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Water:ANaturalWonder
FacultyResourceandOrganizationalGuide(FROG)
TableofContents
MaterialsforChapter1Activities................................................................................................6
ReagentsforChapter1Activities.................................................................................................6
Section1.1. PhasesofMatter.....................................................................................................7
LearningObjectivesforSection1.1:...........................................................................................7
ConsiderThis1.1.Whatdoyoualreadyknowaboutwater?.....................................................7
ConsiderThis1.2.Howdothevolumesofliquidandsolidwatercompare?............................7
Section1.2. AtomicModels........................................................................................................7
LearningObjectivesforSection1.2:...........................................................................................7
InvestigateThis1.4.Whatelectricaleffectscanyouobserve?..................................................8
ConsiderThis1.5.DoelectricaleffectsexplainyourInvestigateThis1.4results?.................10
ConsiderThis1.6.CananelectrostaticmodelexplaintheInvestigateThis1.4results?.........10
Section1.3. MolecularModels.................................................................................................11
LearningObjectivesforSection1.3:.........................................................................................11
Section1.4. ValenceElectronsinMolecularModels............................................................11
LearningObjectivesforSection1.4:.........................................................................................11
PersonalTutorrelevanttoSection1.4:......................................................................................11
Section1.5. ArrangingElectronPairsinThreeDimensions................................................11
LearningObjectivesforSection1.5:.........................................................................................11
PersonalTutorrelevanttoSection1.5:......................................................................................11
InvestigateThis1.14.Whatarrangementofballoonsaroundapointisstable?......................11
ConsiderThis1.15.Whatisthegeometryoffourvalenceelectronpairs?..............................13
ConsiderThis1.16.HowisaLewisstructuretranslatedintoamolecularmodel?..................13
Section1.6. PolarityoftheWaterMolecule...........................................................................14
LearningObjectivesforSection1.6:.........................................................................................14
ConsiderThis1.17.Howmightanelectricchargeaffectpolarmolecules?............................14
ConsiderThis1.21.Howdoesmoleculargeometryaffectmoleculardipoles?.......................15
Section1.7. WhyisWaterLiquidatRoomTemperature?..................................................16
LearningObjectivesforSection1.7:.........................................................................................16
PersonalTutorrelevanttoSection1.7.......................................................................................16
InvestigateThis1.22.Howdoesboilingpointvarywithnumberofmolecularelectrons?.....16
ConsiderThis1.23.Doboilingpointscorrelatewithnumberofmolecularelectrons?...........17
ConsiderThis1.24.Howcandipoledipoleattractionsbevisualized?....................................17
ConsiderThis1.25.Howdoespolarityaffectboilingpoint?...................................................18
ConsiderThis1.26.DoeshydrogenbondingexplaintheboilingpointsofNH3andHF?.......19
November2004
ACSChemistryFROG
Water:ANaturalWonder
Chapter1
Section1.8. FurtherStructuralEffectsofHydrogenBondinginWater............................20
LearningObjectivesforSection1.8:.........................................................................................20
PersonalTutorrelevanttoSection1.8:......................................................................................20
InvestigateThis1.28.Whatkindsofhydrogenbondednetworkscanyouconstruct?............21
ConsiderThis1.29.Howdothestructuresofliquidandsolidwatercompare?......................22
InvestigateThis1.30.Whatarethetemperaturesinanicewatermixture?.............................22
ConsiderThis1.31.Howdoyouinterpretthetemperaturesofanicewatermixture?............24
ConsiderThis1.32.Whataretheconnectionsbetweenwaterdensityandtemperature?........25
Section1.9. HydrogenBondsinBiomolecules.......................................................................26
LearningObjectivesforSection1.9:.........................................................................................26
InvestigateThis1.33.HowdotheDNAbasesfittogether?....................................................26
ConsiderThis1.34.HowdoeshydrogenbondingaffectthethermalstabilityofDNA?.........28
Section1.10. PhaseChanges:LiquidtoGas............................................................................28
LearningObjectivesforSection1.10:.......................................................................................28
PersonalTutorrelevanttoSection1.3:......................................................................................28
InvestigateThis1.35.Whathappenswhenyousweat?............................................................29
ConsiderThis1.36.Whatisthepurposeofsweating?.............................................................29
ConsiderThis1.37.Whatarethesignsoftheenergychangesforsweating?..........................30
ConsiderThis1.39.Howareenergyleveldiagramscorrelated?.............................................30
InvestigateThis1.40.Doallliquidsevaporateatthesamerate?.............................................31
ConsiderThis1.41.Whataretherelativeenergiesofvaporizationofdifferentliquids?........32
Section1.11. CountingMolecules:TheMole...........................................................................33
LearningObjectivesforSection1.11:.......................................................................................33
PersonalTutorrelevanttoSection1.11:....................................................................................33
ConsiderThis1.44.Howcanyoucountobjectsbymeasuringmass?.....................................34
ConsiderThis1.50.WhichcompoundsinTable1.2formhydrogenbonds?..........................34
Section1.12. SpecificHeatofWater:KeepingtheEarthsTemperatureStable.................35
LearningObjectivesforSection1.12:.......................................................................................35
InvestigateThis1.53.Whatisobservedwhenliquidsareheatedatthesamerate?................35
ConsiderThis1.54.Howdoestemperaturechangeinheatedliquids?....................................37
ConsiderThis1.59.AreyourcalculationsrelatedtoInvestigateThis1.53?...........................38
Section1.14. ExtensionLiquidViscosity..............................................................................39
LearningObjectivesforSection1.11:.......................................................................................39
InvestigateThis1.60.Howfastdodifferentliquidsflowfromapipet?..................................39
ConsiderThis1.61.Howareviscositiesrelatedtomolecularattractions?..............................40
ConsiderThis1.62.Doeshydrogenbondingexplainviscositiesinothercompounds?...........41
ConsiderThis1.63.Arethemodelsforspecificheatandviscosityofwaterrelated?.............42
SolutionsforChapter1CheckThisActivities:.........................................................................43
CheckThis1.3.Molecularlevelrepresentationofboilingwater.............................................43
CheckThis1.7.Numberofvalenceandcoreelectrons...........................................................43
CheckThis1.9.Trendsinatomicsizes....................................................................................43
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
CheckThis1.11.WritingLewisstructures..............................................................................43
CheckThis1.13.Lewisstructureofethane..............................................................................43
CheckThis1.18.Predictingbonddipoles................................................................................44
CheckThis1.20.Predictingmoleculardipoles........................................................................44
CheckThis1.27.Predictingrelativeboilingpoints..................................................................44
CheckThis1.38.Interpretinganenergydiagram.....................................................................45
CheckThis1.43.Conversionofenergyunits...........................................................................45
CheckThis1.46.Masstomolesandmolestomassconversions.............................................45
CheckThis1.48.Calculatingmolarmass................................................................................45
CheckThis1.49.Comparingamountsofcompounds..............................................................46
CheckThis1.52.VaporizationenergiesinInvestigateThis1.40............................................46
CheckThis1.56.Specificheatandtemperaturerise................................................................46
CheckThis1.58.Thermalenergychangeinethanol................................................................46
SamplesfromtheClassroom......................................................................................................47
DailyClassLogsforPrinciplesofChemistryCH103..............................................................47
ClassAssignmentsforPrinciplesofChemistryCH103...........................................................51
Chapter1QuizzesforPrinciplesofChemistryCH103............................................................54
Chapter1HourExamforPrinciplesofChemistryCH103......................................................57
SolutionsforChapter1EndofChapterProblems....................................................................59
Problem1.1................................................................................................................................59
Problem1.2................................................................................................................................59
Problem1.3................................................................................................................................59
Problem1.4................................................................................................................................59
Problem1.5................................................................................................................................60
Problem1.6................................................................................................................................60
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ACSChemistryFROG
Water:ANaturalWonder
Chapter1
Problem1.25..............................................................................................................................66
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Chapter1
Water:ANaturalWonder
Problem1.69..............................................................................................................................86
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ACSChemistryFROG
Water:ANaturalWonder
Chapter1
MaterialsforChapter1Activities
Activity
Material
Quantity
1.4
115cmofthinplasticsheet
Dependson
classsize
1.4,1.40
Scissors
1.14
Four8or10roundballoonspergroup
Dependson
numberof
groups
1.14
3/4inchplastictransparenttape
1roll
1.15,1.28,1.29,
1.33,150
Modelkits
1/student
1.30
2Lplasticbeveragecontainer
1.30
Sturdystirringrod
1.30,1.53
Laboratorythermometersorcomputer
interfacedtemperatureprobes
1.30,1.53
Ringstandwithtwosmallclamps
1,2
1.40
Papertowels
1.40
Pipetsordroppers
1.53
250mLStyrofoamcups
1.53
Beakers
1.53
Electricimmersionheaters
1.60
9"glassPasteurpipets
1.60
Containers
ReagentsforChapter1Activities
Activity
Reagent
1.30
Crushedice
1.30,1.40,1.53,
1.60
Water
1.40,1.60
Hexane,C6H14
1.40
Methanol,CH3OH
1.53
Ethanol
ACSChemistryFROG
Quantity
120150g
Chapter1
Water:ANaturalWonder
Section1.1.
PhasesofMatter
LearningObjectivesforSection1.1:
Describesolids,liquids,andgasesintermsoftheirmacroscopicpropertiesandwriteordraw
molecularleveldescriptionsthatexplaintheseproperties.
ConsiderThis1.1.Whatdoyoualreadyknowaboutwater?
Goal:
Thisisanintroductoryactivitytohelpstudentsfocusonthepropertiesofwaterandhowwater
isessentialforlife.
Classroomoptions:
Allow35minutesforstudents,workinginsmallgroups,toanswerthesequestions.Thenyou
canleadthediscussion,summarizinganswersonthechalkboardoranoverheadtransparency
orhavestudentsdoso.
Followupdiscussion:
Thisactivityallowstheinstructortodiscussthephysicalpropertiesofwateraswellasphase
changes.
NOTE: Thisactivitydemonstratestostudentsthattheydoknowalotaboutwater.Thus,it
helpsbuildtheirconfidencetolearnchemistry.
Followupactivity:
ConsiderThis1.2.Howdothevolumesofliquidandsolidwatercompare?
ConsiderThis1.2.Howdothevolumesofliquidandsolidwatercompare?
Goal:
Comparethevolumesofliquidandsolidwater.
Classroomoptions:WebCompanion[part(b)]
Allow35minutesforstudents,workinginsmallgroups,toanswerthesequestionsand
completeadrawingthatillustratestheiranswers.Thenyoucanleadthediscussion,
summarizinganswersonthechalkboardoranoverheadtransparency.
Thisactivitycouldalsobeassignedasahomeworkproblemandthendiscussedatthenext
classsection.
Thisactivitycanbeconductedasanopenclassdiscussion.
Instructornotes:
Studentsshouldreasonandconclude:
(a)Thevolumeofthesolidiceislargerthantheliquidwater.Thedensityofthesolidisless
thanthedensityoftheliquid,so,foragivensampleofwater,thevolumeofsolidformedmust
begreaterthanthevolumeoftheliquid.
(b)Yes.Waterfreezingintheplasticbottlehasexpanded,tearingthelabel.
Followupactivities:
Endofchapterproblems1.1through1.13.
ACSChemistryFROG
Water:ANaturalWonder
Chapter1
Section1.2.
AtomicModels.
LearningObjectivesforSection1.2:
Makedrawingsthatshowhowtheelectricalnatureofmatterexplainstheresultsof
electrostaticexperiments.
Usethenuclearatomicmodel,theshellmodelfortheirelectrons,andtheperiodictableto
determinethechargeontheatomiccoreandthenumberofvalenceelectronsinanatom.
Usetheperiodictableandtheatomicshellmodeltopredicttrendsinatomicsizeand
electronegativities.
InvestigateThis1.4.Whatelectricaleffectscanyouobserve?
Goal:
Studentswillobserveelectrostaticinteractionsthatoccurfromrubbingtwopiecesofplastic
sheetstogether.
Setuptime
5minutes(classdemonstration);30minutes(classactivity)
Timeforactivity:
5minutes
Equipment:
115cmstripofthinplasticsheetfromaplasticcarryoutbag.
Scissors.
Procedure:
NOTE:Thisactivitycanbeconductedasademonstration.Studentscanalsoworkinsmall
groupstocompletethisactivityandthendiscusstheirobservations.Also,studentscould
performthisactivityasatakehomeassignmentthatcanbediscussedatthenextclasssession.
Onhumiddays,thisactivitymaynotworkverywell.
Drapetheplasticstripoveronefingersothatequallengthshangdownoneachside.
Placeonefingerofyourotherhandbetweenthetwohalvesoftheplasticstrip.
Quicklyslideyourhanddownthefulllengthofthefreeendsofthestrip,withtheplastic
pinchedbetweenyourfingersandthumb.
Immediatelyreleasethefreeends.
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
Analternativeprocedure:
Dr.JonathanMitschele,St.JosephsCollege,suggestsusingstickytapeexperimentsadapted
fromR.ChabayandB.Sherwood,Matter&Interactions(Wiley,NewYork,2002),Chapter14.
Thetapeischargedbystickingitonandthenpullingitoffasmoothsurface.Achargedtapeis
attractedtoneutralobjects.Twosimilarlychargedtapesrepeleachother.Havestudentsdiscuss
howtheycouldmaketapesofoppositechargeandthentesttheirproperties.Ifstuck,lead
studentstotheanswer:sticktwolengthsoftapetogether,makesuretheyarenotcharged,and
thenpullthemapart.
Reference
P.Williams,J.Chem.Educ.2000,77,1520
Cleanup:
Recycleplasticstrips.
Anticipatedresults:
Theplasticstripsrepeleachother.Rubbingwiththefingersproducesthesamechargeonboth
halvesoftheplasticstrips.
Followupdiscussion:
UseConsiderThis1.5tofacilitatediscussion.Studentsshouldproposepossibleexplanations
basedontheirobservations.
Followupactivities:
ConsiderThis1.5.DoelectricaleffectsexplainyourInvestigateThis1.4results?
ConsiderThis1.6.CananelectrostaticmodelexplaintheInvestigateThis1.4results?
SampleStudentReportSheetforInvestigateThis1.4
Name:
NamesofGroupMembers:
SummaryofProcedure:Youwillobserveelectricaleffectsofrubbingtwoplasticstrips
betweenyourfingers.
Observations:
ACSChemistryFROG
Water:ANaturalWonder
Chapter1
AdditionalNotes:
NOTE:Thisstudentreportsheetservesasasampleonly.Itcanbemodifiedaccordingtoyour
classroomneeds.ThesereportsheetscanbeusedforbothInvestigateThisandConsiderThis
activities.
ConsiderThis1.5.DoelectricaleffectsexplainyourInvestigateThis1.4results?
Goal:
StudentsdiscusswhetherandhowelectricaleffectsexplaintheresultsforInvestigateThis1.4
andrelatethemtosimilarexperiencestheyhavehad.
Classroomoptions:
Allow35minutesforstudents,workinginsmallgroups,toanswerthequestions.Thenyou
canleadthediscussion,summarizinganswersonthechalkboardoranoverheadtransparency
orhavestudentsdoso.
Thisactivitycouldalsobeassignedasahomeworkproblemandthendiscussedatthenext
classsession.
Instructornotes:
Studentsshouldreasonandconcludethatelectricchargesonthestripscouldberesponsiblefor
theirrepulsion(mostwillprobablyrecallthatlikerepelslike)andprovideexamplesofscuffing
acrossacarpetorcarseatandthengettinganelectricshockand/orseeingaspark.
Followupdiscussion:
Discusselectricalnatureofmatter.
DisplayanddiscussFigure1.4.
Defineelectrostaticattraction/repulsion.
Followupactivity:
ConsiderThis1.6.CananelectrostaticmodelexplaintheInvestigateThis1.4results?
ConsiderThis1.6.CananelectrostaticmodelexplaintheInvestigateThis1.4results?
Goal:
StudentssketchanelectrostaticmodelthatexplainstheirobservationsinInvestigateThis1.4.
Classroomoptions:
Allow35minutesforstudents,workinginsmallgroups,tocreatetheirdrawingsandanswer
thequestions.Thenyoucanleadthediscussion,summarizinganswersonthechalkboardor
anoverheadtransparencyorhavestudentsdoso.
Thisactivitycouldalsobeassignedasahomeworkproblemandthendiscussedatthenext
classsection.
Instructornotes:
Beforeconductingthisactivity,reviewtheresultsfromInvestigateThis1.4.
Studentsshouldsketchsomethinglikethisandconcludethatafterrubbingtheplasticstrips
betweentheirfingers,likechargesbuilduponthestrips.Sincelikechargesrepeleachother,
theplasticstripsmoveawayfromeachother.
10
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
Followupdiscussion:
Usethisactivitytoleadintodiscussingatomsandelements.
Followupactivities:
CheckThis1.7.Numberofvalenceandcoreelectrons.
WorkedExample1.8.Trendsinatomicsize.
CheckThis1.9.Trendsinatomicsize.
Endofchapterproblems1.14through1.21.
Section1.3.
MolecularModels
LearningObjectivesforSection1.3:
Describetherelationshipsamongdifferentmolecularmodelsandtheinformationthateachof
themprovides.
Section1.4.
ValenceElectronsinMolecularModels
LearningObjectivesforSection1.4:
Describetherelationshipsamongdifferentmolecularmodelsandtheinformationthateachof
themprovides.
DrawLewisstructuresformoleculeswhosemolecularformulascontainonlyfirstandsecond
periodelements.
PersonalTutorrelevanttoSection1.4:
IfstudentsneedextraassistanceindrawingLewisstructures,pleasehavethemstudythe
PersonalTutorLewisstructureexercises.
Section1.5.
ArrangingElectronPairsinThreeDimensions
LearningObjectivesforSection1.5:
Describetherelationshipsamongdifferentmolecularmodelsandtheinformationthateachof
themprovides.
Usedrawings,physicalmodels,andwordstodescribethegeometryofthevalenceelectrons
andnucleiformoleculeswhosemolecularformulascontainonlyfirstandsecondperiod
elements.
ACSChemistryFROG
11
Water:ANaturalWonder
Chapter1
PersonalTutorrelevanttoSection1.5:
Ifstudentsneedextraassistanceinunderstandingmolecularshapes,pleasehavethemstudythe
PersonalTutormolecularshapeexercises.
InvestigateThis1.14.Whatarrangementofballoonsaroundapointisstable?
Goal:
Usingfourroundballoonsofthesamesize,studentswillfindtheclosestpackingarrangement
oftheballoonsaroundacentralpoint.
Setuptime:
Dependsonthesizeofyourclass.Forstudentsworkinginsmallgroups,fourballoonscanbe
placedinazipclosurebagfordistributingtoyourclass.
Timeforactivity:
1015minutes.
Equipment:
Four8or10inchroundballoonspergroup.
3/4inchplastictransparenttape.
Procedure:
NOTE:Studentscanworkinsmallgroupstocompletethisactivity.Ifyouhaveasmallclass,
studentscanalsocompletethisactivityathomeanddiscusstheirresultsatthenextclass
session.Ifyouhavealargeclass,askfor23studentvolunteerstocompletethisactivityor
conductasaninstructorledactivity.
Distributeballoonstostudentgroups.
Inflateallballoonstothesamesizeandtieofftheirstemssotheyremaininflated.
Attachtwooftheballoonstogetherbytapingtheirstemstogetherortwistingthestems
together.
Attachathirdandthenafourthballooninthesameway.
Trytomakedifferentgeometriesofthefourattachedballoons.
Forthemoststablearrangementyoucanfind,describeandrecordthegeometryofthecenters
oftheballoonswithrespecttotheirmutualpointofattachment.
12
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
Anticipatedresults:
Studentsshoulddiscussthisgeometryandconcludethatthismoststablearrangementof
ballooncentersabouttheirpointofattachmentistetrahedral(formatetrahedronifconnected).
Followupdiscussion:
UseConsiderThis1.15tofacilitatediscussion.
Discussionshouldleadtothecorrelationbetweenarrangingtheballoonsaroundacentral
pointandarrangingfourvalenceelectronpairsaroundapositivelychargedcentralatomic
core.
Followupactivities:
ConsiderThis1.15.Whatisthegeometryoffourvalenceelectronpairs?
Endofchapterproblems1.35through1.38.
ConsiderThis1.15.Whatisthegeometryoffourvalenceelectronpairs?
Goal:
Studentsfindthegeometryofthemoststablearrangementoffourvalenceelectronsandmodel
itwiththeirmolecularmodels.
Classroomoptions:
Allow57minutesforstudents,workinginsmallgroups,todrawthemoststablearrangement
andconstructtheirmodel.
Thisactivitycouldalsobeassignedasahomeworkproblemandthendiscussedatthenext
classsession.
Instructornotes:
Studentsneedtobringtheirmodelkittoclass.
ThisactivityisafollowupactivityandextensiontoInvestigateThis1.14.Itlinksthe
geometryofthemoststablearrangementofballoonstothemoststablearrangementoffour
valenceelectronpairsandrepresentsthelatterwithamodel.
ACSChemistryFROG
13
Water:ANaturalWonder
Chapter1
Studentsshouldreasonandconcludethatthetetrahedralarrangementisthemoststable
arrangementoffourvalenceelectronpairs,asshowninFigure1.13,ballandsticktetrahedral
arrayofsticks(representingelectronpairs).
Followupdiscussion:
DisplayanddiscussFigure1.12,tetrahedralarrangementoffourballs,andFigure1.13,ball
andsticktetrahedralarrayofsticks(representingelectronpairs).
Followupactivities:
ConsiderThis1.16.HowisaLewisstructuretranslatedintoamolecularmodel?
Endofchapterproblems1.39and1.40.
ConsiderThis1.16.HowisaLewisstructuretranslatedintoamolecularmodel?
Goal:
Studentsconstructmolecularmodelsofwater,methane,ammoniaandhydrogenfluoridebased
ontheircorrespondingLewisstructures.
Classroomoptions:
Allow35minutesforstudents,workinginsmallgroups,tocompletethisactivity.Thenyou
canleadthediscussion,summarizingtheirdescriptionsonthechalkboardoranoverhead
transparencyandstudentscandemonstratetheirmodels.
Assigneachgrouponemolecule.
Thisactivitycouldalsobeassignedasahomeworkproblemandthendiscussedatthenext
classsession.
Instructornotes:
Studentsshouldusetheirmodelkits.
Studentsshouldreasonandconcludeinpart(b)that
WaterisangularorVshaped.
Methaneistetrahedral.
Ammoniaistripod(trigonal)shapedoratriangularpyramidwithNattheapex.
Hydrogenfluorideislinear.
Followupdiscussion:
Studentsshouldunderstandthelimitationsofusingtheirmolecularmodels.Theyhelp
visualizetheshapeofthemolecule,butdonotprovideinformationonelectrondensities
withinthemodels.
Followupactivities:
Endofchapterproblems1.35through1.40.
Section1.6.
PolarityoftheWaterMolecule
LearningObjectivesforSection1.6:
Usetheperiodictableandtheatomicshellmodeltopredicttrendsinatomicsizeand
electronegativities.
Describetherelationshipsamongdifferentmolecularmodelsandtheinformationthateachof
themprovides.
Predictthedirectionandrelativemagnitudeofbonddipolesandthedirectionoftheresultant
moleculardipoleforsimplemolecularstructures.
14
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
ConsiderThis1.17.Howmightanelectricchargeaffectpolarmolecules?
Goal:
Studentssketchtheorientationofpolarmoleculesbetweentwooppositelychargedmetalplates.
Classroomoptions:
Allow35minutesforstudents,workinginsmallgroups,toanswerthesequestionsand
completeadrawingthatillustratestheiranswers.Thenyoucanleadthediscussion,
summarizinganswersonthechalkboardoranoverheadtransparencyorhavestudentsdoit.
Thisactivitycouldalsobeassignedasahomeworkproblemandthendiscussedatthenext
classsession.
Thisactivitycanbeconductedasanopenclassdiscussion.
Instructornotes:
Beforeconductingthisactivity,discussthefollowingconceptswithyourstudents:polar
molecules,electricdipoles,andnonpolarmolecules.
Figure1.15,schematicillustrationsof(a)polarand(b)nonpolarmolecules,canbeshownto
providestudentsamodelforpolarmolecules.
StudentsshouldsketchadrawingsimilartoFigure1.16(b).
Followupdiscussion:
ExplainFigure1.16(b).
Discusswhywatermoleculesarepolar,perhapsevenextendingFigure1.16toshowhow
watermoleculeswouldalignthemselvesbetweenoppositelychargedplates.
Introducehowcomputergeneratedmodelssuchasthechargedensitymodelillustratedin
Figure1.17(a)candemonstrate,basedoncolorcoding,whereelectronsarefound.
Theclassdiscussionshouldprovideatransitiontotheconceptsofdipolemoments,bond
polarity,andelectronegativitycanbedescribed.
Keepinmindthatmolecularmodelsareusedthroughoutthistext.It'simportantforstudents
tounderstandtheirusefulnessandlimitationsandtohavetheseideasreinforcedoften.
Followupactivities:
CheckThis1.18.Predictingbonddipoles.
WorkedExample1.19.Predictingmoleculardipoles.
CheckThis1.20.Predictingmoleculardipoles.
ConsiderThis1.21.Howdoesmoleculargeometryaffectmoleculardipoles?
Endofchapterproblems1.41through1.45.
ConsiderThis1.21.Howdoesmoleculargeometryaffectmoleculardipoles?
Goal:
Basedontheirgeometryandbonddipolesdeterminewhethercarbondioxideandboron
trihydride(borane)arepolarornonpolarmolecules.
Classroomoptions:WebCompanioncomponent
Allow35minutesforstudents,workinginsmallgroups,tosketchCO2andtoanswerthese
questions.Thenyoucanleadthediscussion,summarizingtheiranswersonthechalkboardor
anoverheadtransparencyorhavestudentsdoso.
Thisactivitycouldalsobeassignedasahomeworkproblemandthendiscussedatthenext
classsession.
Thisactivitycanbeconductedasanopenclassdiscussion.
ACSChemistryFROG
15
Water:ANaturalWonder
Chapter1
Instructornotes:
Beforeconductingthisactivity,discussbonddipolesandmoleculardipoles.
Studentsshouldreasonandconcludethat:
(a)Incarbondioxide,thetwobonddipolesareequal,butpointinginoppositedirections.
Thebonddipolescancelout,resultinginnooverallmoleculardipole.Thus,bythiscriterion
(nopermanentdipolemoment),carbondioxideisanonpolarmolecule.
(b)ThepolarityoftheBH3moleculeissimilartoCO2because,asinCO2,theindividual
bonddipoles,whichareidenticalandpointingat120angles,cancelout,resultinginno
overallmoleculardipole.Bythiscriterion,BH3isnonpolar.Thechargedensitysketchfor
CO2shouldbeanalogoustothatforBH3providedintheWebCompanion,Chapter1,Section
1.6,page4.ThenegativechargedensityisfoundontheoxygenatomsofCO2.
NOTE:YoumightdrawstudentsattentiontothefactthatmoleculeslikeCO2andBH3that
havenopermanentdipolemoment(andarecallednonpolar)stillhavesubstantialcharge
separationandpositiveandnegativecentersthatmightinteractwithotherpositiveandnegative
centers.Thismakesthesenonpolarmoleculesdifferentfromthosethathavelittleofnocharge
separation,suchashydrocarbonsornitrogenandoxygenmolecules.InChapter2,forexample,
wewillfindthatCO2dissolvesinwatertogiveanacidicsolutionbecausethemoleculereacts
withwaterbyanucleophileelectrophileinteractionthatwillbeintroducedinChapter6.Not
includedinthistextisthestructureofdiborane,whichcanbethoughtofastheresultofthe
interactionofthepositiveboroncentersandnegativehydridesofboranetoformthreecenter
H B H B H
H
H
H
hydrogenbridgedbonds:
Followupdiscussion:
ImportantpointslistedinReflectionandprojection,especiallythereasonwhyweare
developingmolecularmodels,shouldbediscussed.
Followupactivities:
Endofchapterproblems1.41through1.49.
Section1.7.
WhyisWaterLiquidatRoomTemperature?
LearningObjectivesforSection1.7:
Usedrawings,physicalmodels,andwordstodescribetheoriginofintermolecular
interactionsduetoLondondispersionforces,dipolarattractions,andhydrogenbonding.
Useintermolecularattractionstopredictand/orexplaintrendsinboilingpointsandenergies
ofvaporizationforaseriesofcompoundswhosemolecularstructuresyouknoworcan
determine.
PersonalTutorrelevanttoSection1.7
Ifstudentsneedextraassistanceinunderstandinggraphs,pleasehavethemstudythePersonal
Tutorunderstandinggraphexercises.
16
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
InvestigateThis1.22.Howdoesboilingpointvarywithnumberofmolecularelectrons?
Goal:
Determinetherelationshipbetweenboilingpointsandnumberofelectrons/moleculefromthe
datainFigure1.21.
Setuptime:
0minutes
Timeforactivity:
510minutes.
Preactivitydiscussion:
Discussanddefineboilingpoint.
NOTE:Thisactivitycanbeconductedinclasswithstudentsworkinginsmallgroupsorasan
openclassdiscussion.
Procedure:
ProjectFigure1.21,boilingpointvs.numberofelectrons/moleculeforgroupIVhydrides.
Studentsshould:
Describetherelationshipbetweentheboilingpointandnumberofelectrons/molecule.
Drawconclusionsabouttherelativeattractionsbetweenmoleculesinthesecompounds.
Discusshowyoumightexplainanytrendsyousee.
Anticipatedresults:
Studentsshouldreasonandconcludethat:
Asthenumberofelectrons/moleculeincreases,theboilingpointincreases.
Thismeansthatalthoughthesemoleculesarenonpolar,theintermolecularattractionsamong
thembecomestrongerasthenumberofelectronsinthemoleculesincreases.
Followupdiscussion:
Nonpolarmoleculeshavesmalltransientdipolemoments.(Atanyinstant,electron
distributioncanbeskewedinonedirectionoranother.)Thesesmalldipolemomentscan
inducedipolesinnearbymoleculesandthuscreatefleetingattractionsbetweenthemolecules.
