Hydrogen - Wikipedia, The Free Encyclopedia

8/21/2015
HydrogenWikipedia,thefreeencyclopedia
Hydrogen
FromWikipedia,thefreeencyclopedia
Thisarticleisaboutthechemistryofhydrogen.Forthephysicsofatomichydrogen,seeHydrogen
atom.Forothermeanings,seeHydrogen(disambiguation).
Hydrogenisachemicalelementwithchemical
symbolHandatomicnumber1.Withanatomicweight
of1.007 94u,hydrogenisthelightestelementonthe
periodictable.Itsmonatomicform(H)isthemost
abundantchemicalsubstanceintheuniverse,constituting
roughly75%ofallbaryonicmass.[9][note1]Nonremnant
starsaremainlycomposedofhydrogeninitsplasma
state.Themostcommonisotopeofhydrogen,termed
protium(namerarelyused,symbol1H),hasoneproton
andnoneutrons.
Theuniversalemergenceofatomichydrogenfirst
occurredduringtherecombinationepoch.Atstandard
temperatureandpressure,hydrogenisacolorless,
odorless,tasteless,nontoxic,nonmetallic,highly
combustiblediatomicgaswiththemolecularformulaH2.
Sincehydrogenreadilyformscovalentcompoundswith
mostnonmetallicelements,mostofthehydrogenon
Earthexistsinmolecularformssuchasintheformof
waterororganiccompounds.Hydrogenplaysa
particularlyimportantroleinacidbasereactionsas
manyacidbasereactionsinvolvetheexchangeof
protonsbetweensolublemolecules.Inioniccompounds,
hydrogencantaketheformofanegativecharge(i.e.,
anion)whenitisknownasahydride,orasapositively
charged(i.e.,cation)speciesdenotedbythesymbolH+.
Thehydrogencationiswrittenasthoughcomposedofa
bareproton,butinreality,hydrogencationsinionic
compoundsarealwaysmorecomplexspeciesthanthat
wouldsuggest.Astheonlyneutralatomforwhichthe
Schrdingerequationcanbesolvedanalytically,[10]study
oftheenergeticsandbondingofthehydrogenatomhas
playedakeyroleinthedevelopmentofquantum
mechanics.
Hydrogengaswasfirstartificiallyproducedintheearly
16thcentury,viathemixingofmetalswithacids.In
176681,HenryCavendishwasthefirsttorecognizethat
https://en.wikipedia.org/wiki/Hydrogen
Hydrogen,1H
Purpleglowinitsplasmastate
Spectrallinesofhydrogen
Generalproperties
Name,symbol
hydrogen,H
Appearance
colorlessgas
Pronunciation
/hadrdn/[1]
HYdrjn
Hydrogenintheperiodictable
Li
hydrogenhelium
Atomicnumber
Standardatomic
weight(Ar)
1.008[2](1.007841.00811)
Elementcategory
diatomicnonmetal,could
beconsideredmetalloid
Group,block
group1,sblock
Period
period1
Electron
configuration
1s1
pershell
[3]
1
Physicalproperties
Color
colorless
Phase
gas
Meltingpoint
13.99K
(259.16C,
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hydrogengaswasadiscretesubstance,[11]andthatit
produceswaterwhenburned,apropertywhichlatergave
ititsname:inGreek,hydrogenmeans"waterformer".
Industrialproductionismainlyfromthesteamreforming
ofnaturalgas,andlessoftenfrommoreenergyintensive
hydrogenproductionmethodsliketheelectrolysisof
water.[12]Mosthydrogenisemployednearitsproduction
site,withthetwolargestusesbeingfossilfuelprocessing
(e.g.,hydrocracking)andammoniaproduction,mostly
forthefertilizermarket.Hydrogenisaconcernin
metallurgyasitcanembrittlemanymetals,[13]
complicatingthedesignofpipelinesandstoragetanks.
