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ChemicalPropertiesof
Water

ChemicalPropertiesofWater

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ChemicalStructure

Waterisaspecialchemicalsubstanceconsistingoftwoatomsofhydrogenandoneatomof
oxygen.
OHbondlength=95.7picometers
HOHangle=104.5
OHbondenergy=450kJ/mol
Dipolemoment=1.83debyes
Thehydrogenatomsare"attached"toonesideoftheoxygenatom,resultinginawatermolecule
havingapositivechargeonthesidewherethehydrogenatomsareandanegativechargeonthe
otherside,wheretheoxygenatomis.
Sinceoppositeelectricalchargesattract,watermoleculestendtoattracteachother,
makingwaterkindof"sticky."
Thesidewiththehydrogenatoms(positivecharge)attractstheoxygenside(negativecharge)
ofadifferentwatermolecule.
Thewatermoleculemaintainsabentshapebecauseoftwoconsiderations:
1.Thetetrahedralarrangementaroundtheoxygen.
2.Thepresenceoflonepairelectronsontheoxygen.
Twoelectronsnotinvolvedinthecovalentbondsarecalledlonepairelectrons.
Thepairsofelectronsareleftalone.
Theselonepairsareverynegativecontainingtwonegativeelectronseachandwantto
stayawayfromeachotherasmuchaspossible.
Theserepulsiveforcesacttopushthehydrogensclosertogether.Thenetresultisa
terahedralarrangement.
Tetrahedralmeans"foursided".Itisthearrangementoffouratomsaroundacentralatom
suchthatthedistancebetweenthemismaximized.
Thearrangementadoptedwillbetheformofaregulartetrahedron.
Ithasregularbondanglesof109.5.
Ifwedoasimilararrangementofwater,puttingoxygeninthecenter,andusingthe
twohydrogensandtwolonepairsatthecorners,wealsocomeupwithatetrahedral
arrangement.
However,thereisoneimportantdifferencethebondanglesforwaterare
not109.5.Becauseofthepresenceoftheverynegativelonepairelectrons,
thetwohydrogensaresqueezedtogetherasthetwolonepairstrytogetaway
fromeachotherasfaraspossible.Theresultinganglegiveswatera104.5bondangle.
Becausewedon't"see"theelectrons,theresultingtetrahedron"looks"BENT

LinksbetweenChemicalStructureandPhysicalProperties
Twootherfeaturesofthewatermoleculearealsoimportantforitsproperties
#thesmallsizeofmolecule
#themoleculeisstronglydipolar.
Thispropertymakeswateraneffectivesolvent,particularlyforcrystallinesalts.
Thesmallsizeofhydrogenatomsmakesitpossibleformoleculesofwatertoeffectively
bondtogetherorchemicallyassociate,particularlyatlowertemperatures.
Thisgiveswateritssurfacetensionandliquidpropertiesandalsogiveswaterit'sunique
physicalproperties[linkhere].
However,wateralsopartiallydissociatesintoveryminuteconcentrationsofacid
[H3O+]andbase[OH]ions,acharacteristicwhichleadstotheuseofthepHscale
tomeasurerelativeacidityoralkalinity.ThisalsohelpsindissolvingionsandtransportingH+ions.

MajorChemicalPropertiesofWater
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Polarity
Twoatoms,connectedbyacovalentbond,mayexertdifferentattractionsfortheelectronsofthe
bond.Insuchcasesthebondispolar,withoneendslightlynegativelycharged()andtheother
slightlypositivelycharged(+).
Althoughawatermoleculehasanoverallneutralcharge(havingthesamenumberofelectronsand
protons),theelectronsareasymmetricallydistributed,whichmakesthemoleculepolar.
Theoxygennucleusdrawselectronsawayfromthehydrogennuclei,leavingthesenucleiwitha
smallnetpositivecharge.Theexcessofelectrondensityontheoxygenatomcreatesweakly
negativeregionsattheothertwocornersofanimaginarytetrahedron.
Waterstructurehydrogenbonds
Becausetheyarepolarized,twoadjacentH2Omoleculescanformalinkageknownasahydrogen
bond.Hydrogenbondshaveonlyabout1/20thestrengthofacovalentbond.
Ahydrogenbondisthereforeaweakchemicalbondbetweenahydrogenatominonepolar
moleculeandaveryelectronegativeatomofasecondpolarmolecule.
Thehydrogenofonewatermoleculewillbeattractedtotheoxygenofanotherwatermolecule.
Theareusually48moleculespergroupinliquidwater.
Thesurfacetensionofwaterisduetothehydrogenbondingintheassociatedgroupsof
watermolecules.
Hydrogenbondsarestrongestwhenthethreeatomslieinastraightline.
Thecohesivenatureofwater,throughthehydrogenbondingandthesmallsizeofthemolecule,
allowingthemoleculestopacktogether,isresponsibleformanyofitsunusualproperties,
suchashighsurfacetension,specificheat,andheatofvaporization.
Moleculesofwaterjointogethertransientlyinahydrogenbondedlattice.
Evenat37oC,15%ofthewatermoleculesarejoinedtofourothersinashortlivedassembly
knownasa"flickeringcluster."