StudentsshouldconnectthisexplanationwiththechangesshowninFigure1.23,induced
dipoleattractionbetweennonpolarmolecules,andtheanimationsintheWebCompanion,
Chapter1,Section1.7,page1.
Induceddipoleattractionsarecategorizedasdispersionforces.
Followupactivities:
ConsiderThis1.23.Doboilingpointscorrelatewithnumberofmolecularelectrons?
ConsiderThis1.24.Howcandipoledipoleattractionsbevisualized?
ConsiderThis1.25.Howdoespolarityaffectboilingpoint?
EndofChapterproblems1.53,1.58,and1.59.
ConsiderThis1.23.Doboilingpointscorrelatewithnumberofmolecularelectrons?
Goal
Correlatetheboilingpointsofalkaneswithnumberofmolecularelectrons.
Classroomoptions:
Allow35minutesforstudents,workinginsmallgroups,tocompletethisactivity.Thenyou
canleadthediscussion,summarizinganswersonthechalkboardoranoverheadtransparency
orhavestudentsdoso.
ACSChemistryFROG
17
Water:ANaturalWonder
Chapter1
Thisactivitycouldalsobeassignedasahomeworkproblemandthendiscussedatthenext
classsession.
Thisactivitycanbeconductedasanopenclassdiscussion.
Instructornotes:
Thisactivityallowsstudentstoapplyandextendtheirknowledgeofdispersionforcesto
alkanes.
DisplayFigure1.21whilestudentscompletethisactivity.
Studentsshouldreasonandconclude:
(a)ThemoreCH2groups,eachadding8electronstothetotal,inthesemolecules,themore
induceddipoleattractionstherewillbe.Thus,theboilingpointswillincrease.
(b)Yes,asthenumberofmolecularelectronsincreases,thecorrespondingboilingpoints
increase.
(c)TheF2andI2moleculesanimatedintheWebCompanion,Chapter1,Section1.7,page1,
followthesamepatternofvolatilityasseenforthehydrocarbonsandgroupIVhydrides.F2,
withfewerelectrons,isagasatroomtemperatureandI2,withmoreelectrons,isasolid.
Theirboilingpointsdifferby362C.
Followupdiscussion:
Reiteratethatdispersionforcesincreaseasthesizesofthemoleculesincreasebecausemore
electronsareavailableforinstantaneousdipoles.
Followupactivities:
ConsiderThis1.24.Howcandipoledipoleattractionsbevisualized?
ConsiderThis1.25.Howdoespolarityaffectboilingpoint?
ConsiderThis1.24.Howcandipoledipoleattractionsbevisualized?
Goal:
Findandsketchfavorablearrangementsfordipoledipoleattractionsamongfourdipolesand
comparearrangementsamongthestudents.
Classroomoptions:
Allow510minutesforstudents,workinginsmallgroups,tosketchtheirdipolar
arrangements.Thenyoucanleadthediscussion,summarizingthesketchesonthechalkboard
oranoverheadtransparencyorhavestudentsdoso.
Thisactivitycouldalsobeassignedasahomeworkproblemandthendiscussedatthenext
classsection.
Amongthepossibilitiesstudentsmightsketcharearrangementslikethese:
18
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
Followupdiscussion:
Discusswithstudentsthatindividualpolarattractionsarestrongerthandispersionforcesin
smallmolecules,butthatdispersionforcesarequitelargeformoleculeswithmanyelectrons
(astheyhaveseenpreviously)andoftendominatetheirinteractions.
Setthestageforintroducingtheconceptofhydrogenbondsasanotherattractiveinteraction
thataccountsforthehighboilingpointofwater.
Followupactivities:
ConsiderThis1.25.Howdoespolarityaffectboilingpoint?
ConsiderThis1.26.DohydrogenbondsexplaintheboilingpointsofNH3andHF?
CheckThis1.27.Predictingrelativeboilingpoints.
ConsiderThis1.25.Howdoespolarityaffectboilingpoint?
Goal:
Determineandanalyzethepatternsofboilingpointsvs.numberofelectrons/moleculeforthe
groupIVthroughVIIhydridesshowninFigure1.24.
Timeforactivity:
510minutes.
Classroomoptions:
Thisactivitycanbeconductedinclasswithstudentsworkinginsmallgroupsorasanopen
classdiscussion.
Instructornotes:
RemindstudentsthatthepolarityofthehydridesgenerallyincreasesfromgroupIVthrough
groupVII.
Studentsshouldsuggestpatternssuchasthese:
Thefirstmemberofeachseries(thesecondperiodhydride)ofgroupsVthroughVIIisoutof
linewiththeothersinthatseries.
Theremainingmembersofeachseriesincreaseinboilingpointasthenumberofmolecular
electronsincreases,justasforgroupIV.
TheseriestendtoparalleloneanotherwiththegroupboilingpointsintheorderIV<VII<V
<VI.
HClhasalittlehigherboilingpointthanwouldbepredictedbythetrendoftheheaviergroup
VIIhydrides.
Studentsshouldreasonalongtheselinestosearchforexplanations:
ACSChemistryFROG
19
Water:ANaturalWonder
Chapter1
(a)Theelectronegativitiesoftheelementsinagroup(column)oftheperiodictabledecrease
aswegodownthegroup(shownforthesecondandthirdperiodsinFigure1.20).Thus,the
differenceinelectronegativitybetweenthehydrogenatomandtheelementalatomtowhichit
isbondedwilldecreaseand,hence,thepolarityofthehydrideswilltendtodecrease.The
boilingpointsinFigure1.24areplottedasafunctionofincreasingelectronspermolecule,
whichisthedirectiongoingdownthegroupsoftheperiodictable,soweexpectthepolarities
ofthemoleculesgenerallytodecreasefromlefttorightonthegraph.Ifthemajorfactor
influencingtheboilingpointsofthehydrideswerepolarity,wewould,therefore,expectthe
boilingpointstodecreasefromlefttoright.
(b)Dispersionforcesdependonthenumberofelectronsinamolecule:themorethereare,
thegreaterthepossibilitiesforinduceddipoleattractions.Sincethenumberofelectronsper
moleculeincreasesfromlefttorightonthegraph,wewouldexpecttoseegenerally
increasingboilingpointsasthemoleculesattractoneanothermorestrongly.
(c)Sincethegeneraltrendinboilingpoints(ignoringthesecondperiodhydrides,except
CH4)isincreasingwithgreaternumberofelectronspermolecule,itappearsasthoughthe
majorcontributortothesevaluesistheattractionduetodispersionforces.Thehydridesof
period2areoutoflinewiththegeneraltrend(asisthethirdperiodhydride,HCl,which
seemsabithigherthanwewouldexpectfromtheotherhalogenhalides).Perhapsforthese
quitepolarmolecules(exceptCH4),thereissomepolarinteractionthatdominatesdispersion
effects.(Wewillseeinthesubsequentdiscussionthatthisinteractionistheformationof
hydrogenbonds.)
Followupdiscussion:
Revisittheconceptofdipoledipoleattractionsasanintroductiontohydrogenbonding.
Considerwhatfactors(highlyelectronegativeatomsbondedtohydrogen)mightenterintoan
explanationofthehighboilingpointsofthesecondperiodhydrides(exceptCH4).
Followupactivities:
ConsiderThis1.26.DoeshydrogenbondingexplaintheboilingpointsofNH3andHF?
CheckThis1.27.Predictingrelativeboilingpoints.
EndofChapterproblems1.50through1.60.
ConsiderThis1.26.DoeshydrogenbondingexplaintheboilingpointsofNH3andHF?
Goal:
Usemodels(drawings)ofhydrogenbondinginNH3andHFtoframeanexplanationoftheir
relativelyhighboilingpointsandwhythesearelowerthantheboilingpointofwater.
Classroomoptions:
Allow510minutesforstudents,workinginsmallgroups,tosketchtheirhydrogenbonded
structures.Thenyoucanleadthediscussion,summarizingthesketchesonthechalkboardor
anoverheadtransparencyorhavethestudentsdoit.
TheinstructorcanassignhalfthegroupstosketchhydrogenbondingamongNH3molecules
andtheotherhalftosketchthehydrogenbondingamongHFmolecules.
Thisactivitycouldalsobeassignedasahomeworkproblemandthendiscussedatthenext
classsection.
20
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
Instructornotes:
Asapreludetothisactivity,showFigure1.24andremindtheclassofthetrendsshown.
Thisisanextensionofthetextdiscussionofhydrogenbondinginwater.
Studentsketchesmightlooksomethinglikethesetoshowthemaximumnumberofmolecules
F
H
H
H
H
H
H
H
H
H
H
H
H
H
thatcanbehydrogenbondedtoasinglecentralmolecule:
(a)TheabovehydrogenbondedmodelsexplainwhytheboilingpointsofNH3andHFare
higherthantheyshouldbe,iftheyfollowedthetrendoftheothergroupVandVIIhydrides
inFigure1.24.Thehydrogenbondsarestrongattractiveinteractionsthatkeepthemolecules
together.Highertemperaturesarerequiredtoprovideenoughenergytofreemoleculesto
enterthegasphase.
(b)IndividualNH3andHFmoleculesarecapableofformingfourHbondseach,aswehave
showninthesketchesforpart(a).However,NNH3moleculeshave3Nhydrogenatoms,but
onlyNnonbondingelectronpairs,sotheyarelimitedtoamaximumofNhydrogenbonds.A
similaranalysisappliestoHFforwhichthesingleHoneachmoleculelimitsthenumberof
hydrogenbonds.
(c)ThereislessoverallHbondingpossibleforNH3andHFandhencelessoverallattraction
amongtheirmolecules,sotheirboilingpointsarelowerthanforH2O.
NOTE:Anticipatingthenextsection,wecouldconstructtwocyclichexamersofHF,andfind
thatthereisnownowaytojointhehexamerstogetherwithhydrogenbondsbecauseallofthe
availablehydrogensarealreadyhydrogenbonded.Thisisalsotrueofthecyclichexamersof
ammoniawherethenonbondedelectronpairsonthenitrogenarethe"limitingreactant".
Followupdiscussion:
Thefollowupdiscussionshouldsetthestageforintroducingfurthereffectsofhydrogen
bondinginwaterinSection1.8.
Followupactivities:
CheckThis1.27.Predictingrelativeboilingpoints.
Endofchapterproblems1.50through1.60.
Section1.8.
FurtherStructuralEffectsofHydrogenBondinginWater
LearningObjectivesforSection1.8:
Usedrawings,physicalmodels,andwordstodescribehowthestructureofthewatermolecule
isresponsibleforthedensitiesofsolidandliquidwater,thetemperaturedependenceofthe
densityofliquidwater,andtheconsequencesforlifeonEarth.
ACSChemistryFROG
21
Water:ANaturalWonder
Chapter1
PersonalTutorrelevanttoSection1.8:
Ifstudentsneedextraassistanceinunderstandinggraphsandmolecularstructures,pleasehave
themstudythePersonalTutorexercisesintheseareas.
InvestigateThis1.28.Whatkindsofhydrogenbondednetworkscanyouconstruct?
Goal:
Usingtheirmodelkits,studentswillconstructanetworkofhydrogenbondedwatermolecules
tohelpvisualizethethreedimensionalhydrogenbondedstructure.
Setup:
Duringthepreviousclasssession,remindstudentstobringtheirmodelkitstothenextclass
session.
Timeforactivity:
1015minutes
Materials:
Modelkits.
Procedure:
NOTE:Studentsworkinsmallgroupstocompletethisactivity.Beforebeginningthisactivity,
youmightprojectFigure1.25(c)toshowthecomplexityofthethreedimensionalicestructure.
Amodelcanbemademorenearlytoscaleifthelongyellowsticksareusedinsteadofthewhite
ones.However,twostudentswillhavetocombinekitsinordertoget24yellowsticksneededto
constructthemodelsshowninFigures1.28(b)and(d),ifyouwishtoextendtheactivitytodo
this.Thesestructureswillbealittlelessrigidthanthosemadewiththewhitesticks.
Constructaboutadozenballandstickmodelsofwatermolecules.
Ustheshortest(pink)sticksforthehydrogenoxygenbonds.
Connectoneofyourwatermoleculestofourothersbyhydrogenbondsusingthelonger
(white)sticksforthehydrogenbonds.
Continuetoaddwatermoleculestoseehowanetworkofhydrogenbondedwatermolecules
mightform.
Constraintheconstructionbytryingtoformaringofhydrogenbondedmoleculesinwhich
nobondsticksarebentandallhydrogenbondsarelinear(pinkandwhitesticksinaline).
Studentsshould:
Determinehowmanymoleculesarerequiredtoformanunstrainedring.
ComparetheirstructuretotherepresentationshowninFigure1.28(a).
Drawconclusionsabouttheconnectionsintheicestructure.
Alternateprocedure:Molecularmodelingsoftwarecanbeused.Theinstructorcancreatethe
hydrogenbondnetworkofwatermoleculesforthestudentsorhavethestudentscreatethis
networkasahomeworkassignment.
Anticipatedresults:
StudentsshouldhaveconstructedamodelsimilartoFigure1.28(a).
Followupdiscussion:
Discusstheextendedstructureofice,focusingonthehydrogenbondnetworkthatcreatesthe
stackedsixmemberrings.Ifyouwish,havestudentscombinetheirrings,asinFigure1.28(b)
and(d)togetafurtherfeelforthethreedimensionalstructurethatishardtogetjustfrom
drawingsorphotos.
22
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
Followupactivities:
ConsiderThis1.29.Howdothestructuresofliquidandsolidwatercompare?
InvestigateThis1.30.Whatarethetemperaturesinanicewatermixture?
ConsiderThis1.31.Howdoyouinterpretthetemperaturesinanicewatermixture?
ConsiderThis1.32.Whataretheconnectionsbetweenwaterdensityandtemperature?
Endofchapterproblems1.61and1.64.
ConsiderThis1.29.Howdothestructuresofliquidandsolidwatercompare?
Goal:
RelatethebreakingofthemodelsmadeinInvestigateThis1.28tothecollapseoftheice
structurespresentedinFigure1.28andtherelativedensitiesoficeandwater.
Classroomoptions:
Allow35minutesforstudents,workinginsmallgroups,toanswerthesequestions.Then
youcanleadthediscussion,summarizinganswersonthechalkboardoranoverhead
transparencyorhavestudentsdoit.
ShowtheanimationoficemeltingfromtheWebCompanion,Chapter1,Section1.1,page3.
Instructornotes:
ThisactivityisappropriateforfollowupdiscussiontoInvestigateThis1.28.
Beforeconductingthisactivity,reviewthemodelsshownFigure1.28andthosestudents
constructedinInvestigateThis1.28.
Studentsshouldreasonandconclude:
Ifthehydrogenbondsarebroken,thewatermoleculescanmoveclosertogether(ratherthan
beingheldapartintherigidicestructure).
Yes,thiscollapseisrelatedtotherelativedensitiesoficeandwater.Asicemeltsandsomeof
thehydrogenbondsbreak,theopenicestructurebeginstocollapseandwatermoleculescan
moveclosertogether.Theliquidisnowdenserthantheice(therearemoremoleculesperunit
volume).
Followupdiscussion:
Trytobesurestudentsunderstandthereasonfortherelativedensitiesoficeandliquidwater.
Thisdiscussionispreparationforthenextactivitieswherewefindthatwatermolecules
continuetomoveclosertogetherintheliquidasthetemperatureincreasesandreacha
maximumdensityatatemperatureof3.98C.Abovethistemperature,theincreasingmotion
ofthewatermoleculesresultsinlargerdistancesbetweenthemandthedensitydecreases.
Followupactivities:
InvestigateThis1.30.Whatarethetemperaturesinanicewatermixture?
ConsiderThis1.31.Howdoyouinterpretthetemperatureinanicewatermixture?
ConsiderThis1.32.Whataretheconnectionsbetweenwaterdensityandtemperature?
Endofchapterproblems1.61,1.64,and1.65.
InvestigateThis1.30.Whatarethetemperaturesinanicewatermixture?
Goal:
Correlateliquidwaterdensitywithtemperatureinacolumnoficeandwater.Theactivity
modelstheseasonalturnoverofwater/nutrientsinalakebyexaminingthetemperaturechanges
inanice/watermixtureoveratimeperiodof3060minutes.
ACSChemistryFROG
23
Water:ANaturalWonder
Chapter1
Setuptime:
10minutes
Timeforactivity:
3060minutes.
Equipment:
One2Lplasticbeveragecontainer,cutoffattheshoulder.
Sturdystirringrod.
Twostandardlaboratorythermometersortemperatureprobes.
Ringstandwithtwosmallclamps.
Chemicals:
Crushedice.
Water.
Instructornotes:
Thisactivityisrecommendasaclassactivity.Itmightbedifficulttoconductduringlecture
duetorecordingthetemperatureevery5minutesfor3060minutes,butstudentscouldbe
assignedthistaskwithoutinterruptingtheclassdiscussion.Withtemperatureprobesand
automateddatacollection,theresultscanbecollectedanddisplayedasconvenient.Students
mightbegiventhesedataasahandoutorviatheWebanddoananalysisasahomework
assignment.Theactivitycanalsobeconductedinthelaboratorywiththeresultsanddata
discussedthereorinclass.
Procedure:
SAFETYNOTE
Wearsafetygoggles
Fillatallnarrowtransparentcontainerwithcrushediceandaddcoldwateruntilitisfull.
Placetwothermometersorothertemperatureprobesinthemixturewithonemeasuringthe
temperaturenearthetopandtheothernearthebottomofthemixture.
Stirthemixturevigorouslyforaboutaminutetogetthetemperatureofthemixtureuniformat
0C.Boththermometersshouldread0C.
Pictureofsetup:
24
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
Allowthesystemtoremainundisturbedwhileyourecordthetemperatureofboth
thermometersevery5minutesfor3060minutes(thelongerthebetter).
Plotthedata.
Iftimeisshort,studentscanplottheirdataoutsideofclassanddiscusstheirresultsatthenext
classsession.
Results:
Fora2Lplasticbeveragebottlefilledcompletelywithawater/icemixture.Atlongertimes
thebottomtemperatureremainsatabout45Caslongasthereisstillaseveralcentimeter
layeroficeatthetop.
Time,
min
Topwatertemp,
C
Bottomwatertemp,
C
10
15
20
25
2.5
30
35
40
45
Cleanup:
Disposeice/watermixturedownthedrain.
Followupdiscussion:
ConsiderThis1.31canbeusedforfollowupdiscussion.
Studentsshouldnotethatthetemperatureatthebottomofthebottlerisesto45Candstays
atthattemperatureaslongasiceispresentatthetop,wherethetemperatureremainsat0C.
Theimportanceofthisactivityisthatitdemonstrateshownutrientsandoxygenare
distributedinalakethroughouttheseasons.
Followupactivities:
ConsiderThis1.32.Whataretheconnectionsbetweenwaterdensityandtemperature?
ConsiderThis1.31.Howdoyouinterpretthetemperaturesofanicewatermixture?
Goal:
BasedupontheirobservationsfromInvestigateThis1.30,studentsreasonthatthedensityof
waterishigherat45Cthanat0C.
ACSChemistryFROG
25
Water:ANaturalWonder
Chapter1
Classroomoptions:
Allow35minutesforstudents,workinginsmallgroups,toanswerthesequestions.Then
youcanleadthediscussion,summarizinganswersonthechalkboardoranoverhead
transparencyorhavestudentsdoso.
Thisactivitycouldbeconductedasanopenclassdiscussion.
Instructornotes:
ThisdiscussionshouldbeconductedimmediatelyaftercompletingInvestigateThis1.30.
Studentsshouldreasonandconclude:
Thedenserwaterisatthebottomofthebeaker.Astheicemelts,thedensewatersinkstothe
bottomofthebeaker.Atthebottomofthebeaker,thetemperatureisapproximately45C,
indicatingthatthisisthetemperatureatwhichwaterismostdense.
Followupactivities:
ConsiderThis1.32.Whataretheconnectionsbetweenwaterdensityandtemperature?
ConsiderThis1.32.Whataretheconnectionsbetweenwaterdensityandtemperature?
Goal:
StudentsconnecttheirresultsfromInvestigateThis1.30towaterdensityasafunctionof
temperature.
Classroomoptions:
Allow35minutesforstudents,workinginsmallgroups,toanswerthequestions.Thenyou
canleadthediscussion,summarizingtheirexplanationsonthechalkboardoranoverhead
transparencyorhavestudentsdoso.
Thisactivitycouldalsobeassignedasahomeworkproblemandthendiscussedatthenext
classsession.
Thisactivitycouldbeconductedasanopenclassdiscussion.
Instructornotes:
Studentsshouldreasonandconcludethat:
Yes,thedensitypropertiesofwaterandicedosupporttheobservationthatthe45Cwaterat
thebottomofthebottleisdensest.
Inthesummer,thesunlightwarmslakewatersothelessdensewater(temperaturegreater
than4C)isonthesurfaceofthewater.Asthetemperaturedecreasesinthefall,thewater
temperaturefalls,itsdensityincreases,andwindscanstirthewatermoreuniformlydense
watercolumn.Thenutrientsinthelakemix.Inthewinter,thelessdensewater(temperature
lessthan4C)freezesoverthesurfaceofthelake.Asitmeltsinthespring,themixingof
nutrientsoccursagainasthewatercolumnwarmsandthemoreuniformlydensewater
columnagaincanbestirred.
Followupdiscussion:
Pointoutthat,asenergy(heat)entersthebottleinInvestigateThis1.30,someoftheicemelts.
Waterthatisformedisdenserthaniceandsinksasitwarmsslightly.Asthewatercontinues
towarm,itcontinuestosink,asnotedbytheinitialtemperatureincreaseatthebottomofthe
bottle.Finally,thetemperatureatthebottomstabilizeswhenthewaterdensityisamaximum.
Aslongasiceispresent,thetopandbottomtemperaturesremainconstant,eventhough
energyfromthesurroundingscontinuestoenterthebottle.
26
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
Thewateratthebottommustcontinuetoabsorbenergyandsomeofitmustbegintowarm
above5C.Whathappenstothiswarmerwater?Itmustbelessdenseandbeginstorisein
thebottle,butexchangesenergywiththecolderwatersinkingfromthetop,sothereisa
continuousexchangeofenergyamongthewatermoleculesthatmaintainsatemperature
gradientdownthebottle.
Followupactivities:
Studentsmightbechallengedtoproveordisprovethemodeljustdescribed,beginningwitha
hypothesisaboutthewaythegradientwouldchangewithtime.
Endofchapterproblems1.61through1.65.
Section1.9.
HydrogenBondsinBiomolecules
LearningObjectivesforSection1.9:
Describesomeoftheplaceswherehydrogenbondingoccursinbiomoleculesandexplainhow
hydrogenbondingisimportantforthefunctionsofthesemolecules.
InvestigateThis1.33.HowdotheDNAbasesfittogether?
Goal:
Students,workinginsmallgroups,willusetheirmodelkitstobuildadenine,guanine,cytosine,
andthymineandthenmodelDNAbasepairing.
Setuptime:
0minutes.Remindstudentstobringtheirmodelkitstotheclasssessionwhenthisactivityis
tobedone.Or,assignstudentstobuildabasepairasahomeworkassignmentpriorto
conductingthisactivityinclass.
Timeforactivity:
1520minutes.
Equipment:
Molecularmodelkits.
NOTE:Therearetwononequivalentsetsofholesinthelightblueanddarkgraypolyhedra.
Therearetwoapicalholesthatare180apartandthreeequatorialholesthatare120from
eachotherandperpendiculartotheaxisoftheapicalholes.Studentswilluseonlythe
equatorialholes.(Seewww.iupac.org/goldbook/A00415.pdfforabriefdiscussionofthis
geometricnomenclature).
Procedure:
Havestudentsshouldworkingroupsoffourandeachstudentbuildoneofthebases.
ProjectFigure1.34sostudentscanvisualizehowtoconstructtheirmodels.
UsethedarkgrayandlightbluepolyhedrafortheCsandNs(equatorialtrigonalholes),
respectively,intherings.
Usethestandardblack,darkblue,andredpolyhedrafortheotherCs,Ns,andOs.TheseC
andNatomshavetetrahedral(sp3)holes.
ShowhowtheATandGCpairscanbeheldtogetherbytwoandthreehydrogenbonds,
respectively.
Trytomakethealternativepairs,ACandGT.
ACSChemistryFROG
27
Water:ANaturalWonder
Chapter1
NOTE:AlltheNatomsintheDNAbasepairsaretrigonal(sp2).Studentshavebeeninstructed
tousethetetrahedralNatoms(darkblue)forthenonringNs.Ifyouchoosetohavestudents
usethelightblue(trigonal)NatomsforallNsinthemolecules,pairsofstudentswillneedto
sharethelightblueNsintheirmodelkitstomakeabasepair.WhicheverNisusedhastobe
turnedsothattheNandtwoofitsbondsareintheplaneoftheringinordertomakethecorrect
hydrogenbondconnection.
Alternativeprocedure:UsemolecularmodelingsoftwaretobuildDNAbasepairsandtomodel
hydrogenbondingbetweenbasepairs.
Anticipatedresults:Dottedlinesindicatehydrogenbonds(forwhichstudentscanusetheir
yellowstickstoshowhowthepairsfit).
Guaninecytosinebasepair(sp3nonringNatoms):
Adeninethyminebasepair(sp3nonringNatoms):
Guaninecytosinebasepair(sp2nonringNatoms):
28
ACSChemistryFROG
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Water:ANaturalWonder
Adeninethyminebasepair(sp2nonringNatoms):
Followupdiscussion:
DiscussthecriticalroleofhydrogenbondsintheoverallstructureofDNAaswellastheir
roleindeterminingtheactiveformsofotherbiomoleculessuchasproteins,asshownin
Figure1.31fortheahelix.
Pointoutthedifferentrolesthathydrogenbondsandstrongercovalentbondsplayinthese
molecules.
Followupactivities:
ConsiderThis1.34HowdoeshydrogenbondingaffectthethermalstabilityofDNA?
ConsiderThis1.34.HowdoeshydrogenbondingaffectthethermalstabilityofDNA?
Goal:
Studentsapplytheirknowledgeofhydrogenbondingtodeterminehowitaffectsthethermal
stabilityofDNA.
Classroomoptions:
Allow35minutesforstudents,workinginsmallgroups,toanswerthesequestions.Then
youcanleadthediscussion,summarizinganswersonthechalkboardoranoverhead
transparencyorhavestudentsdoso.
Thisactivitycouldalsobeassignedasahomeworkproblemandthendiscussedatthenext
classsession.
Thisactivitycouldbeconductedasanopenclassdiscussion.
Instructornotes:
Beforecompletingthisactivity,completeInvestigateThis1.33anddiscusshydrogenbonding
inDNA,Figure1.33.
DiscusswhatdenaturationmeansforDNAandrelatetoproteindenaturation.
Studentsshouldreasonandconcludethat:
EachGCpairformsthreehydrogenbonds,whileeachATpairformstwohydrogenbonds
asshowninFigure1.33andfoundinInvestigateThis1.33.DNAheliceswithahigherGCto
ATratioaremorethermalstable.Moreenergywillberequiredtobreakthreehydrogen
bondsperDNAbasepairthantwohydrogenbonds.
Followupdiscussion:
Discusstheroleofhydrogenbondingindeterminingtheactiveformsofbiomolecules.
Followupactivities:
Endofchapterproblems1.66through1.71.
ACSChemistryFROG
29
Water:ANaturalWonder
Chapter1
Section1.10.PhaseChanges:LiquidtoGas
LearningObjectivesforSection1.10:
Describeanduseenergydiagramstoillustratethedirectionofenergytransferfromone
substancetoanotherwhenphasechangesoccur.
Usetherelationshipamongenergychange,temperaturechange,mass,andspecificheatto
makequantitativecomparisonsbetweentwosubstancesthatgainorlosethermalenergy.
PersonalTutorrelevanttoSection1.3:
Ifstudentsneedextraassistanceunderstandinggraphs,pleasehavethemstudythePersonal
Tutorgraphingexercises.
InvestigateThis1.35.Whathappenswhenyousweat?
Goal:
Studentsexperienceandobservetheevaporationofwater.
Setuptime:
0minutes.
Timeforactivity:
1minute.
Procedure:
NOTE:Students'handsshouldbecleananddry.
Eachstudentshouldwetafingerononehandandthenwavethathandintheair.
Havestudentsreportanydifferencetheynotebetweenthewetfingerandtheothers.
Followupdiscussion:
UseConsiderThis1.36toinitiatediscussionoftheobservationsfromthisactivity.
Followupactivities:
ConsiderThis1.37.Whatarethesignsoftheenergychangesforsweating?
CheckThis1.38.Interpretinganenergydiagram.
ConsiderThis1.39.Howareenergyleveldiagramscorrelated?
InvestigateThis1.40.Doallliquidsevaporateatthesamerate?
ConsiderThis1.36.Whatisthepurposeofsweating?
Goal:
Studentsreasonthatevaporationofwater(liquidtogasphasechange)requiresenergy,because
theevaporationinInvestigateThis1.35tookenergyfromtheirskinandmadetheirwetfingers
feelcool.
Classroomoptions:
Allow35minutesforstudents,workinginsmallgroups,toanswerthesequestions.Then
youcanleadthediscussion,summarizinganswersonthechalkboardoranoverhead
transparencyorhavestudentsdoso.
Instructornotes:
InvestigateThis1.35shouldbecompletedpriortothisactivity.
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ACSChemistryFROG
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Water:ANaturalWonder
Remindstudentsaboutthephasechangesintroducedearlierinthechapterand,inparticular,
theenergyrequiredfortheliquidtogaschangethatwasanimportantpartoftheargument
aboutintermolecularforcesandboilingpointsinSection1.7.
Studentsshouldreasonandconclude:
Thewetfingerfeelsdifferentasyourhandiswavedintheair,becauseenergyfromtheskinis
usedtoevaporatethesalivaonthefinger.Thelossofenergyrequiredtomakethegaseous
moleculesleavetheskin,makesthefingerfeltcool.
Followupdiscussion:
Discussionshouldreinforcetheconceptsofvaporizationandphasechanges.Although
studentsaregenerallyquitefamiliarwithconceptofevaporationandcoolingbyevaporation,
mostlackafirmgraspofthemolecularleveleventsthatareresponsible.Trytofocusthe
discussionatthismechanisticlevel,includingtheenergetics,andthesourceoftheenergy(the
skin).
