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TheChemistryofNitrogenandPhosphorous

TheChemistryofNitrogenand
Phosphorous
TheChemistryof TheSynthesisof
Nitrogen
Ammonia

TheSynthesisofNitric
Acid

Negative
Oxidation
Numbersof
NitrogenBesides
3

PositiveOxidation
NumbersforNitrogen:
TheNitrogenHalides

TheChemistryof
Phosphorus

TheEffectofthe
Differencesinthe
SingeandTripleBond
Strengths

Intermediate
Oxidation
Numbers
Positive
Oxidation
Numbersfor
Nitrogen:The
NitrogenOxides

TheEffectof
TheEffectof
TheEffectof
Differencesinthe
Differencesin
Differencesinthe
AbilitiesofPhosphorus
theStrengthsof Electronegativities
andNitrogento
P=XandN=X ofPhosphorusand
ExpandTheirValence
DoubleBonds
Nitrogen
Shell
TheChemistryofNitrogen
Thechemistryofnitrogenisdominatedbytheeasewithwhichnitrogenatomsformdoubleand
triplebonds.Aneutralnitrogenatomcontainsfivevalenceelectrons:2s22p3.Anitrogenatom
canthereforeachieveanoctetofvalenceelectronsbysharingthreepairsofelectronswith
anothernitrogenatom.

Becausethecovalentradiusofanitrogenatomisrelativelysmall(only0.070nm),nitrogen
atomscomecloseenoughtogethertoformverystrongbonds.Thebonddissociationenthalpy
forthenitrogennitrogentriplebondis946kJ/mol,almosttwiceaslargeasthatforanO=O
doublebond.
ThestrengthofthenitrogennitrogentriplebondmakestheN 2moleculeveryunreactive.N 2is
soinertthatlithiumisoneofthefewelementswithwhichitreactsatroomtemperature.

6Li(s) + N2(g)
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2Li3N(s)
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InspiteofthefactthattheN 2moleculeisunreactive,compoundscontainingnitrogenexistfor
virtuallyeveryelementintheperiodictableexceptthoseinGroupVIIIA(He,Ne,Ar,andso
on).Thiscanbeexplainedintwoways.First,N 2becomessignificantlymorereactiveasthe
temperatureincreases.Athightemperatures,nitrogenreactswithhydrogentoformammonia
andwithoxygentoformnitrogenoxide.

N2(g) + 3H2(g)

2NH3(g)

N2(g) + O2(g)

2NO(g)

Second,anumberofcatalystsfoundinnatureovercometheinertnessofN 2atlowtemperature.

TheSynthesisofAmmonia
Itisdifficulttoimaginealivingsystemthatdoesnotcontainnitrogen,whichisanessential
componentoftheproteins,nucleicacids,vitamins,andhormonesthatmakelifepossible.
Animalspickupthenitrogentheyneedfromtheplantsorotheranimalsintheirdiet.Plants
havetopickuptheirnitrogenfromthesoil,orabsorbitasN 2fromtheatmosphere.The
concentrationofnitrogeninthesoilisfairlysmall,sotheprocessbywhichplantsreduceN 2to
NH3

or"fix"N 2

isextremelyimportant.

Although200milliontonsofNH3areproducedbynitrogenfixationeachyear,plants,by
themselves,cannotreduceN 2toNH3.Thisreactioniscarriedoutbybluegreenalgaeand
bacteriathatareassociatedwithcertainplants.Thebestunderstoodexampleofnitrogen
fixationinvolvestherhizobiumbacteriafoundintherootnodulesoflegumessuchasclover,
peasandbeans.Thesebacteriacontainanitrogenaseenzyme,whichiscapableofthe
remarkablefeatofreducingN 2fromtheatmospheretoNH3atroomtemperature.
Ammoniaismadeonanindustrialscalebyaprocessfirstdevelopedbetween1909and1913by
FritzHaber.IntheHaberprocess,amixtureofN 2andH2gasat200to300atmand400to
600oCispassedoveracatalystoffinelydividedironmetal.

