsomsalt:
MgSO4magnesiumsulfate;(c)PlasterofParis:CaSO4calciumsulfate;(d)Caustic
soda:NaOHsodiumhydroxide;(e)Sodaash:Na2CO3sodiumcarbonate.
2.33.

Equation(2.1)canbebrokendownintotwosteps:(1)lossofanelectronbyasodium
atom,NaNa++e,and(2)gainofanelectronbyachlorineatom,Cl+eCl.Write
theappropriatereactionequationsforformationofthecommoncationsoranionsofthese
elements.
(a) potassium

(d) sulfur

(b) calcium
(e) bromine
+
Answer2.33:(a)K(g)K (g)+e
(b)Ca(g)Ca2+(g)+2e
(c)S(g)+2eS2(g)

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(d)Br(g)+eBr(g)

2.34.

Intermsofelectricalattraction[CoulombsLaw,equation(2.2)],explainwhythe
ionizationenergyforallelementalatomsalwayshasapositivevalue.Forexample,the
energyrequiredforthereaction,NaNa++e,istheionizationenergy,Eionization=
496kJmol1,forsodiumatoms.
Answer2.34:Bydefinition,ionizationalwaysinvolvestheseparationofanegative
charge(anelectron)andapositivecharge(thecationthatremainsaftertheelectronhas
departed).Ifenergyisreleasedwhenoppositechargescometogether(energyhasa
negativevaluefortheprocess),thenthereverseprocessrequirestheinputofenergy
(energyhasapositivevaluefortheprocess).Mathematically,Coulombslawexpresses
theenergyofattractionofoppositecharges.Thisattractionmustbeovercome(areversal
ofthemathematicalsignfromnegativetopositive)inordertoseparatetheopposite
charges.

2.35.

ExaminethelatticeenergiesinTable2.3.ArethesedataconsistentwithCoulombslaw?
Explainthereasoningforyouranswer.
Answer2.35:
Given:Tableoflatticeenergies.
AskedFor:ArethesedataconsistentwithCoulombsLaw?
Recall:CoulombsLawstatesthat
Energy

q 1q 2
d2

ThisisEquation(2.3)foundinSection2.4.
Plan:Latticeenergyisproportionaltothechargeonthecationsandanions.Thus,the
higherthelatticeenergyshouldimplythehigherthechargesonthecationsand
anions.So,wewillrandomlyinspectchargesonthecationsandanionsinsomeof
theabovesaltsandseeifwecanobserveifthedataisconsistentwithCoulombs
Law.Letsstartbyconstructinganothertabletocomparevarioussalts,their
correspondingions,theirlatticeenergies,and q1q2 .Fromthistable,weshouldbe
abletoconcludeifthedataisconsistentwithCoulombsLaw.

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Salt
NaBr
MgF2
MgO

Cation
Na+
Mg+2
Mg+2

q+
1+
2+
2+

Anion
Br
F
O2

q
1
1
2

q+q
1
2
4

Latticeenergy
751kJmol1
2961kJmol1
3406kJmol1

Answer:Byinspectionoftheabovetable,thelatticeenergyisdirectlyproportional
to q1q2 .Thus,thedatainthistableisconsistentwithCoulombsLaw.
2.36.

(a) BasedonCoulombsLaw,inwhichcrystal,KBrorCaBr2,wouldthegreatestforces
ofattractionandrepulsionbeobserved?Explainyourreasoning.Assumethatthe
distanceseparatingthechargesisthesameforbothcrystals.
(b) DothedatainTable2.3supportyouranswerinpart(a)?Ifso,explainhow.Ifnot,
explainwhynot.
Answer2.36:
(a)ThedoublechargeofCa2+willresultinalargercoulombicforce.Theformula
forCoulombsLawshowsthatthereisadirectrelationshipbetweenthechargesize
andtheforce.
(b)Yes,thedatainTable2.3supportsthisanswer.ThelatticeenergyforCaBr2is
almostthreetimesthelatticeenergyofKBr.

2.37.

Thelatticeenergyforcalciumchloride,CaBr2,crystalsis2176kJmol1.Thegaseous
reactionformingtheionsfromtheatoms,
Ca(g)+2Br(g)Ca2+(g)+2Br(g),
requires966kJmol1.Drawanenergydiagram,analogoustoFigure2.14,anduseitto
findExtalformfortheformationofioniccrystalsofCaBr2fromthegaseousatoms.
Answer2.37:

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Chapter2

2.38.

AqueousSolutionsandSolubility

Considertheselatticeenergiesforsomeionicsolids.AllvaluesareinkJmol1.
F

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Cl

Br

Li+

1046

861

818

Na+

929

787

751

K+

826

717

689

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19

Chapter2

AqueousSolutionsandSolubility

(a) Usethesedatatodiscusshowthelatticeenergychangeswiththesizeoftheanion,
keepingthesizeofthecationconstant.Hint:Thesizeoftheionsinagroup(column)of
theperiodictableincreasesasonegoesdownthegroup.
(b) Usethesedatatodiscusshowthelatticeenergychangeswiththesizeofthecation,
keepingthesizeoftheanionconstant.
(c) Whatgeneralizationcanbedrawnaboutthesizeofionsandthelatticeenergiesof
theirsalts?
(d) Useyourgeneralizationfrompart(c)topredicthowthelatticeenergyofCsI
compareswiththatofNaCl.
Answer2.38:
(a)ForeachGroupIAcationlisted,thelatticeenergyofitscorresponding
GroupVIIAsaltdecreasesastheatomicnumberincreases.
(b)ForeachGroupVIIAanionlisted,thelatticeenergyofits
correspondingGroupIAcationsaltdecreasesastheatomicnumber
increases.
(c)Thelatticeenergyofasaltdecreasesasthesizeofitsionsincreases.
Thelatticeenergiesarelargestwhentheionsarethesmallest.
(d)ThelatticeenergyofCsI,withevenlargerions,shouldbeconsiderablysmaller
thanthatofNaCl.

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Chapter2
2.39.

AqueousSolutionsandSolubility

ConsiderthisenergydiagramfortheformationofonemoleofioniccrystalsofMgCl2.
GaseousIons
ofMg2+,Cl
1490kJadded

2524kJreleased

GaseousAtoms
ofMg,Cl

1034kJ
Released
1.00moleof
MgCl2crystal

(a) Whatisthelatticeenergyforthiscompound?Explainhowyougetyouranswer.
(b) Howmuchenergyisrequiredforthereaction:Mg(g)+2Cl(g)Mg2+(g)+2Cl
(g)?Explainhowyougetyouranswer.

(c) Whatistheenergyassociatedwiththeformationofioniccrystalsfromthegaseous
atoms?Explainhowyougetyouranswer.
(d) HowdothethreeenergiesassociatedwiththeformationforMgCl2comparewith
thoseforNaCl,giveninFigure2.13?
Answer2.39:
(a)Thelatticeenergyis2524kJ.mol1.(b)Theenergyrequiredtochange
gaseousatomstogaseousionsis1490.5kJ.mol1.(c)Theenergyassociated
withtheformationofioniccrystalsfromgaseousatomsisthedifference
betweenthesetwoenergies,1033.5kJ.mol1.
(d)
Substance

MgCl2
NaCl

2.40.

Lattice Energy,
kJ.mol1

Energy,
Gaseous Atoms
to Gaseous Ions,
kJ

2524
787

1490.5
145

Energy,
Formation of
Ionic Crystals
kJ.mol1
1033.5
642

(a) Theenergyrequiredtoremoveelectronsfromgaseoussilveratomstoformgaseous
silvercationsis731kJmol1.Whengaseousiodineatomsgainelectronstoformgaseous
iodideanions,296kJmol1ofenergyisreleased.Calculatetheenergyforthisreaction:
Ag(g)+I(g)Ag+(g)+I(g)

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(b) ThelatticeenergyforAgI(s)crystalsis887kJmol1.Drawanenergydiagram
analogoustoFigure2.14anduseittofindExtalformfortheformationofioniccrystalsof
AgIfromthegaseousatoms.
Answer2.40a:Energyforthisreaction=435kJmol1.
Answer2.40b:

2.41.

Thelatticeenergyforpotassiumbromide,KBr,crystalsis689kJmol1.Theformationof
separategaseousatomsofpotassium,K(g),andbromine,Br(g),fromtheioniccrystal
wouldrequire594kJmol1.Howmuchenergyisrequiredforthereactionofthegaseous
potassiumandbromineatomstoformionsinthegasphase?
K(g)+Br(g)K+(g)+Br(g)
ExplainhowyougetyouransweranddrawanenergydiagramanalogoustoFigure2.14
illustratingyouranswer.

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Answer2.41:93kJmol1
(BranzPENDINGneeddiagram)
2.42.

Whatisthelatticeenergyformagnesiumfluoride,MgF2?Theformationofioniccrystals
ofMgF2fromthegaseousatomsreleases1424kJmol1.Thereactionoftheatomsto
formionsinthegasphase,Mg(g)+2F(g)Mg2+(g)+2F(g),requires1533kJmol1.
ExplainhowyougetyouransweranddrawanenergydiagramanalogoustoFigure2.14
illustratingyouranswer.
Answer2.42:2957kJmol1
(BranzPENDINGneeddiagram)

Section2.5.
EnergyChangesWhenIonicCompoundsDissolve
2.43.

Whenammoniumacetate,NH4C2H3O2[=(NH4+)(C2H3O2)],isdissolvedinwater,the
mixturebecomesquitecold.(Ammoniumacetateisthesaltusedinsomecoldpacks.)
(a) Isthedissolvingofammoniumacetateendothermicorexothermic?Explain.
(b) Whataretherelativemagnitudesofthecrystallatticeenergyandhydrationenergy
forammoniumacetate?Useanenergydiagramtoexplainthereasoningforyouranswer.
(c) Writeformulasfortheionsinsolutionusingstandardchemicalnotation.
(d) Sketchthehydratedionsinthewaywehavetriedtoshowmolecularlevel
interactionsinFigure2.9.

Answer2.43:
Given:Ammoniumacetate,NH4C2H3O2(s)[=(NH4+)(C2H3O2)]dissolvesinwater.
Themixturefeelsquitecold.
(a)
AskedFor:Explanationoftherelativemagnitudesoflatticeenergyandhydration
energies.
Recall:InSection2.5,latticeenergyandhydrationenergyarediscussed.
Explanation:.Themixtureturnscoldwhenthesoliddissolves,meaningthatthe
averageenergyofmotionhasdecreased.Thus,thisenergyisnowassociatedwith
dissolvingthesaltinwater,whichinvolvesboththelatticeenergyandthehydration
energy.Inthiscase,moreenergyisusedtobreakthecrystallatticethantohydrate
theindividualions.
(b)
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AskedFor:Isthedissolvingofammoniumacetatedescribedasendothermicor
exothermic?
Recall:InSection2.5,thedefinitionsandexamplesofendothermicandexothermic
reactionsaregiven.
Explanation:Thisprocessisendothermicbecausethermalenergyisabsorbedfrom
themotionofmoleculesinsolution.

(c)
AskedFor:Writetheformulasfortheionsinsolutionusingstandardchemical
notation.
Recall:Theionspresentinthelatticearethesameasinsolution.
Answer:ThetwoionsareNH4+andC2H3O2.

(d)

AskedFor:Sketchthehydratedionsinthewaywehavetriedtoshowmolecular
levelinteractionsintheFigure2.9.
Recall:InSection2.3,iondipoleattractionsresultfromwatermoleculesinteracting
withions.Withrespecttowater,thepartiallynegativelychargedoxygenatom
interactswithcations,whilethetwopartiallypositivelychargedhydrogenatoms
interactwithanions.
H

H
O

H
O

H
O

H
H
H

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+
H

C
H

O
C
O

H
+
H
O
H

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24

Chapter2

AqueousSolutionsandSolubility

Recap:Theprocessofdissolvingsaltsinwaterinvolvestwotypesofenergy.Lattice
energyisrequiredtobreaktheCoulombicattractionsbetweencationsandanionsinthe
latticewhilehydrationenergyisreleasedaswatermoleculessurroundtheseions.The
differencebetweenthesetwoenergieswilldeterminewhetherthermalenergywillbe
absorbed(endothermic)orreleased(exothermic)bythedissolvingprocess.
2.44.

(a) WhenLiCldissolvesinwater,istheprocessexothermicorendothermic?Usean
energydiagramtoexplainthereasoningforyouranswer.
(b) WhenKBrdissolvesinwater,istheprocessexothermicorendothermic?Usean
energydiagramtoexplainthereasoningforyouranswer.
Answer2.44:
(a)exothermic

(b)endothermic

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Chapter2

2.45.

AqueousSolutionsandSolubility

Lithiumsulfate,Li2SO4,isquitesolubleinwater(261gL1)whilecalciumsulfate,
CaSO4,isessentiallyinsoluble(4.9mgL1).Whationionand/oriondipoleinteractions
areresponsibleforthisdifference?Beasspecificasyoucan.
Answer2.45:
Given:Lithiumsulfate,Li2SO4,isverysolubleinwater(261gL1)while
calciumsulfate,CaSO4,isessentiallyinsoluble(4.9mgL1).
AskedFor:Toidentifywhationionand/oriondipoleinteractionsareresponsiblefor
thisdifferenceinsolubilities.

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Plan:Weneedtounderstandtheprocessofdissolvingasaltinwater.Thisconceptis
discussedinSection2.5.
Explanation:SinceLi2SO4isverysolubleinwater,theattractiveinteractionsbetween
Li+andSO42andwatermoleculesmustbemuchmorestrongerthantheCoulombic
attractionsintheLi2SO4crystallattice.ToexplainwhyCaSO4issoinsolublein
water,thereversemustbetrue.TheCoulombicattractionsbetweenCa+2andSO42
inthecrystallatticemustbemuststrongerthantheinteractionsbetweentheseions
andwater(iondipoleinteractions).
2.46.

Therearemanywaystodescribeorrepresentwhathappenswhensodiumsulfate,
Na2SO4,dissolvesinwater.Firstgiveanexplanationinwords.Next,writeanionic
equationtorepresentthesolutionprocess.Thenuseamolecularlevelrepresentationto
illustratewhathappenswhensodiumsulfatedissolvesinwater.(SeeFigures2.9,2.17,
and2.22.)
Answer2.46:
Given:Sodiumsulfate,Na2SO4,dissolvesinwater.
AskedFor:WeneedtoexplainhowNa2SO4dissolvesinwater.Thenweneedtowritea
netionicequationandfinallydrawaparticulatediagramtoshowthisprocess.
Recall/Plan:Weneedtoreviewhowwatermoleculesinteractwithsaltcrystalsinorder
todissolvesalts.Thisprocessinvolvesbothlatticeenergyandhydrationenergy.
ThisinformationwillhelpusdescribehowNa2SO4dissolvesanddrawaparticulate
diagram.Wealsoneedtoinvestigatesolubilityrulesandwritingnetionic
equations.
Explanation:WatermoleculeswillbeattractedtotheNa+andSO42ionsinthecrystal
lattice.ThenegativeoxygensinwatermoleculeswillbeattractedtotheNa+and
positivehydrogensinwaterwillbeattractedtoSO42.Theseiondipoleattractions
aregreaterthanthelatticeholdsNa+andSO42inthecrystal.Oncetheionsbreak
awayfromthecrystal,watermoleculessurroundeachioncreatingahydrationlayer.
Thesehydrationlayerscreateashield,makingitdifficultforhydratedionsthatare
oppositelychargedtogettooclosetoeachother.Inourexample,hydratedNa+will
notbeabletogetclosetohydratedSO42andvisaversa.