Discusshowenergyisinvolvedinphasechanges.
Specifically,introducestudentstotheEnomenclature.
Followupactivities:
ConsiderThis1.37.Whatarethesignsoftheenergychangesforsweating?
CheckThis1.38.Interpretinganenergydiagram.
ConsiderThis1.39.Howareenergyleveldiagramscorrelated?
InvestigateThis1.40.Doallliquidsevaporateatthesamerate?
Endofchapterproblem1.72.
ConsiderThis1.37.Whatarethesignsoftheenergychangesforsweating?
Goal:
BasedontheirresultsfromInvestigateThis1.35andunderstandingofphasechanges,students
reasonoutthesignsoftheenergychanges,E,forsweating.
Classroomoptions:
Allow5minutesforstudents,workinginsmallgroups,toanswerthequestions.Thenyoucan
leadthediscussion,summarizinganswersonthechalkboardoranoverheadtransparencyor
thestudentscandoso.
Thisactivitycouldbeconductedasanopenclassdiscussion.
Instructornotes:
CompleteInvestigateThis1.35andConsiderThis1.36beforeconductingthisactivity.
Studentsshouldreasonandconclude:
(a)WhenyouwavedyourfingerintheairinInvestigateThis1.35,thewaterevaporated.
Energymustenterthewatertocauseevaporation.Thesignoftheenergychangeinthewater
ispositive.
(b)Energyleavesyourskin.Thesignofthisenergychangeisnegative.Yes,thedifference
betweenthewetfingerandthedryfingersisthatthewetfingerfeltcooluponevaporation
becauseenergywasleavingittoprovidetheenergyfortheliquidtogasphasechange.
Followupdiscussion:
Discussandreinforcethesignsforenergychanges.
IntroduceenergyleveldiagramsusingFigure1.35.
ACSChemistryFROG
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Water:ANaturalWonder
Chapter1
NOTE:Atthispointinthetext,thesediagramsaretobeusedmainlyqualitatively,althoughwe
doaskforaquantitativeresultinConsiderThis1.39(b).
Followupactivities:
CheckThis1.38.Interpretinganenergydiagram.
ConsiderThis1.39.Howareenergyleveldiagramscorrelated?
InvestigateThis1.40.Doallliquidsevaporateatthesamerate?
ConsiderThis1.41.Whataretherelativeenergiesofvaporizationofdifferentliquids?
ConsiderThis1.39.Howareenergyleveldiagramscorrelated?
Goal:
StudentsunderstandhowthesignofEisrelatedtothedirectionofitsrepresentationasan
arrowonanenergyleveldiagramandgetafeelfortheconservationofenergy.
Classroomoptions:
Allow35minutesforstudents,workinginsmallgroups,toanswerthesequestions.Thenyou
canleadthediscussion,summarizinganswersonthechalkboardoranoverheadtransparency
orhavestudentsdoso.
Instructornotes:
Beforedoingthisactivity,discusstheinterpretationofenergydiagrams,Figure1.35,andhave
studentsdoCheckThis1.38.
Studentsshouldreasonandconclude:
(a)AdownwardpointingarrowrepresentsanegativeE,thatis,adecreaseinenergyfrom
theinitialtothefinalconditions.
(b)Thelengthoftheenergychangearrowshouldbethesamelengthastheenergychange
arrowshowninFigure1.35(Anenergydiagramforevaporationofthesameamountofasis
evaporatedfromtheskininthisprocesswater).Theenergylostbytheskintocause
evaporationisequal(butoppositeinsign)totheenergyrequiredfortheevaporation.
Followupactivities:
InvestigateThis1.40.Doallliquidsevaporateatthesamerate?
ConsiderThis1.41.Whataretherelativeenergiesofvaporizationofdifferentliquids?
Endofchapterproblems1.72,1.74,and1.75.
InvestigateThis1.40.Doallliquidsevaporateatthesamerate?
Goal:
Determineifequalvolumesofwater,methanol,andhexaneevaporateatthesamerateorwhat
theirorderofevaporationis.
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Water:ANaturalWonder
Setuptime:
510minutes.
Timeforactivity:
Lessthan5minutes.
Materials:
Threeidenticalpapertowels.
Youcanusesmallspongesattachedtowoodensplintsasanalternate.Usingascissors,make
apointatoneendofthesplintandinsertonesponge.
Threepipetsordroppers.
Chemicals:
Hexane,C6H14.
Methanol,CH3OH.
Water.
Procedure:
Thisshouldbeconductedasaclassactivity.Requestthreestudentvolunteerstoconductthis
activity.
SAFETYNOTES
Wearsafetygoggles
Hexaneandmethanolareflammablenoflames,fire
extinguisher
Simultaneouslyplace10dropsofwaterononepapertowel,10dropsofmethanolonasecond
papertowel,and10dropsofhexaneonathirdone.
Holdthetowelsupsothattheclasscanseetheliquidspotandstudentscantimehowlongit
takeseachofthespotstodisappearcompletely.
Studentsshouldnotewhichliquidevaporatesfastestandwhichslowest.
Alternateprocedure:Youcanusethisprocedureifyouhaveachalkboardinyourclassroom.
Placetheequalamountsofliquidonthreesmallspongesandsimultaneouslywipetheliquids
ontothechalkboardinthreeplaces.Itiseasytoobservetheorderinwhichtheliquidfilms
disappear.
Anticipatedresults:
Hexaneevaporatesalmostbeforethetowelcanbeshown.
Methanolevaporateswithinafewseconds.
Waterevaporateswithinaboutaminuteortwo.
Cleanup:
Methanolandhexanespongesshouldbeallowedtodrycompletelybeforebeingstoredor
properlydisposedof.
Followupdiscussion:
UseConsiderThis1.41toinitiatediscussionoftheobservationsfromthisactivity.
Followupactivities:
WorkedExample1.42.Conversionofenergyunits.
CheckThis1.43.Conversionofenergyunits.
ACSChemistryFROG
33
Water:ANaturalWonder
Chapter1
ConsiderThis1.41.Whataretherelativeenergiesofvaporizationofdifferentliquids?
Goal:
BasedontheirresultsfromInvestigateThis1.40,studentsdeterminetherelativeenergiesof
vaporizationofwater,methanol,andhexaneaswellassketchenergydiagramsfortheir
vaporization.
Classroomoptions:
Allow35minutesforstudents,workinginsmallgroups,toanswerthesequestions.Then
youcanleadthediscussion,summarizinganswersonthechalkboardoranoverhead
transparencyorhavestudentsdoso.
Instructornotes:
PointouttostudentsthatalltheliquidfilmsinInvestigateThis1.40gainedenergyfromthe
towels(orspongesorchalkboard).Weassumethateachliquidgainedenergyatthesamerate,
buttheydidnotvaporizeatthesamerate.Thismeansthatdifferentquantitiesofenergyof
vaporizationarerequiredforeachsample.
Studentsshouldreasonandconclude:
(a)Eispositivebecausealltheliquidsevaporated.Efinal(gas)isgreaterthanEinitial(liquid).
(b)Sincehexaneevaporatedfirst,itrequirestheleastenergyandhasthesmallestvalueof
Eforvaporization.Sincewaterevaporatedlast,ithasthelargestvalueofEfor
vaporization.
(c)Thisisanenergydiagramthatcomparestheenergychangesforthehexane,methanol,
andwaterevaporationinInvestigateThis1.40.NOTE:Wearenotimplyingthattheenergies
ofthethreeliquidsarethesame.(Wehavenoinformationabouttheirabsoluteenergies.)
Theyareputatthesamelevel,tomakeiteasytocomparethechangesuponevaporation.
Followupdiscussion:
DiscusswhatoccurredinInvestigate1.40andtheanswersforthisactivity.
Reiteratethatthepapertowels(spongesorchalkboard)suppliedtheenergiesforvaporizing
theliquidsandweassumethattheliquidsgainedenergyatthesamerate.Theirvaryingrates
ofevaporationindicatethatdifferentamountsofenergyarerequiredforeachsampleto
evaporate.
Introduceenergyunitsandconversionofunits.
Raisetheissueaboutthenumberofmoleculesthatevaporateineachsampleandwhetherthe
comparisonsmadethusfararefairindicationsoftheenergyrequiredtoevaporatethesame
quantityofeachliquid.Whatquantityisappropriatetocompare?
Followupactivities:
WorkedExample1.42.Conversionofenergyunits.
34
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
CheckThis1.43Conversionofenergyunits.
Endofchapterproblems1.72through1.76.
Section1.11.CountingMolecules:TheMole
LearningObjectivesforSection1.11:
Becomefamiliarwiththechemistsunitofquantity,themole,Avogadrosnumberof
particles.
Beabletodefine,calculate,andusethemolarmassofacompound,determinedfromthe
relativeatomicmassesofitsconstituentatoms,tocalculatethenumberofmolesinagiven
massofthecompound.
Useintermolecularattractionstopredictand/orexplaintrendsinboilingpointsandmolar
energiesofvaporizationforaseriesofcompoundswhosemolecularstructuresyouknowor
candetermine.
Usetherelationshipamongenergychange,temperaturechange,mass,andspecificheatto
makequantitativecomparisonsbetweentwosubstancesthatgainorlosethermalenergy.
PersonalTutorrelevanttoSection1.11:
Ifstudentsneedextraassistanceinunderstandingthemoleconceptand/orgraphsandtables,
pleasehavethemstudythePersonalTutorexercises.
ConsiderThis1.44.Howcanyoucountobjectsbymeasuringmass?
Goal:
Studentsdeterminehowtocountobjectsbymeasuringtheirmass.
Classroomoptions:
Allow35minutesforstudents,workinginsmallgroups,toanswerthequestions.Thenyou
canleadthediscussion,summarizinganswersonthechalkboardoranoverheadtransparency
orhavestudentsdoso.
Thisactivitycanbeassignedasahomeworkexerciseandthendiscussedaspartofthe
introductiontothissession.
Instructornotes:
Usethisactivitytointroducetheconceptofthemole.
Studentsshouldcalculate:
12.7dozen(=24.1gdividedby1.9gdozen1)
152tickets(=12.7dozenmultipliedby12ticketsdozen1)
Followupdiscussion:
Discussanswersandusetheanalogyofdozentointroducetheconceptofthemole.Use
studentresultsfromthefollowupactivitiestosparkclassdiscussionaboutmasstomole
conversions.
Followupactivities:
AssigntheWebCompanion,Chapter1,Section1.11,ashomeworkoruseitinlectureto
reinforcethemoleconceptandmassandmolerelationships.
WorkedExample1.45.Calculatingnumbersofmoles.
CheckThis1.46.Masstomolesandmolestomassconversions.
ACSChemistryFROG
35
Water:ANaturalWonder
Chapter1
WorkedExample1.47.Calculatingmolarmass.
CheckThis1.48.Calculatingmolarmass.
CheckThis1.49.Comparingamountsofcompounds.
Endofchapterproblems1.77through1.82(afterconceptofmoleisdiscussed).
ConsiderThis1.50.WhichcompoundsinTable1.2formhydrogenbonds?
Goal:
ByanalyzingthemolecularstructuresoftheliquidslistedinTable1.2,studentswilldetermine
whichonesformhydrogenbonds.
Classroomoptions:
Allow35minutesforstudents,workinginsmallgroups,toanswerthesequestions.Thenyou
canleadthediscussion,summarizinganswersonthechalkboardoranoverheadtransparency
orhavethestudentsdoso.
Eachgroupcanbeassignedoneliquid.
Thisactivitycanbeassignedasahomeworkexerciseandthendiscussedatthenextclass
session.
Preparation:
Remindstudentsatthepreviousclasssessiontobringtheirmolecularmodelkitstoclassfor
thisactivity.
Instructornotes:
Studentsshouldreasonandconclude:
(a)Amoleculeofmethanol(orethanol)canformhydrogenbondstothreeothermethanol
(orethanol)molecules.
(b)Buildmolecularmodelstoshowthesehydrogenbondinginteractionsinthreedimensions
andtoshowthatnosuchinteractionsarepossiblefortheothertwomoleculeswhichdonot
containOH,NH,and/orFHbondsthatarerequiredtoformhydrogenbonds.
O
CH 3
H
O
H 3C
CH2CH3
H
CH3
H 3CH 2C
CH3
CH 2CH 3
CH2 CH3
Followupdiscussion:
Usethisfollowupdiscussiontoreviewthemolecularattractionspreviouslyintroducedand
applythemtothecompoundspresentedinTable1.2,notingthedifferencesbetweenalcohols,
ethers,andalkanes(hexanes)andtheeffectsonmolarvaporizationenergies.
Followupactivities:
CheckThis1.52.VaporizationenergiesinInvestigateThis1.40.
Endofchapterproblems1.83through1.85.
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ACSChemistryFROG
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Water:ANaturalWonder
Section1.12.SpecificHeatofWater:KeepingtheEarthsTemperature
Stable
LearningObjectivesforSection1.12:
Usetherelationshipamongenergychange,temperaturechange,mass,andspecificheatto
makequantitativecomparisonsbetweentwosubstancesthatgainorlosethermalenergy
Usedrawings,physicalmodels,andwordstodescribethemolecularbasisforthedifferences
inspecificheatsamongdifferentcompounds.
Understandtherelationshipbetweenthepropertiesofwaterandthestabletemperatureofthe
Earth.
InvestigateThis1.53.Whatisobservedwhenliquidsareheatedatthesamerate?
Goal:
Providedatatoguideadiscussionthatwillleadtotheconceptofspecificheat.
Setuptime:
510minutes.Thisactivityshouldbeconductedasaclassactivity.
Timeforactivity:
46minutes.
Materials:
Two250mLStyrofoam cups.
Twobeakers(Styrofoam cupsshouldfitsnuglyintobeakersforsupport).
Twoelectricalimmersionheaters.
Twostandardlaboratorythermometersorcomputerinterfacedtemperatureprobes.
Tworingstandsandsmallclampstosupportthethermometersandimmersionheatersinthe
liquids.
Chemicals:
120150g(preweighed)ofwateratroomtemperature.
120150g(preweighedsameasmassofwater)ofethanolatroomtemperature.
Procedure:
Thisshouldbeconductedasaclassactivity.Usetwostudentvolunteersforeachsampleto
conductthisactivity.Onestudentwillbethetimerandrecorderandtheothershouldreadthe
thermometerat10secondintervals.(Ifcomputerinterfacedtemperatureprobesareused,the
paralleldatacanbeprojectedastheyaretaken.)
SAFTYNOTES:
Wearsafetygoggles
Ethanolisflammablenoflames,fireextinguisher
Addtheweighed120150gofroomtemperaturewatertoa250mLStyrofoam cup.
Addthesamemassofroomtemperatureethanoltoasecondidenticalcup.
Clampidenticalimmersionheatersandthermometersineachcupwiththethermometers
aboutonecentimeterfromtheheaters.
Readandrecordthetemperatureoftheliquidsevery10secondsforaboutoneminute.
ACSChemistryFROG
37
Water:ANaturalWonder
Chapter1
Simultaneouslyplugbothheatersintoelectricaloutlets.Thisiseasiesttodoifbothheatersare
pluggedintothesamemultipleoutletextensioncordthatispluggedintotheoutlettostartthe
heating.
Continuereadingthetemperatureevery10secondsuntiloneoftheliquidsreachesabout
70C.
Unplugtheheaters.
Plotthetemperaturesasafunctionoftime.Iftimeisshort,studentscouldplottheirdata
outsideofclassandbringtheirplotsandinterpretationstodiscussatthebeginningofthenext
classsession.
Alternativeprocedures:Usetwobeakersfortheliquidsandplacethemsimultaneouslyonahot
plate.ThissetupeliminatestheneedforStyrofoam cupsandimmersionheaters.Insteadof
beakers,aluminummuffincupscanbeused.
NOTE:Immersingatesttubeofwaterandatesttubeofethanolintoahotwaterbathand
monitoringthetemperaturechangedoesnotwork.
Anticipatedresults:
Sampledataforwaterand91%2propanol(rubbingalcohol):
Temperature/C
38
time/sec
water
alcohol
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
21.1
21.1
21.1
21.1
21.1
21.1
21.1
21.1
21.1
21.1
21.4
21.7
22.3
23.3
24.2
25.1
26.4
27.9
29.2
30.7
32.3
33.8
35.4
22.0
22.0
22.0
22.0
22.0
22.0
22.0
22.0
22.0
22.3
22.6
23.6
24.8
26.4
28.6
30.7
33.2
35.7
38.5
41.3
44.1
46.9
50.0
ACSChemistryFROG
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Water:ANaturalWonder
115
120
125
130
135
140
37.0
38.5
39.8
41.6
42.9
44.4
52.8
55.6
58.7
61.5
64.6
68.4
Cleanup:
Disposeethanoldownthedrainwithcopiousamountsofwater.
Followupdiscussion:
UseConsiderThis1.54toinitiatediscussionoftheobservationsfromthisactivity.
Thisactivitycanbeusedtointroduceanddiscusstheconceptofspecificheat.
Studentsshouldnotethatwaterdoesresistchangeintemperaturewhenthermalenergyis
added.Thisisreflectedinitshighspecificheat.Mostofthethermalenergyisusedtobreak
hydrogenbonds,nottoincreasemolecularmotion.
Followupactivities:
WorkedExample1.55.Specificheatandtemperaturerise.
CheckThis1.56.Specificheatandtemperaturerise.
WorkedExample1.57.Thermalenergychangeinwater.
CheckThis1.58.Thermalenergychangeinethanol.
ConsiderThis1.59.AreyourcalculationsrelatedtoInvestigateThis1.53?
ConsiderThis1.54.Howdoestemperaturechangeinheatedliquids?
Goal:
FromtheirresultsforInvestigateThis1.53,studentswillconsiderhowtemperaturechangesin
heatedliquids.
Classroomoptions:
Allow35minutesforstudents,workinginsmallgroups,toanswerthequestions.Several
minuteslongertimewillberequired,ifthestudentshavenotplottedthedataoutsideofclass.
Alternately,useanoverheadtransparencywithagridlinesandhaveastudentplotthedatafor
theentireclass.Thenyoucanleadthediscussion,summarizinganswersonthechalkboardor
anoverheadtransparencyorhavestudentsdoso.
ThisactivitycanbeassignedasahomeworkactivityafterInvestigateThis1.53iscompleted.
Instructornotes:
Beforegettingintothediscussion,reviewthedataplottobesureeveryoneisworkingfrom
thesamerepresentationofthedata.
Studentsshouldreasonandconclude:
(a)Thetemperatureincreasedinbothliquids.However,thealcohol(91%2propanolshown
here)reachedhighertemperaturesthanwaterduringthesametimeinterval.Alternatively,as
shownonthisplot(begunat60secondsinthetablepresentedwithInvestigateThis1.53
above),ittakeslonger,thatis,requiresmoreenergy,toraisewaterthantoraisethealcohol
tothesametemperature.
ACSChemistryFROG
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Chapter1
(b)Thespecificheatofwater(theenergyrequiredtoraiseonegramoftheliquidbyone
degree)isgreaterthanthespecificheatofalcohol(ethanolor2propanol).Moreenergyis
requiredtoraisethewatertemperatureagivenamountthantoraisethealcoholtemperature
thesameamount.
Followupactivities:
WorkedExample1.55.Specificheatandtemperaturerise.(Drawattentiontothediscussion
oftheimplementation.)
CheckThis1.56.Specificheatandtemperaturerise.
WorkedExample1.57.Thermalenergychangeinwater.
CheckThis1.58.Thermalenergychangeinethanol.
ConsiderThis1.59.AreyourcalculationsrelatedtoInvestigateThis1.53?
ConsiderThis1.59.AreyourcalculationsrelatedtoInvestigateThis1.53?
Goal:
Findoutwhetherspecificheatcalculationsforwater,WorkedExample1.57,andethanol,
CheckThis1.58,areconsistentwiththeresultsfromInvestigateThis1.53.
Classroomoptions:
Allow35minutesforstudents,workinginsmallgroups,toanswerthequestions.Thenyou
canleadthediscussion,summarizinganswersonthechalkboardoranoverheadtransparency
orhavestudentsdoso.
Thisactivitycouldalsobeassignedasahomeworkproblemandthendiscussedatthenext
classsession.
Thisactivitycouldbecompletedasanopenclassdiscussion.
Instructornotes:
ReviewresultsfromInvestigateThis1.53,CheckThis1.58,andtemperaturechangeforthe
samemassofwaterfromWorkedExample1.57beforeconductingthisactivity.
Studentsshouldreasonandconcludethat:
ThespecificheatcalculationsarerelatedtotheresultsfromInvestigateThis1.53.Theamount
ofenergyrequiredtoraisethetemperatureofthewaterby23.4Ciscalculatedtoraisethe
temperatureofthesamemassofethanolby40.0C.Thespecificheatofethanolislower,so
thesameamountofenergywillmakeitwarmer.
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Followupdiscussion:
Havestudentsexplain(fromamolecularpointofview)intheirownwordswhywaterhasa
highspecificheatandwhyitisimportantforconditionsofEarth.
Reviewoutcomesforthechapterand/orcontinueonwithSection1.14.
Followupactivity:
Endofchapterproblems1.86through1.97.
Section1.14.ExtensionLiquidViscosity
LearningObjectivesforSection1.11:
Usethebackgroundfromthechaptertodevelopamolecularlevelexplanationforviscosity,
anotherpropertyofliquids.
InvestigateThis1.60.Howfastdodifferentliquidsflowfromapipet?
Goal:
Studentsobserveandcomparetheratesofoutflowofwaterandhexanefromapipetand
developapictureofhowviscosityisrelatedtomolecularattractions.
Setuptime:
10minutes.Thisactivityshouldbeconductedasaclassactivity.
Timeforactivity:
1015minutes.
Materials:
Two9"glassPasteurpipets.
Twocontainerstocatchtheoutflowfromthepipets.
Chemicals:
Approximately10mLofwater,H2O.
Approximately10mLofhexane,C6H14.
Procedure:
Thisshouldbeconductedasaclassactivity.Usetwostudentvolunteerstoconducttheactivity.
SAFETYNOTES
Wearsafetygoggles
Hexaneisflammablenoflames,fireextinguisher
UsetwoidenticalglassPasteurpipetsforthisinvestigation.
Markeachpipetatthesameplaceabout3cmfromthetop.
Drawwaterintoonepipetuntilitisabovethemark.
Holdthepipetverticalwithitstipoveracontainertocatchthewater.
Timehowlongittakesthewatertodrainoutofthepipet,startingfromthetimeitstop
surfacepassesthemark.
Repeattobesurethetimeisreproducibleto1or2seconds.
Usethesecondpipettorepeatthesameprocedurewithhexane.
Anticipatedresults:
Ittakeslesstimeforhexanetoflowoutofthepipet.
ACSChemistryFROG
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Chapter1
Cleanup:
Watercanbedisposeddownthedrain.Hexaneshouldbeplacedinaproperlylabeledwaste
containerorstoredforfurtheruseinotheractivities/experiments.
Followupdiscussion:
UseConsiderThis1.61tostimulatediscussionoftheresultsfromthisactivity.
Discusstheconceptofviscosityandhowrelativeviscositiesarerelatedtotheoutflowtimes
fromthepipets.
Followupactivities:
ConsiderThis1.62.Doeshydrogenbondingexplainviscositiesinothercompounds?
ConsiderThis1.63.Arethemodelsforspecificheatandviscosityofwaterrelated?
Endofchapterproblems1.98through1.100.
ConsiderThis1.61.Howareviscositiesrelatedtomolecularattractions?
Goal:
Studentsreasonoutamolecularmodeltorelatetheobservedrelativeviscositiestomolecular
interactions.
Classroomoptions:
Allow510minutesforstudents,workinginsmallgroups,toanswerthesequestions.Then
youcanleadthediscussion,summarizinganswersonthechalkboardoranoverhead
transparencyorhavestudentsdoso.
Eachgroupcanbeassignedonequestiontoanswer.
Instructornotes:
ThisactivityisbasedontheobservationsinInvestigateThis1.60andwhatstudentshave
previouslylearnedaboutmolecularattractions.
Studentsshouldreasonandconclude:
(a)Theoutflowofhexaneismuchfasterthantheoutflowforwater.Waterhasthehigher
viscosityduetoitssloweroutflowratecomparedtohexane:thehighertheviscositythe
slowertheflow.
(b)Yes,sincemostoftheindividualwatermoleculesarehydrogenbondedwithotherwater
molecules,theyarenotmovingfreelyandindependently.Thepresenceofhydrogenbonding
meansthatmanymoleculeshavetomovetogethertoflowoutofthepipetandmakesthe
flowraterelativelyslow.Weinterprettheslowflowasduetoahighviscosity.
(c)No,hexanedoesnotformhydrogenbonds.Dispersionforcesamongthemoleculesare
notdirected,sothemoleculescanmoverelativelyindependentlyofoneanother.Thus,the
hexanemoleculesdonotinterferemuchwithoneanotherastheyflowoutofthepipetand
theflowisrelativelyfast.Weinterpretthefastflowasduetolowviscosity.
(d)Therelativeviscosityofhexanewithoutdirectionalattractionsamongthemoleculesis
lessthanthatofwaterwithitshighlydirectionalnetworkofhydrogenbondsaroundeach
molecule.
Followupdiscussion:
UseConsiderThis1.62tostimulatefurtherdiscussionbasedonthedatainTable1.4andthe
modeljustdeveloped.
42
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
Followupactivities:
ConsiderThis1.62.Doeshydrogenbondingexplainviscositiesinothercompounds?
ConsiderThis1.63.Arethemodelsforspecificheatandviscosityofwaterrelated?
Endofchapterproblems1.98through1.100.
ConsiderThis1.62.Doeshydrogenbondingexplainviscositiesinothercompounds?
Goal:
UsingthedatapresentedinTable1.4,studentsdetermineifhydrogenbonding(orlackthereof)
explainstheviscositiesinothercompounds.
Classroomoptions:
Allow58minutesforstudents,workinginsmallgroups,toanswerthequestions.Thenyou
canleadthediscussion,summarizinganswersonthechalkboardoranoverheadtransparency
orhavestudentsdoso.
Ifnecessary,assignquestion(a)tohalfthegroupsandquestion(b)totheremaininggroups.
Thisactivitycouldalsobeassignedasahomeworkproblemandthendiscussedatthenext
classsession.
Thisactivitycanbeconductedasanopenclassdiscussion.
Instructornotes:
ReferstudentstothedatainTable1.4astheydothisactivity.
Drawattentionduringthediscussionoftheanswerstothefactthatacetoneanddiethylether
botharepolarandhaveanoxygenatomthatcouldparticipateinhydrogenbonds,butdonot
haveahydrogenatombondedtoN,O,orF,sohavenohydrogentoformahydrogenbond.
Studentsshouldreasonandconclude:
(a)Water,methanol,ethanolandethyleneglycolcanformhydrogenbonds.Yes,thereisa
correlationbetweenviscosityandamolecule'sabilitytoformhydrogenbonds.Those
compoundsthatformhydrogenbondshavehigherviscosities,presumablybecausethe
moleculesinteractstronglywithoneanotherandhavetomovemoreorlesstogether(getting
inoneanothersway)inordertoflow.
(b)Themuchhighviscosityofethyleneglycolcanbeexplainedbythefactthateach
moleculecanformamaximumofsixhydrogenbonds,comparedtothethreeformethanol
andethanolandfourforwater.Theclustersofhydrogenbondedethyleneglycolmolecules
willbelargerthanthoseinthesimplealcoholsandwaterandwillgetinoneanothersway
OH OH
H
evenmore,thusprovidinggreaterresistancetoflow.
Followupactivities:
ConsiderThis1.63.Arethemodelsforspecificheatandviscosityofwaterrelated?
Endofchapterproblems1.98through1.100.
ACSChemistryFROG
43
Water:ANaturalWonder
Chapter1
ConsiderThis1.63.Arethemodelsforspecificheatandviscosityofwaterrelated?
Goal:
Studentscorrelatethemodelsforspecificheatandviscosityofwater.
Classroomoptions:
Allow510minutesforstudents,workinginsmallgroups,toanswerthequestions.Thenyou
canleadthediscussion,summarizinganswersonthechalkboardoranoverheadtransparency
orhavestudentsdoso.
Thisactivitycouldalsobeassignedasahomeworkproblemandthendiscussedatthenext
classsection.
Thisactivitycanbeconductedasanopenclassdiscussion.
Instructornotes:
Recalltostudentsourmodelthatsaysthatwater'shighspecificheatisduetobreakingof
hydrogenbonds.Astemperatureincreases,moreofthehydrogenbondsmustbebroken(in
ordertokeepthespecificheathigh),sothenumberofhydrogenbondsbetweenwater
moleculesdecreasesastemperatureincreases.
Studentsshouldreasonandconclude:
Asthetemperatureincreases,theviscositydecreases.Ourmodelpredictsthattherearefewer
hydrogenbondsbetweenwatermoleculesathighertemperatures.Fewerhydrogenbonds
shouldmeanthatthewatermoleculesaresomewhatmorefreetomoveindependently.At
highertemperaturesthereshouldbelessresistancetoflow,thatis,lowerviscosity,justas
Figure1.41shows.
Followupactivities:
Endofchapterproblems1.98through1.100.
44
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
SolutionsforChapter1CheckThis
Activities:
CheckThis1.3.Molecularlevelrepresentationofboilingwater
Answerforpart(a)canbefoundintheWebCompanion,Chapter1,Section1.1,pages5and6.
Theintentofthisactivityistohavethestudentslearnthatthegasinsidethebubblesofboiling
wateriscomposedonlyofwatermoleculesthatarefarapartandmovingalmostindependently
ofoneanother.Thus,thesketchesshouldshowthesamerepresentationofmoleculesinthe
liquidandsolid.Prevalentmisconceptionsarethatthegasinthebubblesisair(whichwillbe
gonefromtheliquidbythetimeitboils)oramixtureofhydrogenandoxygen(decomposition
productsofwater).Theideathatmostofthebubbleisemptyspaceisoftenhardforstudentsto
appreciatefully.