N2(g) + 3H2(g)

Fe

2NH3(g)

Almost20milliontonsofNH3areproducedintheUnitedStateseachyearbythisprocess.
About80%ofit,worthmorethan$2billion,isusedtomakefertilizersforplantsthatcan'tfix
nitrogenfromtheatmosphere.Onthebasisofweight,ammoniaisthesecondmostimportant
industrialchemicalintheUnitedStates.(Onlysulfuricacidisproducedinlargerquantities.)
Twothirdsoftheammoniausedforfertilizersisconvertedintosolidssuchasammonium
nitrate,NH4NO3ammoniumphosphate,(NH4)3PO4ammoniumsulfate,(NH4)2SO4andurea,

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H2NCONH2.Theotherthirdisapplieddirectlytothesoilasanhydrous(literally,"without
water")ammonia.Ammoniaisagasatroomtemperature.Itcanbehandledasaliquidwhen
dissolvedinwatertoformanaqueoussolution.Alternatively,itcanbecooledtotemperatures
below33oC,inwhichcasethegascondensestoformtheanhydrousliquid,NH3(l).

TheSynthesisofNitricAcid
TheNH3producedbytheHaberprocessthatisnotusedasfertilizerisburnedinoxygento
generatenitrogenoxide.

4NH3(g) + 5O2(g)
Nitrogenoxide

4NO(g) + 6H2O(g)

ornitricoxide,asitwasonceknown

isacolorlessgasthatreactsrapidly

withoxygentoproducenitrogendioxide,adarkbrowngas.

2NO(g) + O2(g)

2NO2(g)

NitrogendioxidedissolvesinwatertogivenitricacidandNO,whichcanbecapturedand
recycled.

3NO2(g) + H2O(l)

2HNO3(aq) + NO(g)

Thus,byathreestepprocessdevelopedbyFriedrichOstwaldin1908,ammoniacanbe
convertedintonitricacid.

4NH3(g) + 5O2(g)

4NO(g)

+ 6H2O(g)

2NO(g) + O2(g)

2NO2(g)

3NO2(g) + H2O(l)

2HNO3(aq) + NO(g)

TheHaberprocessforthesynthesisofammoniacombinedwiththeOstwaldprocessforthe
conversionofammoniaintonitricacidrevolutionizedtheexplosivesindustry.Nitrateshave
beenimportantexplosiveseversinceFriarRogerBaconmixedsulfur,saltpeter,andpowdered
carbontomakegunpowderin1245.

16
KNO3(s)

+ S8(s) +

24
C(s)

8
24
+
K2S(s)
CO2(g)

8
Ho=571.9
+

N2(g)
kJ/molN2

BeforetheOstwaldprocesswasdevelopedtheonlysourceofnitratesforuseinexplosiveswas
naturallyoccurringmineralssuchassaltpeter,whichisamixtureofNaNO3andKNO3.Oncea
dependablesupplyofnitricacidbecameavailablefromtheOstwaldprocess,anumberof
nitratescouldbemadeforuseasexplosives.CombiningNH3fromtheHaberprocesswithHNO3

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fromtheOstwaldprocess,forexample,givesammoniumnitrate,whichisbothanexcellent
fertilizerandacheap,dependableexplosivecommonlyusedinblastingpowder.

2NH4NO3(s)

2N2(g) + O2(g) + 4H2O(g)

Thedestructivepowerofammonianitrateisapparentinphotographsofthe
AlfredP.MurrahFederalBuildinginOklahomaCity,whichwasdestroyedwitha
bombmadefromammoniumnitrateonApril19,1995.

IntermediateOxidationNumbers
Nitricacid(HNO3)andammonia(NH3)representthemaximum(+5)andminimum(3)
oxidationnumbersfornitrogen.Nitrogenalsoformscompoundswitheveryoxidationnumber
betweentheseextremes(seetablebelow).
CommonOxidationNumbersforNitrogen

Oxidation

Number

Examples

NH3,NH4+,NH2,Mg3N2

N2H4

NH2OH

1/3

NaN3,HN3

N2

+1

N2O

+2

NO,N2O2

+3

HNO2,NO2,N2O3,NO+

+4

NO2,N2O4

+5

HNO3,NO3,N2O5

NegativeOxidationNumbersofNitrogenBesides3
AtaboutthetimethatHaberdevelopedtheprocessformakingammoniaandOstwaldworked
outtheprocessforconvertingammoniaintonitricacid,Raschigdevelopedaprocessthatused
thehypochlorite(OCl )iontooxidizeammoniatoproducehydrazine,N 2H4.