[14]
Contents
1Properties
1.1Combustion
1.2Electronenergylevels
1.3Elementalmolecularforms
1.4Phases
1.5Compounds
1.5.1Covalentandorganic
compounds
1.5.2Hydrides
1.5.3Protonsandacids
1.6Isotopes
2History
2.1Discoveryanduse
2.2Roleinquantumtheory
3Naturaloccurrence
4Production
4.1Metalacid
4.2Steamreforming
4.3Thermochemical
4.4Anaerobiccorrosion
4.5Geologicaloccurrence:the
serpentinizationreaction
4.6Formationintransformers
5Applications
5.1Consumptioninprocesses
5.2Coolant
5.3Energycarrier
5.4Semiconductorindustry
6Biologicalreactions
7Safetyandprecautions
8Notes
13.99K
(259.16C,
Meltingpoint
434.49F)
Boilingpoint
20.271K
(252.879C,
423.182F)
Densityatstp(0C
and101.325kPa)
0.08988g/L
whenliquid,atm.p.
0.07g/cm3
(solid:0.0763gcm3)[4]
whenliquid,atb.p.
0.07099g/cm3
Triplepoint
13.8033K,
7.041kPa
Criticalpoint
32.938K,1.2858MPa
Heatoffusion
(H2)0.117kJ/mol
Heatof
vaporization
(H2)0.904kJ/mol
Molarheat
capacity
(H2)28.836J/(molK)
vaporpressure
P(Pa)
1 10 100
1k
atT(K)
10k
100k
15
20
Atomicproperties
Oxidationstates
1,+1
(anamphoteric
oxide)
Electronegativity
Paulingscale:2.20
Ionizationenergies
1st:1312.0kJ/mol
Covalentradius
315pm
VanderWaals
radius
120pm
Miscellanea
Crystalstructure
hexagonal
Speedofsound
1310m/s(gas,27C)
Thermal
conductivity
0.1805W/(mK)
Magneticordering
diamagnetic[5]
CASRegistry
Number
1333740
History
Discovery
HenryCavendish[6][7]
(1766)
Namedby
AntoineLavoisier[8] (1783)
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8Notes
9References
10Furtherreading
11Externallinks
Moststableisotopes
iso
Properties
NA
halflife DM DE (MeV) DP
1H
99.9885% 1His stablewith0 neutrons
2H
0.0115% 2Hisstablewith1neutron
3H
trace
12.32y
0.01861
3 He
Combustion
Hydrogengas(dihydrogenormolecularhydrogen)[15]ishighlyflammable
andwillburninairataverywiderangeofconcentrationsbetween4%and
75%byvolume.[16]Theenthalpyofcombustionforhydrogenis
286kJ/mol:[17]
2H2(g)+O2(g)2H2O(l)+572kJ(286kJ/mol)[note2]
Hydrogengasformsexplosivemixtureswithairifitis474%concentrated
andwithchlorineifitis595%concentrated.Themixturesmaybeignited
byspark,heatorsunlight.Thehydrogenautoignitiontemperature,the
TheSpaceShuttleMain
temperatureofspontaneousignitioninair,is500C(932F).[18]Pure
Engineburnthydrogenwith
hydrogenoxygenflamesemitultravioletlightandwithhighoxygenmixare
oxygen,producinganearly
nearlyinvisibletothenakedeye,asillustratedbythefaintplumeofthe
invisibleflameatfullthrust.
SpaceShuttleMainEnginecomparedtothehighlyvisibleplumeofaSpace
ShuttleSolidRocketBooster.Thedetectionofaburninghydrogenleakmay
requireaflamedetectorsuchleakscanbeverydangerous.Hydrogenflamesinotherconditionsareblue,
resemblingbluenaturalgasflames.[19]ThedestructionoftheHindenburgairshipwasaninfamousexample
ofhydrogencombustionthecauseisdebated,butthevisibleorangeflamesweretheresultofarich
mixtureofhydrogentooxygencombinedwithcarboncompoundsfromtheairshipskin.