CheckThis1.7.Numberofvalenceandcoreelectrons
(a)BromineingroupVIIhas7valenceelectronssimilartootherhalogenatoms.Students
might/shouldwonderaboutthe10extraelectronsaddedacrossthemiddleoftheperiod(the
transitionelements)andaskwhytheyarenotcountedasvalenceelectrons.Weinvoketheshell
modelandindicatethatthese10electronsareinashellclosertothenucleuswheretheyare
heldsotightlybythehighnuclearchargethattheydonotparticipateinbondingofbromineto
otheratoms.
(b)StrontiumingroupIIhas2valenceelectrons.
(c)SeleniumingroupVIhas6valenceelectrons.Thesamecommentasforbromineapplies
hereaswell.
CheckThis1.9.Trendsinatomicsizes
Arsenic,selenium,andbrominearefoundingroupsV,VI,andVII,respectively,ofthesame
period.Atomicsizedecreasesacrossaperiodfromlefttoright(lowertohigheratomic
number),sothesizesoftheseatomsareintheorder:arsenic>selenium>bromine.
CheckThis1.11.WritingLewisstructures
(a)NH3has8valenceelectrons,soweplacethisoctetaroundtheNandthenaddHstoform
H
H
N
H
threeelectronpairbonds:
(b)HFhas8valenceelectrons,soweplacethisoctetaroundtheFandthenaddtheHtoforman
electronpairbond:
CheckThis1.13.Lewisstructureofethane
HH FH
H C C
H
ACSChemistryFROG
45
Water:ANaturalWonder
Chapter1
Table1.1showsthatCformsfourcovalentbondsinitscompoundsandeachCintheethane
Lewisstructurehasfourelectronpaircovalentbonds.Apossiblelineformulaforethanethat
moreclearlyexpressesitsconnectivityisCH3CH3.WeseethatthreeHsareassociatedwith
eachCandtheremainingconnectionontheCsmustbetooneanother.Anotherpossibleline
formulaisH3CCH3,althoughthisislesscommonlyused.
CheckThis1.18.Predictingbonddipoles
(i)
(iv)
Cl
(ii)
(v)
(iii)
(vi)
Li
(a)Iftheelectronegativitydifferenceisgreaterthan0.5ENunits,asignificantbonddipole
existsbetweenthetwoatomsthatformacovalentbond.ForHF,thereisa1.78ENunit
differencesoasignificantbonddipoleexistsbetweenthesetwoatoms.Thisisalsothecasefor
NH(0.84ENunitdifference),CCl(0.61ENunitdifference),NF(0.94ENunitdifference),
andHLi(1.2ENunitdifference).AsmallbonddipoleexistsbetweenHS(0.38ENunit
difference).
(b)ThechargedensitymodelforLiHintheWebCompanion,Chapter1,Section1.6,page2,
showshighelectrondensityontheHendofthemolecule,whichiswhatourbonddipolearrow
predicts.Similarly,forHF,thereishighelectrondensityontheF,aswewouldpredictfromthe
bonddipolearrowshowninpart(a).
CheckThis1.20.Predictingmoleculardipoles
CheckThis1.27.Predictingrelativeboilingpoints
Inorderofincreasingboilingpoint:
CH3CH2CH2CH3<CH3CH2OCH3<CH3CH2CH2OH
Butaneisanonpolarmoleculewhosemoleculesareheldtogetherintheliquidonlyby
dispersionforces(induceddipoleattractions).Butaneisarelativelysmallmoleculewithonly
34electrons,sotheseintermolecularattractionsarenotverystronganddonotrequiremuch
energytovaporizeintothegasphase;theboilingpointislow(seethegraphinConsiderThis
1.23).Ethylmethyletheralsohas34electrons,butalsohasapermanentmoleculardipolethat
addstotheattractionsamongitsmoleculesandgivesitahigherboilingpointthanbutane(buta
lowerboilingpointthanpropanol).Propanolisapolarmolecule,alsowith34electrons,which
46
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
canhydrogenbondwithitself.Thus,moleculesofpropanolneedmoreenergytobreaktheir
hydrogenbondsandenterthegasphase,soitsboilingpointisthehighestofthethree.
CheckThis1.38.Interpretinganenergydiagram
(a)Energyleavesthewaterwhenthewaterchangesfrom50Cto25C.Thearrowispointing
downbecausetheenergyofthesampleat25Cislowerthanitsenergyat50C.
(b)E<0,becauseenergyleavesthewater.(Thinkofthisassubtractionprocessandweusea
negativesigntodesignatesubtraction,sothechangeinenergyhasanegativesignislessthan
zero.)Itisrepresentedonthediagrambythearrowpointingdown,indicatingthatthechangein
energyhasanegativesign.
CheckThis1.43.Conversionofenergyunits
4.184 J
(a)92calg1=(92calg1)
=3.8102Jg1ofhexane.Theresultshownsuggeststhat
1cal
theuncertaintyintheresultisabout1partin38.Thevaluewestartwith,92calg1,hasan
implieduncertaintyofabout1partin90.Thus,ouranswerisgivenwithabitlessprecisionthan
isjustified,buttogiveitas385Jg1suggestsmuchbetterprecisionthanwehave.Thenumber
ofsignificantfigurestoshowinacalculatedresultisnotalwaysclearcut.
(b)Sinceitrequires8timesmoreenergytovaporize1gofH2O,wemightconcludethatthe
molecularattractionsamongwatermoleculesaremuchstrongerthanthoseamonghexane
molecules.ThisisconsistentwiththemodelsinSection1.7.Watermoleculescanhydrogen
bondwithoneanother.Hexanemoleculesareattractedtooneanotheronlybydispersionforces.
Forarelativelysmallmoleculelikehexane(50electrons),theoverallattractionmaynotbevery
large.Theproblemhere,aswewillseeinthenextsection,isthatthehexanemoleculeisagood
dealmoremassivethanthewatermolecule:theratiois86to18(or4.8to1).Thus,inequal
massesofhexaneandwater,thereareonlyaboutonefifthasmanyhexanemoleculesaswater
moleculesandthismaybethereasonittakeslessenergytovaporizethem.
CheckThis1.46.Masstomolesandmolestomassconversions
1mol
(a)0.5g=(0.5g)
=0.03molH2O
18g
1000g 1mol
(b)2.26kg=(2.26kg)
=6.61molofsugar
1kg 342g
58.5g
(c)12.6molNaCl=(12.6mol)
=737gofNaCl(sodiumchloride)
1mol
CheckThis1.48.Calculatingmolarmass
(a)Thereare12molesofcarbonatoms,22molesofhydrogenatoms,and11molesofoxygen
atomsinonemoleofsucrose(C12H22O11).
12.01g
12molC=(12molC)
=144.1g(massofCinonemoleC12H22O11)
1molC
1.008g
22molH=(22molH)
=22.2g(massofHinonemoleC12H22O11)
1molH
ACSChemistryFROG
47
Water:ANaturalWonder
Chapter1
16.00g
11molO=(11molO)
=176.0g(massofOinonemoleC12H22O11)
1molO
molarmassC12H22O11=342.3g
(b)Thereisonemoleeachofsodiumatomsandchlorineatomsinonemoleofsodiumchloride.
23.0g
1molNa=(1molNa)
=23.0g(massofNainonemoleNaCl)
1molNa
35.5g
1molCl=(1molCl)
=35.5g(massofClinonemoleNaCl)
1molCl
molarmassNaCl=58.5g
ThesearethemolarmassesgiveninCheckThis1.46.
CheckThis1.49.Comparingamountsofcompounds
1molCH 3OH
0.4gCH3OH=(0.4gCH3OH)
=0.01molCH3OH
32g
1molC 6 H 14
0.3gC6H14=(0.3gC6H14)
=0.003molC6H14
86g
InInvestigateThis1.40thelargestnumberofmolesevaporatingwaswater(0.04mol)andthe
smallestnumberofmolesevaporatingwashexane(0.003mol),withmethanolintermediate.
CheckThis1.52.VaporizationenergiesinInvestigateThis1.40
(a)EnergiesrequiredtovaporizethemethanolandhexanesamplesinInvestigateThis1.40are:
39kJ
0.01molCH3OH=(0.01molCH3OH)
=0.4kJforCH3OH
1molCH 3OH
32kJ
0.003molC6H14=(0.003molC6H14)
=0.1kJforC6H14
1molC 6 H 14
(b)Hexanerequirestheleastenergytovaporizethesampleandshouldevaporatefirstfollowed
bymethanolandthenwater(1kJ).ThisisthepatternobservedinInvestigateThis1.40.
CheckThis1.56.Specificheatandtemperaturerise
Hexanewillreachthehighertemperaturebecauseithasalowerspecificheat.Thesameamount
ofenergy(sametimeofheating)increasesthetemperatureofhexane(sp.ht.=2.27Jg1C1)
morethanthatofanequalmassofmethanol(sp.ht.=2.53Jg1C1).Theeffectisnotaslarge
aswefoundforwaterandalcohol,whichhavealargerdifferenceinspecificheats.
CheckThis1.58.Thermalenergychangeinethanol
T=(11700J)/(120g)(2.44Jg1C1)=40.0C
48
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
SamplesfromtheClassroom
ThefollowingClassLogs(notesandrecordsoftheclassforthatday),Assignments,Quizzes,
andChapterHourExaminationwerecontributedbyDr.JonathanMitschele,SaintJosephs
College,Standish,ME.Thesearemeanttogiveaflavorforthewayoneinstructorwitha
relativelysmallclassstructuredhiscourseashebegantheyearwithChapter1.Someediting
hasbeendonetotightenupspacing(leavingoutthespacesforanswersinquizzesandtests,for
example),butnoneofthecontenthasbeenchanged.
DailyClassLogsforPrinciplesofChemistryCH103
GenChemClassNotes9.04.02
Introductiontothecourse.
Dailyreading(typicallyaboutsevenoreightpagesperclass)andproblemassignments:
essentialthatthesebedonebeforecomingtoclass.
Weeklyhomework(dueMondays)andquizzes(Fridays).
Groupactivitiesformostofeachperiod:briefproblems,interactivedemonstrations,class
experiments.
Usingthetext:
Useembeddedexercisestocheckyourunderstanding;answerswillbeposted.
Examinations(oneperchapter)willbescheduledoutsideofclasstime.
1.1ConsiderThis:Whatdoyouknowaboutwater
Studentlist:
H2O
solidliquidvaporshowedsamplesofice,water,andcondensationonabeakerplacedin
freezerforafewminutestoillustratethatallthreephasescanexistatordinarytemperatures
andpressures
FP0C
BP100C
Makesupalargefractionofbody
Densityofphasesg<s<lstudentsknewicelessdensethanwater(showedicefloatingin
watertomakethepoint),butwhenprobedaboutthedensityofthegaswerepuzzled.Referred
toFig.1.2,andagainaskedaboutrelativedensity.Couldseethatgaswaslessdense.Asked
aboutsalientdifferencesbetweenliquidandsolidorderedsolid/disorderedliquid.Asked
howmicroscopicorderinsolidisreflectedmacroscopically(snowflakes).Askedwhichwere
closer,moleculesiniceorinwater.Studentsagainconfused,sodiscussionofthesignificance
oflowerdensityofice:ledstudentstoseethatyoucanfitmoreH2Omoleculesaswaterintoa
givenvolumethanH2Omoleculesasiceintothesamevolume(Dwater=Mwater/V>Dice=
Mice/V).Anexampleofreasoningfromthemacroscopictothemicroscopic.
Evaporates,condensesfroms,l,andg.
Wettingpropertiessurfacedependence.
Covalentbondinginmolecule.
Polarity.
Universalsolvent.
ACSChemistryFROG
49
Water:ANaturalWonder
Chapter1
Acid/base.
Catalyst(nospecificexamplegiven).
Osmosis.
Meniscus.
1.2
ConsiderThis:Howdothevolumesofsolidandliquidwatercompare?
1.4
InvestigateThis:Whatelectricaleffectscanyouobserve?
DemonstratecreatingaUtape,showthatitisattractedtoneutralobjects,andaskfor
explanation(electricalchargediscussion).
MakeasecondUtapeandaskwhatthechargeonitis(samediscussionaboutwhyandhow
toprove).ShowtwoUtapesrepeleachother.
Askhowwecouldmakeatapeofoppositechargeandthenproveithadoppositecharge
(discussionnotingcarefullychargedobjectsattractneutralobjects!).Ifstuck,leadstudents
totheanswer,andmakeLtape.
DeterminechargeonUandLtapes.Usethefactthataplasticcomborrulerrubbedonhair
createsanegativechargeontheplastic.
Demonstratewithgoldleaforequivalentelectroscopethedifferencebetweenconductorsand
insulatorsplasticisagoodinsulator,metalobjectsgoodconductors,butonahumidday
manythingsconductwellenoughtodischargeanelectroscope,e.g.paper!
ENDOFCLASS
GenChemClassNotes9.05.02
ReadingQuizoverSections1.31.5(5minutes)
Discussionofhomeworkwithingroups,reportingtoclassonconsensusforeach.(20minutes
total)
1.3CheckThisMolecularlevelrepresentationofboilingwater.
http://www.whfreeman.com/acsgenchemhome
1.5ConsiderThisDoelectricaleffectsexplainyourInvestigateThis1.4results?
1.6ConsiderThisCananelectrostaticmodelexplaintheInvestigateThis1.4results?
1.7CheckThisNumberofvalenceandcoreelectrons.
1.9CheckThis:Trendsinatomicsizes.(5minutes)
ClassDiscussion:Whatarevalenceandcoreelectrons?Howdowecountthem?Whatare
Lewisstructures?HowarecoreandvalenceelectronsrepresentedinaLewisstructure?How
doyouwritecorrectLewisstructures?(25minutes)
1.11CheckThis:WritingLewisstructures.(5minutes)
1.13CheckThis:Lewisstructureofethane.(10minutes)
1.14InvestigateThis:Whatarrangementofballoonsaroundapointisstable?("Carbon"
atomsinsteadofballoons.)(1015minutes)
5MinuteBreak.
50
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
Whatisthemeaningofmeasurement,precision,accuracy,anduncertainty?3electronic
balanceswithdifferentprecisionandacentimeter/inchmeterstick.(25minutes)
BackoftheEnvelopeCalculations:Howmanypingpongballswouldittaketofillthelab?
(remainingtime)
ENDOFCLASS
GenChemClassNotes9.06.02
ReadingQuizoverSection1.6(1.19WorkedExample)
(5minutes)MolecularModel:convertfromammoniatomethanebysubstitutingN(darkblue)
atomsforHatoms.
Discussionofhomeworkresults.(10minutes)
1.15ConsiderThisWhatisthegeometryoffourvalenceelectronpairs?(Wedidthisinclass
Thursday.)
1.16ConsiderThisHowisaLewisstructuretranslatedintoamolecularmodel?(Bringeachof
yourmodelstoclasswithyouFridayforthereadingquiz.)
ClassDiscussion:Theconsequencesofunequalsharingofbondingelectrons.(25minutes)
(1) LewisstructuresforCl2andHCl.
(2) Definehomonuclearandheteronuclear.
(3) Defineelectronegativity(EN)andEN.
(4) HowarebondingelectronssharedinCl2andHCl?InHClthereisapermanentcharge
separation,+and.
(5) Definedipolemoment,polarandnonpolarmolecules.
(6) Definebonddipole;examplesCH,CCl,HCl
(7) Definemoleculardipole;tugofwaranalogyforaddingbonddipoles;examplesHCl,
H2O,BCl3,NH3,CH3Cl,CCl4.
1.17ConsiderThisHowmightanelectricchargeaffectpolarmolecules?(remainingtime)
WeeklyQuiz1(15minutes)
ENDOFCLASS
GenChemClassNotes9.09.02
ReadingQuizoverSection1.7(5minutes)
WeeklyHomeworkisdue:1.12,1.21,1.25,1.341.36
ResultsforPingPongLabaredue.
ReviewQuiz1:Stickytape,electroscope,conductorsandinsulators.(1015minutes)
Discussionofhomeworkresults.(1015minutes)
1.18CheckThisPredictingbonddipoles.CHCONO
1.20CheckThisPredictingmoleculardipoles.H2SPCl3BeCl2
1.21ConsiderThisHowdoesmoleculargeometryaffectmoleculardipoles?
1.22InvestigateThisHowdoesboilingpointvarywithnumberofmolecularelectrons?(5
minutesgroup/510minutesclass)
ACSChemistryFROG
51
Water:ANaturalWonder
Chapter1
ClassDiscussion:Whatareinduceddipoles?Canapermanentdipoleinduceadipoleinanother
molecule?Whateffectwillthishaveonintermolecularattractions?(5minutes)
1.24ConsiderThisHowcandipoledipoleattractionsbevisualized?(remainingtime)
ENDOFCLASS
GenChemClassNotes9.11.02
ReadingQuizoverSection1.8(5minutes)
ClassDiscussion:Whatarehydrogenbonds?Whenandhowaretheyformed?Whydothey
form?(continuedfrompreviousclass,30minutes)
Discussionofhomeworkresults.(510minutes)
1.23ConsiderThisDoboilingpointscorrelatewithnumberofmolecularelectrons?
1.25InvestigateThisHowdoespolarityaffectboilingpoints?
IbeginbyaskingwhyIhaddonethestickytapedemonstration.(Answers:toshowexistence
ofelectricchargeoftwovarieties+and;todemonstratethatneutralobjectsarenotattracted
toeachotherbutareattractedtochargedobjects,becauseofpolarizationofneutralobjectsby
chargedones;toshowhowtheamountofchargeandthedistancebetweenchargesdetermines
thestrengthoftheinteraction;andbecauseallattractiveinteractionsofinterestinchemistry
involvetheattractionofoppositecharges.)
Isuggestthenthatifelectricallyneutralmoleculescanattracteachothertoformliquidsand
solids,theremustbetransientdipolesinvolved.IshowagraphoftheboilingpointsofCl2,
Br2,I2,andIClandask(1)WhatisthesignificanceoftheresultsforCl2,Br2,andI2?
(Answers:BP,andpresumablythestrengthofattractiveforces,increasewithincreasing
numbersofelectrons.)Ithenaskfor(2)anexplanationoftheBPforICl,whichhasthesame
numberofelectronsasBr2.(Answer:IClisapolarmolecule;presumablytheincreaseinBP
overthatofBr2isduetoasmalldipolecontributiontotheattractiveforces.)
Finally,IshowBPvs.numberofelectronsforGroupIVhydridesand,afterdiscussing
polarityofallsubstancesinvolved(hydridesofelementsinGroupsIVandV),askfora
predictionoftheBPvs.numberofelectrongraphofGroupVhydrides,withjustification.
TheyshouldmakesimilarpredictionsforhydridesofGroupVandVIelements:BPvs.
numberofelectronplotsforGroupsV,VI,andVIIshouldbeparalleltoGroupIVplots,but
displacedtohigherBP's.ShowingFig.1.24notatallinagreementwithreasonable
predictionsmakesclearthenecessityofintroducinganewkindofintermolecular
interaction,thehydrogenbond.
AtthispointwediscusswhatelementsXonewouldselecttomakeanHXbondhighlypolar
(answers:F,O,Cl,N),andaskaboutthereasonClisnotinvolvedinHbonding(answer:
size).WealsodiscusswhyHisinvolved:itisthesmallestatomthatformsbonds.
WeranoutoftimesoIassignedtheremainingexercisesforhomework.Tomorrowisalab
day,sowecancatchup.
1.26ConsiderThisDoeshydrogenbondingexplaintheboilingpointsofNH3andHF?Hint:
UseyourmodelkitstomakesixmemberedringsforH2O,NH3,andHF.(10minutes)
1.27CheckThisPredictingrelativeboilingpoints.(510minutes)
1.28InvestigateThisWhatkindsofhydrogenbondednetworkscanyouconstruct?
52
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
1.29ConsiderThisHowdothestructuresofliquidandsolidwatercompare?(remainingtime
forbothactivities)
ENDOFCLASS
ACSChemistryFROG
53
Water:ANaturalWonder
Chapter1
ClassAssignmentsforPrinciplesofChemistryCH103
Chapter1Reading,Problem,andExperimentAssignments
Class/Date
Discussion/Demonstration/Activity/Laboratory
StartofWeek1
1September4 Introductiontothecourse,assigngroups,hand
outmaterialsfortheday'sactivities.(15minutes)
1.1ConsiderThis:Whatdoyoualreadyknow
aboutwater?(5minutesgroup/510minutes
class)
ClassDiscussion:Whatismeantbytheterms
density,solid,liquid,andgas?(10minutes)
1.2ConsiderThis:Howdothevolumesofliquid
andsolidwatercompare?(5minutesPart(a),5
10minutesPart(b))
1.4InvestigateThis:Whatelectricaleffectscan
youobserve?(remainingtime)
Reading/Problems/HW
Readingfortoday:Sections1.11.2
HWfordiscussionThursday:
1.3CheckThisMolecularlevel
representationofboilingwater.
1.5ConsiderThisDoelectrical
effectsexplainyourInvestigateThis
1.4results?
1.6ConsiderThisCanan
electrostaticmodelexplainthe
InvestigateThis1.4results?
1.7CheckThisNumberofvalence
andcoreelectrons.
HWforSeptember9:1.12,1.21
2September5 ReadingQuizoverSections1.31.5(5minutes)
Readforclass:Sections1.31.5
LabSession Discussionofhomeworkwithingroups,reporting HWfordiscussionFriday:
toclassonconsensusforeach.(20minutestotal) 1.15ConsiderThisWhatisthe
1.9CheckThis:Trendsinatomicsizes.(5minutes) geometryoffourvalenceelectron
ClassDiscussion:Whatarevalenceandcore
pairs?
electrons?Howdowecountthem?Whatare
1.16ConsiderThisHowisaLewis
Lewisstructures?Howarecoreandvalence
structuretranslatedintoamolecular
electronsrepresentedinaLewisstructure?How model?(Bringeachofyourmodels
toclasswithyouFridayforthe
doyouwritecorrectLewisstructures?(25
minutes)
readingquiz.)
HWforSeptember9:1.25,1.34,
1.11CheckThis:WritingLewisstructures.(5
1.35,1.36
minutes)
1.13CheckThis:Lewisstructureofethane.(10
minutes)
1.14InvestigateThis:Whatarrangementof
balloonsaroundapointisstable?(1015
minutes)
5MinuteBreak.
Whatisthemeaningofmeasurement,precision,
accuracy,anduncertainty?(25minutes)
BackoftheEnvelopeCalculations:Howmany
pingpongballswouldittaketofillthelab?
(remainingtime)
3September6 ReadingQuizoverSection1.6(5minutes)
Readforclass:Section1.6
Discussionofhomeworkresults.(10minutes)
HWfordiscussionMonday:
ClassDiscussion:Whatismeantbytheterms
1.18CheckThisPredictingbond
54
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
polarmolecule,dipolemoment,electronegativity,
bonddipole,andmoleculardipole?(25minutes)
1.17ConsiderThisHowmightanelectriccharge
affectpolarmolecules?(remainingtime)
WeeklyQuiz1(15minutes)
StartofWeek2
4September9 ReadingQuizoverSection1.7(5minutes)
ReviewQuiz1.(10minutes)
Discussionofhomeworkresults.(1015minutes)
1.22InvestigateThisHowdoesboilingpointvary
withnumberofmolecularelectrons?(5minutes
group/510minutesclass)
ClassDiscussion:Whatareinduceddipoles?Can
apermanentdipoleinduceadipoleinanother
molecule?Whateffectwillthishaveon
intermolecularattractions?(5minutes)
1.24ConsiderThisHowcandipoledipole
attractionsbevisualized?(5minutes)
ClassDiscussion:Whatarehydrogenbonds?
Whenandhowaretheyformed?Whydothey
form?(remainingtime)
5September ReadingQuizoverSection1.8(5minutes)
11
Discussionofhomeworkresults.(10minutes)
1.26ConsiderThisDoeshydrogenbonding
explaintheboilingpointsofNH3andHF?(10
minutes)
1.27CheckThisPredictingrelativeboiling
points.(510minutes)
1.28InvestigateThisWhatkindsofhydrogen
bondednetworkscanyouconstruct?
1.29ConsiderThisHowdothestructuresof
liquidandsolidwatercompare?(remainingtime
forbothactivities)
6September ReadingQuizoverSections1.91.10(5minutes)
12
UsingaComputerforDataCollection:Starting,
LabSession calibratingprobes,collectingdata,saving,and
stopping.(30minutes)
1.30InvestigateThisWhatarethetemperatures
inanicewatermixture?start(15minutesto
begindatacollection)
ClassDiscussion:Whatareproteinsandnucleic
acids?Whatdoesdenaturationmean?(15
ACSChemistryFROG
dipoles.
1.20CheckThisPredicting
moleculardipoles.
1.21ConsiderThisHowdoes
moleculargeometryaffectmolecular
dipoles?
HWforSeptember16:1.47,1.48
Readforclass:Section1.7
HWfordiscussionWednesday:
1.23ConsiderThisDoboilingpoints
correlatewithnumberofmolecular
electrons?
1.25InvestigateThisHowdoes
polarityaffectboilingpoints?
HWforSeptember16:1.56,1.57,
1.59,1.60
Readforclass:Section1.8
HWforSeptember16:1.65
Readforclass:Sections1.91.10
HWfordiscussionFriday:
1.31ConsiderThisHowdoyou
interpretthetemperaturesinanice
watermixture?
1.32ConsiderThisWhatarethe
connectionsbetweenwaterdensity
andtemperature?
1.39ConsiderThisHowareenergy
55
Water:ANaturalWonder
7September
13
Chapter1
minutes)
1.33InvestigateThisHowdotheDNAbasesfit
together?(1520minutes)
1.34ConsiderThisHowdoeshydrogenbonding
affectthethermalstabilityofDNA?(510
minutes)
5MinuteBreak.
1.35InvestigateThisWhathappenswhenyou
sweat?
1.36ConsiderThisWhatisthepurposeof
sweating?(1015minutesforbothactivities)
ClassDiscussion:Whatismeantbythesymbol
E?(510minutes)
1.37ConsiderThisWhatarethesignsofthe
energychangesforsweating?(510minutes)
ClassDiscussion:Whatareenergydiagrams?(5
10minutes)
1.38CheckThisInterpretinganenergydiagram.
(5minutes)
1.40InvestigateThisDoallliquidsevaporateat
thesamerate?(510minutes)
1.30InvestigateThisWhatarethetemperatures
inanicewatermixture?conclusion.(remaining
time)
ReadingQuizoverSection1.11Part1(5
minutes)
Reminder:Chapter1HourExamination
Discussionofhomeworkresults.(2025minutes)
CountingbyWeighing:Large(P)andsmall(p)
paperclipsthat"react"1:1toformPp
"molecules."Definingapaperclip"mole"anda
paperclip"atomicmassunit(u)."(remaining
time)
WeeklyQuiz2(15minutes)
StartofWeek3
8September ReadingQuizoverSection1.11Part2(5
16
minutes)
ReviewQuiz2.(10minutes)
Discussionofhomeworkresults.(2530minutes)
1.50ConsiderThisWhatcompoundsinTable1.2
formhydrogenbonds?(remainingtime)
56
ACSChemistryFROG
diagramscorrelated?
1.41ConsiderThisWhatarethe
relativeenergiesofvaporizationof
differentliquids?
1.43CheckThisConversionof
energyunits.
HWforSeptember16:1.62,1.63,
1.66,1.67,1.75,1.76
Readforclass:Section1.11toendof
p.162
HWfordiscussionMonday:
1.44ConsiderThisHowcanyou
countobjectsbymeasuringmass?
1.46CheckThisMasstomolesand
molestomassconversions.
1.48CheckThisCalculatingmolar
mass.
1.49CheckThisComparingamounts
ofcompounds.
HWforSeptember23:1.79,1.80,
1.81
Readforclass:CompleteSection
1.11
HWfordiscussionWednesday:
1.52CheckThisVaporization
energiesinInvestigateThis1.40.
HWforSeptember23:1.82,1.85
Chapter1
Water:ANaturalWonder
9September
18
ReadingQuizoverSection1.12(5minutes)
Discussionofhomeworkresults.(10minutes)
1.53InvestigateThisWhatisobservedwhen
liquidsareheatedatthesamerate?
1.54ConsiderThisHowdoestemperature
changeinheatedliquids?(1015minutesforboth
activities)
ClassDiscussion:Whatismeantbytheterms
specificheatandheatcapacity?(1015minutes)
ClassDiscussion:Whatpropertiesofwater
accountforitslargespecificheat?(remaining
time)
10September ReadingQuizoverSection1.14(5minutes)
19
ScheduleChapter1HourExamination(10
LabSession minutes)
Discussionofhomeworkresults.(1015minutes)
ClassDiscussion:Whatisviscosity?Howmight
wemeasurerelativeviscosities?(510minutes)
1.60InvestigateThisHowfastdodifferent
liquidsflowfromapipet?
1.61ConsiderThisHowareviscositiesrelatedto
molecularattractions?(2025minutesforboth
activities)
5MinuteBreak.
Timeremaininginthislabsessionwillbedevoted
tocatchuporreviewfortheChapter1Hour
Examination.
11September Discussionofhomework.(10minutes)
20
CatchuporreviewofChapter1(40minutes)
WeeklyQuiz3(15minutes)
Readforclass:Sections1.121.13
HWfordiscussionThursday:
1.56CheckThisSpecificheatand
temperaturerise.
1.58CheckThisThermalenergy
changeinethanol.
1.59ConsiderThisAreyour
calculationsrelatedtoInvestigate
This1.53?
HWforSeptember23:1.95,1.96,
1.97
Readforclass:Section1.14
HWfordiscussionFriday:
1.62ConsiderThisDoeshydrogen
bondingexplainviscositiesinother
compounds?
1.63ConsiderThisArethemodels
forspecificheatandviscosityof
waterrelated?
HWforSeptember30:1.99,1.100
HWfordiscussionMonday:
2.1ConsiderThisWhatwater
solubleandwaterinsoluble
substancesdoyouknow?
HWforSeptember30:1.108
Revised8/25/02
Chapter1QuizzesforPrinciplesofChemistryCH103
CH103Quiz1Name:_____________
Howcouldyouusestickytapeandacombtoprovethat:
1. Anobjecthadanelectricalchargeonit?Beclearandcompleteleavenowiggleroom
fordoubt!