2NH3(aq) + OCl(aq)
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N2H4(aq) + Cl(aq) + H2O(l)

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ThisreactioncanbeunderstoodbynotingthattheOCl ionisatwoelectronoxidizingagent.
ThelossofapairofelectronsandapairofH+ionsbyneighboringNH3moleculeswould
produceapairofhighlyreactiveNH2molecules,whichwouldcombinetoformahydrazine
moleculeasshowninthefigurebelow.

Hydrazineisacolorlessliquidwithafaintodorofammoniathatcanbecollectedwhenthis
solutionisheateduntilN 2H4distillsoutofthereactionflask.Manyofthephysicalpropertiesof
hydrazinearesimilartothoseofwater.

H2O

N2H4

Density

1.000g/cm3 1.008g/cm3

MeltingPoint 0.00oC

1.54oC

BoilingPoint 100oC

113.8oC

Thereisasignificantdifferencebetweenthechemicalpropertiesofthesecompounds,however.
Hydrazineburnswhenignitedinairtogivenitrogengas,watervapor,andlargeamountsof
energy.

N2H4(l) + O2(g)

N2(g) + 2H2O(g) Ho=534.3kJ/molN2H4

Theprincipaluseofhydrazineisasarocketfuel.Itissecondonlytoliquidhydrogeninterms
ofthenumberofkilogramsofthrustproducedperkilogramoffuelburned.Hydrazinehas
severaladvantagesoverliquidH2,however.Itcanbestoredatroomtemperature,whereas
liquidhydrogenmustbestoredattemperaturesbelow253oC.Hydrazineisalsomoredense
thanliquidH2andthereforerequireslessstoragespace.
Purehydrazineisseldomusedasarocketfuelbecauseitfreezesatthetemperatures
encounteredintheupperatmosphere.HydrazineismixedwithN,Ndimethylhydrazine,
(CH3)2NNH2,toformasolutionthatremainsaliquidatlowtemperatures.Mixturesofhydrazine
andN,NdimethylhydrazinewereusedtofueltheTitanIIrocketsthatcarriedtheProjectGemini
spacecraft,andthereactionbetweenhydrazinederivativesandN 2O4isstillusedtofuelthe
smallrocketenginesthatenablethespaceshuttletomaneuverinspace.
Theproductofthecombustionofhydrazineisunusual.Whencarboncompoundsburn,the
carbonisoxidizedtoCOorCO2.Whensulfurcompoundsburn,SO2isproduced.When
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hydrazineisburned,theproductofthereactionisN 2becauseoftheunusuallystrongnitrogen
nitrogentriplebondintheN 2molecule.

N2H4(l) + O2(g)

N2(g) + 2H2O(g)

Hydrazinereactswithnitrousacid(HNO2)toformhydrogenazide,HN 3,inwhichthenitrogen
atomformallyhasanoxidationstateof1/3.

N2H4(aq) + HNO2(aq)

HN3(aq) + 2H2O(l)

Purehydrogenazideisanextremelydangeroussubstance.Evendilutesolutionsshouldbe
handledwithcarebecauseoftheriskofexplosions.Hydrogenazideisbestdescribedasa
resonancehybridoftheLewisstructuresshowninthefigurebelow.Thecorrespondingazideion,
N 3,isalinearmolecule,whichisaresonancehybridofthreeLewisstructures.

HN3
N3

PositiveOxidationNumbersforNitrogen:TheNitrogenHalides
Fluorine,oxygen,andchlorinearetheonlyelementsmoreelectronegativethannitrogen.Asa
result,positiveoxidationnumbersofnitrogenarefoundincompoundsthatcontainoneormore
oftheseelements.
Intheory,N 2couldreactwithF2toformacompoundwiththeformulaNF3.Inpractice,N 2istoo
inerttoundergothisreactionatroomtemperature.NF3ismadebyreactingammoniawithF2in
thepresenceofacoppermetalcatalyst.