H2reactswitheveryoxidizingelement.Hydrogencanreactspontaneouslyandviolentlyatroom
temperaturewithchlorineandfluorinetoformthecorrespondinghydrogenhalides,hydrogenchlorideand
hydrogenfluoride,whicharealsopotentiallydangerousacids.[20]
Electronenergylevels
Mainarticle:Hydrogenatom
Thegroundstateenergyleveloftheelectroninahydrogenatomis13.6eV,[21]whichisequivalenttoan
ultravioletphotonofroughly91nmwavelength.[22]
TheenergylevelsofhydrogencanbecalculatedfairlyaccuratelyusingtheBohrmodeloftheatom,which
conceptualizestheelectronas"orbiting"theprotoninanalogytotheEarth'sorbitoftheSun.However,the
electromagneticforceattractselectronsandprotonstooneanother,whileplanetsandcelestialobjectsare
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attractedtoeachotherbygravity.Becauseofthediscretizationofangularmomentumpostulatedinearly
quantummechanicsbyBohr,theelectronintheBohrmodelcanonlyoccupycertainalloweddistances
fromtheproton,andthereforeonlycertainallowedenergies.[23]
Amoreaccuratedescriptionofthehydrogenatomcomesfromapurelyquantummechanicaltreatmentthat
usestheSchrdingerequation,DiracequationoreventheFeynmanpathintegralformulationtocalculate
theprobabilitydensityoftheelectronaroundtheproton.[24]Themostcomplicatedtreatmentsallowforthe
smalleffectsofspecialrelativityandvacuumpolarization.Inthequantummechanicaltreatment,the
electroninagroundstatehydrogenatomhasnoangularmomentum
atallanillustrationofhowthe"planetaryorbit"conceptionof
electronmotiondiffersfromreality.
Depictionofahydrogenatomwith
sizeofcentralprotonshown,andthe
atomicdiametershownasabouttwice
theBohrmodelradius(imagenotto
scale)
Elementalmolecularforms
Seealso:Spinisomersofhydrogen
Thereexisttwodifferentspinisomersofhydrogendiatomicmoleculesthat
differbytherelativespinoftheirnuclei.[25]Intheorthohydrogenform,the
spinsofthetwoprotonsareparallelandformatripletstatewithamolecular
spinquantumnumberof1(12+12)intheparahydrogenformthespinsare
antiparallelandformasingletwithamolecularspinquantumnumberof0
(1212).Atstandardtemperatureandpressure,hydrogengascontainsabout
25%oftheparaformand75%oftheorthoform,alsoknownasthe"normal
form".[26]Theequilibriumratiooforthohydrogentoparahydrogendepends
ontemperature,butbecausetheorthoformisanexcitedstateandhasa
higherenergythantheparaform,itisunstableandcannotbepurified.At
verylowtemperatures,theequilibriumstateiscomposedalmostexclusively
oftheparaform.Theliquidandgasphasethermalpropertiesofpure
parahydrogendiffersignificantlyfromthoseofthenormalformbecauseof
differencesinrotationalheatcapacities,asdiscussedmorefullyinspin
Firsttracksobservedin
liquidhydrogenbubble
chamberattheBevatron
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isomersofhydrogen.[27]Theortho/paradistinctionalsooccursinotherhydrogencontainingmoleculesor
functionalgroups,suchaswaterandmethylene,butisoflittlesignificancefortheirthermalproperties.[28]
TheuncatalyzedinterconversionbetweenparaandorthoH2increaseswithincreasingtemperaturethus
rapidlycondensedH2containslargequantitiesofthehighenergyorthoformthatconvertstotheparaform
veryslowly.[29]Theortho/pararatioincondensedH2isanimportantconsiderationinthepreparationand
storageofliquidhydrogen:theconversionfromorthotoparaisexothermicandproducesenoughheatto
evaporatesomeofthehydrogenliquid,leadingtolossofliquefiedmaterial.Catalystsfortheorthopara
interconversion,suchasferricoxide,activatedcarbon,platinizedasbestos,rareearthmetals,uranium
compounds,chromicoxide,orsomenickel[30]compounds,areusedduringhydrogencooling.[31]
Phases
Compressedhydrogen
Liquidhydrogen
Slushhydrogen
Solidhydrogen
Metallichydrogen
Compounds
Furtherinformation:Hydrogencompounds
Covalentandorganiccompounds
WhileH2isnotveryreactiveunderstandardconditions,itdoesformcompoundswithmostelements.