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Chapter2

AqueousSolutionsandSolubility
Netionicequation:
Na2SO4(s)2Na+(aq)+SO42(aq)

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Chapter2

AqueousSolutionsandSolubility

Particulate Diagram:

S
S
S

S S
+

2 S

S S

S
+

+ = sodium cation
2 = sulfate dianion
S = solvent
Section2.6.
PrecipitationReactionsofIonsinSolutions
NOTE: Whenever you write a chemical reaction equation, remember to
include the appropriate state notation, (s), (l), (g), or (aq), for each species in
your equation.
2.47.

Whenaqueoussolutionsofpotassiumphosphate,K3PO4,andcalciumbromide,CaBr2,
aremixed,awhiteprecipitateisformed.Whentestedforelectricalconductivity,both
startingsolutionstestpositive.Followingthemixingandprecipitation,theproduct
solutionalsotestspositiveforelectricalconductivity.
(a) PrepareatablemodeledafterTable2.4tosummarizewhathashappened.

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(b) Whatnewcombinationsofcationsandanionsarepossiblefollowingmixing?Oneof
thesenewcombinationsistheprecipitateandtheotherissolubleinwater.Whichis
which?Explainyourreasoning.
(c) DrawamolecularlevelrepresentationsimilartoFigure2.17toillustratewhat
happenswhenthetwosolutionsaremixed.
(d) Writeacompleteionicequationdescribingthereactionthatoccurswhenthese
solutionsaremixed.
(e) Writeanetionicequationdescribingthereactionthatoccurswhenthesesolutions
aremixed.
Answer2.47:
(a)
BeforeMixing

Positiveion(s)
Negativeion(s)
Conductivity?

Na3PO4

CaBr2

solution

solution

Na+
(aq)

PO4(aq)
yes

AfterMixing
Na3PO4andCaBr2

Ca2+(aq)

Na+(aq)+Ca2+(aq)

Br(aq)

PO4(aq)+Br(aq)

yes

yes

Precipitate?

yes

(b)ThenewcombinationsareNaBrandCa3(PO4)2.Sincesodiumbromide(NaBr)isa
solublecompound(accordingtothesolubilityrulesforioniccompounds(Section2.7,
page238)),calciumphosphate(Ca3(PO4)2)mustbetheprecipitate.Thethirdsolubility
rulepredictsthationiccompoundsofamultiplychargedcationandamultiplycharged
anoinarelikelytobeinsoluble.
(c)6Na+(aq)+2PO4(aq)+3Ca2+(aq)+6Br(aq)>
6Na+(aq)+6Br(aq)+Ca3(PO4)2(s)
(d)3Ca2+(aq)+2PO4(aq)>Ca3(PO4)2(s)
2.48.

(a) Whenaqueoussolutionsofpotassiumchloride,KCl,andsodiumbromide,NaBr,are
mixed,noprecipitateisformed.Whatcanyouconcludeaboutthewatersolubilityof
NaCl(s)andKBr(s)?Explainyourreasoning.
(b) DrawamolecularlevelrepresentationsimilartoFigure2.17toillustratewhat
happenswhenthetwosolutionsaremixed.

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(b) Writeacompleteionicequationdescribingwhatoccurswhenthesesolutionsare
mixed.Whatwouldyouwriteforthenetionicequation?Explain.
Answer2.48:
(a)Botharesolubleinwater,basedonthesolubilityrules.
(b)

(c)K+(aq)+Cl(aq)Na+(aq)+Br(aq)K+(aq)+Cl(aq)Na+(aq)+Br(aq);no
netionicequation.
2.49.

Ba2+(aq)isextremelytoxictohumans.However,whenphysiciansneedtoxraythe
gastrointestinal(GI)tractstomachandintestines,theyfillthepatientsGItractwith
bariumsulfateandwater.Howcanitbethatthepatientisnotharmedbythisprocedure?
Answer2.49:Thesolubilityrulesindicatethatmultiplechargedcationsandanionstend
toforminsolubleioniccompoundsoraprecipitate.Inthiscase,themixturethatdoctors
usecontainsatinyamountofBa2+cation.Thisconcentrationisbelowthetoxiclevelof
Ba2+,sothepatientisnotharmed.

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Chapter2
2.50.

AqueousSolutionsandSolubility

Differencesinsolubilitycanbeusedtohelpseparatecationsfromsolutionswherethey
aremixedtogether.Theprocessiscalledselectiveprecipitation.Considerthistableof
solubilities,andthensuggestasequenceofprecipitationreactionstoseparateAg+,Ba2+,
andFe3+fromsolution.Explainyourapproachandwriteanetionicequationforeach
reactionthattakesplace.
Cation
TestSolution

Ag+(aq)

Ba2+(aq)

Fe3+(aq)

NaCl

ppt

noppt

noppt

NaOH

ppt

noppt

ppt

Na2SO4

noppt

ppt

noppt

Answer2.50:
Given:Datafromtableofsolubilities.
AskedFor:Proposeasequenceofprecipitationreactionstoseparatethesecations.
Explainyouransweraswellaswritethenetionicequations.
Plan:Weneedtoexaminetheabovetableverycarefully,notingtheconsequences
ofchoosingoneionoveranother.Wewilldeterminethesequenceaswellasthe
explanationsjustifyingourapproach.Youshouldnotethattherecouldbemorethan
onecorrectapproach.
Recall:Thisprobleminvolvesapplyingyourknowledgeofsolubilityrules.
Explanation:Letsbeginbywritingtheformulasfortheprecipitatedsalts.
Ag+

Ba2+

Fe3+

NaCl

AgCl

no ppt

no ppt

NaOH

AgOH

no ppt

Fe(OH)3

Na2SO4

no ppt

BaSO4

no ppt

Cation
Test Solution

WewillinspecttheoutcomesoftheNaOHtestsolutions,notingthatbothAgOHand
Fe(OH)3 are solid precipitates. This solution is not a good place to begin our
separationsincewewouldnotbeabletodistinguishbetweenAg +andFe3+.So,we
will arbitrary begin with the results from the NaCl test solution and label this
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32

Chapter2

AqueousSolutionsandSolubility
strategy,Scenario1.Wewilluseflowchartstoillustrateourwork.Spectatorions
willbeomitted.
=precipitate

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=watersolubleions

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Chapter2

AqueousSolutionsandSolubility

Scenario1:
Ag+,Ba2+,Fe3+
AddNaCl

AgClBa+2,Fe+3

AddNaOH

Fe(OH)3Ba2+
AddNa2SO4
BaSO4

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Scenario2:InScenario1,werealizethatafterprecipitationAgCl,wecouldhavechosen
Na2SO4beforeaddingNaOH.Scenario2willshowtheoutcomeofthisselection.

Ag+,Ba2+,Fe3+
AddNaCl

AgClBa+2,Fe+3

AddNa2SO4

BaSO4Fe3+
AddNaOH
Fe(OH)3

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Scenario3:InsteadofstartingwithNaCl,letsstartwithNa2SO4.

Ag+,Ba2+,Fe3+
AddNa2SO4

BaSO4Ag+,Fe3+

AddNaCl

Note: If we
added NaOH,
we would
have
precipated
both Ag+ and

AgClFe3+
AddNaOH
Fe(OH)3
NetIonicEquations:
FormationofAgCl:Ag+(aq)+Cl(aq)AgCl(s)
FormationofFe(OH)3:Fe3+(aq)+3OH(aq)Fe(OH)3(s)
FormationofBaSO4:Ba2+(aq)+SO42(aq)BaSO4(s)
2.51.

Aluminumnitrate,Al(NO3)3,issolubleinwater.Soissodiumoxalate,Na2C2O4.Whenan
aluminumnitratesolutionismixedwithasodiumoxalatesolution,aprecipitateforms.
(a) Whatistheprecipitate?Statethereasoningforyourprediction.
(b) Writeanetionicequationforthereactionthatoccurs.
Answer2.51:
Given:Aluminumnitrate,Al(NO3)3,issolubleinwater.Soissodium
oxalate,Na2C2O4.Whenanaluminumnitratesolutionismixedwithasodium
oxalatesolution,aprecipitateforms.

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Sincetherearetwopartsforthisproblem.Wewillsolvethisproblemintwoparts.

Part(a):
AskedFor:(a)Whatistheprecipitate?Statethereasoningforyourprediction.
Plan:WecandeducethisanswerfromanalyzingtheresultsfromInvestigateThis2.24.
Explanation:WhenAl(NO3)3ismixedwithNa2C2O4,thesolutioncontainsAl3+,NO3.,
Na+,andC2O42ions.Thenewioniccompoundsthatcouldbeformedbycombining
thecationsandanionstogiveneutralproductsareAl2(C2O4)3andNaNO3.Our
solubilityrulessaythatsodiumandnitrateioniccompoundsaresoluble,sothe
precipitatemustbeAl2(C2O4)3(s).
Part(b):
AskedFor:Writeanetionicequationforwhathappens.
Plan:First,wewillwritethebalancedchemicalequationbyinspectiontosatisfythe
conservationofmass.
Fromthebalancedchemicalreaction,wecandeterminetheionsinvolvedinthe
reaction,thespectatorions,theprecipitate,andsubsequentnetionicreaction.The
totalionicequationwillhelpusidentifythespectatorions,sowecanwritethenet
ionicequation.
Equations:
BalancedChemicalReaction:
2Al(NO3)3(aq)+3Na2C2O4(aq)

Al2(C2O4)3(s)+6NaNO3(aq)

TotalIonicEquation:
2Al3+(aq)+6NO3(aq)+6Na+(aq)+3C2O42(aq)Al2(C2O4)3(s)+6Na+(aq)+
6NO3(aq)
SinceNa+andNO3arepresentonbothsidesoftheequation,theyarethespectatorions
andcancelout.
NetIonicEquation:
2Al3+(aq) + 3C2O42-(aq)
2.52.

Al2(C2O4)3(s)

Asolutionoflithiumnitrateismixedwithasolutionofsodiumphosphate.Awhite
precipitateisobservedtoform.
(a) Whatisthewhiteprecipitate?Statethereasoningforyourprediction.

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(b) Writeanetionicequationforthereactionthatoccurs.
Answer2.52:
(a)Thewhiteprecipitateinthisreactionmustbelithiumphosphate.The
solubilityrulespredictthatallnitratesaresoluble.Althoughcompoundsof
GroupIAaregenerallyexpectedtobesoluble,notethatthatlithiumis
discussedasanexceptiontothegeneralrule.
(b)3Li+(aq)+PO43(aq)>Li3PO4(s)
2.53.

Whatdoesitmeanifthereisaforwardarrowoverabackwardarrow,,inan
equation?
Answer2.53:Thereactiongoesinbothdirections.

Section2.7.
SolubilityRulesforIonicCompounds
2.54.

Asolutionofcadmiumchloride,CdCl2,ismixedwithasolutionofammoniumsulfide,
(NH4)2S.Ayelloworangeprecipitateisobservedtoform.
(a) Whatistheorangeyellowprecipitate?Statethereasoningforyourprediction.
(b) Writeanetionicequationforthereactionthatoccurs.
Answer2.54:
(a)CdS(s).Basedonthesolubilityrules,CdS(s)isthelikelychoice.
(b)Cd2+(aq)+S2(aq)CdS(s)

2.55.

Predicttheproductsofeachofthefollowingreactionsbetweenaqueoussolutions.Ifno
visiblechangewilloccur,writeNOAPPARENTREACTIONtotherightofthearrow.
Givethereasoningforyourpredictionineachcase.Writethebalancedcompleteionic
reactionequationandthenetionicreactionequationforeachcasewherereactionoccurs.
(a) bariumchloride(aq)+sodiumsulfate(aq)
(b) silvernitrate(aq)+magnesiumchloride(aq)
(c) strontiumnitrate(aq)+potassiumnitrate(aq)
(d) ammoniumphosphate(aq)+calciumbromide(aq)

Answer2.55:
Given:Fourreactionsinwater.
AskedFor:Therearemanyitemsthatwehavetoaddressinansweringthisproblem.We
willorganizethemasfollows:
Predicttheproductsofeachofthefollowingreactionsbetweenaqueoussolutions.
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Givethereasoningforyourpredictionineachcase.
Writethebalancedmolecularequationforeachreaction.
Alsowritethenetionicreactionforeachone.Ifnovisiblechangewilloccur,writeNO
APPARENTRXNtotherightofthearrow.Putintheproperstatesymbolsforeach
compound.
Recall:Thisproblemsinvolvesunderstandingthestrategiesneededforpredictingthe
correctproductsandwritingchemicalformulas(Section2.4),balancedmolecular
equations,netionicequations(Section2.7).
Plan:Foreachreactionwewillneedtopredicttheproductsandwritethecorrectchemical
formulasforbothreactantsandproducts.Wewillneedtoexplainwhywechosethese
productsaswell.Thenwewillwritethebalancedchemicalequationfollowedbythenet
ionicequation,followingtheformatweusedinpreviousproblems.
Equation(a):
bariumchloride(aq)+sodiumsulfate(aq)
Letswritetheformulasforthereagents:
Bariumchloride:BaCl2
Sodiumsulfate:Na2SO4
Tofigureoutwhattheproductsare,weknowthattwonewsaltswillform.So,Ba+2must
gowithSO42andNa+mustgowithCl.TheproductsarethenBaSO4andNaCl.
Wenowmustconsiderthesolubilitiesofthesesalts.Weknowthatallsodiumsalts
aresoluble,butBaSO4isinsolubleinwater.
Thebalancedmolecularequationis
BaCl2(aq)+Na2SO4(aq)BaSO4(s)+2NaCl(aq)
Wewillnowwritethetotalionicequation,sowecandeterminethespectatorions.
Ba+2(aq)+2Cl(aq)+2Na+(aq)+SO42(aq)BaSO4(s)+2Na+(aq)+2Cl(aq)
Tofigureoutwhichionsarethespectatorions,weneedtoexaminiethetotalionicequation
andfindoutwhichionsarepresentinsoloutioninboththereactantsandtheproducts.In
thiscase,thespectatorionsareNa+andCl.Whenwewritethenetionicequation,we
canceltheseionsout.Thenetionicequationforthisreactionis
Ba2+(aq)+SO42(aq)BaSO4(s)
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Wewillrepeatthisstrategyforsolvingtherestoftheequations.
Equation(b):
silvernitrate(aq)+magnesiumchloride(aq)