2. Anobjecthadapositiveelectricalchargeonit?Beclearandcompleteleavenowiggle
roomfordoubt!
ACSChemistryFROG
57
Water:ANaturalWonder
Chapter1
3. Anobjecthadnoelectricalchargeonit?Beclearandcompleteleavenowiggleroom
fordoubt!
CH103Quiz2Name:_____________
1. DrawtheLewisstructureofethanol,CH3CH2OH.
2. Kryptoniteisanunusualmetal.Foronething,itrendersSuperman(butevidentlynot
Superwoman)helpless;foranother,therearetwoexceedinglydensecrystalstructuresof
kryptonitethatexistatroomtemperature,theformthathasadensityof18.3gmL1,andthe
formthathasadensityof23.7gmL1.
(a) Aretheremore,fewer,orthesamenumberofkryptoniteatomsin1.00goftheform
thanin1.00goftheform?Circleyouranswer.
(b) Aretheremore,fewer,orthesamenumberofkryptoniteatomsin1.00mLoftheform
thanin1.00mLoftheform?Circleyouranswer.
(c) Aretheremore,fewer,orthesamenumberofkryptoniteatomsin1.00cm3oftheform
thanin1.00cm3oftheform?Circleyouranswer.
(d) Whatarethevolumesof1.00goftheformand1.00goftheform?
CH103Quiz3Name:_____________
1. Defineaccuratelythefollowingessentialterms:
(a) atomicmassunit(amu)
(b) dipolemoment
(c) electronegativity
(d) meltingpoint
2. DrawLewisstructuresforN2O(NNO),NO2,andNO2.Identifywhichstructuresviolate
which"rules"forLewisstructures.
3. DrawLewisstructuresforH2SandH2Se.
(a) Whatistheshapeofeachofthesemolecules?
(b) Clearlylabelbonddipolesforeachmolecule.Whichofthesemolecule(s)arepolar?
Explainyourreasoningclearly.
CH103Quiz4Name:____________
1. Threeintermolecularforcescanexistbetweenmolecules.Describe(a)thecauseofeach
force,(b)whatkindsofmoleculesareinvolvedforeach,and(c)therelativestrengthofeach.
dispersionforcesdipoleforceshydrogenbonds
2. DrawLewisstructuresforpropane,CH3CH2CH3,methylether,CH3OCH3,andethanol,
CH3CH2OH.
(a) Predictwhichofthesecompoundshasthehighestandwhichthelowestboilingpoints
andgiveacompleteexplanationofyourreasoning.
(b) Whichofthesecompoundscanformhydrogenbondsinthepureliquid?
(c) Whichpair(s)(propanemethylether,propaneethanol,methyletherethanol)ofthese
compoundscanformhydrogenbondswitheachother?Forthosepairs,chooseonemolecule
ofthepairastheacceptoranddrawaLewisstructureofthismoleculehydrogenbondedtoas
manyoftheothermoleculeaspossible.
58
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
CH103Quiz5Name:____________
1. Ifyouweighout1.00gofethanol(CH3CH2OH),
(a) howmanymolesofethanoldoyouhave?
(b) howmanymolesofcarbondoyouhave?
(c) howmanygramsofcarbondoyouhave?
2. Sketchenergydiagramsthatdescribethefollowingprocesses.Makesureyoudrawan
arrowthatrepresentsthedirectionofthechangeandthatyouindicatethesignofEforthese
processes.
(a) Freezingwater.
(b) Burningasampleofmethanol(CH3OH)inoxygen(O2)toproducewaterandcarbon
dioxide.Thisprocesscanbedescribedbytheequation:
CH3OH(l)+3/2O2(g)CO2(g)+2H2O(g)+energy
CH103Quiz6Name:____________
1. Whatisthedifferencebetweenheatandtemperature?Youcanuseaclearexampleto
answerthisquestion.
2. Distinguishbetweenamixtureandasolution.
3. Theoverallsolutionprocessfordissolvingammoniumchloride,NH4Cl,inwateris
endothermic.Drawanenergydiagramforthisprocessthatincludesallenergychanges
involved.
ACSChemistryFROG
59
Water:ANaturalWonder
Chapter1
Chapter1HourExamforPrinciplesofChemistryCH103
CH103Chapter1HourExaminationName:____________
Atotalof100pointsispossible.Youmayusetheperiodictableprovidedwiththisexamination,
amodelingkit,andacalculator.
1.
2.
3.
Giveanontrivialexplanationforeachofthefollowing:
(a) Youexperienceacoolingeffectwhenyouleaveapoolonabreezyday.(5points)
(b) Iceislessdensethanliquidwater.(5points)
(c) Lakesfreezefromthetoptothebottom.(5points)
Completethefollowingtable:(0.5pointsforeachanswer)
AtomorIon #of
#ofelectrons
#ofvalence
protons
electrons
Mg
Mg2+
O
O2
Al
Al3+
CoreCharge
#ofcore
electrons
ConsiderthetwomoleculesH2OandCO2.
(a) DrawLewisstructuresforeachmolecule.(5points)
(b) Comparetheshapeofeachofthesemolecules.Youwillfindmakingamodelofeach
veryhelpful.UseblackatomsforcarbonandredatomsforoxygeninCO2.Useredatoms
foroxygenandlightblueatomsforhydrogeninH2O.Usetwobluecurvedrodstomake
doublebondsifneeded,whiterodsforsinglebonds,andpaddlesfornonbondingelectron
pairs.(5points)
(c) Comparethebonddipolesineachmolecule(treatbonddipolesfordoublebondsas
identicaltothoseforsinglebondsinagivenmolecule).(5points)
(d) Comparetheoverallelectricdipoleofeachmolecule.(5points)
4. Explainintermsofintermolecularforcesandtheeffectsofperiodictrendsonthoseforces
theboilingpointsofHF(292.7K),HCl(189.5K),HBr(206.8K),andHI(237.8K).(5points)
5. Giveaplausibleexplanationintermsofhydrogenbondingforeachofthefollowing
observations.Youmayfindmolecularmodelsuseful.
(a) Theboilingpointofwater,H2O,(100C)isgreaterthanthatofmethanol,CH3OH,(65
C).(5points)
(b) OrdinaryproteinsdenatureatsomewhatlowertemperaturesthandoesordinaryDNA.(5
points)
6. Sketchenergydiagramsthatdescribethefollowingprocesses.Makesureyoudrawan
arrowthatrepresentsthedirectionofthechangeandthatyouindicatewhetherEispositiveor
negativefortheseprocesses.
(a) Theevaporationofnaphthalene(mothballs).(5points)
(b) Thecondensationofmoistureinyourbreathonamirror.(5points)
60
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
7. Explainwhyitrequireslessenergytoevaporatewateratitsboilingpointthanatroom
temperature.(5points)
8. Ifthespecificheatofmethanolis2.53J g1 C1,whatwillthetemperaturechangeof1.50
moleofmethanol(CH3OH)beifyouadd75Jofenergytoit?(5points)
9.
Ifyouhave1.50gramsofpropanol(CH3CH2CH2OH),
(a) Howmanymolesofpropanoldoyouhave?(5points)
(b) Howmanymolesofcarbondoyouhave?(5points)
(c) Howmanygramsofcarbondoyouhave?(5points)
ACSChemistryFROG
61
Water:ANaturalWonder
Chapter1
SolutionsforChapter1EndofChapterProblem
s
Problem1.1
(a) __P__
(b) __C__
(c) __P__
(d) __P__
(e) __C__
(f) __P__
Waterisclearandcolorless.
Somemetalsreactwithwatertoproducehydrogengas.
Waterhasadensityof1.0gcm3at4C.
Waterboilsat100C.
Wateristheproductofareactionbetweenanacidandabase.
Waterisapolarmolecule.
Thedistinctionbetweenphysicalandchemicalpropertiesisnotalwaysclearcut.Somewould
classifythepolarityofthewatermoleculeasachemicalproperty,sincethispropertyisnot
apparenttooursenses,butisinterpretedfromvariousmeasurementsandmodelsofmatter.
Problem1.2.
Solids
Liquids
Gases
Definitevolume?
Yes
Yes
No
Definiteshape?
Yes
No
No
Fixedorchanging
positionof
molecules?
Fixed
Changing
Changing
Smallorlarge
averagedistance
betweenmolecules?
Small
Small
Large
Problem1.3.
Solidsandliquidsarecalledcondensedphases.Inbothofthesephases,moleculesarerelatively
closetogetherandarelikelytointeractwithoneanother.Themoleculesinthegasphase,by
contrast,arespreadapartwithsignificantlylesschanceforinteraction.Whiletheprocessof
condensationusuallyreferstotheproductionofliquidfromthegas(vapor)phase,bothliquid
andsolidphasesaretermedcondensedphases.
62
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
Problem1.4.
(a)
(b)Upwardpointingarrows(vaporizationandmelting)representprocessesthatabsorbor
requireenergy.Intheenergydiagramsinthetext,thesearrowsareshowninred.Downward
pointingarrows(condensationandfreezing)representprocessesthatreleaseorgiveoffenergy.
Intheenergydiagramsinthetext,thesearrowsareshowninblue.
Problem1.5.
Manycommonsubstances,includinggasoline,rubbingalcohol,andcookingoilareliquidat
STP,thatis,atoneatmosphere(nowonebar)pressureand0C(273K).
Problem1.6.
Manysubstances,includingthecomponentsoftheEarthsatmosphere,nitrogen(N2),oxygen
(O2),argon(Ar),carbondioxide(CO2),andwatervapor,aregasesatSTP.
Problem1.7.
Whenwaterfreezesthevolumeofthesolidisgreaterthanthevolumeoftheliquid.Ifaclosed
glassbottleinitiallyfilledentirelywithwateriskeptoutsideatatemperaturebelowthefreezing
pointofwater,thewaterwillfreeze,expand,andbreakthebottle.Notethatthisiswhatis
showninthesepicturesfromWebCompanion,Chapter1,Section1.1,page3,inwhichaplastic
bottlefilledwithwaterruptureswhenthewaterfreezes:
Problem1.8.
(a)IfoneboilsasolutionofNaCl(aq)andwater,thewaterwillevaporate(vaporize)andthe
saltwillbeleftbehindduetothefactthatwaterhasamuchlowerboilingpointthantablesalt,
whichisasolidat100C.
(b)Alaboratorydistillationapparatusfortheseparationofasodiumchloridesolutionisshown
here.Boilingthesolutionevaporatesthewater,whichiscondensedintheinnertubeofthe
ACSChemistryFROG
63
Water:ANaturalWonder
Chapter1
condenser,andrunsdowntobecollectedinthereceivingflask.Afterallthewaterhasboiled
away,NaCl(s)remainsintheboilingflask.
Amuchsimplerapparatusisasolarstill,thatis,adistillationapparatusthatusestheenergyof
sunlighttoseparatepurewaterfromsaltwater.Thepicturehereshowsaverysimpleversion
consistingofaclear,colorlesscontainer,apieceofplasticwrapsecuredtothetopofthe
container,acuptocatchthepurewater,andasmallobjecttoweightthecenteroftheplastic
wrapcovering.Saltwaterisplacedinthecontainerandthenitissetupasshownandplacedin
thesun.Asthesunwarmsthesaltwater,watermoleculesleavethesurfaceandtheinsideofthe
containerfillwithinvisiblewatervapor.Theplasticwrapremainsataboutthetemperatureof
thesurroundingairandeventuallythereisenoughwatervaporinthecontainertobeginto
condenseonthecoolersurfaceoftheplasticwrap.Thecondensateflowsdowntheinsideofthe
plasticwrapandformsdropletsatthelowestpoint.Asthedropletsgrow,theybecomeheavy
enoughtodropoffintothecup,whichfillsupwithpurewater.Iftheprocessisallowedtogo
onuntilallthewaterinthesaltsolutionhasevaporated,condensed,andcollectedinthecup,
solidsaltwillbeleftbehindinthelargercontainer.Notethatthewaterneverboilsinthisstill,
butsimplyevaporatesatasomewhatelevatedtemperature(comparedtoroomtemperature)due
tothegreenhouseeffectofthisenclosedsystem.
Problem1.9.
Averydirectexperimenttodeterminetherelativedensitiesoftwoimmiscibleliquids(liquids
thatdonotdissolveinoneanother)istopourafewdropsofeitheroneintotheother.Ifthe
addedliquidsinks,thenitismoredense.Iftheaddedliquidremainsonthesurface,thenitisless
dense.
64
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
Problem1.10.
Mixingsamplesofasolidanditsliquidwillquicklyallowyoutodeterminetheirrelative
density.Ifthesolidismoredense,thenitwillsinkintheliquid(whichisthecaseformost
substances).Ifthesolidislessdense,thenitwillfloatintheliquid[asisthecaseforsolidwater
(ice)inliquidwater].
m
Vm
d
7
Problem1.11.
Figure3.1showsthatthedensityofsolidparaffinisgreaterthanthatliquidparaffinbutthatthe
densityofliquidwaterisgreaterthanthatofsolidwater(ice).Whatisnotknownishowthe
densityofsolidparaffincompareswiththatofliquidwater,whichiswhatweneedtoknowto
predictifthesolidparaffinwillsink,float,orremainjustbuoyantlysuspendedwhendropped
intoliquidwater.Therelativedensityvaluescouldbedeterminedexperimentally(avarianton
thepreviousproblem)orbylookingupthedensitiesinareferencehandbook.
Problem1.12.
NOTE:Thisproblemissomewhatpoorlyandambiguouslystated,becausethereisno
indicationwhattheuncertaintymightbeinthedimensionsgiven.Ifweassumethatthezeroin
the20cmmeasurementsissignificant,inthesensethatitisuncertaintoaboutoneunit,then
thedimensionsareknowntoaboutonepartin20or5%inthiscaseandourresultingvolume
shouldbereportedtoabout5%.
Thevolumeofblockoficeis:
V=(20cm)(20cm)(20cm)=8103cm3=8103mL
Theimplicationoftheresultreportedlikethisisthatthevolumeisknowntoaboutonepartin
eightorisuncertainbyabout12%.Reportingthevolumeas8.0103mLwouldimplymuch
lessuncertainty,closertoabout1%,andthisisnotjustifiedbytheassumptionabove.Tofind
themassofthisamountofice(andthewateritproduces)weuseitsdensity,d,andrearrange
theequationthatdefinesdensitytodeterminemass(fromthedensityofice):
d=
isrearrangedtom=dV=(8103mL)(0.917gmL1)=7103g
Tofindthevolumeoftheliquidpuddle,weagainrearrangetheequationthatdefinesdensityto
determinevolume(fromthedensityofwater):
d=
isrearrangedtoV=
=7103mL
Problem1.13.
Weonlyneedtoknowthataphasechangefromsolidtoliquid(orfromliquidtogas)doesnot
changetheamountofmatterinvolvedinthephasechange.Massisconservedinallphase
changes,sothemassofthemoltenironmustbe100.0g.
Problem1.14.
Alltheatomsofachemicalelementarethesameandthenamesoftheelementsarelistedinthe
periodictableinthefrontofthetextorthealphabeticallistintheback.Usethiscriterionto
decidewhichofthelistedsubstancesisanelement.
ACSChemistryFROG
65
Water:ANaturalWonder
Chapter1
(a)Weknowthatwateriscomposedofhydrogenandoxygenatoms,soitcannotbeachemical
element.
(b)Saltwater consistsoftwosubstances,neitherofwhichisanelement,mixedtogether,soit
cannotbeachemicalelement.
(c)Ironislistedintheperiodictable,soitmustbeanelement.
(d)Thenameironoxidetellsusthatthissubstancemustbemadeupofironatomsandsome
otheratoms(oxidetellsusitsoxygenatoms).
(e)Nitrogenislistedintheperiodictable,soitmustbeanelement.
(f)Diamondisatrickyone.Thenamediamonddoesnotappearintheperiodictableandthe
namegivesnocluetoitscomposition,sowehavetorecallsomeinformationwelearned
someplaceorgotoareferencebook,likethedictionary.Thedictionarysaysthatdiamondisa
mineralconsistingofnearlypurecarbon.Carbonisintheperiodictable,sodiamond(pure
carbon)mustbeanelement.
Problem1.15.
Valenceelectronsareelectronsintheoutermostshellofanatom.Coreelectronsareelectronsin
theinnershellsclosertoandstronglyattractedbythenucleus,sotheydonotinteractwith
electronsfromotheratoms.Valenceelectronsarefurthestfromthenucleusandinteractwith
otheratoms.
Problem1.16.
UsetheinformationinFigure1.7,whichshowsthenumberofvalenceandcoreelectronsinthe
first20elements,andanalogiesofthisfiguretotheperiodictableinthefrontofthetexttoget
thenumberofcoreandvalenceelectronsintheseelementalatoms.
(a)Thesodiumatomhasonevalenceelectronand10coreelectronsthatbalancethechargeof
the11protonsinthenucleus(Figure1.7).
(b)Thebromineatomisinfamily(column)oftheperiodictablewithfluorineandchlorine,
eachofwhichhassevenvalenceelectrons(Figure1.7).Thus,wereasonthatbrominealsohas
sevenvalenceelectrons.Tobalancethe35protonsinthenucleus(bromineisatomicnumber
35),theremustbe28moreelectronsintheinnershells,sothereare28coreelectrons.
(c)Thebariumatomisinthefamily(column)oftheperiodictablewithberyllium,magnesium,
andcalcium,eachofwhichhastwovalenceelectrons(Figure1.7).Thus,wereasonthatbarium
alsohastwovalenceelectrons.Tobalancethe56electronsinthenucleus(bariumisatomic
number56),theremustbe54moreelectronsintheinnershells,sothereare54coreelectrons.
(d)Thephosphorusatomhasfivevalenceelectronsand10coreelectronsthatbalancethe
chargeofthe15protonsinthenucleus(Figure1.7).
(e)Thesulfuratomhassixvalenceelectronsand10coreelectronsthatbalancethechargeof
the16protonsinthenucleus(Figure1.7).
Problem1.17.
(a)Thenumberofprotonsineachionisgivenbytheatomicnumberoftheelementalatomfrom
whichtheionisformed.Thenumberofelectronsisthenthenumberneededtocanceloffenough
66
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
ofthenuclearcharge(protons)oraddmorethanenoughtogivetheoverallchargeonthe
ion.AswedidinProblem1.17,weuseFigure1.7,whichshowsthenumberofvalenceandcore
electronsinthefirst20elements,andanalogiesofthisfiguretotheperiodictableinthefrontof
thetexttogetthenumberofcoreelectrons(lastcolumnofthetable)intheelementalatomsfrom
whichtheseionsareformed.Thetotalnumberofelectronsminusthenumberofcoreelectronsis
thenumberofvalenceelectrons.Thenumberofprotons(atomicnumber)minusthenumberof
coreelectronsisthecorecharge.
Ion
#of
protons
#of
electrons
#ofvalence
electrons
Core
charge
#ofcore
electrons
Na+
11
10
+1
10
K+
19
18
+1
18
Mg2+
12
10
+2
10
Ca2+
20
18
+2
18
Cl
17
18
+7
10
Br
35
36
+7
28
(b)Theionscommonlyformedbythemetallicelementsonthefarleftoftheperiodictable,Na+,
K+,Mg2+,andCa2+,havezerovalenceelectrons.Theseelementalatomslosealltheirvalence
electronswhentheyformtheionswefindintheircompounds.Theionscommonlyformedby
theelementsonthefarleftoftheperiodictable(halogens),ClandBr,haveeightvalence
electrons.Theseelementalatomsgainavalenceelectroswhentheyformtheionswefindintheir
compounds.Toformions,metalslosevalenceelectronsandnonmetalsgainvalenceelectrons.
NOTE:Thenumberofelectronsforeachionincolumnthreeofthistableisthenumberinthe
noblegasthatjustprecedes(forthemetals)orcomesjustafter(forthenonmetals)theelemental
atom.Thiscorrelationsometimesleadstotheideathatthereissomespecialstabilityassociated
withtheelectronicstructuresofthenoblegases.Keepinmindthatcorrelationdoesnot
necessarilyimplycausation.
Problem1.18.
Elementsinthesameperiodoftheperiodictablehavethesamenumberofcoreelectrons.
Problem1.19.
Elementsinthesamegroupoftheperiodictablehavethesamenumberofvalenceelectrons.
Problem1.20.
Recallthatchemicalreactionsandinteractionsdirectlyinvolveonlythevalenceelectrons.
Therefore,elementsinthesamegroup(columnorfamily)havesimilarchemicalproperties,
sincetheyhaveidenticalnumbersofvalenceelectrons.
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Chapter1
Problem1.21.
Usetheperiodictabletogetthenumberofprotons(=atomicnumber)ineachelementalionand
thensubtractthechargeontheiontogetthenumberofelectronsleftafterenoughhavebeen
removedtogivethepositivechargeontheion.
Ion
Mn2+
Fe2+
Fe3+
Cu2+
Zn2+
#ofprotons
25
26
26
29
30
#ofelectrons
23
24
23
27
28
Problem1.22.
Theoctetsofelectronshavebeencircledforeachoftheproducts.Notethateachcovalentbond
iscomposedoftwoelectrons,oneformallycontributedbytheatomsateachendofthebond.
(a)HF(hydrogenfluoride)
H
(b)NH3(ammonia)
H
(c)CH3OH(methanol)
H
H
H
O
(d)H2O2(hydrogenperoxide)
H
Problem1.23.
The(b)bondangle,(c)bondlength,and(f)numberofnonbondingpairsofelectronsonoxygen
arenotdirectlyobservableandarethereforemicroscopic(orbetter,molecular)properties
characteristicofindividualwatermolecules.The(a)boilingpointand(e)densityofwaterand
its(d)abilitytodissolvesaltaredirectlymeasurableorobservablewithbulksamplesofwater
andarethereforemacroscopicproperties.Thesemacroscopicpropertiesarenotpropertiesof
individualwatermolecules,onlylarge(macroscopicallyobservable)collectionsofwater
68
ACSChemistryFROG
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Water:ANaturalWonder
molecules.Ofcourse,themolecularstructureandmacroscopicpropertiesarerelatedandmuch
ofthechemistrywewillstudyisconcernedwiththeserelationships.
Problem1.24.
Model1
NH3
Model2
Model3
Model4
H N H
H
(a)Theseareallmodelsoftheammoniamolecule.Model1isamolecularformula,sometimes
calledalineformula;Model2isanelectrondotmodel(alsocalledaLewisstructure,Section
1.4);Model3isaballandstickrepresentation;and,Model4isacomputergeneratedmodel.
(b)Themolecularformulaorlineformulatellsyouthereare3atomsofhydrogencombined
withoneatomofnitrogen,formingonemoleculeofammonia.Theelectrondotmodelshows
thecompositionofthemoleculeandalsoshowstheconnectivitywithintheammoniamolecule
andlocatesthevalenceelectrons.Theballandstickmodelshowsthecompositionand
connectivityandalsogivessomeinformationaboutthebondangleswithinthemolecule.Note
thatthismodeldoesnotshowthepairofnonbondedelectrons.Thecomputergeneratedmodel
showsthecomposition,theconnectivityandbondangles,andaboundarysurfaceforthe
valenceelectronsthatiscolorcodedtoshownetelectricalchargeonvariouspartsofthe
molecule.
(c)Thepaddlemodelcanbeusedtoshowthelocationofnonbondedelectronpairsinaball
andstickmodel(seeFigure1.14andthemarginalfigurewithWorkedExample1.19).Space
fillingmodels[seeFigure1.8(f)]showconnectivity,bondanglesandgiveapproximate
representationsofthespace(volume)occupiedbyelectronsaroundeachatomiccoreinthe
ammoniamolecule.
Problem1.25.
Themolecularformula(lineformula)isgivenwiththemodelsofthecompoundsrepresented:
(a) SF4
(c) PCl3
(b) CH4
(d) CH3COOH
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Problem1.26.
(a)Themolecularformulaforglucose,C6H12O6,isgivenintheIndexofthetextbookunderthe
headingglucose.
(b)Themolecularformulafornitrousoxide,N2O,isgiveninthedictionarywithitsdefinition.
(c)Themolecularformulaformethanol,CH3OH,usuallyusedbychemistsisgivenintheIndex
ofthetextbookundertheheadingmethanol.Sometimesyoumightfindtheformulawrittenas
CH4O,butthisformulagivesnoindicationhowtheatomsarejoinedinthemolecule.The
connectivityisbetterrepresentedbythefirstformula.
(d)Themolecularformulaforacetylene,CHCH,isgivenintheIndexofthetextbookunderits
scientificnameethyne(whichisthereferencegivenunderacetylene).Theformulaisoften
writtenC2H2,becauseweknowthatthereisonlyonewaytoconnectthesefouratoms,butthe
firstformuladoesbetterrepresenttheconnectivityoftheatoms.
Problem1.27.
(a)FromaLewisstructure,youcandeterminethenumberofatomiccoresofeachkindthatare
bondedtogetherinamoleculeofthecompoundofinterestandtheconnectivityamongthese
atomiccores.Thedistributionofvalenceelectronsamongtheatomiccoresintwoelectron
bondsorasnonbondingelectronsisalsorepresented.
(b)Withoutfurtherinformationaboutthegeometricdistributionofvalenceelectronpairs
(Section1.5andChapter5)aboutatomiccores,Lewisstructuresconveynoinformationabout
theshapeofamolecule(bondlengthsandbondangles)anditsassociatedproperties(molecular
dipolesandpolarity).
Problem1.28.
(a)Theelectrondotmodelfortheammoniumion,
H
H N H
,showsthattherearefour
hydrogenatomiccorescombinedwithonenitrogenatomiccoreandthatthereareeightvalence
electrons.Thereisapositivechargeontheionbecausethesumoftheatomiccorechargesis9
[=4(1+)+(5+)]andthereareonly8electronstobalancethischarge.Theconnectivityandtwo
electronbondswithinthemoleculeareclearlyshownbythismodel.
(b)Theelectrondotmodelprovidesnoinformationaboutbondangles,bondlengths,or
distributionofcharge(althoughtheequivalenceofthefourbondssuggeststhatthechargeis
probablysymmetricallydistributed)withintheammoniumion.
(c)Whenrewrittenusingdashesfortwoelectronbonds,themodelis:
H
H N H
H
Thissubstitutionofdashesforpairsofdotsdoesnotinanywaychangetheinformationfound
inthemodel.Itisjustaconveniencetoreplaceeachpairofdotswithadash.
(d)Themethaneandammoniumionstructuresareverysimilarelectronically.
70
ACSChemistryFROG
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Water:ANaturalWonder
H
H N H
Methane: H C H
H
Bothshowfourpairsofelectronsandfourhydrogenatomiccoresgroupedaroundthecentral
atomiccore.Thenitrogenatomiccorehasonemorepositivechargethanthecarbonatomiccore
(atomicnumber7comparedtoatomicnumber6)andthereforeonetoofewvalenceelectronsto
balancethecorecharges,leavingtheionwithapositivecharge.
Ammoniumion:
Problem1.29.
Thetwothirdperiodexamplescitedinthisproblemstatement,siliconandsulfur,areinthe
carbonandoxygenfamilies(columns),respectively,oftheperiodictable.Theymightbe
expectedtohaveproperties(suchastypicalnumberofcovalentbonds)thataresimilartothe
atomsinthesecondperiod.Thus,itmakessensethatsilicontypicallyformsfourcovalent
bondsandsulfurtypicallyformstwocovalentbonds,becauseTable1.1showsusthatthisis
whathappensforthesecondperiodelements,carbonandoxygen.Wemightextendthis
reasoningtootherthirdperiodandalsotofourthperiodelements.
(a)Phosphorusisthethirdperiodelementinthenitrogenfamily,soweexpectittypicallyto
formthreecovalentbonds.
(b)Chlorineisthethirdperiodelementinthefluorine(halogen)family,soweexpectit
typicallytoformonecovalentbond.
(c)Seleniumisthefourthperiodelementintheoxygenfamily,soweexpectittypicallytoform
twocovalentbonds.
(d)Bromineisthefourthperiodelementinthefluorine(halogen)family,soweexpectit
typicallytoformonecovalentbond.
NOTE:AlmostallcovalentcompoundsofC,N,O,andFfollowthepatternshowninTable1.1,
buttheirthirdandhigherperiodcounterpartsdonot,aswewillexplaininChapter5.The
objectiveofthisproblemistothinkaboutpredictionsthatcanbemadefromtheperiodicityof
theperiodictable.Laterwecandelvemoredeeplyintothenatureofbondinganditsvariation
downafamily.
Problem1.30.
(a)IfthepatterninTable1.1isextendedtothenextperiodtwoelement,neon,theresultiszero
covalentbonds(sincetheirnumberdecreasesmonotonicallyacrossthetable)andfour
nonbondingpairsofelectrons(sincetheirnumberincreasesmonotonicallyacrossthetable).
Theimplicationhereisthatneoncanformnocompounds.
(b)Inchemistry,inertmeansincapableofreacting.Chemicalreactionsaredefinedbythe
makingandbreakingofchemicalbonds.Ifitistrue,asisimpliedbytheanswerinpart(a),that
neoncannotformcovalentbonds,itcouldbecharacterizedasinert.Formanyyears,textbooks
saidthattheelementsHe,Ne,Ar,Kr,Xe,andRn,allinthesamefamily(group)oftheperiodic
table,wereinert,becausenocompoundscontainingtheseelementshadeverbeenmade.
Calculationsbysomechemists,includingLinusPauling,suggestedthatitshouldbepossibleto
synthesizesomecompoundsofthesegases,butnonehadbeen.In1962,reasoningaboutwhy
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theseelementswereinertwasupsetbythesynthesisofthefirstcompoundofxenonbyNeil
Bartlett,thenintheChemistryDepartmentattheUniversityofBritishColumbia.Sincethat
timecompoundsofargon,xenon,krypton,andradonhavebeensynthesizedandstudied.The
mostrecentlydiscoveredcompoundsareformedatlowtemperatureswithuraniumatoms.
Althoughthesegasesarenotinert,theyarenothighlyreactiveandrequireveryreactive
partnerstogetthereactionstogo.Now,thesegasesareusuallycallednoble,whichimplies
thattheydonotreactwithjustanyotherreactant,butareabitaloof.