Hydrogencanformcompoundswithelementsthataremoreelectronegative,suchashalogens(e.g.,F,Cl,
Br,I),oroxygeninthesecompoundshydrogentakesonapartialpositivecharge.[32]Whenbondedto
fluorine,oxygen,ornitrogen,hydrogencanparticipateinaformofmediumstrengthnoncovalentbonding
calledhydrogenbonding,whichiscriticaltothestabilityofmanybiologicalmolecules.[33][34]Hydrogen
alsoformscompoundswithlesselectronegativeelements,suchasthemetalsandmetalloids,inwhichit
takesonapartialnegativecharge.Thesecompoundsareoftenknownashydrides.[35]
Hydrogenformsavastarrayofcompoundswithcarboncalledthehydrocarbons,andanevenvasterarray
withheteroatomsthat,becauseoftheirgeneralassociationwithlivingthings,arecalledorganic
compounds.[36]Thestudyoftheirpropertiesisknownasorganicchemistry[37]andtheirstudyinthecontext
oflivingorganismsisknownasbiochemistry.[38]Bysomedefinitions,"organic"compoundsareonly
requiredtocontaincarbon.However,mostofthemalsocontainhydrogen,andbecauseitisthecarbon
hydrogenbondwhichgivesthisclassofcompoundsmostofitsparticularchemicalcharacteristics,carbon
hydrogenbondsarerequiredinsomedefinitionsoftheword"organic"inchemistry.[36]Millionsof
hydrocarbonsareknown,andtheyareusuallyformedbycomplicatedsyntheticpathways,whichseldom
involveelementaryhydrogen.
Hydrides
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Compoundsofhydrogenareoftencalledhydrides,atermthatisusedfairlyloosely.Theterm"hydride"
suggeststhattheHatomhasacquiredanegativeoranioniccharacter,denotedH,andisusedwhen
hydrogenformsacompoundwithamoreelectropositiveelement.Theexistenceofthehydrideanion,
suggestedbyGilbertN.Lewisin1916forgroupIandIIsaltlikehydrides,wasdemonstratedbyMoersin
1920bytheelectrolysisofmoltenlithiumhydride(LiH),producingastoichiometryquantityofhydrogenat
theanode.[39]ForhydridesotherthangroupIandIImetals,thetermisquitemisleading,consideringthe
lowelectronegativityofhydrogen.AnexceptioningroupIIhydridesisBeH2,whichispolymeric.In
lithiumaluminiumhydride,theAlH4 anioncarrieshydridiccentersfirmlyattachedtotheAl(III).
Althoughhydridescanbeformedwithalmostallmaingroupelements,thenumberandcombinationof
possiblecompoundsvarieswidelyforexample,thereareover100binaryboranehydridesknown,butonly
onebinaryaluminiumhydride.[40]Binaryindiumhydridehasnotyetbeenidentified,althoughlarger
complexesexist.[41]
Ininorganicchemistry,hydridescanalsoserveasbridgingligandsthatlinktwometalcentersina
coordinationcomplex.Thisfunctionisparticularlycommoningroup13elements,especiallyinboranes
(boronhydrides)andaluminiumcomplexes,aswellasinclusteredcarboranes.[42]
Protonsandacids
Furtherinformation:Acidbasereaction
OxidationofhydrogenremovesitselectronandgivesH+,whichcontainsnoelectronsandanucleuswhich
+
isusuallycomposedofoneproton.ThatiswhyH isoftencalledaproton.Thisspeciesiscentralto
discussionofacids.UndertheBronstedLowrytheory,acidsareprotondonors,whilebasesareproton
acceptors.
+
Abareproton,H ,cannotexistinsolutionorinioniccrystals,becauseofitsunstoppableattractiontoother
atomsormoleculeswithelectrons.Exceptatthehightemperaturesassociatedwithplasmas,suchprotons
cannotberemovedfromtheelectroncloudsofatomsandmolecules,andwillremainattachedtothem.
However,theterm'proton'issometimesusedlooselyandmetaphoricallytorefertopositivelychargedor
+
cationichydrogenattachedtootherspeciesinthisfashion,andassuchisdenoted"H "withoutany
implicationthatanysingleprotonsexistfreelyasaspecies.