(a)

Letswritetheformulasforthereagents:
Silvernitrate:AgNO3
Magnesiumchloride:MgCl2
Tofigureoutwhattheproductsare,weknowthattwonewsaltswillform.So,Mg+2
mustgowithNO3andAg+mustgowithCl.TheproductsarethenMg(NO3)2and
AgCl.Wenowmustconsiderthesolubilitiesofthesesalts.WeknowthatallNO3
saltsaresoluble,butAgClisinsolubleinwater.
Thebalancedmolecularequationis
2AgNO3(aq)+MgCl2(aq)2AgCl(s+Mg(NO3)2(aq)
Wewillnowwritethetotalionicequation,sowecandeterminethespectatorions.
2Ag+(aq)+2NO3(aq)+Mg2+(aq)+2Cl(aq)
2AgCl(s)+Mg2+(aq)+2NO3(aq)
Tofigureoutwhichionsarethespectatorions,weneedtoexaminethetotalionicequation
andfindoutwhichionsarepresentinthereactantsandtheproducts.Inthiscase,the
spectatorionsareMg2+andNO3.Whenwewritethenetionicequation,wecancelthese
ionsout.Thenetionicequationforthisreactionis
2Ag+(aq)+2Cl(aq)2AgCl(s)
Lookatthisnetionicequationcarefully.A2isinfrontofbothreactantsandtheproduct.
Ifwedividethereactionby2,wearriveatthepreferrednetionicequationforthistypeof
situation.
Ag+(aq)+Cl(aq)AgCl(s)
Equation(c):
(b)

strontiumnitrate(aq)+potassiumnitrate(aq)

Beforeweevenwritetheformulasforthesetwosalts,weobservethattheyhavethe
sameanion,thenitrateion.Weknowthatallnitratesaresoluble,butinthiscase,wedo

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notformanynewsaltsasproducts.Whatdoesthismean?Thismeansthatthereisno
netionicequationandnochemicalreaction.Letsinvestigatethissituationfurther.
Theformulasforthereactantsare:
Strontiumnitrate:Sr(NO3)2
Potassiumnitrate:KNO3
Wellwritethebalancedchemicalequationnext.
Sr(NO3)2(aq)+KNO3(aq)Sr(NO3)2(aq)+KNO3(aq)
Theproductsandthereactantsarethesame!!Whathappenswhenwewritethetotal
ionicequation?
Sr2+(aq)+3NO3(aq)+K+(aq)Pb2+(aq)+3NO3(aq)+K+(aq)
Alltheionsarespectatorions.Therefore,theyallcanceloutandthereisnonetionic
reaction.
Equation(d):
Balancedcompleteionicreactionequation:
6NH4+(aq)+2PO43(aq)+3Ca2+(aq)+6Br(aq)Ca3(PO4)2(s)+6NH4+(aq)+
2PO43(aq)
Netionic:
3Ca2+(aq)+2PO43(aq)Ca3(PO4)2(s)
2.56.

Writebalancednetionicequationsforreactionsthatwouldbesuitableforlaboratory
preparationofthefollowingsolidioniccompounds.Suggestcompoundswhoseaqueous
solutionsyoucouldusetocarryoutthesepreparations.
(a) BaSO4

(c) Ca3(PO4)2

(b) AgCl

(d) CaC2O4

Answer2.56:
(a)Ba2+(aq)+SO42(aq)>BaSO4(s).OnemaymixsolutionsofBa(NO3)2
andNa2SO4toproduceBaSO4.
(b)Ag+(aq)+Cl(aq)AgCl(s).OnemaymixsolutionofAgNO3and
KCltoproduceAgCl.
(c)3Ca2+(aq)+2PO43(aq)Ca3(PO4)2(s).Onemaymixsolutionsof
CaCl2andK3PO4toproduceCa3(PO4)2.
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(d)Ca2+(aq)+C2O42(aq)CaC2O4(s).OnemaymixsolutionsofK2C2O4
andCaCl2toproduceCaC2O4.

Section2.8.
ConcentrationsandMoles
2.57.

Youhaveprepared1Lofa0.1MsolutionofNaOH.Next,youaccidentallyspilledabout
200mLofthissolution.Whathashappenedtotheconcentrationoftheremaining
solution?
Answer2.57:Sincetheconcentrationofthesolutionisuniformthroughouttheentire
volume,spillingwillnotchangetheconcentration.

2.58.

YouhavebeenaskedtoassistwithachemicalinventoryofaGeneralChemistry
stockroomandhavefounda0.5Lbottleabouthalffullofasolutionlabeled,"0.5M
CaCl2."
(a) Whatdoesthislabeltellyouaboutthesolution?
(b) CanyoutellabouthowmanymolesofCaCl2areinthebottle?Ifso,showhow.If
not,tellwhatfurtherinformationyouneedtoanswerthequestion.
(c) CanyoutellabouthowmanygramsofCaCl2areinthebottle?Ifso,showhow.If
not,tellwhatfurtherinformationyouneedtoanswerthequestion.
Answer2.58:
(a)Thesolutionscontains0.5molesofCaCl2(aq)perliterofsolution.Thereare0.5
molesofCa2+(aq)perliterofsolutionand1moleofCl(aq)perliterofsolution.
(b)Ifthe0.5Lbottleisabouthalffull,thenitcontainsapproximately0.250Lof0.5M
CaCl2solution.

0.5mol
0.250L = 0.125 mol of CaCl2
L
111.1g
(c) 0.125 mol of CaCl2
= 13.9 g of CaCl2
molCaCl 2
Number of moles of CaCl2 =

2.59.

RefertothemolecularstructureofvitaminC,showninProblem2.15.
(a) WhatisthemolecularformulaofvitaminC?
(b) WhatisamolarmassofvitaminC?Explainyourwork.
(c) HowmanymolesofvitaminCarepresentina500mgtabletofthevitamin?
Explainyourreasoning.
(d) HowmanymoleculesofvitaminCarepresentineach500mgtablet?Explainyour
reasoning.
Answer2.59:

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(a)C6H8O6
(b)Molarmass=(612.011)+(81.008)+(615.999)=176.124g
(c)0.003moles
(d)1.7x1021molecules
2.60.

Calculatethemass(ingrams)ofthefollowing.Showyourreasoningclearly.
(a) 2.5moleoftheartificialsweeteneraspartame,C14H18N2O5
(b) 0.040moleofaspirin,C9H8O4
(c) 2.5x1023moleculesofcholesterol,C27H46O
(d) 1.2x1022moleculesofcaffeine,C8H10N4O2
Answer2.60:
(a)1moleofaspartameweighs:(1412.011)+(181.008)+(214.007)+(215.999)
=246.310g;2.5moleofaspartameweighs2.5246.310=615.8grams.
(b)1moleofaspirinweighs(912.011)+(81.008)+(415.999)=180.159g;0.04
moleofaspirinweighs0.04180.159g=7.21grams.
(c)1moleofcholesterolcontains6.02x1023moleculesanditweighs(2712.011)+(46
1.008)+15.999=386.664g;2.5x1023molecule=0.42molesofcholesterolthereforeits
massis0.42x386.664g=162.49grams.
(d)1moleofcaffeinecontains6.021023moleculesanditweighs(812.011)
+(101.008)+(414.007)+(215.999)=194.194g;
1.21022molecules=0.02molethereforeitsmassis0.02194.194g=
3.88grams.

2.61.

Howmanyatomsofcarbonaretherein5mgofniacin?Showyourreasoningclearly.
H
H
H

C
C

C
N

O
C
C

C
H

niacin
Answer2.61:
Given:5mgofniacinaswellasthestructureofniacin.
Asked for: Number of carbon atoms in 5mg of niacin.

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Recall: This problem involves understanding and applying the


concept of the mole. Remember, one mole of anything =
molar mass of anything = 6.02 X 1023 particles of anything.
Plan: We will use the structure of niacin to calculate its molar
mass and then use unit factors to calculate the number of
atoms of carbon in 5mg of niacin. We will need to convert
from mg to g, since the units of molar mass are
grams/mole.
Calculations: Given the structure of niacin, we can figure out its
molecular formula, which is C6H6N2O. Note, if you wrote its
formula as ON2C6H6 or another way, thats OK for now. The
format we used in C 6H6N2O has been agreed upon by
chemists as the appropriate format.

List carbon first,

hydrogen second, then all other elements in alphabetical


order.
Now, from the formula, C6H6N2O, we know that each molecule of
niacin contains 6 carbons.
handy

for

We will keep this unit factor

later

in

the

calculation.

1moleculeC 6 H 6 N 2 O
6atomsC
1molC 6 H6 N2 O
Unitfactor: 6molC 1molC 6 H6 N 2 O;1
6molC
Remember, we can write the above unit factor using moles:
Unitfactor: 6atomsC 1moleculeC 6 H 6 N 2 O;1

Forthenextstep,wewillcalculatethemolarmassforniacin.
We now sum the individual masses. The result is the molar mass
of niacin.

MolarMassofNiacin
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152.14g
1molC 6 H6 N2 O

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Since the units of mole are in grams per mole, we need to


5mg

1g
0.005g
1000mg

convert from mg to
WenowarereadytosetupanexpressiontocalculatethenumberofC.Lets
summarizeourdatabeforeproceeding:
6 C per molecule of C6H6N2O
definition of a mole
molar mass of C6H6N2O (152.14 g per 1 mol C6H6N2O)
0.005 g niacin
However we arrange our data, the bottom line for our
answer will be the numerical answer plus the appropriate
units.

So we must arrange our data to see if we can

1molC 6 H6 N2 O 6.02x10 23 molecules


6C
20

1.19x10 C
152.14g
1molC 6 H6 N2 O
1moleculeC 6 H6 N2 O
calculate the number of C in 5 mg of C6H6N2O.

0.005gC

Recap:Itseemsthatittookalotoftimetocalculatethisanswer,butthestrategy
involvedcarefullyexaminingourdatatomakesurewehadallthepieces.Notethatthe
problemdidnotgiveustheunitfactorforconvertingtogfrommg,orinformationonthe
mole.Wehadtodevelopastrategyforsolvingthisproblem.
2.62.

BacteriagenerallycontainasinglemoleculeofDNAthatencodesalltheirgenetic
information.Whatistheconcentration,molL1,ofDNAinasphericalbacteriumthathas
adiameterof106m=1m?Clearlyexplainhowyouarriveatyouranswer.
Answer2.62:
Given:BacteriagenerallycontainasinglemoleculeofDNAthatencodesall
theirgeneticinformation.

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AskedFor:Weneedtocalculatetheconcentration,molL1,ofDNAinaspherical
bacteriumthathasadiameterof106m=1m.Also,wewillexplainhowwe
arrivedatouranswer.
Recall:Thevolumeofasphereis4/3r3.Wealsoneedtorememberthat1cm3isequal
to1mL.
Plan:Wewillworkontheunitconversionsforvolume.Sincethediameterofthecellis
giveninmeters,wewillconverttocentimeters.Thiswillallowustousethe
conversionof1cm3isequalto1mL.ThiswillallowustoconverttoL.Then,we
2DNA.
Calculations:Thediameterofthebacteriumis106meters.Thismeanstheradiusis
equalto5x107m.Wewillconverttocentimetersbeforecalculatingthevolumeof
thecell.
Now,wewillcalculatethevolumeofthecell:
5 10

100cm
5
5 10 cm
1m

3
4
p5 10 5 cm 5.24 10 13
cm 3
1mL
5.24 101 3 cm 3
3
3

1L
5.24 10 1 6 L
1000mL

1cm
1moleculeDNA
1mole
9

3.17
10 M
16
23
5.24 10 L
6.023 10 molecules
WecannowconverttoL.ThiswillbethevolumeofthebacteriuminL.

WewillnowcalculatethemolarityofDNAinthecell:

2.63.

Bloodserumistypicallyabout0.14MinNaCl.Calculatethenumberofsodiumionsin
50mLofbloodserum.Showyourreasoningclearly.
Answer2.63:
Given:TheconcentrationofNaClinbloodserum(0.14MNaCl).
AskedFor:Thenumberofsodiumionsin50mLofbloodserum.
Plan:FromtheconcentrationofNaClinbloodserum,weknowthatthereare0.14moles
ofNaClperliterofbloodserum.Wewillneedtorecalltheconceptsofthemole
andsolutionstoichiometry.WenotethatthereisoneNa+1perempiricalformulaof
NaCl.

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Calculation:WefirstneedtocalculatethenumberofmolesofNaClin50mLofblood
serum.Beforewecansetupthiscalculation,wewillneedtoconvertfrommLtoL.
50 mLbloodserum

1L
0.050 Lbloodserum
1000mL

Now,wewillcalculatethenumberofmolesofNaClin0.050Lbloodserum:
0.14 molNaCl
0.050Lbloodserum 0.007molNaCl
1Lbloodserum

TofindthenumberofNa+inthissample,wesetupthefollowingcalculation:
0.007molNaCl

6.02 10 23 moleculesNaCl
1Na

4.22 10 23 Na
1molNaCl
1moleculeNaCl

Recap:Insteadofperformingthiscalculationinastepbystepfashion,wecouldhave
alsosetuponecalculationasfollows:
50 mLbloodserum

1L
0.14molNaCl
6.02 10 23 moleculesNaCl

1000mL 1Lbloodserum
1molNaCl
1Na
4.22 1021 Na
1moleculeNaCl

Section2.9.
MassMoleVolumeCalculations
2.64.

Calculatethenumberofgramsofsolutepresentineachofthefollowingsolutions.Show
yourreasoningclearly.
(a) 350mLof0.105MK2Cr2O7
(b) 50mLof1.0MFeCl36H2O
(c) 0.3Lof1.70MKCl
Answer2.64:
(a)ThemolecularweightofK2Cr2O7is294.22g/mole.10.81gofsoluteispresentin
thissolution.
(b)ThemolecularweightofFeCl36H2Ois270.34g/mole.13.52gofsoluteispresentin
thissolution.
(c)ThemolecularweightofKClis74.56g/mole.38.03gofsoluteispresentinthis
solution.

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2.65.

