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WaterChemistry

Waterisanunusualcompoundwithuniquephysicalproperties.
Asaresult,itsthecompoundoflife.Yet,itsthemostabundant
compoundinthebiosphereofEarth.Thesepropertiesare
relatedtoitselectronicstructure,bonding,andchemistry.
However,duetoitsaffinityforavarietyofsubstances,ordinary
watercontainsothersubstances.Fewofushasused,seenor
testedpurewater,basedonwhichwediscussitschemistry.
Thechemistryofwaterdealswiththefundamentalchemical
propertyandinformationaboutwater.Waterchemistryis
discussedinthefollowingsubtitles.
Compositionofwater
Structureandbondingofwater
MolecularVibrationofwater
Symmetryofwatermolecules
Formationofhydrogenbondinginwater
Structureofice
Autoionization
Levelingeffectofwaterandacidbasecharacters
Amphiproticnature
Reactivityofwatertowardsalkalimetalsalkalineearthmetalshalogenshydridesmethaneoxides
andoxygenions.
Electrolysisofwater

Compositionofwater
Waterconsistsofonlyhydrogenandoxygen.Bothelementshavenaturalstableandradioactiveisotopes.
Duetotheseisotopes,watermoleculesofmassesroughly18(H216O)to22(D218O)areexpectedtoform.
IsotopesandtheirabundancesofHandOaregivenbelow.Fromthesedata,wecanestimatetherelative
abundancesofallisotopicwatermolecules.
Abundances(%orhalflife)ofhydrogenandoxygenisotopes
2D
3T
H
99.985% 0.015% 12.33y
14O

15O

16O

17O

18O

70.6s

122s
99.762% 0.038% 0.200%
Relativeabundanceofisotopicwater

H216O

H218O

H217O

99.78%
18

0.20%
20

0.03%
19

16
HD16O D2 O
HT16O
0.0149% 0.022ppm trace
19
20
20amu

ThepredominantwatermoleculesH216Ohaveamassof18amu,butmoleculeswithmass19and20occur
significantly.Becausetheisotopicabundancesarenotalwaysthesameduetotheirastronomicalorigin,The
isotopicdistributionofwatermoleculesdependsonitssourceandage.Itsstudyislinkedtoothersciences.
(SeeDojlido,J.R.&Best,G.A.(1993)ChemistryofWaterandWaterPollution,EllisHarwoodforisotopic
distributionofwater.)
Inparticular,D216Oiscalledheavywater,anditisproducedbyenrichmentfromnaturalwater.Propertiesof
heavywaterareparticularlyinterestingduetoitsapplicationinnucleartechnology.

Structureandbondingofthewatermolecule
Purewater,H2O,hasauniquemolecularstructure.TheOHbondlengthsare0.096nmandtheHOHangle
=104.5.Thisstrangegeometrycanbeexplainedbyvariousmethods.
Fromcarbontoneon,thenumbersofvalenceelectronsincrease
from4to8.Theseelementsrequire4,3,2,1,and0Hatomsto
shareelectronsinordertocompletetheoctetrequirement.Their
Lewisdotstructuresareshownontheright,andnotethetrendin
bondlengths.
Therearesixvalanceelectronsontheoxygen,andoneeachfrom
thehydrogenatominthewatermolecule.Theeightelectronsform
twoHObonds,andlefttwolonepairs.Thelongpairsandbonds
stayawayfromeachotherandtheyextendtowardsthecornersof
atetrahedron.SuchanidealstructureshouldgiveHOHbond
angleof109.5,butthelonepairsrepeleachothermorethanthey
repeltheOHbonds.Thus,theOHbondsarepushedcloser,
makingtheHOHanglelessthan109.

LewisDotStructures
HH
||""
HCHHN:HO:HF:
|||
HHH"
CH3NH3H2OHF
Bondlength/pm
CHNHOHHF
1091019692

Aftertheintroductionofquantummechanics,theelectronic
configurationforthevalenceelectronofoxygenare2s22p4.
Sincetheenergylevelsof2sand2pareclose,valence
electronshavecharactersofbothsandp.Themixtureis
calledsp3hybridization.Thesehybridizedorbitalsare
shownontheright.ThestructuresofCH4,NH3,andH2O
canallexplainedbythesehybridorbitalsofthecentralatoms.
Theaboveapproachisthevalencebondtheory,andboththe
CHbondsandloneelectronpairsarecountedasVSPER
pairsintheValenceshellElectronPairRepulsion(VSEPR)
model,accordingtowhich,thefourgroupspointtothe
cornersofatetrahedron.
Fortriatomicmoleculessuchaswater,molecularorbital(MO)approachcanalsobeappliedtodiscussthe
bonding.Theresulthoweverissimilartothevalencebondapproach,buttheMOtheorygivestheenergy
levelsoftheelectronforfurtherexploration.