Problem1.31.
ThefirststepsinwritingaLewisstructureforamoleculearetodeterminethetotalnumberof
valenceelectronsinthemoleculeandthepossibleconnectivityoftheatomiccores.Thenplace
twovalenceelectronsbetweeneachpairofatomiccoresanddistributeanythatareleftoverto
giveeverysecondperiodelementeightelectronssurroundingitsatomsymbol.Eachcarbonhas
4valenceelectrons,eachhydrogenhas1valenceelectron,andoxygenhas6valenceelectrons.
ThetotalnumberofvalenceelectronsinC2H6Ois:
2(4)+6(1)+1(6)=20valenceelectrons
Therearetwopossiblewaystoconnectthesesecondperiodatomiccores:CCOorCOC.
Thealternativeformulasgivenintheproblem,C2H5OHandCH3CH2OH,showusthatthefirst
oftheseconnectivitiesisthecorrectone.Placethehydrogenatomiccoresaroundthecarbon
andoxygencoressothateachcarboncorehas4covalentbondsandeachoxygencorehas2
covalentbonds:
H H
H C C O
H H H
H H
or H C C O
H H H
Thisstructureuses16ofthe20valenceelectronstoformthecovalentbonds.Theoxygen
atomiccorehasonlyfourvalenceelectrons,sotheremainingfourvalenceelectronsareplaced
ontheoxygencoreasnonbondingpairstogivetheoxygencoreeightvalenceelectrons.
H H
H C C O
H H H
H H
or H C C O
H H H
Problem1.32.
NOTE:Thisproblemandthenexttwogoastepbeyondthematerialpresentedinthischapter
becausetheyinvolvemultiplebonds,whicharenotformallyintroduceduntilChapter5.The
nexttwoproblemshavethedoublebondsincludedinLewisstructuresalreadywritten,butthis
onerequireswritingthemdenovo,whichisabigleap.Inaddition,thestructuresinthis
problemdonotobeythepatternshowninTable1.1,becauseoneoftheoxygenatomiccoresin
eachmolecularstructuremustbeshownwithonecovalentbondandthreenonbondingpairs.
Additionally,thecentralatomiccoreinO3andSO2,musthavethreecovalentbondsandone
nonbondinginpair,againincontradictiontoTable1.1(anditsextrapolationtothethirdperiod,
asinProblem1.29).Thus,thisisamuchmoredifficultproblemthantheothersandcertainly
shouldhavebeenlocatedfollowingtheothertwoorperhapsunderGeneralProblemsasa
challengeproblem.
72
ACSChemistryFROG
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Water:ANaturalWonder
Startsolvingthisproblembydeterminingthenumberofvalenceelectronsineachofthe
moleculesorions:
O3:
3(6)=18valenceelectrons
SO2:
6+2(6)=18valenceelectrons
NO2 : 5+2(6)+1=18valenceelectrons
Thus,allthreespecieshavethesamenumberofvalenceelectronsandthesamenumberof
secondorthirdperiodelements.Moleculesand/orionsthathavethesamenumberofvalence
electronsandthesamenumberofsecondorhigherperiodelementsareoftencalled
isoelectronicmoleculesand/orionsbecausetheyhavethesame(=iso)numberofelectrons.For
thisproblem,wewillassumethatsulfuractslikeoxygeninitsbondingcharacteristics,sothe
Lewisstructuresforthethreeisoelectronicspeciesarelikelytobeverysimilar.Thisisthecase
forallisoelectronicspecies[seeProblem1.28(d)].FirstwriteaLewisstructureforozone,O3,
andthenapplyittosulfurdioxide,SO2,andnitriteion,NO2.Theconnectivityandbonding
betweentheoxygenatomiccoresinO3,gives:
OOO
Thisstructureusesfourofthe18valenceelectrons,sowehave14moretodistributetotryto
giveeachoxygenatomiccoreeightvalenceelectrons.Wemighttrytoputenoughnonbonding
pairsoneachoxygencoretogiveeacheightelectrons,butwewouldneed16electronstodo
thisandwehaveonly14.Whenwemeetasituationlikethis,aswewillfindinChapter5,the
solutionistoplacemorethanasinglepairofelectronsintocovalentbondsbetweentheatomic
cores.Thisgiveseachofthecoresanotherpairofelectrons,because,asweknow,electrons
sharedbetweenapairofatomscounttowardsatisfyingtheoctetruleforbothatoms.Thus,the
nextstepinwritingtheLewisstructureistoplacetwoelectronpairsbetweentwooftheoxygen
cores:
O O O
Nowwehaveusedsixofthevalenceelectronstoformcovalentbondsandwehave12leftover
thatwecandistributeasnonbondingpairs:
O O O
All18valenceelectronsareaccountedforinthisLewisstructureandeachoxygenatomiccore
hasanoctetofelectrons.Fortheisoelectronicspeciessulfurdioxide,SO2,andnitriteion,NO2,
wehave:
O S O
O N O
Notecarefullythattherightmostoxygenatomineachofthesestructuresdoesnotfitthepattern
inTable1.1,buthasonecovalentbondandthreenonbondingelectronpairs.Thecentraloxygen
atomonozoneandthesulfuratominsulfurdioxidealsodonotfitthepatternforoxygenfamily
elementsinTable1.1.ThesearenottheonlyproblemswiththeseLewisstructures.Wewill
learnhowtodealwithmoleculesandionsliketheseinChapter5.
Problem1.33.
(a)ThisLewisstructure, N C C
eachofthenitrogenatomiccores.
,isnotgood,becauseithasonlysevenelectronsaround
ACSChemistryFROG
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Chapter1
(b)ThisLewisstructure, N C C
eachofthenitrogenatomiccores.
(c)ThisLewisstructure, N C C
rightmostnitrogenatomiccore.
(d)ThisLewisstructure, N C C
octetofelectrons.
(e)ThisLewisstructure,
,isnotgood,becauseithasonlysixelectronsaround
,isnotgood,becauseithasonlysixelectronsaroundthe
,issatisfactory,becausealltheatomiccoreshavean
N C C N
,isnotgood,becauseithasonlyfourelectronsaround
N C C N
,isnotgood,becauseithasonlysixelectronsaroundthe
thenitrogenatomiccores.
(f)ThisLewisstructure,
leftmostnitrogenatomiccoreandrightmostcarbonatomiccore.
Problem1.34.
Lewisstructuresformolecules(a)and(c)arecorrect.Eachstructurehasthecorrectnumberof
valenceelectronsandeachofthesecondorhigherperiodatomiccoresisshownwithanoctet
ofelectrons.Theothersareincorrect:
(a)HOCl
(b)CS2
H O Cl
S C S
CS2has16valenceelectrons[=2(6)+4]andthisstructurehasonly12.Inaddition,noneofthe
atomiccoreshasanoctetofelectrons.Thesedeficienciescanbothbesolvedbyplacinganother
pairofbondingelectronsbetweenthecarboncoreandeachofthesulfurcores:
S
(c)
NH3
H N H
H
O
(d)
(HO)2CO
H O
O H
Thenumberofvalenceelectronsrepresentediscorrect,butthecarboncoreisshownwith10
valenceelectrons.Moveoneofthedoublepairbetweenthecarboncoreandthelowerlefthand
oxygencoreontotheoxygencore(soithasthesameelectronicconfigurationastheoxygen
coreontheright):
O
(e)
74
H2Se
O H
H Se H
ACSChemistryFROG
Chapter1
2
Water:ANaturalWonder
2
Se H
Problem1.35.
Withrespecttothecentralatomiccore,tetrahedralorientationrequiresatotaloffourpairsof
bondingandnonbondingelectronsarrayedaroundthiscore.Forthisproblem,allhavefive
moleculesandionsshownhaveeightvalenceelectrons(fourpairs)andatetrahedralorientation
ofthebondingandnonbondingpairsaboutthecentralatomiccore.
2
r22c2
Problem1.36.
Althoughthebondingandnonbondingelectronpairsarearrangedtetrahedrallyaroundeach
centralatomiccoreinthemoleculesinProblem1.35,theshapeofeachmoleculeisdescribed
bythepositionoftheatomiccoreswithrespecttooneanother.Inparticular,weareconcerned
herewiththeorientationoftheHatomiccoreswithrespecttothecentralatomiccore.
(a)H2Sisbent,likethewatermolecule.
(b)NH4+istetrahedralwiththeHatomiccoresarrangedtetrahedrallyaroundthenitrogencore.
(c)NH3hasatrigonal(ortriangular)pyramidalstructure,withthenitrogenatomiccoreatthe
apexofatriangularpyramidandtheHatomiccoresattheverticesofthetriangularbaseofthe
pyramid.
(d)NH2isbent,likethewatermolecule.
(e)CH4istetrahedralwiththeHatomiccoresarrangedtetrahedrallyaroundthecarboncore.
Problem1.37.
UsethePythagoreantheoremtofind,c,thelengthofthediagonalof
thesquarewithsidesoflength2r:
c2=(2r)2+(2r)2=4r2+4r2=8r2
c=
Thedistancefromthecenterofanyoftheballstothecenterofthe
squareishalfthelengthofthediagonal:
distancefromballtocenterofsquare=
Problem1.38.
(a)UsethePythagoreantheoremtofindthelengthofthecubeedge,
e,wherethediagonalofeachfaceofthecubehasalength2r:
e2+e2=(2r)2=2e2=4r2
e=
ACSChemistryFROG
75
tesrq
au
d
2
hdlistance
6
6
62
28
Water:ANaturalWonder
Chapter1
UsethePythagoreantheoremagaintofindthelengthofthecubediagonal,d:
d2=(2r)2+
=4r2+2r2=6r2
d=
Thedistancefromanycornerofthecube,thatis,thecenterofanyoftheballs,tothecenterof
thetetrahedronisonehalfthelengthofthediagonal:
distancefromballtocenteroftetrahedron=
6
2 r
(b)Callthedistancecalculatedinpart(a)thetetrahedraldistanceandthedistancecalculatedin
Problem1.37thesquaredistanceandcomparethem:
=
<1
Thisresultshowsthatthedistancefromthecenterofaballtothecenterofatetrahedral
arrangementisshorterthanthedistancefromthecenterofaballtothecenterofasquare
arrangementandhelpstojustifythestatementinthetextthatthetetrahedralarrangementputs
alltheballsascloseaspossibletothecentralpoint.
Problem1.39.
(a)Siliconatoms,inthecarbonfamily(group),have4valenceelectronsandchlorineatoms
have7valenceelectrons.ThetotalnumberofvalenceelectronsinSiCl4is:
4+4(7)=32valenceelectrons.
Assumethatthesiliconatomiccoreisthecentralatomcoreandconnecteachchlorineatom
coretothiscentralsiliconatomcore.Thisgivessilicon4covalentbonds(likecarboninits
compounds)andgiveseachchlorineonecovalentbond.Eachchlorinecorealsohas3pairsof
nonbondingelectrons:
Cl
Cl Si Cl
Cl
or
Cl
Cl
Si
Cl
Cl
(b)ThisLewisstructureissimilartothatformethane,CH4,inthatthecentralatomineachcase
hasfourcovalentbondsbondingittofourotheridenticalatomcores.Siliconisinthesame
familyoftheperiodictableascarbon,soalsobrings4valenceelectronstothestructure.Each
hydrogenatomcoreinmethanecanhaveonlyonebondedpairofelectrons.Similarlyeach
chlorineatomiccoreinsilicontetrachloridehasonebondedpairofelectrons.Thechlorine
atomiccoresalsohavethreenonbondingpairsofelectronsthatdonotaffectthegeometryofthe
molecule.
76
ACSChemistryFROG
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Water:ANaturalWonder
H
H C H
Methane
Cl
Silicontetrachloride Cl Si Cl
Cl
(c)TheshapeofSiCl4,likethatofCH4,istetrahedralwiththefourcovalentbondingpairsof
electrons(andfouridenticalatomcores)arrangedsymmetricallyaboutthecentralcore.
Problem1.40.
(a)Borane,BH3,hasonlysixvalenceelectrons[=3+3(1)].Thus,thecentralboronatomiccore
canhaveonlyasextetofelectrons(shownhereaslineseachrepresentingabondingelectron
pair):
Becausetheboronatomiccoredoesnothavethefulloctet(eightelectrons)weassociatewith
thesucceedingsecondperiodelementsintheircompounds,itiscalledelectrondeficient.
Electrondeficiencyhastobedefinedrelativetosomestandard(theoctet,inthiscase),butthis
issomewhatarbitrary.Thereisnothingmagicabouttheoctet.
(b)Thebestarrangementofthreespheres(orballoons,asinInvestigateThis1.14)ascloseas
possibletoacentralpointisinatriangulararraywherethecentersofthesphereslieatthe
verticesofanequilateraltriangle.Thiswouldbethearrangementofthethreeelectronpairs
makingupthethreeelectronpairbondsinborane.Thehydrogencoreswouldalsotakeup
positionssymmetricallyarrangedabouttheboroncore,asshowninthestructureinpart(a).As
showninthedrawing,boraneistrigonalplanar(allfouratomiccentersinthesameplane)with
theHBHbondanglesallequalto120.ThisisalsothestructurerepresentedintheWeb
Companion,Chapter1,Section6,pages3and4,byballandstickandchargedensitymodels:
Problem1.41.
Electronegativityisameasureoftheattractionofanatomiccoreforthebondingelectronsit
shareswithanotheratomiccoreinamolecule.Thereareseveralwaystoassignnumericvalues
torelativeelectronegativies.LinusPaulingdevelopedoneofthemostcommonanditishis
valuesthataregiveninFigure1.20inthetextbook.
Problem1.42.
(a)Fluorineistheelementwiththehighestelectronegativityvalue.
ACSChemistryFROG
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Water:ANaturalWonder
Chapter1
(b)Theelementswiththelowestelectronegativitiesarefoundatthebottomlowerleftofthe
periodictableontheinsidefrontcoverofthetextbook.
(c)Theelementswiththehighestelectronegativitiesarefoundatthetopright(excludingnoble
gases)oftheperiodictable.
(d)Electronegativitygenerallydecreasesasyougofromthetoptothebottomwithinagroupof
theperiodictable.
(e)Electronegativitygenerallyincreasesasyougofromthelefttotherightacrossaperiodof
theperiodictable.
(f)Generally,aselectronegativityincreasesatomicsizedecreases.Thismakessense;themore
tightlyanatomicnucleusholds/attractsitselectrons(higherelectronegativity),thecloserthey
willbetothenucleus(smallersize).
Problem1.43.
(a)FhasgreaterelectronegativitythanS.Fisthemostelectronegativeelement,soitmusthave
agreaterelectronegativitythananyother.Basedontrendsinelectronegativity,Fisinperiod
twocomparedtoSinperiodthreeandelectronegativityincreasesgoingupagroup.Fisfurther
totherightintheperiodictablethanSandelementsincreaseinelectronegativityfromleftto
rightacrossaperiod.Bothofthesetrendsgiveanelementthatliesaboveandtotherightof
anotherintheperiodictableahigherelectronegativity.
(b)Basedonourinterpretationofperiodicityrepresentedintheperiodictableontheinside
frontcoverofthetextbook,CandHcanbeconsideredtobeinthesamegroupinmanyoftheir
properties.SinceHisinthefirstperiodandCinthesecond,wewouldpredictgreater
electronegativityforH.Figure1.20indicatesthatthispredictionisincorrect:Chasasomewhat
higherelectronegativitythanH.
(c)OhasgreaterelectronegativitythanH.AlthoughOisasecondperiodelementandHafirst
periodelement,OistwoelementsfurthertotherightontheperiodictablenexttoF,themost
electronegativeelement.
(d)OhasgreaterelectronegativitythanC.TheseelementsarebothinthesecondperiodandO
isfurthertotherightthanC.
Problem1.44.
Oneoftheelementsineachofthepairshereisthesame,soitistheotherelementineachpair
thatwefirsthavetocompare.Thenwecancompareeachofthesetotheatomthatisthesameto
seewhichelectronegativitydifferenceislargestand,hence,whichbondwillbemorepolar.
(a)TheHFbondismorepolarthantheHClbond.FismoreelectronegativethanCl(higherin
theirgroupoftheperiodictable),andbotharemoreelectronegativethanH,sothedifferencein
electronegativitybetweenFandHisgreaterthanthedifferencebetweenClandH.
(b)TheNHbondismorepolarthantheCHbond.NismoreelectronegativethanC(tothe
rightintheirperiodoftheperiodictable),andbotharemoreelectronegativethanH,sothe
differenceinelectronegativitybetweenNandHisgreaterthanthedifferencebetweenCandH.
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ACSChemistryFROG
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Water:ANaturalWonder
(c)TheKSbondismorepolarthantheNaSbond.KislesselectronegativethanNa(lowerin
theirgroupoftheperiodictable),andbotharelesselectronegativethanS,sothedifferencein
electronegativitybetweenKandSisgreaterthanthedifferencebetweenNaandS.
(d)TheNOismorepolarthantheOObond.Sincethereiszeroelectronegativitydifference
betweenthetwoOatomsinOO,thelargerelectronegativitydifferenceisbetweenthe
dissimilaratomsinNO.
Problem1.45.
NOTE:ThisproblemisprobablymisplacedandoughttogointotheGeneralProblemsatthe
endoftherestoftheproblems,sincemanyoftheimportantpropertiesofwater,including
hydrogenbonding,havenotbeendiscussedatthispointinthetext.
Thereisnosingleanswertothisproblem,butanswersoughttoinvolveanunderstandingthata
linearwatermoleculewillhavenopermanentdipolemoment,sincethebondmomentswillbe
pointinginoppositedirectionsandcanceloneanotherout.Ifthehydrogenatomiccoresareon
oppositesidesoftheoxygenatomiccore,thenonbondingelectronpairsarealsolikelytobeon
oppositesides(forsymmetry),sothearrayofbondingandnonbondingpairsmightbe
visualizedassquareplanar:
Achargedensitymodelmightresembleanellipsewithhighnegativechargedensity(red)
arounditsmiddleandpositivechargedensity(bluepositivechargesnotcompletelycancelled
bytheelectrondensity)atitsends.Hydrogenbondswouldprobablystillbepossibleandcould
formplanarsheetsofmoleculesinwhicheachhydrogenisbondedtofourothers,asintheleft
handpicturebelow.Suchlayerscouldstackononeanotherorsmallarraysofthemcould
jumbletogetherlikepotatochipsinabagintheliquidphase.Threedimensionalstructuresare
alsopossible,asintherighthandpicture,alsowithfourhydrogenbondstoeachmolecule,but
thisthreedimensionalstructuremustbequiteopenwithlargeholes.Smallnumbersoflinear
watermoleculesmightcometogetherthisway,butanextendedstructurewouldprobablynotbe
stable.
Withoutapermanentdipolemoment,theattractionsamonglinearwatermoleculeswouldnotbe
asstrongandwaterwouldmeltandboilatlowertemperatures.TheliquidmightexistonEarth
ACSChemistryFROG
79
Water:ANaturalWonder
Chapter1
atthepresenttemperatureandstillbecompatiblewiththedevelopmentandevolutionoflife,
althoughthepolarnatureofwaterhasastrongroleinthedevelopmentofthebiomolecular
structuresrequiredforlife,asweknowit.Thehydrogenbondingpossibleforlinearwater,
wouldleadtoahigherenergyofvaporizationandspecificheatthanifhydrogenbondingwas
notpossible,butthelackofapermanentdipolewouldprobablymeanlowervaluesthanforthe
bentmolecule.Inturn,thelowerenergyofvaporizationandspecificheatwouldmakelinear
waterlessefficientattrappingradiantenergyfromthesunandwouldprobablyresultinacolder
Earth,whichmightnotbecompatiblewiththeevolutionandmaintenanceofcomplexlife
forms.Whatotherpossibilitiesdidyouenvision?
Problem1.46.
(a)Water,H2O,andhydrogensulfide,H2S,bothhaveeightvalenceelectronsandsimilarLewis
structures:
H O
H
H S
H
(b)BothH2OandH2Shavebentorangularshapes,whichdescribethearrangementofthe
atomiccores.(Thetwobondingandtwononbondingpairsofelectronsonthesemoleculesare
arrangedroughlytetrahedrallyaboutthecentralatomiccore,butthenonbondingelectronsare
notconsideredwhendescribingtheshape.)
(c)ThebonddipolesaredifferentinH2OandH2S.Theelectronegativity(EN)ofoxygenis3.4,
whilethatofhydrogenis2.2.ThedifferenceinENis1.2,makingeachhydrogentooxygen
bondverypolar.Thevalenceelectronsarenotsharedequallybetweentheoxygencoreandeach
hydrogenatomiccore;oxygenhasamuchgreaterattractionforthesharedelectrons.Thisis
representedinFigure1.19.TheENofsulfuris2.6andthatofhydrogenis2.2.Thedifference
inENisonly0.4.Theruleofthumbstatedinthetextisthatasignificantbonddipoleexistsfor
acovalentbondbetweentheatomsoftwoelementsthatdifferby0.5ormoreENunits,sothese
HSbondsareessentiallynonpolar.
(d)BothH2OandH2Shavenonbondingelectronsonthecentralatomthatcreatean
unsymmetricchargedistributioninthemolecule.Theasymmetryislessforthelargersulfur
atombecausetheelectronsoccupyalargervolumeofspacesotheirchargeisnotas
concentrated.TheaffectofthenonbondingelectronsislessforH2SthanforH2O.Inaddition,
thesmallerHSbonddipolescontributelesstothedipoleinH2SthanthelargerHObond
dipolesinH2O.Overall,therefore,weexpecttheH2Stobepolar,butwithaconsiderably
smallerdipolemomentthanH2O.
Problem1.47.
DrawtheLewisstructuresforcarbontetrachloride,CCl4,chloroform,CHCl3,and
dichloromethane,CH2Cl2.Clearlylabelthebonddipolesforeachmolecule.Whichmolecules
arepolarandwhicharenonpolar?Explainyouranswer.
Structuresforcarbontetrachloride,CCl4,chloroform,CHCl3,anddichloromethane,CH2Cl2are
givenhere(withthenonbondingelectronsontheClcoresnotshown,inordertomakethe
pictureslessmessy).Thelinesrepresentingthebondingelectronpairsareshowninawaythat
80
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
isdesignedtohelpusvisualizethethreedimensionalstructuresofthemolecules(seeChapter5,
Section5.8).
Whentheindividualbonddipolescancelout,thenthereisnonetdipoleandthemoleculeis
nonpolar.Iftheindividualbonddipolesdonotcancelout,thenthereisanetdipole.
Problem1.47.
Wearegivenmolecularformulasandaskedwhyallthemoleculeshavedipolemoments=0.
Thedipolemomentofanymoleculeissimplythesumofalltheindividualbonddipoleswith
theirdirectionswithrespecttooneanothertakenintoaccount.Inordertohavenonet
(molecular)dipolemoment,thebonddipolesmusteitherallequalzeroorbesymmetrically
orientedtoexactlycancelout.[Ifyouhavestudiedvectorsinmath,wecanrestatethismore
simply:themoleculardipoleisthevectorsumofthebonddipoles.]Beforeattemptingan
analysisofdipolemoments,weneedtoknowthethreedimensionalshapeofthemolecule.
WriteaLewisstructureanduseittodeterminethegeometricorientationofthebonds.Noteany
specialsymmetry.
(a)N2(molecularnitrogen)hasatriplebondbetweenthetwonitrogenatoms, N N .Since
thetwonitrogenatomsobviouslyhavethesameEN(electronegativity)value,thebonddipole
mustbezero.Asistrueforalldiatomicmoleculesthebonddipoleisequaltothemolecular
dipolemoment.
(b)BH3(borane)hasatrigonal(triangular)planargeometrywithalltheHBHbondangles=
120.Hydrogenismoreelectronegativethanboron,asillustrated.Thecancellationofthebond
dipolesisduetothethreefoldsymmetryofthemolecule.
H
B
ACSChemistryFROG
81
Water:ANaturalWonder
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(c)SiCl4(silicontetrachloride)hasitsfourequivalentSiClbondspointingtothefourcorners
ofatetrahedron.Chlorineismoreelectronegativethansilicon.Thecancellationofthebond
dipolesisduetothetetrahedralsymmetryofthemolecule.
Cl
Cl
Cl
Si
Cl
(d)BeH2(berylliumhydride)isalinearmolecule,withthetwoBeHbonddipoles180apart
opposingoneanother.
Inordertofigureoutthenetdipoleforanymolecule,thereareanumberofstepsrequired.
Eachstepisessentialinordertoarriveatthecorrectanswer.First,drawaLewisstructure.
Withtheexceptionofthelefthandelementsandtheirmolecules(suchasBH3andBeH2),
secondrowelementsshouldsatisfytheoctetrule.Next,figureoutthethreedimensionalshape
ofthemoleculethatwillplacethenegativelychargedvalencepairsofelectronsascloseas
possibletothepositivelychargedatomiccore(s).Usetheelectronegativitydifferencesbetween
atomstoestimatetherelativemagnitudesofindividualbonddipolesand,fromtheirgeometric
sum,predict(qualitatively)amoleculardipoledirectionandmagnitude.
Problem1.49.
Theelectronegativityoftheelementnitrogenisrelativelylarge,sotheNHbonddipoleis
substantial,withitsnegativeendpointingtowardthenitrogenatomiccore.Thenonbondingpair
ofelectronsonthenitrogenaddstothenegativechargeatthenitrogenvertexofthepyramidal
structuretogiveNH3asubstantialmoleculardipolemoment.Theelementsphosphorusand
hydrogenhaveapproximatelythesameelectronegativity,sothePHbonddipoleisalmostzero.
Thisleavesonlythenonbondingpairofelectronsonthephosphorusatomiccoreasprincipal
contributortothePH3moleculardipolemoment,whichwillberathersmall.Wepredict
(correctly)thatNH3hasalargermoleculardipolemomentthanPH3.
Problem1.50.
(a)Themotionofelectronsinmoleculescreatestransientpartialpolarregionseveninnonpolar
molecules.Polarityinonemoleculeinducespolarityinneighboringmoleculesastheelectrons
intheneighborsmovetowardthepositiveregionsininducingmoleculeandawayfromits
negativeregions.Thetransientlypolarizedmoleculesattractoneanother.Theseattractionsare
calledinduceddipoleattractions.
(b)Dipoledipoleattractionsexistbetweenneutralpolarmolecules,thatis,moleculeswitha
permanentmoleculardipolemoment.Polarmoleculesattracteachotherbecausethepositive
andnegativeendsofdifferentmoleculesareattractedtowardoneanother.
(c)Hydrogenbondingisaspecialtypeofintermolecularattractionthatexistsbetweenthe
hydrogenatominapolarbond(particularlyanHF,HO,orHNbond)andanunshared
electronpaironanearbyelectronegativeatom(usuallyanF,NorOatom)onanothermolecule
(orwithinthesamemolecule,asinproteins).
82
ACSChemistryFROG
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Problem1.51.
Bothintramolecularcovalentbondsandintermolecularhydrogenbondsinvolvesharingofa
pairofelectronsbetweentwoatomiccores.Thedifferenceisthatthehydrogenatomiccorein
anintermolecularhydrogenbondisoriginallybondedtoanatomiccoreinonemoleculebya
covalentintramolecularbondingelectronpairandendsupstillbonded(albeitbyalonger
somewhatweakerbond)viathiselectronpairandinadditionsharesasecondpairofbonding
electronsfromanothermoleculeinthehydrogenbond.Thestrengthofthissecondbond,an
intermolecularhydrogenbond,isapproximatelyfivetotenpercentthestrengthofan
intramolecularcovalentbond.Therelativeweaknessofhydrogenbondsmeansthattheycan
breakandformrapidly,whereascovalentbondsaremuchhardertobreakandareresponsible
forthepermanentstructuresofmolecules.
Problem1.52.
(a)Thereareinduceddipoledispersionforcesamongallmolecules.
(b)Therearedipoledipoleattractionsbetweenpolarmoleculesaswellasdispersionforces
amongthem.
(c)Thereisahydrogenbondingattractionbetweenahydrogenatominawatermoleculeanda
nitrogenatominammonia(inamixtureofammoniaandwater).
Problem1.53.
TheboilingpointsfromthefourthtofifthperiodhydridesinFigure1.24increasebyabout35
40Casthenumberofelectronspermoleculeincreasesby18from36to54.Thisincreaseis
roughly2Cperelectron.TheincreaseinnumberofelectronsfromHItoHAtis32(from54to
86).Ifthetrendcontinues,wemightexpectHAttohaveaboilingpointofabout30C,thatis,
about64C[=(2C/electron)(32electrons)]higherthantheHIboilingpoint,35C.
Problem1.54.
Methane,CH4,moleculescannotformhydrogenbondswithoneanotherbecausethemolecules
havenononbondingelectronpairsthatcouldattractapositivelypolarizedhydrogenatom.Even
ifthemoleculeshadnonbondingelectronpairs,theelectronegativityofcarbonissolowthatthe
CHbondisalmostnonpolar,sothehydrogenatomiccorewouldnothaveenoughpositive
charactertobeattracted.Thisisthereasonthathydrogensulfide,H2S,moleculesdonotform
hydrogenbondswithoneanother.Eventhoughthemoleculeshavenonbondingelectronpairs
theelectronegativityofSissolowthattheSHbondisalmostnonpolar,sothehydrogen
atomiccoredoesnothaveenoughpositivecharactertobeattractedtothenonbondingpairs.For
hydrogenbondstoform,Hatomsmustbebondedtoaveryelectronegativeatom,usually
fluorine,nitrogenoroxygen.
Problem1.55.
Threepropertiesofwaterthatcanbeattributedtotheexistenceofthehydrogenbondare:
(1)Waterisaliquidatroomtemperature(ortheaveragetemperatureatthesurfaceofthe
Earth).Atroomtemperature,thehydrogenbondsinwaterarestrongenoughtoholdthe
moleculestogether.Ifthehydrogenbondswerenotpresent,smallmoleculeslikewaterwould
beagasatroomtemperature.