AqueousSolutionsandSolubility

Calculatethemolarconcentrationofsolutepresentineachofthefollowingsolutions.
Showyourreasoningclearly.
(a) 120mLcontaining4.5gramsofNaCl
(b) 0.25Lcontaining1.3gofNH4Cl
(c) 1.3Lcontaining1.85gofAgNO3
Answer2.65:
(a)ThemolecularweightofNaCl=58.45.0.08moleispresentin120ml.Thesolution
is0.64M.
(b)ThemolecularweightofNH4Cl=53.50.0.03moleispresentin0.25L.The
solutionis0.1M.
(c)ThemolecularweightofAgNO3=169.89.0.01moleispresentin1.3L.The
solutionis0.01M.

2.66.

(a)5.405gglucose,C6H12O6,isdissolvedinenoughwatertomake1.000Lofsolutionat
20C.Whatisthemolarityofglucoseinthissolution?Showyourreasoningclearly.
(b) HowmanymLofthesolutionpreparedinpart(a)willyouneedinordertoobtain
0.950millimolesofglucoseat20C?Showyourreasoningandworkclearlyand
completely.
Answer2.66:
(a)
Given:5.405gglucose,C6H12O6,isdissolvedinenoughwatertomake1.000Lof
solutionat20C.
AskedFor:Calculatethemolarityofglucoseinthissolution.
Recall:Thedefinitionofmolarity,M,ismolesofsoluteperliterofsolvent.
Plan:Wearegiventheformulaforglucosefromwhichwecancalculateitsmolarmass.
Remember,theunitsofmolarmassaregramspermole.Sinceweknowhowmuch
glucosewehaveingrams,wesimplyconvertgramsofglucosetomoleofglucose.The
volumeisgivenas1literofsolvent,sowecanjustdividethecalculatedmolesofglucose
by1literofsolution.
Calculations:

molarmassofglucose

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180.18gglucose
literofsolution

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molofglucose 5.405gglucose

1molglucose
2
2.9997 10 molglucose
180.18gglucose

Note:5.405gcontains4significantfigures.Thismeanswewillhavetoroundupto
3.000x102molglucose.

Mofglucose

3.000 102 molglucose


3.000 10 2 Mglucose
1litersolution

Tocalculatethemolarity,simplydivideby1liter:
(b)
Given:FromProblem2.38,wecalculatedthemolarityofsolutionwhichwas3.000x10
M.

AskedFor:NumberofmLofthesolutionpreparedinProblem2.38willyouneedin
ordertoobtain0.950millimolesofglucoseat20oC.
Recall:Thisprobleminvolvessolutionstoichiometryaswellasunitfactorconversions.
Remember,molarityisgivenismolesofsoluteperliterofsolution.
Plan:SinceweneedtocalculatemLofsolution,wewillhavetousetheunitfactorof:
1liter 1000ml; 1

1000ml
1liter

Wearealsoneedtoconvertmolestomillimoles(mmol).Theunitfactorhereis:

1mol 1000mmol; 1

1000mmol
1mol

Now,wehavetoarrangeourdataforourcalculation.Weneedtosolveforthevolumein
mLthatcontains0.950millimolesofglucosegiven3.000x102Mglucose.
Calculations:
Wewillperformthiscalculationinonestep,followingourplandescribedabove.
mLofglucosesolution 0.950mmol

1mol
1liter
1000mL

1000mmol 3.000 102 molglucose


1L

31.7mLofglucose

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Recap:Youmayhavechosenadifferentroutetocalculatethisvolume.ThatsOK.
Thiscalculationdemonstratesthatwecansetupalltheunitfactorsandperformthe
calculationinjustonestep.Youmayhavechosenmorethanstepsandthatsperfectly
acceptableaslongasyouunderstandtheconceptsandarriveatthecorrectanswer.
2.67.

Twostudentswereaskedtopreparea1.00MsolutionofCuSO4.Onestudentfounda
bottle,labeled"CuSO45H2O".Heweighed159.60gofthishydratedcoppersulfate,
transferredittoa1Lvolumetricflaskanddissolveditinasmallquantityofwater.Then,
headdedmorewateruntilthesolutionjustreachedthecalibrationmarketchedonthe
neckoftheflaskandthoroughlymixedthecontentsoftheflask.Thesecondstudent
followedexactlythesameprocedure,butsheusedtheanhydroussaltofcoppersulfate,
CuSO4.Whichstudentpreparedthesolutionwiththecorrectconcentration?Calculatethe
molarconcentrationofCuSO4ineachsolution.
Answer2.67:Molarmassofhydratedcopper(II)sulfate,CuSO45H2O,is249.50g.He
weightedonly159.60gofthishydratedcoppersulfate.Thus,heusedtoolittlesolute
becausehisfinalmolarconcentrationis0.64M.Topreparea1.00Msolution,159.60g
oftheanhydrouscoppersulfate,CuSO4,isrequired.Thesecondstudentpreparethe
correctsolution.

2.68.

Youneedabout170mLof0.10MNaOHforanexperiment.Theconcentrationofthis
solutionhastobefairlyexact.Describehowtopreparethesolution.
Answer2.68:Sinceyouneed170mLofsolution,youcanuse200mLvolumetricflask
topreparethesolution.
(a)CalculatethemassofpureNaOHrequiredtopreparethesolution:
MassofNaOH=(0.1molex0.2Lx39.99g/mole)/1L=0.80g
(b)Weighouttherequiredmassofsubstance,andplaceitinthevolumetricflask
(c)Addsomewaterandagitateuntilthesubstanceisdissolved.
(d)Addwateruptomarkandagitateagaintoensureauniformconcentration
throughout.

2.69.

Normalsaline,asolutiongivenbyintravenousinjection,isa0.90%(masstovolume%)
sodiumchloridesolution.Howmanygramsofsodiumchloridearerequiredtomake250.
mLofnormalsalinesolution?Whatisthemolarityofthissolution?Thedensityofthis
solutionisthesameaswater,1.00gmL1.Showyourreasoningclearly.
Answer2.69:
Given:A0.90%(masstovolume%)sodiumchloridesolution.

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Sincetherearetwoquestionstoanswer,wewillcategorizethefirstquestionasPart(a)
andthesecondquestionasPart(b).
Part(a):
AskedFor:Calculatethenumberofgramsofsodiumchloriderequiredtomakea250.0
mLnormalsalinesolution.
Recall:Weneedtounderstandthatthisisaconcentrationproblem,involvingsolution
stoichiometry.
Plan:Theconcentrationofthissalinesolutionisgivenasapercent.Thisisdifferent
fromtheconceptofmolarity.So,letsdiscusswhatthispercentconcentrationmeans.
Weknowthatpercenthastodowithafractionof100.0.90%(massofsoluteto
volumeofsolution%)meansthatin100mLofwater,0.90gramsofNaClarefound.
TheproblemrequestsustocalculatehowmuchNaClisneededtomakea250.0mL
solution.
Calculation:

0.90gNaCl
250mLofH 2O 2.3gramsNaCl
100mLsolution

Recap:Weneed2.3gramsofNaCltopreparea250mLnormalsalinesolution.
Part(b):
AskedFor:Molarityofthissolution.
Recall:Thedefinitionofmolarityofasolutionismolesofsoluteperliterof
solution.
Plan:Weknowthat2.3gramsofNaClisrequiredtopreparea250mLsolution(answer
toPart(a).WewillneedthemolarmassofNaCltoconvertfromgramsofNaClto
molesofNaCl.Also,mLwillneedtobeconvertedtoL.
Calculations:
Recap:Wecouldhaveperformedthiscalculationinjustonestep:
2.3gNaCl

1molNaCl
3.93 102 molNaCl
58.5gNaCl

250mL

1liter
0.250L
1000ml

3.93 10 2 molNaCl
MolarityofNormalSalinesolution
0.16M
0.250L
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2.3gNaCl
1moleNaCl
1000mL


0.16Msalinesolution
250mLsolution
58.5gNaCl
1liter

Youshouldnotethatusing0.9gramsofNaClin100mLofaqueoussolutiontocalculate
themolarityofthissolutionwouldgivethesameanswer.
2.70.

Whenurineisanalyzed,thenormalrangeforurea,(NH2)2CO,oneofthesolutesinurine,
is1340g(24hr)1.(Forurinalysis,apatientsurineiscollectedovera24hourperiodto
besurethatthesampleisrepresentative.)Apatientslaboratorytestsshowaureacontent
of25g(24hr)1.Supposethenormaloutputofurineforapatientofthisageis2.5L(24
hr)1.Whatisthemolarityoftheureainthepatientsurine?Explainyourreasoning.
Answer2.70:
Given:Thenormalrangeforurea,(NH2)2CO,is1340g/24hr..Apatientslaboratory
testsshowaureacontentof25g/24hr.Thenormaloutputofurineforapatientofthis
ageis2.5L/24hr.
AskedFor:Themolarityoftheureainthepatientsurine.
Recall:Weneedtounderstandthatthisisaconcentrationproblem,involvingsolution
stoichiometry.
Plan:Ina24hrperiod,thepatientexcretes25gofureain2.5Lofurine.Toconvertto
molarity,wewillneedtocovert25gofureatomolesofureausingureasmolarmass
(60.0g/mol).Theunitsforvolumedonotneedtobechanged.
Calculation:

2.71.

Oneoftheioniccompoundsinsportsdrinksispotassiumdihydrogenphosphate,
25gurea
1moleurea

0.17Murea
2.5Lurine
60.0gurea

KH2PO4.Thelabelononeofthesedrinkstellsusthat240mLofthesolutioncontains30
mgofpotassium.KH2PO4istheonlyingredientinthesolutionthatcanprovidethis
potassium.HowmanygramsofKH2PO4aredissolvedin240mLofthesolution?What
isthemolarityoftheKH2PO4,inthissolution?Clearlyshowandexplain,allthework
youdotosolvethisproblem.
Answer2.71:

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Given:Oneoftheelectrolytesinsportsdrinksismonopotassiumphosphate,KH2PO4.
Thelabelononeofthesedrinkstellsusthat240mLofthesolutioncontains30mgof
potassium.KH2PO4istheonlyingredientinthesolutionthatcanprovidethispotassium.
AskedFor:Therearetwopartsofthisproblem.Wewilllabelthefirstquestionas(a)
andthesecondquestionas(b).
HowmanygramsofKH2PO4aredissolvedin240mLofthesolution?
WhatisthemolarityoftheKH2PO4,inthissolution?
Recall:WewillbeginwithQuestion(a).Wearetoldthatthereare30mgofpotassium
in240mLofthissportsdrink.TheonlysourceofpotassiumisKH2PO4.Therefore,this
questioninvolvesstoichiometryusingtheinformationcontainedinthechemicalformula
aswellasthefactthatwearegiven30mgofpotassium.Also,potassiumrefersto
K+.
Plan:WeknowthatforeveryonemoleofKH2PO4producesonemoleofpotassium.
Sincewearegiven30mgofpotassium,wecancalculatethenumberofmolesof
potassiumwhichwillbeequaltothenumberofmolesofKH2PO4.Wewillneedthe
molarmassofpotassiumaswellastheunitfactorfortheconversionfrommgtog.
Then,giventhemolarmassofKH2PO4, we can convert from moles of KH2PO4
to grams of KH2PO4.
Calculations:
# molKH 2 PO 4 30mgK

1molK 1molKH2 PO 4

7.67 10 4 molKH 2 PO 4
39.10gK
1molK

Now,letsusethemolarmassofKH2PO4toconvertfrommolofKH2PO4togramsof
KH2PO4:
# ofgramsofKH 2 PO 4 7.67 10 4 mole

136.09gKH 2 PO4
0.104gKH 2 PO4
1moleKH 2 PO4

Part(b)
Plan:WeknowhowmanymolesofKH2PO4aswellasthevolume(240mL).Weneed
torememberthattheunitsofmolarityareinmolesperliter,sowewillhavetoconvert
mLtoL,usingtheappropriateunitfactor.
Calculation:

GammaDraft

MofKH 2 PO 4

7.67 10 4 moleKH 2 PO 4 1000mL

3.20 10 3 MKH2 PO 4
240mL
1L
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Section2.10.ReactionStoichiometryinSolutions
2.72.

Howmanymoleseachofcarbon,hydrogen,andoxygenatomsarepresentintwomoles
ofammoniumacetate,NH4C2H3O2?Whatisthetotalnumberofmolesofatomsintwo
molesofthecompound?Whatisthetotalnumberofmolesofionsintwomolesofthe
compound?
Answer2.72:
Given:Twomolesofammoniumacetate,NH4C2H3O2.
Part(a):
AskedFor:Numberofmolesofcarbon,hydrogen,andoxygen.
Plan:Wewillassumethatonemoleculeofammoniumacetatecontainstwocarbons,7
hydrogens,1nitrogen,and2oxygens.Therefore,wecanassumethatonemoleof
NH4C2H3O2containstwomolesofcarbon,sevenmolesofhydrogen,onemoleof
nitrogen,and2molesofoxygen.Weneedtosetupaunitfactorthatexpressesthis
relationshipforeachoftheatomsrequested.
Calculations:
# ofmolofC 2 molNH4C2 H3 O2

2molC
4molofC
1molNH 4C2 H3 O2

# ofmolofH 2molNH 4C2 H 3O 2

# ofmolofO 2molNH4 C2H 3O 2

7molH
14molofH
1molNH 4 C2H 3O 2

2molO
4molofO
1molNH 4 C2H 3O2

Part(b):
AskedFor:Totalnumberofmolesofatoms.
Plan:UsingtheinformationgiveninPart(a),wecancalculatethetotalnumberof
molesofatoms.Weknowthat1moleofNH4C2H3O2has12molesofatoms,sowecan
createaunitfactorthatshowsthisinformation.
Calculation:

# ofmolofatoms

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12molatoms
2molNH4 C2H3O2 24molatoms
1molNH4C2 H3 O2
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Part(c):
AskedFor:Totalnumberofmolesofions.
Plan:EachmoleculeofNH4C2H3O2producestwoions,NH4+andC2H3O2.
Therefore,onemoleofNH4C2H3O2producestwomolesofions.
Calculation:

# ofmolofions 2molNH 4 C2H3O2

2molions
4molofions
1molNH4 C2H3O2

Recap:Therecanbemorethanonemethodusedtosolvethesetypesofproblems.You
mighthavesolvedthemdifferently,butyoustillcalculatedthecorrectanswers.You
mighthavesolvedthemdifferently,butifyoucalculatedthecorrectanswers,thatsOK.
2.73.