Hydrophylic('WaterLoving')andHydrophobic('WaterHating')Molecules
HydrophylicMolecules
Substancesthatdissolvereadilyinwateraretermedhydrophilic.
Theyarecomposedofionsorpolarmoleculesthatattractwatermoleculesthroughelectrical
chargeeffects.
Watermoleculessurroundeachionorpolarmoleculeonthesurfaceofasolidsubstanceand
carryitintosolution.
Ionicsubstancessuchassodiumchloridedissolvebecausewatermoleculesareattractedto
thepositive(Na+)ornegative(Cl_)chargeofeachion.
Polarsubstancessuchasureadissolvebecausetheirmoleculesformhydrogenbondswiththe
surroundingwatermolecules.
HydrophobicMolecules
Moleculesthatcontainapreponderanceofnonpolarbondsareusuallyinsolubleinwater
andaretermed'hydrophobic'.Thisistrue,especially,ofhydrocarbons,whichcontain
manyCHbonds.
Watermoleculesarenotattractedtosuchmoleculesasmuchastheyaretootherwater
moleculesandsohavelittletendencytosurroundthemandcarrythemintosolution.
Butthesocalled'HydrophobicEffect'doesnotmeanthatnonpolarmoleculesarenot
attractedtowater!
Wehaveallseenwhathappensaftervinegarandoilsaladdressingarevigorouslyshaken
onedoesgetamixtureofsorts,butafteralittletimetheingredientsseparatewith
thelighteroilontopandadenservinegar/watersolutiononbottom.
Thisisanillustrationofanimportantchemistryprincipleexpressedbytherule
that'likedissolveslike.'Thisreferstothephenomenathatwhentwoliquidsmade
ofmoleculesofsimilarsizeandpolaritiesaremixed,theywillusuallyformasingle
phasesolution,nomatterwhattherelativenumberofmolesofeachspecies.
Thisisexpressedbythejargonthatthetwosubstancesaremiscibleinallproportions.
Incontrast,whenahighlypolarsubstance,suchaswater,ismixedwithanonpolaror
weaklypolarsubstance,suchasmostoils,thesubstanceswillseparateintotwophases.
Thisphenomenonisusuallyrationalizedinintroductorychemistrytextbooksbysaying
thatoilishydrophobic,andthusdoesnotmakesolutionswithwater,whilepolarsmall
organicacids(suchasaceticacidfromwhichhousevinegarismade)arehydrophilic,
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andthusaremisciblewithwater.
Thisexplanationalmostuniversallyleadspeopletobelievethatindividualwaterandoil
repeleachother,oratleastattracteachotherveryweakly.
Nothingcanbefurtherfromthecase!
Anindividualoilmoleculeisattractedtoawatermoleculebyaforcethatismuch
greaterthantheattractionoftwooilmoleculestoeachother.
Wecanobservetheconsequenceofthisgreaterattractionwhenweputadropofoilona
cleansurfaceofwater.
Beforehittingthesurface,theoilwillbeintheshapeofasphericaldroplet.
Thisisbecausetheoilmoleculesareattractedtooneanotherandasphericalshape
minimizesthenumberofoilmoleculesthatarenotsurroundedbyothermolecules.
Whentheoilhitsthesurfaceofthewater,itspreadsouttoformathinlayer.
Thishappensbecausetheattractionsbetweentheoilandwatermoleculesgainedbyspreading
overthesurfaceislargerthantheoiloilattractionlostinmakingalargeoilsurfaceon
topofthewater.
Ifasufficientlysmalldropofoilisputonthesurface,itwillspreadtoformasingle
molecularlayerofoil.
Bymeasuringtheareaproduced,onecangetasimpleestimateforthesizeofeachoil
moleculeandthusAvogadro'snumber.
Giventhesestronginteractions,whydoesnoteachoilmoleculediveintothewatersolution?
andsurrounditselfwiththefavorablewaterattractions?
Thereasonisthattodoso,itmustcomebetweenwatermoleculesthatarealready
attractingeachother!
Thestrengthofwaterwaterattractionismuchhigherthanwateroilinteractions,and
thusthereisanetcostofenergyinputtingtheoilmoleculesintoawatersolution.
Thusthevastmajorityofoilmoleculesstayoutofthewater,thoughasmanyaswill
fitwillhangontothesurfacewatermoleculesthatdonothaveafullcomplementofpartners.
Themeniscusisthecurvedsurfaceofaliquidinagraduatedcylinderoranyother
smalldiameterglassware.Wateradherestothesidesofanycontainercreatinga"cup"
ofsurfacetension.
Thisinducedstructureisveryimportantisitrelatedtothestructureandfunction
ofmembraneswhichareverycharacteristicoflifeasweknowit.
Membranesinbacteriaarecomposedofphospholipidsandproteins.Phospholipidscontaina
chargedorpolargroup(oftenphosphate,hencethename)attachedtoa3carbonglycerol
backbone.Therearealsotwofattyacidchainsdanglingfromtheothercarbonsofglycerol.
Thephosphateendofthemoleculeishydrophilicandisattractedtowater.Thefatty
acidsarehydrophobicandaredrivenawayfromwater.
Becausephospholipidshavehydrophobicandhydrophilicportions,theydoremarkablethings.
Whenplacedinanaqueousenvironment,thehydrophobicportionssticktogether,asdo
thehydrophilic.Averystableformofthisarrangementisthelipidbilayer.
Thiswaythehydrophobicpartsofthemoleculeformonelayer,asdothehydrophilic.
Lipidbilayersformspontaneouslyifphospholipidsareplacedinanaqueousenvironment.
Thecytoplasmicmembraneisstabilizedbyhydrophobicinteractions(i.e.waterinduced)
betweenneighboringlipidsandbyhydrogenbondsbetweenneighboringlipids.Hydrogen
bondscanalsoformbetweenmembraneproteinsandlipids.Theseareknownasmembrane
vesiclesandareusedtostudymembranepropertiesexperimentally.Thereissome
evidencethatthesestructuresmayformabioticallyandmayoccuronparticlesthat
raindownonearthfromspace.