Molecularvibrationofwater
Atomsinamoleculeareneveratrest,andforeachtypeofmolecule,therearesomenormalvibrationmodes.
Forthewatermolecule,thethreenormalmodesofvibrationsaresymmetricstretching,bendingand
assymmetricstretching.
BasicmodesofvibrationforH2O
OOO
/\/\/\
/\/\H\
HHHHHHHH
HHH
symmetrocbendingassymmetric
stretchingstretchinng
v1v2v3

Thevibrationsarequantized,asdoanymicroscopicsystem,andtheirquantumnumbersaredesignatedasv1,
v2andv3.TheobservedtransitionbandsofD2O,H2O,andHDOaregiveninthetableontheright.

Theidealtransitionbandsarecenteredinthegiven
TransitionbandsofD2O,H2O,andHDO
wavenumbers.However,thesewavenumbersare
calculatedbasedonisolatedmoleculeswithnointeraction Quantumnumbers Absorptionwavenumbers
ofupperstate
ofbands/cm1
withanyneighbour.Whenmoleculesinteractwitheach
other,theenergylevelsaremodified,andthebandsshift. v1
v2
v3
D2O
H2O
HDO
Manymorelessintenseabsorptionbandsextendintothe
greenpartofthevisiblespectrum.Theabsorption
spectrumofwatermaycontributetothebluecolorfor
lake,riverandoceanwaters.

Symmetryofwatermolecules

0
1
0
1178
1594
1402
1
0
0
2671
3656
2726
0
0
1
2788
3756
3703
0
1
1
3956
5332
5089
DatafromEisenberg,D.andKauzmann,W.
(1969)Structureandpropertiesofwater,
OxfordUniversitypress.

Thewatermoleculesarerathersymmetricinthatthereare
twomirrorplanesofsymmetry,onecontainingallthreeatomsandoneperpendiculartotheplanepassing
throughthebisectoroftheHOHangle.Furthermore,ifthemoleculesarerotated180(360/2)theshapeof
themoleculeisunperturbed.Thisindicatesthatthemoleculeshavea2foldrotationaxis.Thethree
symmetryelementsare2foldrotation,andtwomirrorplanes.Bothmirrorplanescontaintherotationaxis,
andthistypeofsymmetrybelongstothepointgroupC2v.
O
/\
Apointgrouphasadefinitenumberofsymmetryelementsarrangedincertainfashion.Molecules HH
canbeclassifiedaccordingtotheirpointgroups.Moleculesofthesamepointgrouphavesimilar
spectroscopiccharacters.OthermoleculesofC2vpointgroupareCH2=O,CH2Cl2,thebentO3etc.

Formationofhydrogenbonding
Undercertainconditions,anatomofhydrogenisattractedbyratherstrongforcestotwoatomsinsteadof
onlyone,sothatitmaybeconsideredtobeactingasabondbetweenthem.Thisiscalledhydrogenbond.
ThisstatementisfromLinusPauling(1939)inhisbookTheNatureoftheChemicalBond.Hegavetheion
[F:H:F]asanexample.Atthattime,thehydrogenbondwasrecognizedasmainlyionicinnature.The
energyassociatedwithhydrogenbondis8to40kJ/mol.
Normally,themeltingpointandboilingpointofasubstanceincrease Comparisonofmeltingandboiling
withmolecularmass.Forexamplethemeltingpointsofinertgasesare
pointsforafewsubstances
0.95,24.48,83.8,and116.6KrespectivelyforHe,Ne,Ar,andKr.
Molar
Molecule
m.p. b.p./C
mass
Inthistable,themeltingandboilingpointsforwaterareparticular
NH3
17
77.8 33.5
highforitssmallmolecularmass.Thisisusuallyattributedtothe
formationofhydrogenbonds.ThesmallelectronegativeatomsF,O
H2O
18
0
100
andNaresomewhatnegativelychargedwhentheyarebondedto
H2S
34
85.6 60
hydrogenatoms.ThenegativechargesonF,OandNattractthe
slightlypositivehydrogenatoms,formingastronginteractioncalled H2Se
81
60.4 41.5
hydrogenbond.
H2Te
128.6 51 1.8
CH3OH
Hydrogenbondsamongwatermolecules
32
?
65
H
\/
O....HOH....O
/\/\
HH....O
\
H
HO...H
||
H...OH

Dimer

C2H5OH

46

78

C2H5OC2H5 74

34

Agraphshowingthemeltingpointsandboilingpointsofgroup16providedbyProf.J.Boucherillustrates

thesamepoint.