Cu

NH3(g) + 3F2(g)

NF3(g) + 3HF(g)

TheHFproducedinthisreactioncombineswithammoniatoformammoniumfluoride.The
overallstoichiometryforthereactionisthereforewrittenasfollows.

4NH3(g) + 3F2(g)

Cu

NF3(g) + 3NH4F(s)

TheLewisstructureofNF3isanalogoustotheLewisstructureofNH3,andthetwomolecules
havesimilarshapes.

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AmmoniareactswithchlorinetoformNCl 3,whichseemsatfirstglancetobecloselyrelatedto
NF3.Butthereisasignificantdifferencebetweenthesecompounds.NF3isessentiallyinertat
roomtemperature,whereasNCl 3isashocksensitive,highlyexplosiveliquidthatdecomposes
toformN 2andCl 2.

2NCl3(l)

N2(g) + 3Cl2(g)

AmmoniareactswithiodinetoformasolidthatisacomplexbetweenNI3andNH3.This
materialisthesubjectofapopular,butdangerous,demonstrationinwhichfreshlyprepared
samplesofNI3inammoniaarepouredontofilterpaper,whichisallowedtodryonaringstand.
Aftertheammoniaevaporates,theNH3/NI3crystalsaretouchedwithafeatherattachedtoa
meterstick,resultingindetonationofthisshocksensitivesolid,whichdecomposestoforma
mixtureofN 2andI2.

2NI3(s)

N2(g) + 3I2(g)

PositiveOxidationNumbersforNitrogen:TheNitrogenOxides
Lewisstructuresforsevenoxidesofnitrogenwithoxidationnumbersrangingfrom+1to+5are
giveninthetablebelow.

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Thesecompoundsallhavetwothingsincommon:theycontainN=Odoublebondsandtheyare
lessstablethantheirelementsinthegasphase,asshownbytheenthalpyofformationdatain
thetablebelow.
EnthalpyofFormationDatafortheOxidesofNitrogen

Compound Hof(kJ/mol)
N2O(g)

82.05

NO(g)

90.25

NO2(g)

33.18

N2O3(g)

83.72

N2O4(g)

9.16

N2O5(g)

11.35

Dinitrogenoxide,N 2O,whichisalsoknownasnitrousoxide,canbepreparedbycarefully
decomposingammoniumnitrate.

170to200o C

NH4NO3(s)

N2O(g) + 2H2O(g)

Nitrousoxideisasweetsmelling,colorlessgasbestknowntononchemistsas"laughinggas."
Asearlyas1800,HumphryDavynotedthatN 2O,inhaledinrelativelysmallamounts,produced
astateofapparentintoxicationoftenaccompaniedbyeitherconvulsivelaughterorcrying.
Whentakeninlargerdoses,nitrousoxideprovidesfastandefficientrelieffrompain.N 2Owas
thereforeusedasthefirstanesthetic.Becauselargedosesareneededtoproduceanesthesia,
andcontinuedexposuretothegascanbefatal,N 2Oisusedtodayonlyforrelativelyshort
operations.
Nitrousoxidehasseveralotherinterestingproperties.First,itishighlysolubleincreamfor
thatreason,itisusedasthepropellantinwhippedcreamdispensers.Second,althoughitdoes
notburnbyitself,itisbetterthanairatsupportingthecombustionofotherobjects.Thiscanbe

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explainedbynotingthatN 2OcandecomposetoformanatmospherethatisonethirdO2by
volume,whereasnormalairisonly21%oxygenbyvolume.

2N2O(g)

2N2(g) + O2(g)

Formanyyears,theendingsousandicwereusedtodistinguishbetweenthelowestand
highestofapairofoxidationnumbers.N 2Oisnitrousoxidebecausetheoxidationnumberof
thenitrogenis+1.NOisnitricoxidebecausetheoxidationnumberofthenitrogenis+2.
Enormousquantitiesofnitrogenoxide,ornitricoxide,aregeneratedeachyearbythereaction
betweentheN 2andO2intheatmosphere,catalyzedbyastrokeoflightningpassingthrough
theatmosphereorbythehotwallsofaninternalcombustionengine.