ACSChemistryFROG
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Water:ANaturalWonder
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(2)Thelowerdensityofsolidicecomparedtoliquidwaterisaconsequenceofhydrogen
bonding.Theextendedhydrogenbondedstructureiniceproducesmoreopenspacebetween
watermoleculesthaninliquidwater,wheresomeofthisstructurehascollapsed.Thisstructure,
whichextendsinalldirectionsinspace,permitsthemaximumnumberofhydrogenbonding
interactionsbetweentheH2Omolecules.Becausethestructurehaslargehexagonalholes,iceis
moreopenandlessdensethantheliquid.Ifthehydrogenbondswerenotpresent,icewould
probablybemoredensethantheliquid,asisthecaseformostsubstances.
(3)Thehighspecificheatofliquidwaterisaconsequenceofextensivehydrogenbondinginthe
liquid.Becauseofthehydrogenbonds,moreenergyisneededtodisrupttheintermolecular
attractionsbetweenthemoleculesintheliquidphase,soadditionofenergyraisesthe
temperatureofwaterless(produceslessincreaseinthemotionofthemolecules)thanifthe
thesebondsdidnothavetobebroken.
Otherconsequencesofthepresenceofhydrogenbondsamongwatermoleculesincludehigh
energyofvaporizationandhighenergyoffusion(melting).
Problem1.56.
Fourhydrogenbondsarepossibleforonewatermoleculeinasampleofwater.Thediagram
showsthattwooftheseareformedbythemoleculesownhydrogenatomiccoresattractedto
thenonbondingelectronsontwoothermoleculesandtwoareformedbytheattractionofits
nonbondingelectronstothehydrogenatomiccoresoftwomoremolecules.
Problem1.57
(a)Fourhydrogenbondsarepossibleforoneammoniamoleculeinasampleofliquid
ammonia.Thisdiagramshowsthatthreeoftheseareformedbythemoleculesownhydrogen
atomiccoresattractedtothenonbondingelectronsonthreeothermoleculesandoneisformed
bytheattractionofitsnonbondingelectronstothehydrogenatomiccoresofanothermolecule.
84
ACSChemistryFROG
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Water:ANaturalWonder
H
N
H
H
N H
H
H
N
H
H N H
H
(b)CompareFigure1.27orthediagramaboveinProblem1.56,whichshowthemaximum
hydrogenbondingforwater,withthedrawinginpart(a),whichshowsthemaximumhydrogen
bondingforanammoniamolecule.Everywatermoleculeinacollectionofwatermoleculesis
capableofformingfourhydrogenbondsbecauseitdonatesasmanynonbondingpairs(2)as
hydrogenatomiccores(2).Thesituationforammoniaisquitedifferent.Whileanindividual
ammoniamoleculeiscapableofformingfourhydrogenbonds,notallmoleculesinasampleof
liquidammoniacandothis.Itrequiresanonbondingpairofelectronstoformahydrogenbond
andthereisonlyonenonbondingpairperammoniamolecule.Theimbalanceofhydrogen
atomiccores(3)tononbondingpairsofelectrons(1)meansthat,onaverage,amoleof
ammoniamoleculeswillformonlyonemoleofhydrogenbonds.Theresimplyarentenough
nonbondingpairsofelectronsforeveryavailablehydrogenatomiccore.
Problem1.58.
Inordertoexistasaliquidatroomtemperature,asubstancemusthaveaboilingpointabove
roomtemperature,whichisabout2025C.Thesmallestlinearhydrocarbontofitthis
descriptionispentane(CH3CH2CH2CH2CH3),whichthedataonthegraphinConsiderThis1.23
showhasaboilingpointofabout35C.Thenextsmallerhydrocarbon,butane
(CH3CH2CH2CH3),hasaboilingpointofabout0C.
ACSChemistryFROG
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Water:ANaturalWonder
Chapter1
Problem1.59.
(a)TheplotinFigure1.24withthenoblegasesaddedlookslikethis:
100
IV
50
VI
VII
50
VIII
100
150
200
250
300
10 20 30 40 50 60 70 80
NumberofElectrons/Molecule
90
Theperiods2through5groupVIIInoblegasesfollowatrendthatisremarkablysimilartothe
groupIVhydridesexcept5080Clowerinboilingpoint.Thetrendcontinuestoperiod6,but
therearenohydridesforcomparison.(Theperiod6,groupIVelementisbismuth,whichis
metallicanddoesnotformatetrahydride.)Thereis,ofcourse,noperiod1,groupIVelement,
sonocomparisonwithheliumispossibleeither.
(b)Thesymmetry(sphericalornearspherical)ofthegroupVIIInoblegasesandthegroupIV
hydridesgivesthemsmallsurfaceareasandchargesymmetry,whichmakestheinduceddipole
attractionsamongtheatomsormoleculesrelativelyweakandaccountsfortheirlowboiling
points.Thenuclearchargeonthenoblegasesisfourunitshigherthanthecentralatominthe
correspondingperiodhydride,whichholdstheelectronsclosertothenucleus,reducesthe
surfaceareaoftheatomrelativetothehydrideandresultsinevenweakerinduceddipole
attractions,sotheboilingpointsaresubstantiallylower.Thisisthetrendweseealsointhe
groupVIIhydrides,whichmighthavebeenexpectedtohavehigherboilingpointsthaneither
thegroupVorVI(ifthetrendfromIVtoVtoVIwasfollowed),buthavelowerboilingpoints
(atleastforperiods4and5)thanthegroupVhydrides.
Problem1.60.
pentane
CH3CH2CH2CH2CH3
bp=36C
H HH H
H
H
C
C
C
C H
H C
H H H H
isopentane
(CH3)2CHCH2CH3
bp=28C
H
H
C HH H
H
C
C
C
H
H C
H
H
H
H
neopentane
C(CH3)4
bp=10C
H H
H
H
C
C H
H
C
C H
H C
H
H
H
H
Althoughthemolecularmasses(andmolecularvolumes)arethesameforallthreeisomers,
theirsurfaceareasarenot.Asthedegreeofbranchingofthecarbonskeletonincreases,the
surfaceareadecreases.Asthesurfaceareadecreases,thecontactwithneighboringmolecules
86
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
decreases,thusreducingthedispersionforcesbetweenmolecules.Boilingpointsof
hydrocarbonsareaconsequenceofdispersionforcesandthoseforcesexistacrosstheentire
surfaceofamolecule(page27).Youmayrecallfromgeometrythatasphereisthegeometric
solidwiththelowestsurfaceareatovolumeratio.Examineyourmolecularmodelsofthethree
isomersandyouwillfindthatneopentanemostnearlyresemblesasphere.Pentanehasno
skeletalbranchesandhasthegreatestsurfaceareaandthegreatestboilingpointofthethree.
Problem1.61.
Figure1.29showsthatthedensityofliquidwaterat85Cisabout968gL1(=0.968gcm3).
Thedensityoficeis0.917gcm3.Iceismuchlessdenseeventhanhotwaterandwillfloat
(untilitmelts)inhotwater.Trytheexperiment.
Problem1.62.
(a)4Cisthetemperatureatwhichliquidwateratnormalatmosphericpressurehasits
maximumdensity,Figure1.29,whichexplainswhyitsinkstothebottomofthecontainer.
(b)Warmingthewaterwillreduceitsdensity,andthewarmerwaterwouldbebuoyedupand
rise.Sincethethermalenergyisenteringthewateratthewallsofthecontainer,itisthewater
nexttothewallsthatincreasesintemperatureandrisesuntilitgetsnearthetopwhereit
encounterstheiceandiscooledasitmeltssomeoftheice.Whenwaternearthetopofthe
container,whichiscloseto0C,iswarmed,itsdensityincreasesanditsinksinthecontainer.
Theneteffectoftheseactionsistocreatecurrentsofsinkingwaterinthetemperaturerange0
to45Candrisingwaterwithatemperatureaboveabout5C.Therisingwarmerwateris
cooledasitmixeswithwaternearthetopofthecontainerand,whenitstemperaturefallsbelow
4C,itbeginstosink.Theneteffectisacirculationofthewaterinthecontainerwithrising
warmerwaternearthewallsofthecontainerandsinkingcolderwaternearthemiddleofthe
container.Thecirculationisdrivenbythethermalenergyfromthewarmersurroundingsofthe
roomenteringtheicewatermixture.
(c)Iftheexplanationaboveiscorrect,theconstanttemperaturemeasuredatthebottomofthe
containerisnotthetemperatureofthesamebatchofwatermolecules,butofaconstantly
changingbatchofwatermoleculesasthewarmedwaterisbuoyedupandthecoolerwater
sinks.Ifthetemperaturesatthewallsandinthecenterofthecontaineraremeasuredatthesame
heightinthecontainer,theremightbeadetectabledifference,withthewallwaterat
temperatureabove5Candthecenterbelow5C.Ifadropofdyecouldbeaddedtothewater
withoutdisturbingwhatevercirculationhasbeensetup,themovementofthedyecouldtrace
thecirculationovertime.Moreelaboratesetupshavebeendevisedtocheckwhetherthis
circulationoccurs.Asearchofthewebcouldturnupsomeofthemforyou.
Problem1.63.
InvestigateThis1.30partiallymimicsthesituationrepresentedforWinterinthisfigure,with
iceatthetopofthelake/containerandthedensest4Cwateratthebottom.Thisisarelatively
stablesystemwithlessdenseiceandwaterfloatingonmoredensewater.Whenthesungets
higherintheskyandtheairwarmsupinthespring,theicemelts,wateratthesurfacebeginsto
warmandbecomemoredenseasitapproaches4Candbeginstosink(asdescribedfor
ACSChemistryFROG
87
Water:ANaturalWonder
Chapter1
InvestigateThis1.30inthesolutionforProblem1.62).Asthetemperatureofthelakewater
risestoabout4C,windsatthesurfacecanbegintostirthewater,allofwhichisnowofabout
thesamedensity.ThiscausesthemixingofnutrientsshownintheSpringpanelofthefigure.
IntheSummer,thesunlightandthewarmaircontinuetowarmthewaterandanewrelatively
stablelayeringofthewateroccurswiththewaterthatiswarmer,above4C,inthetoplayersof
thelake.Thislayeringisstableenoughthatwindsdolittletodisturbitandthereislittlemixing
withinthelake.AsthesungetslowerintheskyandtheairtemperaturedecreasesintheFall,
thetoplayersofthelakecoolonceagainandsinkandmixasthewateragaincomestoitsmost
densetemperature,4C.Duringthisperiod,thedensityandtemperatureprofileofthelakeare
changingtothemoreuniformdistributionshownandwindatthesurfaceisagaineffectivein
stirringthewaterandproducinganothernutrientturnover.Theupshotofallthisisthatthe
nutrientsfromthesurface(includingoxygen)andfromthebottomofthelake(minerals)mix
withoneanotherandhelptoprovidewhatisnecessarytosustainlifethroughoutthelake.
Withoutthismixing,thelakewouldbecomestagnantanddead.
Problem1.64.
(a)Theshorterbondlength,100pm,isassociatedwiththe
intramolecularcovalentbondswithinthewatermolecule.The
longerbondlength,180pm,isassociatedwiththeintermolecular
hydrogenbondsbetweenpartialpositivelyandpartialnegatively
chargedregionsofdifferentmolecules.
(b)Inanisolatedwatermolecule,thecovalentOHbondlengthis
94pm.Thisrepresentsthebondlengthassociatedwithsharingofapairofelectronsbetween
thehydrogenandoxygenatomiccoreswithoutattractionstootherchargecenters.Thehydrogen
bondformswhenthehydrogenatomiccoreisattractedtoanonbondingpairofelectronson
anotherwatermolecule.Thereisalreadystrongattractionbyitscovalentelectronpair,sothe
atomiccoreispulledonlyasmalldistance,about6pm,fromthispairandsharesonlyasmall
amountoftheelectrondensityfromthesecondwatermolecule,soisnotattractedascloseto
88
ACSChemistryFROG
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Water:ANaturalWonder
thesecondpairofelectrons.Thus,thehydrogenbondisconsiderablylongerandweakerthan
thecovalentbond.
Compound
mp,C
Problem1.65.
CH4
182
Essentiallythesameexplanationispossibleforthevariationofthe
NH3
77.7
meltingpointsofthesecondperiodhydridesasfortheirboiling
points.Thestructureofsolidwater,Figure1.28(c),showsthateach
H2O
0
watermoleculeishydrogenbondedtofourothers.Methaneforms
HF
83.1
nohydrogenbondsandisonlyheldtogetherbyinduceddipole
attractions(weakinthissmallmolecule)inthesolid(andliquid),soitmeltsatquitealow
temperature.Ammoniaandhydrogenfluorideformhydrogenbonds,butcantformasmany(per
mole)aswater.Anyindividualmoleculecouldformfourhydrogenbonds,butanextended
structureforthesemoleculesisnotpossible(seeProblem1.57solution).Aplotofthemelting
Graphics
are
QuickTime
needed
decompressor
toand
seeathis picture.
pointdataasafunctionofnumberofnonbondingelectronpairsinthemoleculelookslikethis:
0
H2O
-40
NH3
-80
HF
-120
-160
CH4
0
Number
-200 of nonbonding electron pairs
OnecouldarguethatH2OisinlinewithCH4andNH3.Themeltingpointsincreaseasthe
numberofnonbondingelectronpairs,whichmeans,moreimportantly,theamountofhydrogen
bondingincreases.HFmightbeseenasoutofline,butonlyiftheextentofhydrogenbonding
isneglected.Ontheotherhand,thesimilarmeltingpointsofNH3andHFcanbeexplainedasa
resultofaboutthesameamountofhydrogenbondingpossibleinthetwosubstances.Inthis
case,H2Oisoutoflinebecauseithasahighermeltingpoint,but,sinceithasmorehydrogen
bonding,itwouldbeexpectedtohavemoreattractionsandahighermeltingpoint.Arguments
aboutwhatvalueisoutoflineareallbasedonpredictionsortrendsthatlookatonlyone
causativeparameter(numberofelectrons,numberofnonbondingelectronpairs,numberofH
bonds,etc.).Sinceobservablepropertiesaretheresultofmanymolecularlevelinteractionsand
phenomena,itisntsurprisingtofindthatanyoneofthemcantexplaineverything.
Problem1.66.
AttheTm,manyofthehydrogenbondsholdingtogether
thetwostrandsoftheDNAhelix,Figure1.34,break
andthestrandsbegintocomeaparttoformmore
flexiblechainsthatcancurluponthemselvestoform
structuresthataremoreglobularandlessresistantto
flow.Thus,theviscosityofthesolutiondecreases.The
ACSChemistryFROG
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Water:ANaturalWonder
Chapter1
spectroscopicproperties(lightabsorption)bybasepairsstackedoneupontheotherinthe
doublehelixarequitedifferentthanthefreebases.Theabsorptionoflight(intheultraviolet)
changesmarkedlyasthedoublehelixcomesapartandthebasesarenolongerstacked.
90
ACSChemistryFROG
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Water:ANaturalWonder
Problem1.67.
InSection1.9,youlearnthattherearethreehydrogenbonds
betweenGCbasepairsandtwobetweenATbasepairs.
Therefore,moreenergyisrequiredtobreakaGCpairingthan
anATpairing.Highertemperatures(greaterthermalenergyin
thesolution)arerequiredtomeltDNAwithhigher
proportionsofGC(orlowerproportionsofAT)pairs.Thus
theTmdecreasesastheproportionofATincreases,asshownin
thefigure.
Problem1.68.
Whenasolidsuchasicemelts,thetemperatureofthesolidliquidmixtureremainsconstant
untilallofthesolidhasmelted.Thechangefromthehydrogenbondeddoublehelixtoseparate
strandsoccursoverarathershorttemperaturerangewhenthehydrogenbondsinDNAbreakat
themeltingtemperature.Thisrelativelysharpchangeinproperties,especiallythechangein
flowcharacteristics,withinafewdegreetemperaturechangeistheDNAanalogytomelting.
Problem1.69.
Thelargerthenumberofinteractionsamongtheaminoacidsalongtheproteinchain,themore
energywillberequiredtodisruptthefoldedstructureoftheprotein.Theseinteractionscouldbe
hydrogenbonds,ionicattractionsbetweenchargedgroups(Chapter2),and/orhydrophobic
interactionsthatstabilizethefoldedstructurebykeepinghydrophobicgroupsinsidethe
structureawayfromwater(Chapters2and6).Themoresuchinteractions,thehigherthe
temperaturerequiredtoprovideenoughthermalenergytodisrupttheproteinstructure.We
mightpredictthatmicroorganismsthatliveinhotspringsandorganismsthatliveneardeep
oceanthermalventssurviveathightemperaturesbecausetheirproteinshaveevolvedstructures
thathavemoreoftheseinteractions,includinghydrogenbonds.[SeeBurg,Vriend,Veltman,
Venema,andEijsink,Engineeringanenzymetoresistboiling,Proc.Natl.Acad.Sci.1997,
95,20562060,foradiscussionofthispoint.]
Problem1.70.
ThesamekindofreasoningasinProblem1.69appliestothermophilicDNA.Themore
attractionbetweenstrands,themorethermallystabletheDNA(asinProblem1.67).Thus,you
expectthethermophilestohaveahighproportionofGC(withthreeHbonds).Thisis
observed.
Problem1.71.
(a)Cottonclothinggetswrinkledby
beingwornandforcedtoconformto
theshapeofitswearerandotherforces
likechairseats.Theseforcesonthe
fiberscausethemtobebentandpushedandpulledintoshapesthatbreakssomeHbondsand
makesothers.Whentheforcesarenolongeracting,saywhentheclothingisremoved,thenew
Hbondsholdthefibersinthepositionstheyhadtakenduringthetimetheclothingwasworn.
ACSChemistryFROG
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Chapter1
Sincemanyoftheseinvolvethefoldingandcreasingthatgoeswithourmovements,thefabric
isnowfoldedandcreasedonasmallscale,thatis,wrinkled.
(b)Ironinghastwoeffects.TheheatoftheironhelpstomaketheHbondsbreakmorereadily.
ThemassoftheironforcesthefabricflatsothatHbondsthatareremadearenowholdingthe
fabricflat.Thusthewrinklesareremovedandthepressrestored.
(c)Tomakethefabricpermanentpress,youwanttokeepthecellulosechainsinthepositions
theyhaveinthefiberintheunwrinkledfabric.SincetheHbondsaretooweaktoaccomplish
this,youneedtofindawaytobondthechainstooneanother.Youmightdothiswithreagents
thatreactwithOHgroupsthatareclosetooneanothertoformapermanentbondholding
themtogether.
(d)Sincethesoftnessofcottoncomesfromtheabilityofthecellulosechainsandfibermade
fromthemtochangeshapeeasily,preventingtheseeasychangeswillmakethefabriclesssoft.
Thus,bondingthechainstogether,assuggestedinpart(c)wouldprobablymakethefabricless
soft.
4.0c8kalJ1C
1
4.1c8alJ
Problem1.72.
Energyisrequiredtoovercometheintermolecularforcesthatholdmoleculesinpositionwith
respecttooneanotherwhenasubstancechangesfromasolidtoaliquidorincloseproximityin
thechangefromaliquidtoagas.Inthereverseprocesses(freezingandcondensation),energy
isreleasedastheintermolecularforcesagainbegintodominate.Thereverseprocessislike
makingbondsbetweenthemolecules.Althoughthesearetransientbondinginteractionslike
dispersioninteractionsandhydrogenbonding,therearemanysuchinteractionsandcanresultin
asubstantialreleaseofenergytothesurroundingsasthesystemgoestolowerenergy.
Problem1.73.
Ineachcase,theconversionfromoneunittoanothercanmosteasilybemadeusingaunit
conversionfactor(orfactors)toconvertthenumericvalueofthequantity.
(a)4550J=(4550J)
=4.55kJ
(b)250.J=(250.J)
=59.8cal
(c)500.Cal=(500.Cal)
=2.09106J
Problem1.74.
(a)Followingacrossthediagramatthenormalatmospheric
pressureof760mmHg,weobserve,asexpected,thatwaterwill
beinthesolidphasebelow0C,intheliquidphasefrom0C
uptoatemperatureof100C,andtheninthegaseousphase
from100Candabove.Thephasediagramrepresentsagreat
92
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
dealmoreinformationaboutthephaseofwateratdifferenttemperaturesandpressuresthan
thesewithwhichwearemostfamiliar.
(b)Aswaterchangesfromthegaseousphasetotheliquidphase,itsenergydecreases.This
meansthat E (=ElEg)willbelessthanzero;itssignisnegative.
(c)Aswaterchangesfromtheliquidphasetothesolidphase,itsenergydecreases.Thismeans
that E (=EsEl)willbelessthanzero;itssignisnegative.
Problem1.75.
Energydiagramsareshownthatrepresenteachprocess.Redarrowsareusedtorepresent
changesthatrequireenergy(E>0)andbluearrowsforchangesthatreleaseenergy(E<0).
(a)H2O(s)H2O(l),at0C.E>0forthesample.
(b)2H2(g)+O2(g)2H2O(l)+energy
(c)energy+2HgO(s)2Hg(l)+O2(g)
ACSChemistryFROG
93
Water:ANaturalWonder
Chapter1
(d)2Hg(l)+O2(g)2HgO(s)+energy
12m
1
k
c
a
l
.16.0o7l9g
4
8
J
C
H
O
(e)CH4(g)+2O2(g)CO2(g)+2H2O(l):E<0
Problem1.76.
SeeWorkedExample1.42andCheckThis1.43inwhichsimilarcalculationsweredonefor
waterandhexane.Since1kJ=103Jand1kcal=103cal,thenumericalrelationshipbetween
kilojoulesandkilocaloriesisthesameasthatbetweenjoulesandcalories,1kcal=4.184kJ.If
theamountofenergyrequiredtovaporizemethanolis1.22kJg1,thenumberofkcalrequired
tovaporizeonegramofmethanolis:
energy=1.22kJg1=(1.22kJg1)
=0.292kcalg1
Problem1.77.
Notethataformulaunitofdimethyletherandaformulaunitofethanolbothcontainthesame
numberofmolesoftheelements:carbon(2),hydrogen(6),andoxygen(1),thatis,C2H6O.
Therefore,themolarmassisidenticalforeachsubstance:
2molC=(2molC)
=24.02g
6molH=(6molH)
=6.05g
1molO=(1molO)
=16.00g
molarmassof(a)CH3OCH3or(b)CH3CH2OH=46.07g
94
ACSChemistryFROG
Chapter1
.1
2m
6
0
2
.0m
1
8
g
lolgC
o
H
O
2
.
1
0
7
9
g
1
6
.
0
m
o
l
H
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O
58.m
1
l032ga4cetm
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2
.
g
1gH
2O
Water:ANaturalWonder
Problem1.78.
(a)Thenumberofmoleculesofwaterinexactlyonemoleofwateris:
1molH2O=(1molH2O)
=6.0221023molecules
(b)Thenumberofgramsofwaterinexactlyonemoleofwateris:
1molH2O=(1molH2O)
=18.02g
Problem1.79.
(a)Themolarmassacetone,C3H6O,(totheuncertaintyofthismassdatum)is:
molarmass=(3molC)
+(6molH)
+(1molO)
=36.03g+6.05g+16.00g=58.08g
Thus,thenumberofmolesin100.0gofacetoneis:
100.0gacetone=(100.0gacetone)
=1.722molacetone
(b)Thenumberofmolesin100.0gofmethanol,CH3OH(orCH4O),is:
100.0gmethanol=(100.0gmethanol)
=3.121molmethanol
(c)Thenumberofmolesin100.0gofdimethylether,CH3OCH3(orC2H6O),is:
100.0gdimethylether=(100.0gdimethylether)
=2.171moldimethylether
(d)Thenumberofmolesin100.0gofsucrose,C12H22O6,is[seeCheckThis1.48(a)]:
100.0gsucrose=(100.0gsucrose)
=0.2921molsucrose
Problem1.80.
Thenumberofmoleculesinonegramofapuresubstanceisproportionaltothenumberof
molesofthesubstanceinonegram.Theunitconversionfactorisobtainedfromtherelationship
betweenmolesandmolecules:1mol=6.0221023molec.For1gram(assumedtobeanexact
valuetoatleastfoursignificantfiguresofuncertainty)ofwater(H2O),methanol(CH4O),
acetoneC3H6O),ethanol(C2H6O),anddimethylether(C2H6O),wehave:
1gH2O=
=3.3421022molec
ACSChemistryFROG
95
l325.804gC
1
m
o
.
6
0
2
H
O
3
6
m
o
l
6
.
0
2
4
6
.
0
7
g
C
2H
6O
ec
.
1
m
6
0
2
10oplm
1
2
0
p
1
3
5m
.
6
2
1
0
6().025
1130m
.0
6
2
kJ
Water:ANaturalWonder
Chapter1
1gCH4O=(1gCH4O)
=1.8801022molec
1gC3H6O=(1gC3H6O)
=1.0371022molec
1gC2H6O(ethanol)=(1gC2H6O)
=1.3071022molec
1gC2H6O(dimethylether)=1.3071022molec
Problem1.81.
Tofindthelengthofthelineformedbyamoleofargonatoms(eachwithadiameterof
approximately100pm)lineduponeafteranother,wehavetomultiplythenumberofatomsina
moletimesthediameterofeachatom(convertedtometers):
length=
=6.021013m
Togivealittleconcretemeaningtothislength,itcanbecomparedwiththedistancetoourSun:
1.51010m(=93millionmiles).Thepercentagethatthelengthofthelineofargonatomsisto
thedistancetothesunis:
%ofsundistance=
(100%)=4105%thedistancetoourSun
Anotherwaytostatethisresultistothinkaboutthenumberoftimesthelineofargonatoms
couldbefoldedbackandforthtomakeroundtripsfromtheEarthtotheSun.Ourlineofargon
atomswouldbeabletomakeabout2103
roundtripstotheSun!
Problem1.82.
(a)IfeachHatominicestoppedhydrogenbonding,alltheHbondswouldbegone.Anything
thatistrueofrelativenumbersofmoleculesisalsotrueofrelativenumbersofmolesofthose
molecules.EachHatomrepresentsoneHbond;eachmoleofHatomsrepresentsonemoleofH
bonds.Eachmoleculeofwater(ice)hastwoHatoms;eachmoleofwater(ice)hastwomolesof
Hatoms.Therefore,therearetwomolesofHbondsinonemoleofice.
(b)AssumethattheenergyrequiredtobreakHbondsisapproximately21kJ(molHbonds)1.
Further,assumethattheenergyrequiredtomeltice,6.02kJ(molice)1,isallusedtobreakH
bonds.ThenumberofmolesofHbondsbrokenbythismuchenergyisthen:
moleHbondsbroken=
96
ACSChemistryFROG
=0.29(molHbond)(molice)1
Chapter1
m
o
l
H
b
n
d
r
o
k
e
n
t
a
l
.
0
2
9
(m
l
)
o
n
d
Water:ANaturalWonder
Thus,0.29molofHbondsisbrokenwhenonemoleoficemelts.Sincetherearetwomolesof
Hbondsinamoleofice,thepercentageoftotalHbondsbrokenis:
%Hbondsbroken=
=
100%
100%=15%
Ourapproachhasbeentoassumethattheratiooftheenergyrequiredtomelticetotheenergy
requiredtobreakalltheHbondsintheicewouldgivethefractionofHbondsbrokeninthe
meltingprocess.Ourresultindicatesthatonly15%ofthetotalnumberofhydrogenbondsis
brokenwhenicemelts.ThatmeansmostoftheHbondsarestillpresenteventhoughthewater
haschangedfromasolidtoaliquid.Thisisoneoftheresultsthatleadstoanicecluster(or
iceberg)modelofliquidwater(seeProblem1.103).
Problem1.83.
Selfhydrogenbondingrequiresthatamoleculeofthecompoundhaveboth(1)anonbonding
pairofelectronsonanoxygenoranitrogenatomand(2)anOHorNHbond(orbonds).
Water(a),methanol(b),andethanol(d)canselfhydrogenbond,becausethemoleculesofeach
compoundhavetheseessentialfeaturesforhydrogenbonding.Acetone(c)anddimethylether(e)
moleculeslackOHbonds.(Theyarecapableofhydrogenbondingwithwaterorother
moleculeswithOHorNHbonds,butnotwiththemselves.)ThesolutiontoProblem1.56
showsthehydrogenbondingamongwatermolecules.Thehydrogenbondingamongmethanol
(andethanol)moleculesisshownhere:
EthanolislikemethanolwiththeCH3groupreplacedbyCH2CH3.
ACSChemistryFROG
97
Water:ANaturalWonder
Chapter1
Problem1.84.
Sincemoleculesofdimethylether(CH3OCH3)anddiethylether(CH3CH2OCH2CH3)cannot
hydrogenbondwiththemselves,intermolecularinteractionsarelimitedtodipoleattractionsand
dispersionforces.Onamolarbasis,bothethershaveanequalnumberofpolarCObonds.
Therefore,dipolarinteractionscannotberesponsibleforthe60Cdifferenceinboilingpoints.
Dispersionforces(induceddipoleinteractions)mustbethefactorlargelyresponsibleforthe
higherboilingpointofthelargerether,whichhas16moreelectronsthanthesmaller.
Problem1.85.
Dipoledipoleattractionsmustbeamajorcontributortotheforcesholdingacetonemolecules
togetherintheliquid.Becausetheacetonedipolemoment(2.88D)issomuchlargerthanthat
ofdimethylether(1.30D),thepolarattractionsaremuchstrongerbetweenacetonemolecules
anditsboilingpointis81degreeshigher.Thepresenceoftheextraatomofcarbonanditssix
electronscannotincreasetheinduceddipoleattractionsenoughtoaccountforsuchalarge
differenceinboilingpoints,althoughtheydocontributesometothedifference.Theenergyof
vaporizationforacetoneisintermediatebetweendimethyletherandethanol.Theethanoldipole
momentissmallerthanthatofacetone,butthehydrogenbondinginethanolraisesitsboiling
pointandenergyofvaporizationabovethoseofacetone.Althoughacetonehasamolarmass
thatislowerthanthatofhexane,itsenergyofvaporizationandboilingpointarecomparableto
hexane.Thedipoledipoleattractionsinacetone(withatotalofonly32electrons)addtothe
induceddipoleattractionsamongitsmoleculestomaketheattractionscomparabletothelarger
numberofinduceddipoleattractionsamonghexanemolecules(withatotalof50electrons).