Astudentistryingtoprepareartificialkidneystonesinthelaboratory.Howmanygrams
ofcalciumphosphatecanhemakebymixing125.mLof0.100Mcalciumchloridewith
125.mLof0.100Msodiumphosphate?Explainyourreasoningandanyassumptionsyou
makeinsolvingthisproblem.
Answer2.73:
Given:125.0mLof0.100Mcalciumchloridemixedwith125.0mLof0.100Msodium
phosphate.
AskedFor:Numberofgramsofcalciumphosphateareformed.
Recall:ThisprobleminvolvesmanyconceptsdiscussedinChapter2.Wewillneedto
reviewthenomenclatureofsaltsaswellasthedefinitionofmolarityandsolution
stoichiometry.
Plan:Firstandforemost,wewillneedtowritetheformulasforcalciumchloride,sodium
phosphate,andcalciumphosphate.Then,wewillwriteabalancechemicalequationfor
thereaction.Wewillneedtodeterminetheadditionalproduct,besidescalcium
phosphate,thatisformedfrommixingcalciumchlorideandsodiumphosphate.Next,we
willneedtocalculatehowmanymolesofcalciumchlorideandsodiumphosphatewe
have.Weneedtoknowthemolarmassforeachsalt.Ourgoalatthisstepistofigure
outwhichofthetwostartingmaterialsisconsumedcompletelyandwhichoneisin
excess.Oncewehavethisinformation,wecanusethebalancedchemicalreactionto
calculatethenumberofmolesofcalciumphosphateformed.Then,usingthemolarmass
ofcalciumphosphate,wecaneasilyconverttogramsofcalciumphosphate.

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Calculations:Letsbeginwithwritingthecorrectformulasforcalciumchloride,sodium
phosphate,andcalciumphosphate:
Calciumchloride:CaCl2
Sodiumphosphate:Na3PO4
Calciumphosphate:Ca3(PO4)3
Now, we can write the balanced chemical equation. We know that Ca3(PO4)2 is one of
the products. But what is the other product? Lets start by writing what we know so far:
CaCl2(aq) + Na3PO4(aq) Ca3(PO4)2(s) + ?
So, Na+ and Cl- are left over and will be soluble ions. We can write this as NaCl(aq). The
balanced chemical reaction is:
3CaCl2(aq) + 2Na3PO4(aq)

Ca3(PO4)2(s) + 6NaCl(aq)

Next, we need to determine the number of moles of CaCl2 and Na3PO4. Remember, we
are given the same quantities of each starting material (125 mL
of 0.100M CaCl2 and 125 mL of 0.100M Na3PO4). We will need to convert from mL to
L.

#molCaCl 2 #molNa3PO4 0.125L 0.100M 1.25 102 mol


We have now determined that we have 1.25x10-2 mol of CaCl2 and Na3PO4.
In our balanced chemical equation, we do not have a 1:1 ratio of CaCl2 and Na3PO4.
Instead, for every 2 moles of CaCl2, we need 3 moles of Na3PO4. In our reaction, one of
these reagents will be completely consumed and one will have some material remaining.
We will now figure out which one.
Lets consider this possible scenario. We will assume that all of the CaCl2 is completely
used in the reaction. So we will calculate how much Na3PO4 is required. Our calculation
is:

1.25 102 molCaCl 2

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3molNa 3 PO 4
1.88 102 molNa 3 PO 4
2molCaCl 2

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But we only have 1.25 x 10-2 mol of Na3PO4. This means that CaCl2 cannot be
completely used up this reaction, because we simply do not enough Na3PO4.
We will now calculate the second scenario in which we assume that all the Na3PO4 is
completely consumed in this reaction.

1.25 102 molNa 3 PO4

2molCaCl 2
8.33 10 3 molCaCl 2
3molNa 3 PO4

Thus, all of Na3PO4 will be consumed in the reactions, but only 8.33 x 10-3 mol of CaCl2
will be used. This means that 4.17 x 10-3 mol of CaCl2 will remain in solution and not
participate in the reaction.
Now we know how much of Na3PO4 and CaCl2 are used in this reaction. We arbitrary
choose Na3PO4 to calculate the number of moles of Ca3(PO4)2 produced in the reaction.
We know from the balanced chemical reaction, 2 mol of Na3PO4 produce 1 mol of
Ca3(PO4)2. Our calculation is:
2

# ofmolCa 3 (PO4 )3 1.25 10 molNa 3 PO4

1molCa 3 (PO4 )3
3
6.25 10 molCa 3 (PO4 )2
2molNa 3 PO 4

We now need the molar mass of Ca3(PO4)2 to convert from mol to grams of
Ca3(PO4)2. This is our final calculation for this problem and its results will give us our
answer to this problem.
3

6.25 10 molCa 3 (PO4 )2

310.18gCa 3 (PO 4 )2
1.94gCa 3 (PO 4 )2
1molCa 3 (PO4 )2

Recap: There are a variety of strategies that you can use for these types of problems.
You might have chosen a different strategy, but still arrived at the same answer. With
these types of problems, the major hurdle is remembering to figure out which reagent
limits the amount of product(s) formed.

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2.74.

AqueousSolutionsandSolubility

Whatvolumeof0.100MSO32(aq)isneededtoreactexactlyandcompletelywith24.0
mLof0.200MFe3+(aq)?Theequationthatrepresentsthereactionthatoccursis:
2Fe3+(aq)+SO32(aq)+3H2O(l)2Fe2+(aq)+SO42(aq)+2H3O+(aq)
Answer2.74:
Thecoefficientsinthebalancedionicequationgivetherelativenumberofmolesofeach
reactantandproduct;thisratiocanalsobeexpressedinaratioofmillimoles.

0.200mmolFe 3+ (aq) 1mmolSO 3 2 (aq)


1mLSO 32 (aq)
24.0mLFe (aq)

24.0mLSO3 2 (aq)
3+
3+
2
1mLFe (aq)
2mmolFe (aq) 0.100mmolSO3 (aq)
3+

2.75.

Assumethatyoumix50.0mLofasolutionthatis0.45MNa2SO4with50.0mLofa
solutionthatis0.36MBaCl2.
(a) Howmanymolesofeachofthefourions,Na+,SO42,Ba2+,andCl,arepresentin
themixture?Explainyourreasoningclearly.
(b) IftheSO42(aq)inthemixturereactswithBa2+(aq)togiveBaSO4(s),howmanymoles
ofBa2+(aq)arerequiredtoreactwithalltheSO42(aq)inthemixture?Explainyour
reasoningclearly.
(c) IftheBa2+(aq)inthemixturereactswithSO42(aq)togiveBaSO4(s),howmanymoles
ofSO42(aq)arerequiredtoreactwithalltheBa2+(aq)inthemixture?Explainyour
reasoningclearly.
(d) IsBa2+(aq)orSO42(aq)thelimitingreactantinthismixture?Explainhowyoumake
thischoice.

Answer2.75:
Given:Amixtureof50.0mLofasolutionthatis0.45MNa2SO4with50.0mLofa
solutionthatis0.36MBaCl2.
AskedFor:.Howmanymolesofeachofthefourions,Na+,SO42,Ca2+,andCl,are
presentinthemixture?
Recall:Thisproblemrequiresknowledgeinsolutionstoichiometryandtheconcepts
associatedwithmolarity.Thebalancedchemicalequationfortheprecipitationof
BaSO4.
Ba2+(aq)+SO42(aq)CaSO4(s)
Fromthisnetionicreaction,weknowthatNa+andClarethespectatorions.

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Plan:Weneedtocalculatethenumberofmolespresentineachsolution.This
informationwillhelpusdeterminewhichsolutioncontainsthelimitingreagents.
LetsbeginbyarbitrarilychoosingNa2SO4.Remember,wewillneedtoconvert
frommLtoL.

# molNa 2SO 4 50.0mL

1L
0.45mol

0.0225molNa 2 SO 4
1000mL
1L

0.0225molNa 2 SO4

1molSO 4 2
0.023molSO 4 2
1molNa 2SO 4

and
2molNa
0.0225molNa 2SO 4
0.045molNa
1molNa 2 SO4
ForeveryonemoleofNa2SO4,twomolesofNa+andonemoleofSO42areproduced.
Therefore,wehave:

# molBaCl 2 50.0mL

1L
0.36molBaCl 2

0.018molBaCl 2
1000mL
1L

WewillnowcalculatethenumberofmolespresentintheBaCl2solution.
OnemoleofBa2+andtwomolesofClareproducedfromonemoleofBaCl2.So,
0.018molBaCl 2

1molBa 2
0.018molBa 2
1molBaCl 2
and

0.018molBaCl 2

2 molCl
0.036molCl
1molBaCl 2

WewillassumethattheformationofBaSO4goestocompletion.Inthisproblem,the
limitingreagentisBa2+withSO42inexcess.So,all0.018molBa2+and0.018mol
SO42outof0.023molofSO42isconsumed.Thatmeanstherewillbe0.0045molof
SO42areremaininginthesolution,alongwithNa+andCl.

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(b) IftheSO42(aq)inthemixturereactswithBa2+(aq),howmanymolesofBa2+(aq)are
requiredtoreactwithalltheSO42(aq)inthemixture?
Youdon'thaveenoughBa2+(aq)toreactwithalltheSO42(aq).
(c) IftheBa2+(aq)inthemixturereactswithSO42(aq),howmanymolesofSO42(aq)are
requiredtoreactwithalltheBa2+(aq)inthemixture?
(seeaboveinpart(a))
(d) IsCa2+(aq)orSO42(aq)thelimitingreagentinthismixture?Explainwhyyoumake
thischoice.
ThelimitingreagentinthemixtureisBa2+,asexplainedinpart(a).
2.76.

Predictwhatprecipitatewillformwheneachofthefollowingaqueoussolutionmixings
iscarriedout.Determinethelimitingreagentforeachreactionandthemassofthe
precipitate(assumingthatallprecipitationreactionsgotocompletion).Ifthereisno
precipitate,thenwriteNOAPPARENTREACTIONandexplainyourreasoning.
(a) Mix125mLof0.15MBaBr2with125mLof0.15MNa3PO4.
(b) Mix85mLof0.40MNH4Clwith65mLof0.50MKNO3.
(c) Mix85mLof0.40M(NH4)2Swith65mLof0.50MZnCl2.
(d) Mix15.0mLof0.20MAgNO3with15.0mLof0.40MNaBr.
Answer2.76:
(a)AgBr(ppt)ThelimitingreagentisAg+becausethetotalamountofAg+is3.0
mmol(15.0mL0.20mmol/mL),andthetotalamountofBris4mmol(10.0mL0.40
mmol/mL).EquimolaramountsofAg+andBrarerequiredtoformAgBr,sotheyield
ofproductislimitedbytheAg+,whichrunsoutbeforetheBr.
(b)Ba3(PO4)2(ppt)ThelimitingreagentisBa2+.Thereare18.75mmoleachofBa2+
andPO42,butthreeequivalentsofBa2+arerequiredforeverytwoequivalentsofPO42so
theBa2+isdepletedfirst.
(c)NOAPPARENTREACTIONThetwopossiblecrossproducts(NH4NO3and
KCl)arebothwatersolubleioniccompounds.
(d)CdS(ppt)ThelimitingreagentisCd2+.

2.77.

When50.mLofanaqueous0.1MSrCl2solutionaremixedwith50.mLofanaqueous
0.1MNa3PO4solution,awhiteprecipitateisformed.
(a) Howmanymolesofchlorideanionremaininsolutionwhentheprecipitationis
complete?Howmanygramsofchlorideisthis?Explainthereasoningforyouranswers.

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(b) Howmanymolesofeachoftheotherionsremainsinsolutionwhentheprecipitation
iscomplete?Explainthereasoningforyouranswers.
(c) Writeacompleteionicreactionequationforthereactioninthemixture.Usethis
equationandyourresultsfromparts(a)and(b)toshowthatthesolutioniselectrically
neutralaftertheprecipitationiscomplete.Showyourreasoningclearly.
Answer2.77:
<thisquestionshouldhavepart(c)firstbecauseyoucan'tdothecalculationsfor
part(a)and(b)withoutthenetionicequationskipfornow>
Section2.11.SolutionsofGasesinWater
2.78.

Aregasesverysolubleinwater?Explainyourreasoning.
Answer2.78:
Toconsiderthesolubilitiesofgasesinwater,weneedtoexaminethepolarityofthegas
moleculesaswellasthetemperature.Polargasmolecules,likeammonia,tendtobe
moresolubleinwater,whilenonpolargasmolecules,likenitrogenandoxygen,tendto
benotsolubleinwater.Also,inbothcases,thehigherthetemperature,thelesssoluble
thegaswillbe.

2.79.

Predictwhetherthenoblegases(He,Ne,Ar,Kr,andXe)havealowsolubilityinwater
(lessthan1gL1)orahighsolubilityinwater(greaterthan10gL1).Explainclearly.
Answer2.79:RecallfromSect2.11thatonlywhenwaterreactswithagaswillithavea
veryhighsolubility.Sincethenoblegasesallhavecompletevalenceshellsofelectrons
(theoctetrule),theyshownotendencytobondwithwater.Waterdoesdissolvepolar
moleculesreasonablywell.However,theelectroncloudsofthenoblegasesareperfectly
symmetrical,renderingthemnonpolarandthereforehighlyinsoluble.

2.80.

(a) UsethedatainTable2.6forthisproblem.Howmanymolesofnitrogengas,N2(g),
dissolvein10.0Lofwaterwhenthetemperatureis25oCandthepressureofthegasis
101kPa(oneatmosphere)?
(b) Howmanymolesofoxygengas,O2(g),dissolvein0.100Lofwaterwhenthe
temperatureis25oCandthepressureofthegasis101kPa(oneatmosphere)?
Answer2.80:
(a)

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0.018gN 2

1molN 2
6.4 10 4 molesN 2 perkgofwater
28.02gN 2

0.039gO 2

1molO 2
1.2 10 3 molesO 2 perkgofwater
32.00gN 2

(b)

2.81.

ThesolubilityofH2(g)inwaterat25Cis7.68104molL1.Whenthetemperatureis
decreasedto0C,thesolubilityofhydrogenis9.61104molL1.Howdoyouaccount
forthegreatersolubilityatthelowertemperature?
Answer2.81:
Given:SolubilityofH2inwaterat25Cis7.68104molL1.Thesolubilityof
hydrogenat0Cis9.61104molL1.
AskedFor:Explanationofobservations.
Plan:Weneedtoconsiderwhatweknowaboutthesolubilitybehaviorofgasesat
differenttemperatures,asdiscussedinSection2.3.Weknow,too,thatH2isanonpolar
molecule.
Explanation:SincethereisverylittleattractionbetweenH2andH2O,wehaveto
examinethemotionofH2atdifferenttemperatures.At25C,H2aremovingfasterthan
0C.Thus,moremoleculeswillhaveenoughenergytoescapeintothegasphaseat25
Cthanat0C.ThismeansthatthesolubilityofH2willbegreaterat0Cthanat25C.

2.82.

Hydrogenbromidegas,HBr(g),dissolvesinwatertoformanacidicsolution.Whatisthe
nameofthisaqueoussolution?Hint:WhatistheanalogoussolutionofHCl(g)called?
Answer2.82:Hydrobromicacidandhydrochloricacid,respectedly.