N2(g) + O2(g)

2NO(g)

Oneofthereasonsforloweringthecompressionratioofautomobileenginesinrecentyearsis
todecreasethetemperatureofthecombustionreaction,therebydecreasingtheamountofNO
emittedintotheatmosphere.
NOcanbepreparedinthelaboratorybyreactingcoppermetalwithdilutenitricacid.

3Cu(s) + 8HNO3(aq)

3Cu(NO3)2(aq) + 2NO(g) + 4H2O(l)

TheNOmoleculecontainsanoddnumberofvalenceelectrons.Asaresult,itisimpossibleto
writeaLewisstructureforthismoleculeinwhichalloftheelectronsarepaired(seetableof
oxidesofnitrogen).WhenNOgasiscooled,pairsofNOmoleculescombineinareversible
reactiontoformadimer(fromtheGreek,"twoparts"),withtheformulaN 2O2,inwhichallof
thevalenceelectronsarepaired,asshowninthetableofoxidesofnitrogen.
NOreactsrapidlywithO2toformnitrogendioxide(onceknownasnitrogenperoxide),whichis
adarkbrowngasatroomtemperature.

2NO(g) + O2(g)

2NO2(g)

NO2canbepreparedinthelaboratorybyheatingcertainmetalnitratesuntiltheydecompose.

2Pb(NO3)2(s)

2PbO(s) + 4NO2(g) + O2(g)

Itcanalsobemadebyreactingcoppermetalwithconcentratednitricacid,

Cu(s) + 4HNO3(aq)

Cu(NO3)2(aq) + 2NO2(g) + 2H2O(l)

NO2alsohasanoddnumberofelectronsandthereforecontainsatleastoneunpairedelectron
initsLewisstructures.NO2dimerizesatlowtemperaturestoformN 2O4molecules,inwhichall
theelectronsarepaired,asshowninthetableofoxidesofnitrogen.

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MixturesofNOandNO2combinewhencooledtoformdinitrogentrioxide,N 2O3,whichisablue
liquid.TheformationofablueliquidwheneitherNOorNO2iscooledthereforeimpliesthe
presenceofatleastasmallportionoftheotheroxidebecauseN 2O2andN 2O4areboth
colorless.
Bycarefullyremovingwaterfromconcentratednitricacidatlowtemperatureswitha
dehydratingagentwecanformdinitrogenpentoxide.

4HNO3(aq) + P4O10(s)

2N2O5(s) + 4HPO3(s)

N 2O5isacolorlesssolidthatdecomposesinlightoronwarmingtoroomtemperature.Asmight
beexpected,N 2O5dissolvesinwatertoformnitricacid.

N2O5(s) + H2O(l)

2HNO3(aq)

TheChemistryofPhosphorus
Phosphorusisthefirstelementwhosediscoverycanbetracedtoasingleindividual.In1669,
whilesearchingforawaytoconvertsilverintogold,HennigBrandobtainedawhite,waxysolid
thatglowedinthedarkandburstspontaneouslyintoflamewhenexposedtoair.Brandmade
thissubstancebyevaporatingthewaterfromurineandallowingtheblackresiduetoputrefyfor
severalmonths.Hethenmixedthisresiduewithsand,heatedthismixtureinthepresenceofa
minimumofair,andcollectedunderwaterthevolatileproductsthatdistilledoutofthereaction
flask.
Phosphorusformsanumberofcompoundsthataredirectanalogsofnitrogencontaining
compounds.However,thefactthatelementalnitrogenisvirtuallyinertatroomtemperature,
whereaselementalphosphoruscanburstspontaneouslyintoflamewhenexposedtoair,shows
thattherearedifferencesbetweentheseelementsaswell.Phosphorusoftenformscompounds
withthesameoxidationnumbersastheanalogousnitrogencompounds,butwithdifferent
formulas,asshowninthetablebelow.
NitrogenandPhosphorusCompoundswiththeSameOxidationNumbersbutDifferentFormulas