Problem1.86.
Specificheatistheenergyrequiredtoraisethetemperatureof1gramofasubstanceby1C(or
1K).
Problem1.87.
Anintensivepropertyisindependentoftheamountofthesubstancepresent;examplesare
densityandtemperature.Anextensivepropertydependsontheamountofsubstancepresent;
examplesaremassandthermalenergy.
Problem1.88.
(a)Theboilingpointofwaterisanintensivequantity,sinceitisindependentoftheamountof
waterwehave.
(b)Thedensityofwaterisanintensivequantity,sinceitisindependentoftheamountofwater
wehave.Often,anintensivepropertycanbetheratiooftwoextensiveproperties.Density
(intensive),forexample,istheratioofmassandvolume(bothextensiveproperties).
(c)Thespecificheatofwaterisanintensivequantity,sinceitisindependentoftheamountof
waterwehave.
(d)Theratioofhydrogentooxygenatomsinasampleofwater(two)isanintensivequantity,
sinceitisindependentoftheamountofwaterwehave.
98
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
(e)The(maximum)solubilityofsaltinwaterisanintensivequantity,ifthesolubilityis
expressedasaratioofthequantityofsalttoastandardquantityofwater.Solubilityistypically
expressedasaratioofmass(ormoles)ofsubstancedissolvedtovolumeofsubstanceinwhich
itisdissolved(seeChapter2).Itisanextensivequantity,ifthesolubilityisexpressedsimplyas
thequantityofsaltdissolved,sincethentheamountofwaterwehavemakesadifference.
Problem1.89.
ToconverttC=37.0Ctokelvin,usetheconversionshowninthemarginalnoteonpage54
ofthetextbook:
37.0C=(37.0+273.15)K=310.2K
Problem1.90.
Thespecificheatofwaterisusedtocalculatetheamountofenergyrequiredtoincreasethe
temperatureofagivenmassofwaterbyagivenamount.Thespecificheatcanbeexpressedas
4.18Jg1C1or4.18Jg1K1,because1C=1K.Thethermalenergyrequiredtoraisethe
temperatureof1.0gramofwaterby:
(a)10.0Cis(4.18Jg1C1)(1.0g)(10.0C)=41.8J=42J
Thefinalresultisgiventoonlytwofigures,becausetheuncertaintyinthemassofwateris
about1partin10(10%),ifweassumethatthefinalplaceinitsnumericvalueisgoodtoabout
onedigit.
(b)25.0Cis(4.18Jg1C1)(1.0g)(25.0C)=104.5J=1.0102J
(c)25.0Kis(4.18Jg1K1)(1.0g)(25.0K)=1.0102J
Problem1.91.
Theuseofthespecificheatofwatertocalculatetheamountofenergyrequiredtoincreasethe
temperatureofagivenmassofwaterbyagivenamountisshowninProblem1.90.Herewe
calculatethethermalenergyrequiredtoraisethetemperatureoftwosamplesby10.0C.
(a)A10.0gsampleofwaterrequires(4.18Jg1C1)(10.0g)(10.0C)=418J
(b)A25.0gsampleofwaterrequires(4.18Jg1C1)(25.0g)(10.0C)=1.05103J
Problem1.92.
ThesameapproachasinProblems1.90and1.91isapplicablehere,usingthespecificheatof
1propanol,2.39Jg1C1,fromTable1.3inthetextbook.Thethermalenergyrequiredtoraise
thetemperatureof20.0gramsof1propanolby15.0Cis(2.39Jg1C1)(20.0g)(15.0C)=
717J.
Problem1.93.
Theairconditioningsystemdescribedinthisproblemisbasedontheprincipleofevaporative
cooling.Asthehotairflowsoverthemats,heatistransferredfromtheairmoleculestothe
water,theairlosesheatenergy,andthetemperatureoftheairfalls.Theheatenergytransferred
tothewatercausessomeofthewatertoevaporateintotheair.Theheatrequiredtovaporizethe
waterisquitesubstantial(recallthehighenergyofvaporizationofwater)soarelativelysmall
ACSChemistryFROG
99
Water:ANaturalWonder
Chapter1
amountofevaporationcanremovealotofheatfromtheair.Inareasoflowhumiditythis
systemwouldhavetheaddedadvantageofincreasingthehumidityintheairinthebuilding.
Converselyinregionsofhighhumiditythismethodofairconditioningmightnotbeas
advantageoussinceincreasingthehumiditycouldresultinincreasedlevelsofmoldandmildew
andmightcausedamagetosensitiveinstrumentationfromthedamp.Italsowouldntworkwell
inhighhumidity;
Problem1.94.
Evaporativecoolingshouldbemoreeffectiveondrydaysthanhumiddayssincetheamountof
waterthatcanevaporateintotheatmospheredependsupontheamountofwateralreadyinthe
atmosphere.Iftheresalotofwatertherealready,onahumiddayforexample,thentheamount
ofsweatthatcanevaporatewillberelativelylow.Thisisbecauseatagiventemperaturethe
atmospherecanonlyholdacertainamountofwater,onhumiddaystheatmosphereisnear
thissaturationlimit.(Ifthelimitisexceeded,watercondensesorprecipitatesoutoftheair.The
relativehumiditythatyourTVweatherpersontalksaboutisthepercentofwatertheair
containsrelativetothemaximumamountitcancontainatthattemperature.)Littlewaterwill
evaporateandthereforenotmuchevaporativecoolingwilloccur.
Problem1.95.
Ourmodelofliquidwatersaysthatheatenergyaddedtothewatermakesthemoleculesmove
faster(increasesthetemperature)andcausessomeHbondstobebroken.Thetemperaturerise
isnotaslargeasitwouldbeintheabsenceoftheHbondbreakingandthespecificheat(or
heatcapacity)ishighbecauseittakesmoreheattomakeagivenchangeintemperature.Heat
energyaddedtoiceattemperaturesbelow0C(sothesoliddoesnotmelt),breaksnoHbonds;
theenergyonlycausesthemoleculestomovefasterastheyvibrateandjiggleintheposition
theyareheldbytheirfourHbonds.Alltheenergyaddedgoestoraisingthetemperature
(increasingmolecularmotion);ittakeslessheattomakeagivenchangeintemperatureandthe
heatcapacityislowerthanforliquidwater.
Problem1.96.
ThehighheatcapacityofliquidwaterisreviewedinthesolutiontoProblem1.95.Gases
occupysomuchmorespacethanthesameamountofliquid,thatweeitherhavetoassumethat
themoleculesgetalotbiggerorthattheyarefarapartandprobablynotinteractingwitheach
otherverymuch.Gasesareallcompletelymiscible(theymixinanyproportion)withone
another,sothemodelthathasalotofemptyspacebetweenmoleculesseemstofitthisproperty
better.Ifthismodeliscorrect,thenwewouldexpectessentiallynoHbondsbetweenwater
moleculesinthegasphase.IftherearenoHbondsalltheheatenergyweputintothegasgoes
intoincreasingthespeedofmolecularmotion(temperature).Ittakeslessheatenergytomakea
givenchangeintemperatureandtheheatcapacityofthegasislessthanthatoftheliquid.Note
thattheheatcapacitiesofsolidandgaseouswateraresimilar(abouthalfthatofliquidwater,as
giveninthisproblemandinProblem1.95).Thissimilarityisfortuitous;themolecularmotions
involvedinthetemperaturechangesinthesolidandthegasaredifferent.Inthesolid,the
molecularmotionismainlyvibrationandrockinginplaceinthecrystal.Inthegas,themotions
aremainlytranslation(movementfromoneplacetoanother)androtation.
100
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
Problem1.97.
Athighertemperatures,watermoleculeshavegreaterenergyofmotionandfewerHbonds.It
takeslessenergytovaporizewateratahighertemperaturebecausetherearefewerHbondsto
break.Forwatermoleculestovaporizetheymustescapefromtheliquid.Themorehydrogen
bondsholdingthemintheliquidphase,themoreenergythisprocesswilltake.Inadditionto
understandingthedirectionofthisphenomenon,youshouldalsonoteitsmagnitude.Theheat
ofvaporizationdecreasesfromabout10.7kcalmol1at0Ctoabout9.7kcalmol1at100C.
Thisisonlya10%changeovertheentireliquidrange.Theplotshownwiththisproblemmight
givetheimpressionthatthechangeismuchlarger.Whatchoiceofscalewouldyouusetoshow
thatthechangeisactuallyarelativelysmallpercentageofthetotal?
Problem1.98.
TheexpressionslowasmolassesinJanuaryowesitstruthtoviscosity.Viscositymeasuresthe
resistanceoffluidstoflow.Thegreatertheviscosity,themoreslowlytheliquidflows.The
viscosityofaliquidusuallydecreasesastemperatureincreases.Therefore,molasseswouldflow
fasterinJunethanitdoesinJanuary.
Problem1.99.
[ThestickyendedmoleculesinthisproblemweredescribedinScience1997,278,658.]
(a)Thescaleonbothaxesofthefirstplotshownintheproblemislogarithmic.The
concentrationaxiscoversafactorof10inconcentration,whiletheviscosityaxiscoversafactor
of104(fromabout0.1to1000fortheexperimentalresultsshown).Theviscosityincreasesfrom
about.08toabout800onthisscale,whichisafactorof104.Asmoreandmoreofthesticky
endedmoleculesaredissolved,longerandlongerchainsofthemareformed.Thechainsattract
oneanotherbydipoleandinduceddipoleinteractionsandalsocanbecomeentangledwithone
another.Alltheseattractionsmakeitharderforthechainstomovepastoneanother,sothe
viscosityincreases.
(b)Forthesamereasonsthattheviscosityofwaterdecreaseswithincreasingtemperature,these
solutionsshouldshowdecreasingviscositywithtemperature.Thehydrogenbondingis
disruptedasthemoleculesbecomemoreenergeticandmovefaster.
(c)Thesecondplotintheproblemshowsthat,asthefractionofmoleculeswithonlyonesticky
endincreases,theviscositydecreases.Thereisacompetitionamongthestickyendsforone
another.Ifmoleculeswithtwostickyendshydrogenbondtooneanother,alongerchainis
formedthathasahigherviscosityandcouldaddmoredoubleendedmoleculestomakeeven
longerchains.But,ifamoleculewithonestickyendhydrogenbondstoamoleculewithtwo
stickyends,thechaincannolongercontinuetogrowattheendwherethebondingoccurs.As
moreandmoreofthemoleculespresenthaveonlyonestickyend,theprobabilitythatchain
growthwillbestuntedgrowsandthechainsaresmaller.Thesmallerchainsgivethesolutiona
lowerviscosity.Therapiddecreaseintheviscosityforrathersmallamountsofthesingleended
moleculeadded,showthatitdoesnttakemuchstuntingofthegrowthofthechainstohavea
largeeffectontheviscosity.
ACSChemistryFROG
101
Water:ANaturalWonder
Chapter1
Problem1.100.
Thedataforviscosityofheptane(lefthandplot)andforwater(righthandplot)areshown
togetherhereforeaseofcomparison.
Theaxesonbothplotsareidenticalasisthereferencepoint(viscosityat20C)fortherelative
viscosity.Therefore,theshapeandplacementofthetwocurvescanbedirectlycompared.The
viscosityofbothsubstancesdecreaseswithtemperature.Highertemperaturemeansmore
averageenergypermolecule;itiseasierforthemoleculestoovercometheattractionsbetween
themandthereforemovepastoneanothermorereadily.Thelowtemperaturerelativeviscosity
ofheptaneislowcomparedtowateranditsdecreasewithtemperatureislesspronouncedthan
forwater.Theattractionsamongheptanemoleculesareinduceddipoleinteractions(dispersion
forces),whicharerelativelyweaktobeginwithandremainaboutthesameasthetemperature
increasesthemotionsofthemolecules,sothereisarelativelygradualdecreaseinviscosity.The
relativeviscosityofwaterundergoesamuchsteeperdecreasewithtemperature.Thestronger,
moredirectedhydrogenbonds,thatareresponsibleformuchofthehighviscosityatlow
temperaturesaredisruptedathighertemperaturesandtheincreasedmotionofthewater
moleculesmakesthesedirectedbondslesslikelytoformathighertemperatures.Thus,thedrop
inrelativeviscosityforwaterismorethantwicewhatisobservedforheptane.
Problem1.101.
(a)Waterneedsheatfromyourskintoevaporate.Youexperienceacoolingeffectafterwalking
outoftheoceanontoawarm,sandybeach,especiallyonabreezyday,because,while
supplyingtheheatforwatertochangefromaliquidtoagas,youfeelacoolingeffectonyour
skin.
(b)Themoleculesinliquidsareattractedtooneanotherandstayclosetogether,whichis
similartothewaytheybehaveinsolids.Butdescribingaliquidasa"disordered"solidcouldbe
abitmisleading,becausethismightcauseustothinkthatthemoleculesintheliquidremain
prettymuchinthesamelocation(althoughtumblingaboutandnotasfirmlyattractedtoone
another),astheydointhesolid.However,themoleculesinliquidsarefreetomovearound
fromplacetoplaceanywhereinthevolumetheyoccupy,whilestillstayingclosetogether.
(c)Thefactthatthemoleculesinaliquidcanmovearoundfromplacetoplacemakesthem
similartogases.Themoleculesingasesareveryfarapart,movingessentiallyindependentlyof
102
ACSChemistryFROG
Chapter1
Water:ANaturalWonder
oneanother.Sincetherearemanymoremoleculesinagivenvolumeofaliquidcomparedto
thesamevolumeofagas,liquidsmightbedescribedas"densegases.Thiscouldbeabit
misleading,ifweareledtothinkthatthemoleculesintheliquidareasindependentofone
anotherastheyareinthegasphase.Theattractionsbetweenmoleculesintheliquidhavetobe
reasonablylarge,inordertokeepthemintheliquidphase.
(d)Solidwater(ice)floatsonliquidwaterbecausethedensityofliquidwaterisgreaterthanthe
densityofice.Therelativelyopenstructureofthehydrogenbondednetworkofwater
moleculesiniceoccupiesalargervolumethanthesamemoleculesintheliquidphasewhere
someofthehydrogenbondshavebroken.Thus,iceislessdense(lessmatterinagivenvolume)
thanliquidwater.
(e)Duringcondensationofagastoaliquid,agreatdealofenergyisreleasedtothe
surroundings.Thisiswhyyoucanbebadlyburnedbysteam,ifitcondensestowateronyour
skin.
(f)Whenlakesfreezeduringthewinter,icecoversthetopoftheliquidwater.Sinceiceisless
densethanliquidwater,icefloatsanddoesnotfalltothebottomofthelake.Thus,toform
more(thinker)iceheatmustleavethelayerofwaterjustbeneaththesurfaceice.Solidiceisa
prettygoodthermalinsulator,sothisisaslowprocessandonlyveryshallowbodiesofwater
(likeiceskatingrinks,whicharecooledfromthebottomtoavoidtheinsulatoreffect,or
puddles)freezecompletelytothebottom.
(g)Whenwaterfreezesinpipes,theiceexpandsduetothelargervolumeoficecomparedto
liquidwater[seepart(d)].Thiscausesthepipestobreak.SeeConsiderThis1.2(b)andtheWeb
Companion,Chapter1,Section1.1,page3.
Problem1.102.
[Keepabottleofwateratyourdeskandtakefrequentsipsfromit.Onethirdofwateris
oxygen,sodrinkingitwillhelpkeepyoualert,isfromWorkingSmart,Vitality,October
1997(VitalityInc.,Dallas,TX),asquotedinaChemical&EngineeringNews,Newscripts
column.]
Thisisnotaprofoundproblem,butisdesignedtosuggestbeingonthelookoutfor
extraordinaryclaimslikethisone.Onanatombasis,onethirdoftheatomsinwaterareoxygen,
sothetextiscorrectinoneway.Itseemsthattheclaimissomethingaboutthealertness
enhancingqualitiesofoxygen.Youdoneedoxygenmoleculesfromtheairtokeepyour
metabolismgoingandyougettiredmoreeasily,iftheoxygenleveldropssomewhat.(Thats
whyyoufeelstresswhenexertingyourselfathighaltitude,beforeyourbodyacclimatestothe
lowerpressureofairand,hence,ofoxygenintheair.)Theoxygenatomsinwaterare,however,
totallyunavailableforyoutouseinmetabolism.Theyareboundinverystablemolecules.The
bestonecansayaboutthisclaimisthatitcanthurttodrinksomewateranditisfree(unless
youaredrinkingdesignerwatersfromthesupermarketorothervendingsource),thatis,
nothingisbeingsoldhere.
Problem1.103.
[ThedataforthisproblemarefromScience1997,278,658.]
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(a)Theicebergmodelforliquidwaterhassomeofthewatermoleculeshydrogenbondedin
molecularscaleicelikestructureswiththewatermoleculesheldinplaceinthenetworkofH
bondsandothersthatarelessorderlyandmoremobilewithfewerHbondstoholdthemwith
respecttooneanother.Itmakessensethatorderlyanddisorderlywaterstructureswouldbehave
differentlyintermsoftheirabilitytorandomizetheorientationtheyhavebeengivenbythe
experimenters.
(b)Sincethewatermoleculeslockedinanicelikestructurecannotmoveabout
independently,theirmotionsareprobablymoreinhibitedandtakelongertoregainamore
randomorientation.Thus,wewouldexpecttheshorterrandomizationtimetobecharacteristic
ofthelessorderly,moremobilemoleculesandthelongertimecharacteristicofthemoleculesin
theicelikestructures.
(c)Notethatthetimescalesofthechangesobservedherearepicoseconds,1012s.The
moleculesundergoreorientations,whichmeansbreakingsomehydrogenbondsandmaking
othersinaveryshorttime.Averagedoverobservationtimesontheorderofseconds(our
everydaycontactswithwater),suchrapidchangesmakeitimpossibleforustodetectany
differencesamongthemoleculesorpossiblerapidlyinterchangingstructuresintheliquid.Only
cleverexperiments(andcalculations)willenableustogetbetterpicturesofthenatureofliquid
water.
Problem1.104.
(a)Thefactthataheliumfilledballoonwillriseinairsuggeststhatheliumisagooddealless
densethanair(whenbothareatthesametemperatureandpressure).Tobebuoyedupinafluid,
anobjecthastodisplaceavolumeofthefluidwhosemassisgreaterthanthemassoftheobject.
Inthiscasethevolumeofairdisplacedisthevolumeoftheballoonandthemassoftheobject
isthemassoftheheliumplusthemassoftherubberintheballoon,whichissubstantial.In
orderthattheheliumplusrubberhasamasslessthanthedisplacedair,theheliummusthavea
massthatismuchlessthanthemassofthedisplacedair.Heliummustbeagooddeallessdense
thanair.
(b)Thefactthatahotairballoonwillrisein(colder)airsuggeststhathotairislessdensethan
coldair(whenbothareatthesamepressure).Thereasoningisthesamehereasitisinpart(a).
Inthiscase,asyouprobablyknow,ahotairballoonisquitelargecomparedtothebasketor
gondolainwhichthepassengersride.Itrequiresaverylargevolumeofhotairtodisplacea
massofcoolerairlargerthanthetotalmassoftheobject(hotairplusballoonandgondola).Hot
airislessdensethancoolerair(atthesamepressure),butnotagreatdeallessdense.
(c)Thefactthataballoonfilledwithcarbondioxidewillsinkinairsuggeststhatcarbondioxide
iseithermoredensethanair(whenbothareatthesametemperatureandpressure)oris
comparableindensity.Theargumentinpart(a)showsthatthesinkingballoonpluscarbon
dioxidehasmoremassthantheairitdisplaces.Theballoonitselfhasasubstantialmass,soifit
isinflatedwithagasthathasthesamedensityasair,thecombinedmassoftheballoonandthe
airinsidewillbegreaterthanthemassoftheairitdisplacesanditwillsink.(Youprobably
knowthataballoonyoublowupwithyourexhaledair,whichhasessentiallythesamedensity
astheairyouinhale,willnotfloat,butsinks,ifyouletitgo.)Thus,thebestwecanconclude
aboutthedensityofcarbondioxideisthatitissimilartothatofairorpossiblygreater.(Infact,
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carbondioxideismoredensethanairaballoonfilledwithairwillriseinanatmosphereof
carbondioxideatthesametemperatureandpressurebuttheobservationpresentedinthis
problemdoesnotprovideenoughinformationtodrawthisconclusion.)
Problem1.105.
IfanastronautstandingontheMoonletgoofaheliumfilledballoon,itwouldbepulledby
gravitytothesurface.AheliumballoononEarthrisesbecauseitfloatsonthemoredense
gasesoftheEarthsatmosphere[seeProblem1.104(a)].Sincethereisnoatmosphereonthe
Moon,thereisnothingfortheheliumballoontofloatuponorin.
Problem1.106.
(a)The(FHF)Lewisstructure,
F H F
,showstheHatomiccoreapparentlysharingtwo
pairsofelectronsequallywithtwodifferentFatomiccores.TheHatomiccoreusuallyshares
onlyonepairofelectronswithanotheratomiccore,or,inotherHbonds,weshowthesharing
withasecondpairasdifferentandweakerthaninitscovalentbond.
(b)In(FHF),thehydrogenatomiccoreisequidistantfromthetwoelectronegativefluorine
atomiccoreswhichithydrogenbondstogetherwitharatherhighbondenergy.Inthehydrogen
bondbetweentwowatermolecules,thebondfromtheHatomiccoretooneOatomiccoreisa
strongcovalentbondwiththebondingpairsharedsomewhatequallybytheOandHatomic
cores.Thebondtotheotheroxygenisabouttwiceaslongandquiteweak,withthenonbonding
pairofelectronsstilllargelyassociatedwiththeOatomiccore.The(FHF)ionislikelytobe
linear,aswehavesaidthestrongestOHObondsareaswell.Inwatertheformationofthe
hydrogenbondstretchesthecovalentbondfrom94to100pmandtheHbondtotheother
oxygenhasabondlengthof180pm.Inthe(FHF)ion,thecovalentbondfromFtoHinHFis
stretchedfrom93to113pm,whichisquiteabitmorethanforthewatermolecule.Thelength
ofthebondtothesecondFatomiccore,however,isalso113pm,whichissubstantiallyshorter
thanthecorrespondingbondinwaterandisassociatedwiththehighbondenergyforformation
ofthisbondbetweenHFandF.Thedistancebetweenthesecondperiodatomiccentersinthe
waterhydrogenbondis280pm.Thecorrespondingdistancein(FHF)is226pm,whichisvery
muchsmallerandis,again,areflectionofthehighbondenergy.Bondinginthe(FHF)ion
certainlydoesblurthedistinctionbetweenahydrogenbondandacovalentbond.Sincethe
bondsbetweentheHatomiccoreandtheFatomiccoresareidenticalinthision,thereisno
waytotellwhichis(orwas)thecovalentbondandwhichisthehydrogenbond.Thedistinction
makesnosenseforthisionandsuggeststhatthereisacontinuumofbondinginteractionsfrom
weakinduceddipoleinteractionstostrongcovalentbonds.
7
0
Problem1.107.
(a)Assumea70kg(approximately150pound)person.Themolesandmoleculesofwaterin
thisperson(70%water)are:
molH2O=(0.7)
=2.7103molH2O
molecH2O=(2.7103molH2O)(6.021023molecmol1)=1.61027H2Omolec
ACSChemistryFROG
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Chapter1
(b)If2440Oatoms(=numberofNatoms)areincompoundsotherthanwater,then23230(=
256702440)Oatoms(outofevery100000atoms)arepresentinwater.
(c)Frompart(b)weknowthat23230atomsofOarepresentasH2Omoleculesforevery
100000atomsinthebody.Frompart(a)weknowthenumberofmoleculesofH2Ointhebody,
sowecangetthetotalnumberofatomsinthebodyas:
total#atoms=
(1.61027molec)=6.91027atoms
TogetthenumberofatomsofNandC,wetakethefractionofatomsthatareNandCtimesthe
totalnumberofatoms:
atomsN=
molN=
(6.91027atom)=1.71026atom
=2.8102mol
atomsC=
molC=
(6.91027atom)=7.41026atom
=1.2103mol
Graphics
are
QuickTime
needed
decompressor
toand
seeathis picture.
Problem1.108.
(a)Aplotofthedatagivenintheproblemlookslikethis:
45
40
35
30
25
20
15
10
5
10 20 30 40 50 60 70 80
electrons/molecule
0
Theequationfortheline(computergenerated)is:
vaporizationenergy=(0.49kJmol1electron1)(#electrons)+7.3kJmol1
Sincedecanehas82electrons,thisequationgivesitsvaporizationenergyas:
vaporizationenergy=(0.49kJmol1electron1)(82electrons)+7.3kJmol1
=47kJmol1.
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(b)EachCH2groupaddseightelectronsandlengthensthehydrocarbonchainsothatmore
electronsandmoresurfaceareaareavailablefordispersionforce(induceddipole)attractions.
Theincreaseofeightelectronsaddsabout4kJmol1[=(8electron)(0.5kJmol1electron1);
fromtheslopeoftheline)foreachCH2groupadded.
(c)Dimethylether,withavaporizationenergyof23kJmol1,has26electronsandissimilarin
thisregardtopropane,whichhasavaporizationenergyof20kJmol1.Wemightattributethe
extra3kJmol1energyofvaporizationfortheethertodipolarattractionduetothepermanent
electricdipoleofthemolecule.
(d)Diethylether,withavaporizationenergyof29.1kJmol1,has42electronsandissimilarto
pentanewithavaporizationenergyof28kJmol1.Wefoundinpart(c)thatanethermighthave
anextra3kJmol1energyofvaporizationattributabletodipolarattraction,sowemightpredict
anenergyofvaporizationof31kJmol1fordiethylether.Itappearsthatthisisanover
correctionfortheetherwithlargeralkylgroups,whichmightinterferewiththemolecules
abilitytoorientasreadily.Thebutanol,withavaporizationenergyof45.9kJmol1,alsohas42
electronsandwewouldagainexpectacontributionof28kJmol1totheenergyofvaporization
fromdispersionforces.Inaddition,thealcoholcanformhydrogenbondsandthese,according
toourtextualanalysisofthedatainTable1.2mightcontributeanadditional22kJmol1tothe
energyofvaporization,foratotalof50kJmol1.Again,ourpredictionisoffbyabout8%,but
thisisquitegoodagreementconsideringthesimplicityofourassumptionsandthemodels.
Problem1.109.
(a)Thepicturesofourthreemoleculesare:
Theredarrowsshowtherelativesizeanddirectionofthepermanentdipolemomentsforthese
molecules.
(b)Thebonddipolesareprobablyapproximatelyproportionaltothedifferencein
electronegativitybetweentheatomsateachendofthebondanddirectedtowardthemore
electronegativeatom.TheelectronegativitydifferencefortheNHbondsis0.8andthebond
dipolepointstowardtheN.ForNF,theelectronegativitydifferenceis1.0andthebonddipole
pointstowardtheF.ForNCl,theelectronegativitydifferenceis0.2andthebonddipolepoints
towardtheCl.TheNClbonddipolesarequitesmallandpointeddowntowardthebaseofthe
molecule.Thesebonddipolescombinetogiveacontributiontothemoleculardipolethatis
oppositeinthedirectiontowhatisobservedexperimentally.Wewillhavetoseekanother
sourceforthedirectionoftheNCl3moleculardipolemoment,andthedatafortheother
moleculesmighthelpusfindit.TheNHandNFbonddipolesareapproximatelyequalin
magnitude(theelectronegativitydifferencesaresimilar),butoppositeindirection.Inthe
absenceofotherfactorsaffectingthemoleculardipolemoment,wewouldexpectthatNH3and
NF3wouldhaveapproximatelythesamedipolemoments,butinoppositedirections,as
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Water:ANaturalWonder
Chapter1
observed.However,thedipolemomentofNH3ismorethansixtimeslargerthanthatofNF3.
Onepossibleexplanationfortheseresultsisthatthereisanotherlargecomponentofthe
moleculardipolemomentthatisinthedirectiontowardthetopofthemolecules.This
componentwouldaddtotheNHbonddipolestocreatealargedipolemomentintheobserved
direction.ThiscomponentwouldpartiallycounterbalancetheNFbonddipolesand
substantiallyreducethenetmoleculardipolemoment,butleavethedirectiontowardthebaseof
themolecule,asobserved.Whatmightthiscomponentbe?
(c)Thepartofthestructuresthatiscommontoallthreemoleculesisthenonbondingpairof
electronsonthenitrogenatom.Thesewillhelptomakethechargedistributionunsymmetric
andskewedtowardanegativeregionatthetopofthemolecule.Perhapsthesenonbonding
electronsarethecomponentofthemoleculardipolemomentwehavepostulatedinpart(b).A
crudecalculationcanhelpusseewhetherthismightbethecase.Letxbethetotalcontribution
ofthethreeNHbonddipolestothemoleculardipolemomentinNH3andletxbethetotal
contributionofthethreeNFbonddipolestothemoleculardipolemomentinNF3.This
assumesthatthesizeoftheNHandNFbonddipolesisthesame,butinoppositedirections.
Letybethecontributionofthenonbondingelectronpaironthenitrogenatom.Thus,wecan
write,x+y=1.47Dandx+y=0234D.Ifweaddthesetwoequationsandsolvethe
resultingequationfory,wegety=0.62D,and,hence,x=0.85D.Ifweletzbethetotal
contributionofthethreeNClbonddipolestothemoleculardipolemomentinNCl3,then
z+y=0.39D,andz=0.23D.Thisvalueforzisaboutonefourththesizeofx,whichis
consistentwiththemuchsmallerelectronegativitydifferencebetweenNandClcomparedtoN
andHorNandF.Thisexplanationbasedonthecontributionsofthebonddipolesandthe
nonbondingelectronpaironthenitrogenatomhangstogetherandisinternallyconsistent.The
implicationisthatthenonbondingelectronsontheFandClcontributelittletothedipole
momentsofthemolecules.Muchmoresophisticatedmodelsandcomputermodelingare
requiredtosortoutallthefactors,butitislikely,giventheexperimentaldata,thatthe
nonbondingelectronpaironthenitrogenatomwillalwaysturnouttocontributeagooddealto
theoverallmoleculardipolemoments.
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