WaterasaSolventAcids&BasespHHydration
WaterasaSolvent
Manysubstances,suchashouseholdsugar,dissolveinwater.Thatis,theirmoleculesseparate
fromeachother,eachbecomingsurroundedbywatermolecules.
Whenasubstancedissolvesinaliquid,themixtureistermedasolution.
Thedissolvedsubstance(inthiscasesugar)isthesolute,andtheliquidthatdoesthe
dissolving(inthiscasewater)isthesolvent.
Waterisanexcellentsolventformanysubstancesbecauseofitspolarbonds.
Acids
Substancesthatreleasehydrogenionsintosolutionarecalledacids.
Manyoftheacidsimportantinthecellareonlypartiallydissociated,andtheyare
thereforeweakacidsforexample,thecarboxylgroup(COOH),whichdissociatestogive
ahydrogenioninsolution.Notethatthisisareversiblereaction.
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Bases
Substancesthatreducethenumberofhydrogenionsinsolutionarecalledbases.
Somebases,suchasammonia,combinedirectlywithhydrogenions.
Otherbases,suchassodiumhydroxide,reducethenumberofH+ionsindirectly,by
makingOHionsthatthencombinedirectlywithH+ionstomakeH2O.
Manybasesfoundincellsarepartiallydissociatedandaretermedweakbases.
Thisistrueofcompoundsthatcontainanaminogroup(NH2),whichhasaweak
tendencytoreversiblyacceptanH+ionfromwater,increasingthequantityoffreeOHions.
HydrogenIonexchange
Positivelychargedhydrogenions(H+)canspontaneouslymovefromonewatermoleculeto
another,therebycreatingtwoionicspecies.
Sincetheprocessisrapidlyreversible,hydrogenionsarecontinuallyshuttlingbetween
watermolecules.Purewatercontainsasteadystateconcentrationofhydrogenionsand
hydroxylions(both107M).
pH
TheacidityofasolutionisdefinedbytheconcentrationofH+ionsitpossesses.
ForconvenienceweusethepHscale,wherepH=_log10[H+].
Forpurewater[H+]=10_7moles/liter

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