OxidationNumber NitrogenCompound

PhosphorusCompound

N2

P4

+3

HNO2(nitrousacid)

H3PO3(phosphorousacid)

+3

N2O3

P4O6

+5

HNO3(nitricacid)

H3PO4(phosphoricacid)

+5

NaNO3(sodiumnitrate) Na3PO4(sodiumphosphate)

+5

N2O5

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Thesamefactorsthatexplainthedifferencesbetweensulfurandoxygencanbeusedtoexplain
thedifferencesbetweenphosphorusandnitrogen.
1.Nitrogennitrogentriplebondsaremuchstrongerthanphosphorusphosphorustriplebonds.
2.PPsinglebondsarestrongerthanNNsinglebonds.
3.Phosphorus(EN=2.19)ismuchlesselectronegativethannitrogen(EN=3.04).
4.Phosphoruscanexpanditsvalenceshelltoholdmorethaneightelectrons,butnitrogen
cannot.

TheEffectoftheDifferencesintheSingeandTripleBondStrengths
Theratiooftheradiiofphosphorusandnitrogenatomsisthesameastheratiooftheradiiof
sulfurandoxygenatoms,withinexperimentalerror.

Asaresult,phosphorusphosphorustriplebondsaremuchweakerthanNitrogennitrogentriple
bonds,forthesamereasonthatS=SdoublebondsareweakerthanO=Odoublebonds
phosphorusatomsaretoobigtocomecloseenoughtogethertoformstrongbonds.
EachatominanN 2moleculecompletesitsoctetofvalenceelectronsbysharingthreepairsof
electronswithasingleneighboringatom.Becausephosphorusdoesnotformstrongmultiple
bondswithitself,elementalphosphorusconsistsoftetrahedralP4moleculesinwhicheachatom
formssinglebondswiththreeneighboringatoms,asshowninthefigurebelow.

Phosphorusisawhitesolidwithawaxyappearance,whichmeltsat44.1oCandboilsat287oC.
Itismadebyreducingcalciumphosphatewithcarboninthepresenceofsilica(sand)atvery
hightemperatures.

2Ca3(PO4)2(s) + 6SiO2(s) + 10C(s)

6CaSiO3(s) + P4(s) + 10CO(g)

Whitephosphorusisstoredunderwaterbecausetheelementspontaneouslyburstsintoflamein
thepresenceofoxygenattemperaturesonlyslightlyaboveroomtemperature.Although

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phosphorusisinsolubleinwater,itisverysolubleincarbondisulfide.SolutionsofP4inCS2are
reasonablystable.AssoonastheCS2evaporates,however,thephosphorusburstsintoflame.
ThePPPbondangleinatetrahedralP4moleculeisonly60o.Thisverysmallangleproducesa
considerableamountofstrainintheP4molecule,whichcanberelievedbybreakingoneofthe
PPbonds.PhosphorusthereforeformsotherallotropesbyopeninguptheP4tetrahedron.When
whitephosphorusisheatedto300oC,onebondinsideeachP4tetrahedronisbroken,andtheP4
moleculeslinktogethertoformapolymer(fromtheGreekpol,"many,"andmeros,"parts")
withthestructureshowninthefigurebelow.Thisallotropeofphosphorusisdarkred,andits
presenceinsmalltracesoftengiveswhitephosphorusalightyellowcolor.Redphosphorusis
moredense(2.16g/cm3)thanwhitephosphorus(1.82g/cm3)andismuchlessreactiveat
normaltemperatures.

TheEffectofDifferencesintheStrengthsofP=XandN=XDoubleBonds
Thesizeofaphosphorusatomalsointerfereswithitsabilitytoformdoublebondstoother
elements,suchasoxygen,nitrogen,andsulfur.Asaresult,phosphorustendstoform
compoundsthatcontaintwoPOsinglebondswherenitrogenwouldformanN=Odoublebond.
Nitrogenformsthenitrate,NO3,ion,forexample,inwhichithasanoxidationnumberof+5.
Whenphosphorusformsanionwiththesameoxidationnumber,itisthephosphate,PO43,ion,
asshowninthefigurebelow.