Basedontheobservedabsorptionat3546and3691cm1,VanThiel,Becker,andPinmentel(1957,J.Chem.
Phys.27386)suggestedtheformationofwaterdimerwhentrappedinamatrixofnitrogen.
Duetohydrogenbonding,watermoleculesformdimers,trimers,polymers,andclusters.Thehydrogen
bondsarenotnecessarilyliner.

Structureofice
Iceoccursinmanyplaces,includingtheAntarctic.Ifalltheicemelted,thewaterleveloftheoceanswillrise
about70m.Thestructureoficeandthecaptionarefromthislink.
Thedensityoficeisdramaticallysmallerthanthatofwater,duetotheregulararrangementofwater
moleculeviahydrogenbonds.Inanidealizedstructureofice,everyhydrogenatomisinvolvedinhydrogen
bond.Everyoxygenatomissurroundedbyfourhydrogenbonds.

Thisdiagramfromcaltech.edu,showsthestructureofhexagonalicein(a)andcubicicein(b).Arodhere
representsahydrogenbond.Sincethehydrogenbondsarenotlinear,therealstructureisalittlemore
complicated.
Thetetrahedralcoordinationopensupthespacebetweenmolecules.Oneachhydrogenbond,shownbyarod
joiningtheoxygenatoms,liesoneprotoninanasymmetricposition(notshown).Bondlengths,275pm,are
indicated.Ordinaryiceishexagonal.andthehexagonalcaxisislabelled732pm,andoneofthehexagonala

axesislabelled450pm.Ifwatervaporcondensesonverycoldsubstrateat143193K(130to80C)a
cubicphaseisformed.In(b)thecubicunitcellisoutlinedwithdashedlinesdimensionsareinpm
determinedat110K.
Thesediagramscanalsobeusedtorepresentthetwoformsofdiamond,andinthiscase,therodsjoiningthe
atomsrepresentCCbonds.EachCCbondlengthis154pm.Siliconandgermaniumcrystalshavethesame
structure,buttheirbondlengthsarelonger.Thetwodiamondtypesofstructurearerelatedtothepackingof
spheres.ThehexagonaltypehastheABABAB...sequence,whereasthecubictypehastheABCABC...
sequence.Inbothcases,halfofthetetrahedralsitesareoccupiedbytetrahedrallybondedcarbonatoms.
Hexagonaldiamondshavebeenobservedinmeteorites.
Thefourhydrogenbondsaroundanoxygenatomforma
tetrahedroninafashionfoundinthetwotypesofdiamonds.
Thus,ice,diamond,andclosepackingofspheresare
somewhattopologicallyrelated.
Aphasediagramofwatershows9differentsolidphases
(ices).IceIhistheordinaryice.InadditiontoiceIcfrom
vapordeposition,conditionsforninephasesareshown.Aside
fromiceI,otherphasesareformedandobservedunderhigh
pressuregeneratedbymachinesbuiltbyscientists.Sofar,ten
differentformsoficehavebeenobserved,andsomeice
formsexistatveryhighpressure.Thepressuredeepunderthe
polar(Antarctic)icecapisveryhigh,butwearenotableto
makeanydirectobservationorstudy.
Thereisareportofthe11thice,andtheicephasediagram
anddrawingsoficestructuresgivenhereisextremely
interesting.

TheAutoionizationofWater
TheAutoionizationofWaterintheformationofionsaccordingto
HOH(l)+HOH(l)=H3O+ +OH
Thisisanequilibriumprocessandischaracterisedbyanequilibriumconstant,K'w:
[H3O+ ][OH]
K'w=
[H2O]
Since[H2O]=1000/18=55.56M,andremainsratherconstantunderanycircumstance,weusuallywrite
Kw=[H3O+ ][OH]
=1014(or1e14)
pKw=logKw(defined)
=14(at298K)
Forneutralwater,[H3O+ ]=[OH]=1e7atthistemperature.Furthermore,wedefine
pH=log[H3

O+ ]

pOH=log[OH]
pH=pOH=7at298K(inneutralsolutions)

tC

Kw

20
25
35
40

1.14e15
1.00e14
2.09e14
2.92e14

ItisimportanttorealizethatKwdependsontemperatureasshownintheTablehere.