2.83.

IfHBr(g)isbubbledintowateruntilthesolutionissaturated,theresultingsolutionis
approximately8.9MinHBr(aq).Thedensityofthesolutionisabout1.5kgL1.Whatis
thesolubilityexpressedingkg1(asinTable2.6forothergases)?Clearlyexplainthe
reasoningforyouranswer.
Answer2.83:Approximately480gkg1.

2.84.

(a)HCl(g)isquitesolubleindiethylether(CH3CH2OCH2CH3).Variousreason(s)forthis
solubilityaregiven:dipoledipoleinteractions,hydrogenbonding,orHClionization.
DrawapicturetoillustrateeachofthesepotentialinteractionsofHClandether.
(i)dipoledipole

(ii)hydrogenbonding

(iii)HClionization

(b)Whatexperimentcouldbedonetoeliminateorconfirmoneormoreofthese.

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Answer 2.84: (a) For simplicity, diethyl ether, C2H5O C2H5, is written
as ROR in these sketches showing (i) dipole-dipole, (ii) hydrogen
bonding, and (iii) ionization of HCl in ether solution:

(b)Theelectricalconductivityofthesolutioncouldbetested,Ifitconducts,thenwe
knowthatatleastsomeHClionization,interaction(iii),mustoccur.Thisdoesnotrule
outcontributionstothesolubilityfromtheotherinteractions.Ifthesolutiondoesnot
conduct,thenionizationisruledoutasacontributortothesolubility.Theother
interactionsarehardtodistinguishexerimentally.
2.85.

Wouldyouexpecthydrogenchloridegas,HCl(g),tobemoreorlesssolubleinhexane
thaninwater.Explainyourreasoning.
Answer2.85:Hydrogenchloridecanreactwithwaertoformhydroniumchloride
(equation(2.16)).ThisincreasesthesolubilityofHClinwater.Thereisnoparallel
reactionofHClwithhexane,soitshexanesolubilityismuch,muchless.Assumethatthe
amountofagasthatdissolvesinwaterisdirectlyproportionaltoitspressureoverthe
solution;thelowerthepressure,thelessgasdissolved.

2.86.

(a) UsethedatainTable2.6tofigureoutthemassesofnitrogenandoxygenthat
dissolvein1.0Lofwaterat25Cwhenair(80%nitrogenand20%oxygenmole
percents)atatotalpressureof101kPadissolvesinthewater.Stateallyourassumptions
explicitlyandexplainclearlythemethodyouusetoarriveatyouranswer.
(b) Whatpercentofthedissolvedmassofgasisoxygen?Showhowyougetyour
answer.
(c) Isthemasspercentofoxygenintheairgreaterthan,lessthan,orthesameasits
masspercentinthegasesdissolvedinwater?Explainyourreasoning.
Answer2.86:
(a)ThedatainTable2.6areforthesolubilityofthegasesat101kPa(oneatmosphere)
pressure.Inair,thenitrogenpressureis80%ofoneatmosphere,soonly80%asmuch
nitrogenwilldissolve:(0.80)(0.018g(kgwater)1)=0.014g(kgwater)1.Oxygen
pressureis20%ofoneatmosphere:(0.20)(0.039g(kgwater)1)=0.008g(kgwater)1.

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(b) Inonekilogramofwatersaturatedwithgasesfromtheair,thereare0.014gof
nitrogenand0.008gofoxygen,or0.022gtotalofthesegases.Themasspercentof
oxygenis[(0.008g)/(0.022g)]100%=36%.
(c) Inamoleofair(Avogadrosnumberofnitrogenandoxygenmolecules),80%ofthe
moleculesarenitrogenand20%areoxygen.Themassofnitrogeninamoleofairis
(0.80mol)(28gmol1)=22.4g.Themassofoxygenis(0.20mol)(32gmol1)=6.4
g.Themasspercentofoxygeninairis[(6.4g)/(28.8g)]100%=22%.Themass
percentofoxygenfromtheairdissolvedinwaterisgreaterthanthemasspercentinair.

Section2.12.TheAcidBaseReactionofWaterwithItself
2.87.

Whatisanacid?
Answer2.87:AqueoussolutionsthathaveapHbelow7.

2.88.

Whatisabase?
Answer2.88:AqueoussolutionsthathaveapHabove7.

2.89.

IfasolutionofacidAhasapHof1andasolutionofacidBhasapHof3,whatcanyou
tellaboutthetwoacidsolutions?
Answer2.89:AcidAis100timesstrongerormoreacidicthanAcidB.

2.90.

Identifyaqueoussolutionswiththesepropertiesasacidicorbasicorneither.Explain
yourreasoningineachcase.
(a) pH<7

(e) [H3O+(aq)]>1.0107M

(b) [H3O+(aq)]=1.0107M

(f) [OH(aq)]<1.0107M

(c) [OH(aq)]>1.0107M

(g) [H3O+(aq)]<1.0107M

(d) pH>7

(h) [OH(aq)]=1.0107M

Answer2.90:(a)acidic;(b)neutral;(c)basic;(d)neutral;(e)basic;(f)acidic;(g)
acidic;(h)basic;(i)neutral
2.91.

CalculatethepHofeachofthefollowingsolutions.
(a) [H3O+(aq)]=1.0102M

(c) [H3O+(aq)]=5.0104M

(b) [H3O+(aq)]=1.01010M

(d) [H3O+(aq)]=5.0108M

Answer2.91:(a)2.00(b)10.00(c)3.30(d)7.30
2.92.

AssumingthatthereactionofHCl(g)andwatergoestocompletiontoformH3O+(aq)and
Cl(aq),whatisthemolarconcentrationofHCl(aq)thatwillresultinsolutionshaving

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(a) pH=4?

(b) pH=2?

Answer2.92:(a)1104M(b)1102M
2.93.

HCl(g)isnamedhydrogenchloride,butHCl(aq)isnamedhydrochloricacid.Byanalogy,
whatarethenamesofHI(g)andHI(aq)?ofH2S(g)andH2S(aq)?
Answer2.93:HI(g)ishydrogeniodide.HI(aq)ishydroiodicacid.H2S(g)ishydrogen
sulfide.H2S(aq)ishydrosulfuricacid.

2.94.

(WEB)Chap2,Sect2.12.3.Writeabriefessaydescribingtherelationshipofthetwo
WEB
moviestothefigureatthebottomofthepage(whichissimilartoFigure2.26).

Section2.13.AcidsandBasesinAqueousSolutions
2.95.

Phosphoruspentoxide,P2O5(s),isanonmetaloxidewhichreactswithwatertoforma
solutionofphosphoricacid,(HO)3PO(aq)(orH3PO4(aq)).
(a) Writethebalancedchemicalreactionequationforthereactionofphosphorus
pentoxidewithwater.
(b) If1.42gofphosphoruspentoxideismixedwith250.mLofwater,whatisthe
molarityoftheresultingphosphoricacidsolution?Showyourreasoningclearly.
Answer2.96:
(a)P2O5(s)+3H2O(l)2H3PO4(aq)
1molP2 O5 (s)
2molH3 PO 4 (aq)

= 2.00 10-2 mol H3PO4(aq)


142g
1molP2 O5 (s)
2.0 102 molH3 PO4 (aq)
molarity =
= 8.0 10-2 M H3PO4(aq)
0.250L

(b) 1.42 g

2.96.

Giveanameforeachofthefollowingioniccompoundswithoxyanions(shownwith
theirconventionalformulas).SeeTable2.7forthenamesofoxyanions.Hint:Arsenic,
As,isinthesamefamilyasPandformsmanyanalogouscompounds.
(a) Ca(HSO4)2

(d) Ce2SO4

(b) Na2CO3

(e) KHCO3

(c) Al2(HPO4)3

(f) Na3AsO4

Answer2.96:(a)calciumhydrogensulfate(b)sodiumcarbonate(c)aluminum
hydrogenphosphate(d)cesiumsulfate(e)potassiumhydrogencarbonate(f)sodium
arsenate

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2.97.

AqueousSolutionsandSolubility

DrawLewisstructures(showingallnonbondingelectronpairsasapairofdotsandall
covalentbondsaslines)forthenitrate,ethanoate(acetate),andhydrogensulfate
oxyanions.
Answer 2.98:
O

O
O

2.98.

H
O

C
H

O
2+
S O

IdentifyeachBrnstedLowryacidandbaseinthefollowingreactions.Ifnecessary,
writeoutthecompletebalancedionicequationbeforeidentifyingtheacidsandbases.
PlaceanAbeloweachacidandaBbeloweachbase.
(a) H2S(g)+H2O(l)HS(aq)+H3O+(aq)
(b) NaOH(aq)+HCl(aq)NaCl(aq)+H2O(l)
(c) NH3(g)+HCl(g)NH4+Cl(s)
Answer2.98:

(a)A:H2S(g)andH3O (aq);B:H2O(l)andHS (aq).


(b)A:HCl(aq) andH2O(l);B:NaOH(aq) andNaCl(aq).
+

(c)A:HCl(aq) andNH4 (aq);B:NH3(g)andCl (aq)


2.99.

IdentifyeachBrnstedLowryacidandbaseinthefollowingreactions.Ifnecessary,
writeoutthecompletebalancedionicequationbeforeidentifyingtheacidsandbases.
(a) NO2(aq)+H3O+(aq)HNO2(aq)+H2O(l)
(b) 2H3O+(aq)+2ClO4(aq)+Mg2+(OH)2(s)Mg2+(aq)+2ClO4(aq)+2H2O(l)
(c) HNO3(aq)+Al3+(OH)3(s)
(d) HCN(aq)+NaOH(aq)
Answer2.99:
Completedequations:
(c)3HNO3(aq)+Al(OH)3(aq) Al(NO3)3(aq)+3H2O(l)
(d)HCN(aq)+NaOH(aq) NaCN(aq)+H2O(l)
Acidsandbases:(a)Acids:H3O+(aq)andHNO2(aq);Bases:NO2(aq)andH2O(l);
(b)Acids:HClO4(aq)andH2O(l);Bases:Mg(OH)2(s)andMg(ClO4)2(aq);
(c)Acids:3HNO3(aq)andH2O(l);Bases:Al(OH)3(aq)andAl(NO3)3(aq)
(d)Acids:HCN(aq)andH2O(l);Bases:NaOH(aq)andNaCN(aq)

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2.100. TheLewisstructuresofHOCO2,(HO)2PO2,andHOPO32areomittedfromTable2.7.
DrawtheirLewisstructures(showingallnonbondingelectronpairsasapairofdotsand
allcovalentbondsaslines).
Answer 2.100:
O

O
O

O
O

Section2.14.Extentofprotontransferreactions:LeChatelier'sprinciple
2.101. Whenammoniadissolvesinwater,itdoessoastheresultofanacidbasereaction.Two
possibleacidbasereactionsofammoniaandwaterare:
H2O(l)+NH3(g)H3O+(aq)+NH2(aq)
H2O(l)+NH3(g)OH(aq)+NH4+(aq)
(a) IdentifytheBrnstedLowryacidsandbasesineachreactionbyplacinganAbelow
eachacidandaBbeloweachbase.
(b) Usereasoningbasedontherelativeelectronegativitiesofnitrogenandoxygento
predictwhichequationrepresentstheactualacidbasereactionwhenammoniagas
dissolvesinwater.(Youcancheckyourpredictionbyrecallingthat,inInvestigateThis
2.63,youdiscoveredthatanaqueousammoniasolutionhasapH>7.)
Answer2.101:
(a)
H2O(l)+NH3(g)>H3O+(aq)+NH2(aq)
BAA

H2O(l)+NH3(g)>HO(aq)++NH4(aq)
ABB

(b)Thesecondequationrepresentsthecorrectacidbasereaction.Oxygenismore
electronegativethannitrogen.Thefirstequationgeneratesaveryunfavorable(high
energy)nitrogenanion,whereasthesecondequationgeneratesthemorefavorable
hydroxideanion.ThefactthatthepH>7indicatesthatthereishydroxidepresentin
concentrationsgreaterthanfoundinneutralwater(pH=7).

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2.102. Whenmethylamine,CH3NH2(g),dissolvesinwater,aweakelectricalconductivityis
observed.Explainthisobservationusingabalancedequationinyouranswer.Omitany
ions/moleculesthatdonotdirectlyparticipateinthereaction.
Answer2.102:
Given:Whenmethylamineisdissolvedinwater,aweakelectricalconductivityis
observed.
AskedFor:Weneedtoexplainwhythissolutionconductselectricityaswellastowrite
thenetionicequationforthisobservation.
Recall:Ifthesolutionconductselectricityweakly,thismeansthatthereactiondoesnot
proceedveryfartotherightandonlyafewionsareproduced.
Plan:Inexaminingthestructureofmethylamine,weobservethatitsstructureissimilar
toammonia,NH3inwhichoneHfromNH3hasbeenreplacedwithamethyl(CH3)
group.Forreview,weneedtonowexaminethereactionofNH3inwater,asshownin
Section2.13andapplyittomethylamine.
Explanation:Inthisproblem,thebalancedchemicalreactionisthesameasthetotal
ionicequationwhichisalsothesameasthenetionicequation.
CH3NH2(aq)+H2OCH3NH3+(aq)+OH(aq)
Weobservethattwoionsareproducedinthisreaction,CH3NH3+andOH.
Sincethesolutionweaklyconductselectricity,onlyafewionsareproducedandthe
reactiondoesconductelectricity.Weindicatethiswithatwodirectionalequilibrium
arrowinthebalancedequation(asshownabove).
2.103. Ethyleneglycol,HOCH2CH2OH(usedinautomobileantifreezeproducts),ismiscible
withwaterinallproportions.Willtheresultingsolutionbebasic,acidic,orneutral?
Explain.Willtheresultingsolutiondisplayelectricalconductivity?Explain.
Answer2.103:
Given:Ethyleneglycol,CH2(OH)CH2OH,ismisciblewithwaterinallproportions.
AskedFor:Explanationiftheresultingsolutionwillbebasic,acidic,orneutralaswell
asifitwillconductelectricity.
Recall:InSection2.2,solutionsofpolarmoleculesarediscussed.Insection2.13,
reactionsofacidsandbasesarediscussed.
Plan:Weneedtocloselyexaminethestructureofethyleneglycolandtorecognizethatit
containsthesamefunctionalgroupsasglucose.