Toavoidtheimplicationofthenaked"solvatedproton"insolution,acidicaqueoussolutionsaresometimes
+
consideredtocontainalessunlikelyfictitiousspecies,termedthe"hydroniumion"(H3O ).However,even
inthiscase,suchsolvatedhydrogencationsaremorerealisticallyconceivedasbeingorganizedinto
+
clustersthatformspeciesclosertoH9O4 .[43]Otheroxoniumionsarefoundwhenwaterisinacidicsolution
withothersolvents.[44]
AlthoughexoticonEarth,oneofthemostcommonionsintheuniverseistheH3 ion,knownasprotonated
molecularhydrogenorthetrihydrogencation.[45]
Isotopes
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Mainarticle:Isotopesofhydrogen
1
Hydrogenhasthreenaturallyoccurringisotopes,denoted H, H
3
4
7
and H.Other,highlyunstablenuclei( Hto H)havebeen
synthesizedinthelaboratorybutnotobservedinnature.[46][47]
1
Hydrogendischarge(spectrum)tube
Histhemostcommonhydrogenisotopewithanabundance
ofmorethan99.98%.Becausethenucleusofthisisotope
consistsofonlyasingleproton,itisgiventhedescriptivebut
rarelyusedformalnameprotium.[48]
2
H,theotherstablehydrogenisotope,isknownasdeuterium
andcontainsoneprotonandoneneutroninitsnucleus.
Essentiallyalldeuteriumintheuniverseisthoughttohave
Deuteriumdischarge(spectrum)tube
beenproducedatthetimeoftheBigBang,andhasendured
sincethattime.Deuteriumisnotradioactive,anddoesnot
representasignificanttoxicityhazard.Waterenrichedinmolecules
thatincludedeuteriuminsteadofnormalhydrogeniscalledheavy
water.Deuteriumanditscompoundsareusedasanonradioactive
1
labelinchemicalexperimentsandinsolventsfor HNMR
spectroscopy.[49]Heavywaterisusedasaneutronmoderatorand
coolantfornuclearreactors.Deuteriumisalsoapotentialfuelfor
commercialnuclearfusion.[50]
3
Hisknownastritiumandcontainsoneprotonandtwoneutronsin
itsnucleus.Itisradioactive,decayingintohelium3throughbeta
decaywithahalflifeof12.32years.[42]Itissoradioactivethatitcan
Protium,themostcommon
beusedinluminouspaint,makingitusefulinsuchthingsaswatches.
isotopeofhydrogen,hasone
Theglasspreventsthesmallamountofradiationfromgettingout.[51]
protonandoneelectron.
Smallamountsoftritiumoccurnaturallybecauseoftheinteractionof
Uniqueamongallstable
cosmicrayswithatmosphericgasestritiumhasalsobeenreleased
isotopes,ithasnoneutrons
[52]
duringnuclearweaponstests. Itisusedinnuclearfusionreactions,
(seediprotonforadiscussion
[53]asatracerinisotopegeochemistry,[54]andinspecializedself
ofwhyothersdonotexist).
[55]
poweredlightingdevices. Tritiumhasalsobeenusedinchemical
andbiologicallabelingexperimentsasaradiolabel.[56]
Hydrogenistheonlyelementthathasdifferentnamesforitsisotopesincommonusetoday.Duringthe
earlystudyofradioactivity,variousheavyradioactiveisotopesweregiventheirownnames,butsuchnames
2
3
arenolongerused,exceptfordeuteriumandtritium.ThesymbolsDandT(insteadof Hand H)are
sometimesusedfordeuteriumandtritium,butthecorrespondingsymbolforprotium,P,isalreadyinuse
forphosphorusandthusisnotavailableforprotium.[57]Initsnomenclaturalguidelines,theInternational
2
3
2
3
UnionofPureandAppliedChemistryallowsanyofD,T, H,and Htobeused,although Hand Hare
preferred.[58]
History
Discoveryanduse
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Mainarticle:Timelineofhydrogentechnologies
In1671,RobertBoylediscoveredanddescribedthereactionbetweenironfilingsanddiluteacids,which
resultsintheproductionofhydrogengas.[59][60]In1766,HenryCavendishwasthefirsttorecognize
hydrogengasasadiscretesubstance,bynamingthegasfromametalacidreaction"flammableair".He
speculatedthat"flammableair"wasinfactidenticaltothehypotheticalsubstancecalled"phlogiston"[61][62]
andfurtherfindingin1781thatthegasproduceswaterwhenburned.Heisusuallygivencreditforits
discoveryasanelement.[6][7]In1783,AntoineLavoisiergavetheelementthenamehydrogen(fromthe
Greekhydromeaning"water"andgenesmeaning"creator")[8]whenheandLaplace
reproducedCavendish'sfindingthatwaterisproducedwhenhydrogenisburned.[7]
Lavoisierproducedhydrogenforhisexperimentsonmassconservationby
reactingafluxofsteamwithmetallicironthroughanincandescentiron
tubeheatedinafire.Anaerobicoxidationofironbytheprotonsofwater
athightemperaturecanbeschematicallyrepresentedbythesetof
followingreactions:
Fe+H2OFeO+H2
2Fe+3H2OFe2O3+3H2
3Fe+4H2OFe3O4+4H2
Manymetalssuchaszirconiumundergoasimilarreactionwithwater
leadingtotheproductionofhydrogen.