50 5.47e14

Levelingeffectofwaterandacidbasecharacters
Thestrengthofstrongacidsandbasesisdominatedbytheautoionizationofwater.Inaqueoussolutions,the
strongestacidandbasearethehydroniumion,H3O+ ,andthehydroxideionOHrespectively.AcidsHCl,
HBr,HI,HNO3,HClO3,HClO4,andH2SO4completelyionizeinwater,makingthemasstrongasH3O+
duetothelevelingeffectofwater.Furthermore,strongacids,strongbases,andsaltscompletelyionizein
theiraqueoussolutions.
Forexample,HClisastrongeracidthanH2O,andthereactiontakesplaceasHCldissolvesinwater.
HCl+H2O=Cl+H3O+
Asimilarequationcanbewrittenforanotherstrongacid.
Ontheotherhand,astongbasealsoreactwithwatertogivethestongbasespecies,OH.
H2O+B=OH+HB
Forexample,O2,CH3O,andNH3arestrongbases.Thelevelingeffectalsoapplytobases.

Amphiproticspecies
Equilibriaofacidsandbases,areinterestingchemistry.Whenanacidandabasedifferbyaproton,theyare
calledaconjugateacidbasepair.Awatermoleculeisaweakacidandbase,duetoitsabilitytoacceptor
donateaproton.Suchpropertiesmakewateranamphiproticspecies.Infact,H3O+ ,H2OandOHare
amphiprotic,asaresomeotherconjugateacidbasepairsofweakacidsandbases.
Ifseveralacidsandbasesaredissolvedinwater,allequilibriamustbeconsidered.ToestimatethepHof
thesesolutionsrequirestheexacttreatmentofseveralequilibriumconstants.Forexample,manyspecies
dissolveinrainwater,andmanyequilibriamustbeconsidered.Detailconsiderationandexamplesaregiven
inAcidBaseReactions
Carbondioxideintheairdissolveinrainwater,lakesandrivers.AsolutionofCO2involvesthefollowing
reaction:
Reaction
Kformula
Kvalue
H2O(l)+CO2(g)=H2CO3(l)
1/PCO2
?
H2CO3=HCO3+H+

[HCO3][H+ ]/[H2CO3] 5e7

HCO3=CO32+H+

[CO32][H+ ]/[HCO3] 5e11

HOH(l)+HOH(l)=H3O+ +OH [H3O+ ][OH]

1e14

Thesecomplicatedequilibriamakenaturalwaterabuffer.
Example1
Assumethatthepartialpressureofcarbondioxidecausesatotalconcentrationofcarbonic
speciestobe8e4M.EstimatethepHofthissolution.
Solution
Fromthegivendata,wehavethefollowingfiveequationsandfiveunknowns:
Equilibrium
Equations
No.


+
H2CO3HCO3+H+ [HCO3 ][H ]

=5e7

[H2CO3]

(1)

[CO32][H+ ]
HCO3CO32+H+ =5e11
HCO3

(2)

2H2OH3O+ +OH [H3O+ ][OH]=1e14

(3)

Chargebalance
AllspeciescontainingC

[H+ ]
(4)
=[HCO3]+[OH]+2[CO32]
[H2CO3]+[HCO3]+[CO32]
(5)
=8.0e4M
Unknowns

[H+ ],[OH],[H2CO3],[HCO3],[CO32]
Solvingtheseequationsforthe5unknownscanbedoneusingMaple,Mathcad,spreadsheet,or
approximation.Inanycase,weareinterestedinthepH,andwecanmakethefollowing
approximationsorassumptions
AssumeH+ mostly
[H+ ]=[HCO3]
comesfrom(1)
H2CO3isaweakacid
[H2CO3]=8.0e4M
mostunionize

(6)

[HCO3][H+ ]/[H2CO3]

Letx=[HCO3]=[H+ ] =x2/[H CO ]
2
3
=5.0e7

(1)