Similarly,nitrogenformsnitricacid,HNO3,whichcontainsanN=Odoublebond,whereas
phosphorusformsphosphoricacid,H3PO4,whichcontainsPOsinglebonds,asshowninthe
figurebelow.

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TheEffectofDifferencesintheElectronegativitiesofPhosphorusandNitrogen
Thedifferencebetweentheelectronegativitiesofphosphorusandnitrogen(EN=0.85)isthe
sameasthedifferencebetweentheelectronegativitiesofsulfurandoxygen(EN=0.86),within
experimentalerror.Becauseitislesselectronegative,phosphorusismorelikelythannitrogen
toexhibitpositiveoxidationnumbers.Themostimportantoxidationnumbersforphosphorusare
3,+3,and+5(seetablebelow).
CommonOxidationNumbersofPhosphorus

Oxidation

Number
Examples
3

Ca3P2,PH3

+3

PF3,P4O10,H3PO3

+5

PF5,P4O10,H3PO4,PO43

Becauseitismoreelectronegativethanmostmetals,phosphorusreactswithmetalsatelevated
temperaturestoformphosphides,inwhichithasanoxidationnumberof3.

6Ca(s) P4(s)

2Ca3P2(s)

Thesemetalphosphidesreactwithwatertoproduceapoisonous,highlyreactive,colorlessgas
knownasphosphine(PH3),whichhasthefoulestodortheauthorshaveencountered.

Ca3P2(s) + 6H2O(l)

2PH3(g) + 3Ca2+(aq) + 6OH(aq)

SamplesofPH3,thephosphorusanalogofammonia,areoftencontaminatedbytracesofP2H4,
thephosphorusanalogofhydrazine.AsifthetoxicityandodorofPH3werenotenough,
mixturesofPH3andP2H4burstspontaneouslyintoflameinthepresenceofoxygen.
Compounds(suchasCa3P2andPH3)inwhichphosphorushasanegativeoxidationnumberare
faroutnumberedbycompoundsinwhichtheoxidationnumberofphosphorusispositive.
PhosphorusburnsinO2toproduceP4O10inareactionthatgivesoffextraordinaryamountsof
energyintheformofheatandlight.

P4(s) + 5O2(g)

P4O10(s) Ho=2985kJ/molP4

WhenphosphorusburnsinthepresenceofalimitedamountofO2,P4O6isproduced.

P4(s) + 3O2(g)

P4O6(s) Ho=1640kJ/molP4

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P4O6consistsofatetrahedroninwhichanoxygenatomhasbeeninsertedintoeachPPbondin
theP4molecule(seefigurebelow).P4O10hasananalogousstructure,withanadditional
oxygenatomboundtoeachofthefourphosphorusatoms.

P4O6andP4O10reactwithwatertoformphosphorousacid,H3PO3,andphosphoricacid,H3PO4,
respectively.

P4O6(s) + 6H2O(l)

4H3PO3(aq)

P4O10(s) + 6H2O(l)

4H3PO4(aq)

P4O10hassuchahighaffinityforwaterthatitiscommonlyusedasadehydratingagent.
Phosphorousacid,H3PO3,andphosphoricacid,H3PO4,areexamplesofalargeclassof
oxyacidsofphosphorus.Lewisstructuresforsomeoftheseoxyacidsandtheirrelatedoxyanions
aregiveninthetablebelow.

OXYACID

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OXYANION

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TheChemistryofNitrogenandPhosphorous

TheEffectofDifferencesintheAbilitiesofPhosphorusandNitrogentoExpandTheir
ValenceShell
ThereactionbetweenammoniaandfluorinestopsatNF3becausenitrogenusesthe2s,2px,2py
and2pz orbitalstoholdvalenceelectrons.Nitrogenatomscanthereforeholdamaximumof
eightvalenceelectrons.Phosphorus,however,hasempty3datomicorbitalsthatcanbeusedto
expandthevalenceshelltohold10ormoreelectrons.Thus,phosphoruscanreactwithfluorine
toformbothPF3andPF5.PhosphoruscanevenformthePF6ion,inwhichthereare12valence
electronsonthecentralatom,asshowninthefigurebelow.

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