AntoineLaurentdeLavoisier
HydrogenwasliquefiedforthefirsttimebyJamesDewarin1898by
usingregenerativecoolingandhisinvention,thevacuumflask.[7]He
producedsolidhydrogenthenextyear.[7]DeuteriumwasdiscoveredinDecember1931byHaroldUrey,
andtritiumwaspreparedin1934byErnestRutherford,MarkOliphant,andPaulHarteck.[6]Heavywater,
whichconsistsofdeuteriumintheplaceofregularhydrogen,wasdiscoveredbyUrey'sgroupin1932.[7]
FranoisIsaacdeRivazbuiltthefirstdeRivazengine,aninternalcombustionenginepoweredbyamixture
ofhydrogenandoxygenin1806.EdwardDanielClarkeinventedthehydrogengasblowpipein1819.The
Dbereiner'slampandlimelightwereinventedin1823.[7]
ThefirsthydrogenfilledballoonwasinventedbyJacquesCharlesin1783.[7]Hydrogenprovidedtheliftfor
thefirstreliableformofairtravelfollowingthe1852inventionofthefirsthydrogenliftedairshipbyHenri
Giffard.[7]GermancountFerdinandvonZeppelinpromotedtheideaofrigidairshipsliftedbyhydrogenthat
laterwerecalledZeppelinsthefirstofwhichhaditsmaidenflightin1900.[7]Regularlyscheduledflights
startedin1910andbytheoutbreakofWorldWarIinAugust1914,theyhadcarried35,000passengers
withoutaseriousincident.Hydrogenliftedairshipswereusedasobservationplatformsandbombersduring
thewar.
ThefirstnonstoptransatlanticcrossingwasmadebytheBritishairshipR34in1919.Regularpassenger
serviceresumedinthe1920sandthediscoveryofheliumreservesintheUnitedStatespromisedincreased
safety,buttheU.S.governmentrefusedtosellthegasforthispurpose.Therefore,H2wasusedinthe
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Hindenburgairship,whichwasdestroyedinamidairfireoverNewJerseyon6May1937.[7]Theincident
wasbroadcastliveonradioandfilmed.Ignitionofleakinghydrogeniswidelyassumedtobethecause,but
laterinvestigationspointedtotheignitionofthealuminizedfabriccoatingbystaticelectricity.Butthe
damagetohydrogen'sreputationasaliftinggaswasalreadydone.
Inthesameyearthefirsthydrogencooledturbogeneratorwentintoservicewithgaseoushydrogenasa
coolantintherotorandthestatorin1937atDayton,Ohio,bytheDaytonPower&LightCo.[63]because
ofthethermalconductivityofhydrogengas,thisisthemostcommontypeinitsfieldtoday.
Thenickelhydrogenbatterywasusedforthefirsttimein1977aboardtheU.S.Navy'sNavigation
technologysatellite2(NTS2).[64]Forexample,theISS,[65]MarsOdyssey[66]andtheMarsGlobal
Surveyor[67]areequippedwithnickelhydrogenbatteries.Inthedarkpartofitsorbit,theHubbleSpace
Telescopeisalsopoweredbynickelhydrogenbatteries,whichwerefinallyreplacedinMay2009,[68]more
than19yearsafterlaunch,and13yearsovertheirdesignlife.[69]
Roleinquantumtheory
Becauseofitssimple
atomicstructure,
consistingonlyofa
protonandanelectron,
thehydrogenatom,
Hydrogenemissionspectrumlinesinthevisiblerange.Thesearethefourvisiblelines
togetherwiththe
oftheBalmerseries
spectrumoflight
producedfromitor
absorbedbyit,hasbeencentraltothedevelopmentofthetheoryofatomicstructure.[70]Furthermore,the
+
correspondingsimplicityofthehydrogenmoleculeandthecorrespondingcationH2 allowedfuller
understandingofthenatureofthechemicalbond,whichfollowedshortlyafterthequantummechanical
treatmentofthehydrogenatomhadbeendevelopedinthemid1920s.