Combining(1)and(6)gives[H+ ]2=x2=8.0e4*5.0e7=4.0e10.Therefore,
[H+ ]=2.0e5
pH=log(2.0e5)=4.7
Discussion
Generallyspeaking,rainwaterhasapHabout5,ratheracidic.Itdissolveslimestoneandmarble
readily.Duetothedissolvedcarbondioxide,rainwaterisabuffersolution.
Increasedcarbondioxidelevelforcesanincreaseindissolvedcarbondioxide.WouldthiscausespHof
rainwatertodecreaseorincrease?Justifyyouranswerbygivingthereasons.
Since[H+ ]=2.0e5,[OH]=5e9,theamountofH+ fromionizationofwaterisalso5.0e9,small
withrespectto2.0e5fromionizationofH2CO3.Similarly,theionizationfrom
HCO3CO32+H+
isalsosmall.MostoftheCcontainingspeciesisH2CO3
H2CO3isaweakacid,itsionizationissmallindeed.
Now,youmayproceedtoevaluateotherconcentrations:[OH],[HCO3],and[CO32]

Reactivityofwatertowardsmetals

Alkalimetalsreactwithwaterreadily.Contactofcesiummetalwithwatercausesimmediateexplosion,and
thereactionsbecomeslowerforpotassium,sodiumandlithium.Reactionwithbarium,strontium,calcium
arelesswellknown,buttheydoreactreadily.Warmwatermaybeneededtoreactwithcalciummetal,
however.
ManymetalsdisplaceH+ ionsinacidicsolutions.Thisisoftenseenasapropertyofacids.

Electrolysisofwater
Theenthalpyofformationforliquidwater,H2O(l),is285.830andthatofwatervapouris241.826kJ/mol.
Thedifferenceistheheatofvaporizationat298K.Liquidwaterandvaporentropies(S)are69.95and
188.835kJK1mol1respectively,(seeThermodynamicData.Theseareentropies,notstandardentropiesof
formation.Theentropyofformationforwaterisobtainedby,
Sofwater=SowaterSoH20.5SoO2
=69.95130.680.5*205.14(datafromThermodynamicData)
=163.3JK1mol1
Gowater=HTS(noteHinkJ/molandSinJ/mol)
Gowater=285.83298.15*163.3/1000=237.13kJ
TheequilibriumconstantandGibb'senergyarerelated,
Go=RTlnK
K=exp(Go/RT)
=3.5e41atm3/2
Thisisaverylargevaluefortheformationofwater,
H2+0.5O2=0.5H2O(l).
Inotherwords,thereactioniscomplete,andthepossibilityofwaterdissociatedintohydrogenandoxygenis
verysmall.AnegativevalueforGoindicatesanexothermicreaction.
TheGibb'senergyistheenergyreleasedotherthanpressurevolumework.Thisredoxreactiontoformwater
canbeengineeredtoproceedinaDanielcell.Inthiscase,theenergyisconvertedintoelectricenergy
accordingtothisequation.
Gowater=nFE=237.13kJ
wherenisthenumberofelectrons(=2)intheredoxequation,FistheFaradayconstant(=96485C),andE
isthepotentialoftheDanielcell.Thus,
237130J
E=
2*96485C
=1.23V
Ideally,areversevoltageof1.23Visrequiredfortheelectrolysisofwater.Butinreality,alittleovervoltage
isrequiredtocarryouttheelectrolysistodecomposewater.Furthermore,purewaterdoesnotconduct
electricity,andacid,baseorsaltisoftenaddedfortheelectrolysisofwater.Thislinkhasademonstration.
Example2

Inordertocarryouttheelectrolysisofwater,1.50Visapplied.Assumetheenergynotconverted
tochemicalenergyisconvertedtoheat.Howmuchheatisgeneratedfortheelectrolysisof1
molewater?
Solution
Ideally,1.23Vwillbeusedfortheelectrolysis.Energyduetotheovervoltageof1.501.23=
0.27Visconvertedtoheat.
Heat=0.27V*2*96485C
=52102J
=52kJ
Discussion
Theexcessenergycanalsobeevaluatedusing
Heat=nF*1.50237130
Thisproblemalsoillustratestheprincipleofconservationofenergy.

ConfidenceBuildingQuestions
Forthereaction
H2O(l)>H2(g)+0.5OH2(g)
theequilibriumconstantasshownearlieris1/3.5e41=2.9e43atm3/2.Whatisthepartial
pressureofH2(g)?
Hint...

Skill
Evaluatethisvalueplease!
cchieh@uwaterloo.ca