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Explanation:Ethyleneglycolcontainstwoalcoholfunctionalgroups.Thesetwoalcohol
groupscreatehydrogenbondswithwater.Justlikeglucosedissolvinginwater,ethylene
glycolsimplydissolvesinwater.Itdoesnotreactwithwater.Thus,theresulting
solutionisneutralanddoesnotconductelectricity.
2.104. Esterification(whichisdiscussedinChapter6)isoneofthemostimportantreactionsof
carboxylicacidsinbiologicalsystems.Asimpleexampleisthereactionofacetic
(ethanoic)acidwithethanoltoformethylacetate(acommonsolventfoundinfingernail
polishremover)andwaterinthisequilibriumreaction:
CH3C(O)OH+HOCH2CH3CH3C(O)OCH2CH3+H2O
aceticacid

ethanol

ethylacetate

UseLeChateliersprincipletopredictandclearlyexplaintheoutcomeofthesereaction
conditions:
(a) Startingwith0.1moleofaceticacidand0.1moleofethanol,wouldmore,less,or
thesameamountofethylacetatebeformed,ifwaterisaddedtothereactionmixture?
(b) Wouldamixtureof0.2moleofaceticacidand0.1moleofethanolformmore,less,
orthesameamountofethylacetateasamixtureof0.1moleofaceticacidand0.1mole
ofethanol?
Answer2.104:(a)Theadditionofwaterdisturbsthisequilibriuminawaythatwilluse
uptheadditionalwatermoleculesbyincreasingtheextentofthereversereaction.Of
course,thereversereactionusesupethylacetateinadditiontowater,sotheoverallyield
ofesterproductwouldbereduced.
(b)Themixturecontaining0.2molaceticacidwillproducemoreethylacetate.Imagine
adding0.1molof(additional)aceticacidtothesecondequimolarmixture.Theexcess
aceticacidwoulddisturbtheequilibriumbyincreasingtheextentoftheforwardreaction.
2.105. UseexplanationsbasedonLeChateliersprincipletoexplainormakepredictionsineach
ofthefollowingcases.
(a) ConsiderThis2.79examinedthesolubilityofcarbondioxideinwater.Whyisthe
solubilityofcarbondioxidegreaterinanaqueoussodiumhydroxidesolutionthanin
wateritself?
(b) Calciumsulfateisslightlysolubleinwater.Ifsodiumsulfate(solid)isaddedtoa
saturatedaqueoussolutionofcalciumsulfate,whatwillhappentotheconcentrationof
calciumcation,[Ca2+(aq)]?
Answer2.105:
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(a)Considerthefollowingequations:
CO2(g)+H2O (HO)2CO(aq)
(HO)2CO(aq)+H2O H3O+(aq)+HOCO2(aq)
H3O+(aq)+OH(aq) 2H2O
Overall:CO2(g)+OH(aq) HOCO2(aq)
Addingmorehydroxide,OH(aq),willshifttheequilibriumtotheright,
causingmoreCO2(g)toreactwithOH(aq)andproducemoreHOCO2(aq).Thus,
CO2(g)ismoresolubleinaqueoussodiumhydroxide.
(b)Ifsodiumsulfate(solid)isaddedtoasaturatedaqueoussolutionofcalciumsulfate,
moresolidcalciumsulfatewillform,loweringtheconcentrationofcalciumcation,Ca2+,
insolution.
Section2.15.EXTENSIONCO2andLeChateliersPrinciple
2.106. Representeachofthesestatementsasacompletebalancedchemicalequation.
(a) Carbonicacidisformedwhencarbondioxidereactswithwater.
(b) Calciumcarbonate(limestone)reactswithcarbonicacidtoformanaqueoussolution
ofcalciumhydrogencarbonate.
(c) Calciumhydrogencarbonatereactswithcalciumhydroxidetoformcalcium
carbonateprecipitate.
(d) Calciumhydrogencarbonatereactswithsodiumhydroxidetoformcalcium
carbonateprecipitateandthewatersolublesaltsodiumcarbonate.
(e) Themixingofaqueoussolutionsofsodiumhydrogencarbonateandsodium
hydroxideisexothermic.Areactionhasoccurredbutthereisnoprecipitate.
Answer2.106:
(a)Equation(2.27).
(b)CaCO3(s)+(HO)2CO(aq)>Ca(HOCO2)2(aq)
(c)Ca(HOCO2)2(aq)+Ca(OH)2(aq)>2CaCO3(s)+2H2O
(d)Ca(HOCO2)2(aq)+2NaOH(aq)>CaCO3(s)+Na2CO3(aq)+2H2O
2.107. Thenamesstalactiteandstalagmiteforthestructuresthatgrow,respectively,downfrom
theceilingandupfromthefloorofalimestonecave(Figure2.31)arederivedfromthe
Greekwordmeaningtodrip.Indeed,ifyouexaminethetipofastalactite,youwill
oftenfindadropofliquid.Theliquidisanaqueoussolutioncontainingcalciumcations
andhydrogencarbonateanions.SeeCheckThis2.92.
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(a) Asthewaterevaporatesfromthisdrop,whathappenstotheconcentrationof
calciumcations?ofhydrogencarbonateanions?Explainyourreasoning.
(b) WhatreactiondoesLeChateliersprinciplepredictwilloccurintheevaporating
dropofsolutioninpart(a)?Clearlyexplainyourchoice.
(c)Doesyouranswerinpart(b)helpexplainthegrowthofstalactites?Howabout
stalagmites(whichgrowdirectlyunderstalactites)?Giveourreasoningclearly.
Answer2.107:
(a)Asthewaterdropletevaporatestheconcentrationsofthesolutes,calciumcationsand
hydrogencarbonateanions,increase.Thevolumeofsolutionisless,sothenumberof
ionsperunitvolumeisgreater,thatis,ahigherconcentration.
(b)Reaction(2.37)willoccurinreverse:
Ca2+(aq)+2HOCO22(aq)CaCO3(s)+H2O(l)+CO2(g)
Thishappensbecausetheconcentrationsofbothreactantsinthisreactionincreaseasthe
dropletsevaporate(seepart(a)).Theincreasedconcentrationsoftheproductsofreaction
(2.37)areadisturbancetothesystem.LeChateliersPrinciplestatesthatthesystemwill
respondbyminimizingthedisturbance,thatis,byreactinginawaythatdecreasesthe
concentrations.Thereactionthatdoesthisisthereverseofreaction(2.37),whichis
writtenabove.
(c)Theresultofthereactioninpart(b)istoprecipitatesomesolidcalciumcarbonate,
whichcausesthestalactitetogrowdownward(veryslowly).Ifthedropofliquidshould
dropoffthetipofthestalactite,itwillendupdirectlybelowandthesameevaporation
andprecipitationprocessonthefloorofthecavewillbuildstalagmitesupwardtoward
thestalactites.Iftheymeet,theyformacolumn,whichisanothercommonstructurein
limestonecaves.(e)Na(HOCO2)(aq)+NaOH(aq)>Na2CO3(aq)+H2O
2.108. AgasisevolvedwhencalciumcarbonateisplacedinanaqueoussolutionofHCl(g).
(a) Whatisthegas?Explainhowyoureachedthisconclusion.
(b) Writethenetionicequationforthereactionthatproducesthegas.
(c) ShowhowLeChateliersprincipleandyourknowledgeofgassolubilitiesexplain
theobservedresults.
(a)Given:Agasisevolvedwhencalciumcarbonateisplacedinanaqueoussolutionof
HCl(g).
Part(a):
AskFor:Whatisthegas?Howdidyoureachthisconclusion?
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Answer:
Weknowthat:
HCl(g)+H2O(l)H3O+(aq)+Cl(aq)
Then,
CaCO3(s)+H3O+(aq)Ca2+(aq)+HOCO2(aq)
Thebicarbonateion,HOCO2(aq)isaBronstedLowrybase,thatcanthenreactwith
HOCO2(aq)+H3O+(aq)(HO)2CO(aq)+H2O(l)
Carbonicacid,(HO)2CO(aq)willdecomposetoyieldwateranddissolvedcarbon
dioxide(Reaction(2.24)).Someofthiscarbondioxidecanleavethesolutionasagas.
Part(b):
AskedFor:Writeanetionicequationforthereactionthatproducesthegas.
Recall:Wewillapplythestrategyusedforsolvingnetionicequations.
Equations:
(b)BalancedChemicalReaction:
CaCO3(s)+2H3O+(aq)Ca2+(aq)+(HO)2CO(aq)+H2O

Note:Thisbalancedchemicalreactionisalsothetotalionicandnetionicequation.

Sincecarbonicacid,(HO)2CO(aq)decomposestogivecarbondioxideandwater.We
cansubstitutecarbonicacidwithcarbondioxideandwater.Thus,thereactioncanbe
writtenas:
CaCO3(s)+2H3O+(aq)Ca2+(aq)+CO2(g)+2H2O
Recap:Inthisproblem,weneedtorecognizethatcarbonicacid,H2CO3,isveryunstable
anddecomposestowateranddissolvedcarbondioxide.

(c) The reactions that occur to produce the gas are:


CaCO3(s) + 2H3O+(aq) Ca2+(aq) + 2H2CO3(aq) + 2H2O(l)
H2CO3(aq) CO2(g) + H2O(l)
Thereactionofcalciumcarbonatewithhydrochloricacid,thefirstreaction,produces
carbonicacidinthesolution.Carbonicacidisformedbythecombinationofcarbon
dioxidewithwater(thereverseofthesecondreaction).Weknowthatcarbondioxideis
onlysparinglysolubleinwater.Productionofalotofcarbonicacidbythefirstreaction
willdisturbthesecondequilibrium,whichwillreducethedisturbance,LeChateliers
principle,byreactingtoreducetheamountofcarbonicacid,thusformingcarbondioxide
gasthatescapesfromthesolution.Thefirstreactionproducesalotofcarbonicacid
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becausethepresenceofahighconcentrationofhydroniumion(inthehydrochloricacid
solution)isalsoadisturbancethesystemactstoreducebyreactingtolowertheamount
ofhydroniumionpresent.
GeneralProblems
WEB
2.109. (WEB)Sugar(sucrose)crystalsarehardandtheycrunchandbreakwhenyouput
pressureonthem.Greaseissoftandeasilysmearedonasurfaceusinglittlepressure.
HowdotheWebCompanionChap2,Sect2.2.3and5,molecularlevelrepresentationsof
sucroseandgreaseexplaintheobservedmacroscopicbehaviorofthesesubstances?
Clearlyrelateyourexplanationtothestructuresshown.
Answer2.109:Greasecontainslongchainsofhydrocarbonsthathavetheirelectron
cloudsspreadevenlyovereachmolecule.Thus,thehydrocarbonscanslideovereach
otherbecausethereisnopolarity.Sugarmoleculesarepolarandcannotslideofeach
otherbecauseoftheirunevendistributionofelectronswithineachsugarmolecules.
2.110. (a) About2gofcalciumsulfate,CaSO4(s),dissolveinaliterofwater.Whatarethe
molaritiesofCa2+(aq)andSO42(aq)inasaturatedsolutionofcalciumsulfate?Isseawater
saturatedwithcalciumsulfate?(SeeConsiderThis2.54forthecompositionofseawater.)
Explainyourresponse.
(b) Anioniccompoundislesssolubleinasolutionthatalreadycontainseitheritscation
oranion.IsthiseffectconsistentwithLeChateliersprinciple?Explainwhyorwhynot.
(c) Doestheeffectdescribedinpart(b)influenceyourresponsetopart(a)?How?
(d) Doestheeffectdescribedinpart(b)helpexplainwhythecalciumcarbonatein
seashells(seethechapteropening)doesnotredissolveinthesea?Explainyourresponse.
Answer2.110:
(a)Themolarmass(formulamass)ofCaSO4is136gmol1:
Ca 40gmol1
S

32gmol1

4O 4(16gmol1)=64gmol1
Thenumberofmolesthatdissolveinwateris(2gL1)/(136gmol1)=1.5102molL1.
Foreverymoleofthesolidthatdissolves,thesolutioncontainsamoleofcalciumions
andamoleofsulfateions.Thus,asaturatedsolutionofcalciumsulfateis1.5102Min
bothions.Seawatercontains1.0102Mcalciumcationand2.8102Msulfateanion.
Thereisalittlelesscalciumionthaninasaturatedsolutionofcalciumsulfate,butalmost
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twiceasmuchsulfateionasinthesaturatedcalciumsulfatesolution.LeChateliers
Principlewouldsuggestthatincreasingtheamountofthesulfateinasaturatedsolution
ofcalciumsulfate(byaddingsomesodiumsulfate,forexample)shouldcausethe
dissolutionreactiontobereversedtotrytodecreasetheamountofsulfate,which,of
course,alsohastheeffectofdecreasingtheamountofcalciumioninthesolution.When
thehighconcentrationofsulfateisaccountedfor,weareprobablysafeinsayingthatthe
seawaterisclosetosaturationincalciumsulfate.
(b)Theeffectofcationoranionalreadypresentinasolutiononthesolubilityofanionic
compoundthatcontainsoneortheotheroftheseions,wasdiscussedinpart(a)fromthe
pointofviewofadditionofsuchaniontoasaturatedsolutionoftheioniccompound.
Theconclusionwasthattheioniccompoundwillbelesssolublethanitwouldbeinpure
waterbecauseLeChateliersPrinciplefavorstheprecipitation(ordecreasedsolubility).
[From part (a), we find that a saturated solution of CaSO4 contains
about 0.015 M concentrations of the calcium cation and sulfate anion.
Seawater has [Ca2+] = 0.010 M and [SO42] = 0.028 M, so it is not easy
to tell, given where we are in the text, whether seawater is saturated
or not. Ksp from the solubility is 0.00022 and the ion product in
seawater is 0.00028, so the seawater is saturated.]
(c) Seawater contains more sulfate ion than is present in the saturated
solution of calcium sulfate we calculated in part (a). Since seawater
contains more of the anion than could have been present from CaSO4
alone, we can imagine that the CaSO4 dissolves in a solution that
already contains some of the anion. From part (b), we find that the
solubility of the CaSO4 will be lower in such a solution. This is the
direction of the effect we observe; there is less calcium cation in
seawater than would be present in a saturated solution in pure water. It
is likely that the seawater is saturated with CaSO4, in the presence of
extra sulfate anion from some other source. In Chapter 9, we will find
that the product of the concentrations of the cation and anion
characterizes the solubility equilibrium for a saturated solution of a
sparingly soluble salt like CaSO4. For the saturated solution in water,
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we have [Ca2+][SO42] = (0.015 M)(0.015 M) = 0.00022 M2. For


seawater, we have [Ca2+][SO42] = (0.010 M)(0.028 M) = 0.00028 M2.
These two values are almost the same and reinforce the conclusion
that seawater is saturated with CaSO4, in the presence of extra sulfate
anion.
(d) Since seawater already contains a substantial concentration of
calcium anion, the solubility of calcium carbonate will be lower than it
would be in pure water. The solubility of calcium carbonate is very low
in pure water, so lowering it even further helps explain why seashells
do not redissolve (at least not rapidly) in the sea.
2.111. Asampleofsaltwaterwithadensityof1.02gmL1contains17.8ppm(bymass)of
nitrate,NO3(aq).Calculatethemolarityofnitrateioninthesampleofsaltwater.(ppm=
partspermillion).
Answer2.111:
Given:Densityofseawater(1.02gmL1whichcontains17.8ppm(bymass)ofnitrate,
NO3.
AskedFor:Molarity,M,ofNO3intheseawatersample.
Recall:Thisprobleminvolvestheconceptofmolarity.
Plan:WeneedtofocusonconvertingthedensityofseawatertoreflectthegramsofNO3
inasampleofseawater.Sincewearetoldthatseawatercontains17.8ppmNO3,we
canstatethatforeveryonemillion(1x106)gramsofseawater,thereare17.8gramsof
NO3.Now,wecanexpressthisrelationshipintermsofmolaritybyconvertinggofNO3
tomolesofNO3andmLtoL.
Calculation:WeusethedensityofseawaterandtheconcentrationofNO3tocalculate
thegofNO3permL.
1.02 gseawater
17.8gNO 3
1.82 10 5 gNO3

mLseawater
1 10 6 gseawater
mLseawater
5

1.82 10 gNO 3
1molNO 3
2.94 107 molNO 3


mLseawater
62.01gNO3
mLseawater

WewillnowconvertfromgofNO3tomolofNO3inseawater:

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ToarriveatthemolarityofNO3inoursampleofseawater,wesimplyconvertfrommL
seawatertoLseawater:
2.94 10 7 molNO 3 1000ml
4

2.94 10 MNO 3
mLseawater
1L

Recap:Insteadofastepbystepcalculation,wecouldhavesetupthecalculationinone
step:
1.02mLseawater
17.8gNO 3
1molNO 3 1000ml

2.94 104 MNO3


6

1mLseawater
1 10 gseawater 62.01gNO3
1L

2.112. (a) Assumethatseawatermayberepresentedbya3.50%byweightaqueoussolutionof


NaClwhichhasadensityof1.025gmL1.Whatisthemolarityofsodiumchloridein
thisseawater?
(b) Isyourresultinpart(a)consistentwithyouranswertoConsiderThis2.51(b)?
Explainwhyorwhynot.
Answer2.112:
Tofindthemolarity,itisnecessarytofindtheratioofthenumberofmolesofNaClina
literofNaClsolution.Itisconvenienttobreakthiscalculationintotwoparts,finding
firstthenumberofmolesofNaClin100gofsolution,andthenthevolumeof100gof
solution.FindingthenumberofmolesofNaClin100gfromtheweightpercent:
1molNaCl
moles NaCl 3.50gNaCl
=0.0598moles NaCl
58.5gNaCl
Findingthevolumeof100gofsolution:
1mLsolution
1Lsolution
100g solution
3
=0.0976Lsolution
1.025gsolution 10 mLsolution
FindingtheratioofmolesofNaClperliterofsolution:
0.0598molNaCl
0.613molNaCl

0.0976LNaClsolution LNaClsolution
Therefore,themolarityofseawateris0.613M.
Note:Wecannotassumethat1gofsolutionhasavolumeof1mL.Thedensityofthe
solutionisgiven,andshouldbeused.Theanswermakessensebecausethereare35.0g
ofNaClin1Lofwater;thisisabout0.6molNaCl.
2.113. Astudentpreparedasolutionforherbiochemistrylaboratorybyweighing5.15gramsof
acompoundanddissolvingitin10.0gramsofwater.Theconcentrationofthissolution
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was2.7M,anditsdensitywas1.34gmL1.Whichofthefollowingcompoundsdidthe
studentusetopreparethesolution?Explainyourreasoningclearly.
(a) (NH4)2SO4

(c) CsCl

(b) KI
(d) Na2S2O3
Answer 2.113: If we can find out how many moles of compound are
dissolved, we can determine its molar mass and compare the result
with the molar masses of the possible solutes. The known molarity of
the solution, 2.7 M, is equal to the number of moles dissolved divided
by the volume, in liters, of the solution. To get the volume of solution,
we divide the total mass of the solution 15.15 g (= 5.15 g + 10.0 g) by
its density 1.34 gmL1, and get a volume of 11.3 mL or 11.3 103 L..
Therefore, we have:
(moles of compound)/11.3 103 L = 2.7 M
moles = 3.05 102 mol
It is not really legitimate to carry the third significant figure in this
result, since the molarity has only two significant figures (the value is
good to about 3%), but well carry it along and check whether it makes
a difference later. Now we know that 5.15 g of the compound is 3.05
102 mol of the compound, so:
molar mass = (5.15 g)/(3.05 103 mol) = 169 gmol1
Themolarmassesofthefourpossiblecompoundsare:(NH4)2SO4,132gmol1;KI,166
gmol1;CsCl,168gmol1;andNa2S2O3,158gmol1.Themolarmasswecalculatedhas
abouta3%uncertaintyfromtheuncertaintyinthesecondsignificantfigureofmolarity,
sotherangeofpossibilitiesisabout164to174gmol1.Thepossibilities,therefore,are
KIorCsClforthecompoundthestudentdissolved.ThecalculationfitsCsClbest,butthe
uncertaintymakesthisidentificationunsure.Wewouldneedabettervalueforthe
molaritytobesure.

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2.114. Whatpercentage(approximate)ofthewatermoleculesisprotonatedinaqueoussolutions
withthesepHs?Explainyourreasoning.Hint:Themolarityofwaterinpurewaterand
diluteaqueoussolutionsisabout55.5M.
(a) 7

(b) 6

(c) 4

Answer2.114:(a)Approximately10 moleculesofwaterperliterareprotonatedand
7

theconcentrationofpurewaterisapproximately55molesperliter,theratiois107/55=
1.8x109.Multiplythisvalueby100tofindthatthepercentage=1.8x107%.
(b)1.8x106%(c)1.8x104%(orapproximately0.0002%)
2.115. Figure2.24showstheconcentrationofhydroxideion,[OH(aq)],aswellasthe
concentrationofhydroniumion,[H3O+(aq)],correlatedwiththepHofsolutions.
(a) WhenthepHis3,whataretheconcentrationsofthehydroxideandhydroniumions?
Whatisthenumericvalueofthemathematicalproduct[H3O+(aq)][OH(aq)]atthispH?
(b) ForanypHyouchoose,whatisthemathematicalproduct[H3O+(aq)][OH(aq)]?Can
youthinkofareasonforthisresult?
Answer2.115:(a)1014(b)1014
2.116. (a) Thesulfurdioxide,SO2(g),moleculehasapermanentdipolemoment.Whatisthe
shapeofthemolecule?Explainthereasoningforyouranswer.
(b) Whensulfurdioxide,anonmetaloxide,dissolvesinwater,theresultingsolution
conductselectricity.Howcanthisbeexplained?Besuretoincludeanappropriate
chemicalreactionequationtojustifyyouranswer.
Answer2.116:
(a)Sulfurdioxidehasabentstructure,similartowater.
(b)AskedFor:Explanationofthisobservation,includingtheappropriatechemical
equation.
Explanation:WhenSO2dissolvesinwater,ionsmustbeformedsincetheresulting
solutionconductselectricity.FromSection2.13,weknowthattheoxidesofnonmetals
oftendissolveandreactwithwatertogiveacidicsolutions.Thereactionisasfollows:
SO2(g)+H2O(l)(HO)2SO(aq)
Theproduct,sulfurousacid,cantransferoneorbothprotonstowatertoformions:
(HO)2SO(aq)+H2O(l)H3O+(l)+HOSO2(aq)
HOSO2(aq)+H2O(l)H3O+(l)+SO32(aq)

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Sulfurousacidtransfersessentiallyallofitsfirstprotontowater,somanyionswillbe
presentinthesolutiontoconductelectricity.
2.117. (a) Table2.7liststhenameoftheHOCO2ion(orHCO3)ashydrogencarbonateion.
Thisionalsohasthecommonnamebicarbonate,usedinsubstancessuchas
bicarbonateofsoda,NaHCO3.Explainhowthisnamecanberationalized.
(b) TSPisthecommonnameforacleaningproductcontainingsodiumandphosphate
ions.WhatisthechemicalformulaforthemajoringredientinTSPandwhatdothe
lettersTSPrepresent?
Answer2.117:
(a)ThenamebicarbonatedifferentiatestheHCO3ionfromthecarbonateion,CO32.
Itmaybethatthebireferstothetwodifferentcationsthatarepresentincommon
compoundscontainingthision.Forexample,bothsodiumandhydrogenarepresentin
bicarbonateofsoda,NaHCO3.
(b)TSPstandsfortrisodiumphosphate.ThecorrectformulaisNa3PO4.
2.118. Whatvolumeof0.075Msulfuricacid,(HO)2SO2(aq),solutionwillberequiredtoreach
theequivalencepointofthereactionwitheachofthefollowingbasicsolutions?Hint:
Eachsulfuricacidmoleculecanprovidetwohydroniumionstothesolution.
(a) 1.00gofKOH(s)dissolvedin75mLofwater
(b) 1.00gofKOH(s)dissolvedin150mLofwater
Answer2.118:Volumeofbaseddoesnotmatter,justtheactualnumberofmolesof
baseinsolution,whichis1.8102molKOH(s).However,0.075M(HO)2SO2(aq)
produces0.15MH3O+(aq).Thus,120mLof(HO)2SO2(aq)arerequiredtoneutralizethe
base.
2.119. Assumethatyouhaveaonepound(454g)containerofdraincleaner,mostlysolid
sodiumhydroxide,thatyouwishtogetridofbyreactionwithvinegar,about0.9M
ethanoic(acetic)acid.
(a) Writeabalancedchemicalreactionequationforthereactionbetweenthedrain
cleanerandvinegar.
(b) Whatistheminimumvolumeofvinegarrequiredtoreactcompletelywiththedrain
cleaner?Explainyourreasoningclearly.
Answer2.119:
(a)HC2H3O2(aq)+NaOH(aq)NaC2H3O2(aq)+H2O(aq)

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1molNaOH
= 11.4 mol NaOH(aq)
40.0g
11.4 mol NaOH(aq) = (x L) (0.9 M HC2H3O2(aq)); 12.7 L of vinegar

(b) 454 g

is the minimum volume.


2.120. Raindropsdissolvegaseousoxidesofnitrogenandsulfur(formedbybothnatural
processesandbyburningfossilfuels)andformacidicsolutions(acidrain),suchasnitric
andsulfuricacids[seeequation(2.28)].Acidrainhascausedasmallpondtobecomeso
acidicthatmostofitsaquaticlifehasdied.Acommunitygrouphasmadeaproposalto
restorethepondbyaddingenoughlime,CaO(s)(quicklime),toreactwiththehydronium
ionbythisreactionstoichiometry:
2H3O+(aq)+CaO(s)3H2O(l)+Ca2+(aq)
Theyhaveaskedforyourhelptofigureouthowmuchlimetouse.
(a) Thevolumeofthepondisabout4.5104m3(1m3=1000L)andtheH3O+(aq)
concentrationis5.0105M(pH=4.30).Howmanymolesofhydroniumiondoesthe
pondcontain?Explainclearlytheprocedureyouuse.
(b) Howmanymolesoflimehavetobeaddedtoreactwith90%ofthehydroniumion
present?Howmanykilogramsoflimeisthis?Iflimeispurchasedin50poundbags,how
manybagswillbeneeded?Explainclearly,sothecommunitygroupcanunderstand.
(c) EstimatewhatthepHofthepondwillbeafterthelimeisadded.
Answer2.120:

1000L
5.010-5 molL-1 = 2.25103 mol of hydronium
3
1m
ions in the pond.
(b)90%of2.25103mol=2.03103molofhydroniumions
(a) 4.5103

2.03103 mol of H3O+(aq)

1molCaO (s)
56.0g

= 5.67104 g

2molH 3 O (aq)
1molCaO (s)

of CaO(s)
5.67104 g CaO(s)
(c)

1kg
1lb
1bag

= 2.5 bags
1000g
0.454kg
50lb

2.25 10 2 molH 3O+ (aq)


1m 3

= 5.010-6 M H3O+(aq); pH - 5.3


4.5 104 m 3
1000L

2.121. Tocoolthemselves,manyanimalssweatwhentheweatheriswarm(seeChapter1,
Section1.10).Chickens,however,donothavesweatglands,sotheypanttohelpcool
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themselves.Inhotweather,chickenspantalotandlosemorecarbondioxidethannormal
(theyhyperventilate).Thelevelofdissolvedcarbondioxideintheirblooddecreasesand
thehenslayeggswiththinnerandmorefragileshells.
(a) Whyaretheshellslesssturdythanusual?Whatreaction(s)is(are)beingaffected?
(b) Eggfarmersuseasimpleandinexpensivemethodtokeeptheirhensdissolved
carbondioxidelevelsnormalinhotweather.Whatdoyouthinktheydo?
Answer2.121:
Theshellsarelesssturdythanusualbecausetheycontaintoolittlecalciumcarbonate,
whichiswhatmakeaneggshellhard.Theprecipitationofcalciumcarbonateisbeing
affectedbecausetheconcentrationofcarbonateinthechickensbloodstreamgoesdown
whenmorethanthenormalamountofcarbondioxideisexcreted.Thedirectionalflowof
thereactionsis:
CaCO3(s)Ca2+(aq)+CO32(aq)
CO32(aq)+H2O(l)HOCO2(aq)+OH(aq)
HOCO2(aq)+H2O(l)(HO)2CO(aq)+OH(aq)
(HO)2CO(aq)CO2(g)+H2O(l)
AsthechickenpantsandmoreCO2(g)leaves,CaCO3(s)tendstodissolve,asshown,
ratherthanprecipitatetoformstrongeggshells.TocounteractthelossofCO2(g)inthe
chickensbreath,thefarmersgivethemcarbonatedwater,seltzerwater,todrink.
Chickensapparentlyliketheseltzerwaterbetterthanplainwateranddrinkevenmore
thanusual,sothemethodisevenmoreeffectivethanmighthavebeenexpected.
2.122. (WEB)Thechemicalequationswewritetorepresentprecipitationreactionsusually
WEB
looklikethisone:
Ag+(aq)+Cl(aq)AgCl(s)
Thisrepresentationgivesuslittleclueaboutwhatmightbehappeningatthemolecular
levelduringtheprecipitation.Theanimatedmovie,WebCompanionChap2,Sect2.6.3,
showingtheinteractionofchlorideandsilverionsprovidesonewaytovisualizethe
precipitationprocess.Describethestepsintheprocessandillustrateyourdescription
withchemicalreactionequations.Thatis,trytotranslatethemolecularlevel
representationtoasymbolicrepresentation.
Answer2.122:

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