Oneofthefirstquantumeffectstobeexplicitlynoticed(butnotunderstoodatthetime)wasaMaxwell
observationinvolvinghydrogen,halfacenturybeforefullquantummechanicaltheoryarrived.Maxwell
observedthatthespecificheatcapacityofH2unaccountablydepartsfromthatofadiatomicgasbelow
roomtemperatureandbeginstoincreasinglyresemblethatofamonatomicgasatcryogenictemperatures.
Accordingtoquantumtheory,thisbehaviorarisesfromthespacingofthe(quantized)rotationalenergy
levels,whichareparticularlywidespacedinH2becauseofitslowmass.Thesewidelyspacedlevelsinhibit
equalpartitionofheatenergyintorotationalmotioninhydrogenatlowtemperatures.Diatomicgases
composedofheavieratomsdonothavesuchwidelyspacedlevelsanddonotexhibitthesameeffect.[71]
Antihydrogen(H)istheantimattercounterparttohydrogen.Itconsistsofanantiprotonwithapositron.
Antihydrogenistheonlytypeofantimatteratomtohavebeenproducedasof2015.[72][73]
Naturaloccurrence
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Hydrogen,asatomicH,isthemostabundantchemicalelementin
theuniverse,makingup75%ofnormalmatterbymassandover
90%bynumberofatoms(mostofthemassoftheuniverse,
however,isnotintheformofchemicalelementtypematter,but
ratherispostulatedtooccurasyetundetectedformsofmasssuchas
darkmatteranddarkenergy).[74]Thiselementisfoundingreat
abundanceinstarsandgasgiantplanets.MolecularcloudsofH2are
associatedwithstarformation.Hydrogenplaysavitalrolein
poweringstarsthroughtheprotonprotonreactionandtheCNO
cyclenuclearfusion.[75]
Throughouttheuniverse,hydrogenismostlyfoundintheatomic
andplasmastateswhosepropertiesarequitedifferentfrom
molecularhydrogen.Asaplasma,hydrogen'selectronandproton
NGC604,agiantregionofionized
arenotboundtogether,resultinginveryhighelectricalconductivity
hydrogenintheTriangulumGalaxy
andhighemissivity(producingthelightfromtheSunandother
stars).Thechargedparticlesarehighlyinfluencedbymagneticand
electricfields.Forexample,inthesolarwindtheyinteractwiththeEarth'smagnetospheregivingriseto
Birkelandcurrentsandtheaurora.Hydrogenisfoundintheneutralatomicstateintheinterstellarmedium.
ThelargeamountofneutralhydrogenfoundinthedampedLymanalphasystemsisthoughttodominate
thecosmologicalbaryonicdensityoftheUniverseuptoredshiftz=4.[76]
UnderordinaryconditionsonEarth,elementalhydrogenexistsasthediatomicgas,H2.However,hydrogen
gasisveryrareintheEarth'satmosphere(1ppmbyvolume)becauseofitslightweight,whichenablesitto
escapefromEarth'sgravitymoreeasilythanheaviergases.However,hydrogenisthethirdmostabundant
elementontheEarth'ssurface,[77]mostlyintheformofchemicalcompoundssuchashydrocarbonsand
water.[42]Hydrogengasisproducedbysomebacteriaandalgaeandisanaturalcomponentofflatus,asis
methane,itselfahydrogensourceofincreasingimportance.[78]
+
Amolecularformcalledprotonatedmolecularhydrogen(H3 )isfoundintheinterstellarmedium,whereit
isgeneratedbyionizationofmolecularhydrogenfromcosmicrays.Thischargedionhasalsobeen
observedintheupperatmosphereoftheplanetJupiter.Theionisrelativelystableintheenvironmentof
+
outerspaceduetothelowtemperatureanddensity.H3 isoneofthemostabundantionsintheUniverse,
anditplaysanotableroleinthechemistryoftheinterstellarmedium.[79]NeutraltriatomichydrogenH3can
+
onlyexistinanexcitedformandisunstable.[80]Bycontrast,thepositivehydrogenmolecularion(H2 )isa
raremoleculeintheuniverse.
Production
Mainarticle:Hydrogenproduction
H2isproducedinchemistryandbiologylaboratories,oftenasabyproductofotherreactionsinindustry
forthehydrogenationofunsaturatedsubstratesandinnatureasameansofexpellingreducingequivalents
inbiochemicalreactions.
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Metalacid
Inthelaboratory,H2isusuallypreparedbythereactionofdilutenonoxidizingacidsonsomereactive
metalssuchaszincwithKipp'sapparatus.
+
2+
Zn+2H Zn +H2
AluminiumcanalsoproduceH2upontreatmentwithbases:
2Al+6H2O+2OH 2Al(OH)4 +3H2

Theelectrolysisofwaterisasimplemethodofproducinghydrogen.Alowvoltagecurrentisrunthrough
thewater,andgaseousoxygenformsattheanodewhilegaseoushydrogenformsatthecathode.Typically
thecathodeismadefromplatinumoranotherinertmetalwhenproducinghydrogenforstorage.If,
however,thegasistobeburntonsite,oxygenisdesirabletoassistthecombustion,andsobothelectrodes
wouldbemadefrominertmetals.(Iron,forinstance,wouldoxidize,andthusdecreasetheamountof
oxygengivenoff.)Thetheoreticalmaximumefficiency(electricityusedvs.energeticvalueofhydrogen
produced)isintherange8094%.[81]
2H2O(l)2H2(g)+O2(g)
In2007,itwasdiscoveredthatanalloyofaluminiumandgalliuminpelletformaddedtowatercouldbe
usedtogeneratehydrogen.Theprocessalsocreatesalumina,buttheexpensivegallium,whichpreventsthe
formationofanoxideskinonthepellets,canbereused.Thishasimportantpotentialimplicationsfora
hydrogeneconomy,ashydrogencanbeproducedonsiteanddoesnotneedtobetransported.[82]
Steamreforming
Hydrogencanbepreparedinseveraldifferentways,buteconomicallythemostimportantprocessesinvolve
removalofhydrogenfromhydrocarbons.Commercialbulkhydrogenisusuallyproducedbythesteam
reformingofnaturalgas.[83]Athightemperatures(10001400K,7001100Cor13002000F),steam
(watervapor)reactswithmethanetoyieldcarbonmonoxideandH2.
CH4+H2OCO+3H2
Thisreactionisfavoredatlowpressuresbutisnonethelessconductedathighpressures(2.0MPa,20atm
or600inHg).ThisisbecausehighpressureH2isthemostmarketableproductandPressureSwing
Adsorption(PSA)purificationsystemsworkbetterathigherpressures.Theproductmixtureisknownas
"synthesisgas"becauseitisoftenuseddirectlyfortheproductionofmethanolandrelatedcompounds.
Hydrocarbonsotherthanmethanecanbeusedtoproducesynthesisgaswithvaryingproductratios.Oneof
themanycomplicationstothishighlyoptimizedtechnologyistheformationofcokeorcarbon:
CH4C+2H2
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Consequently,steamreformingtypicallyemploysanexcessofH2O.Additionalhydrogencanberecovered
fromthesteambyuseofcarbonmonoxidethroughthewatergasshiftreaction,especiallywithaniron
oxidecatalyst.Thisreactionisalsoacommonindustrialsourceofcarbondioxide:[83]
CO+H2OCO2+H2
OtherimportantmethodsforH2productionincludepartialoxidationofhydrocarbons:[84]
2CH4+O22CO+4H2
andthecoalreaction,whichcanserveasapreludetotheshiftreactionabove:[83]
C+H2OCO+H2
Hydrogenissometimesproducedandconsumedinthesameindustrialprocess,withoutbeingseparated.In
theHaberprocessfortheproductionofammonia,hydrogenisgeneratedfromnaturalgas.[85]Electrolysis
ofbrinetoyieldchlorinealsoproduceshydrogenasacoproduct.[86]
Thermochemical
Therearemorethan200thermochemicalcycleswhichcanbeusedforwatersplitting,aroundadozenof
thesecyclessuchastheironoxidecycle,cerium(IV)oxidecerium(III)oxidecycle,zinczincoxidecycle,
sulfuriodinecycle,copperchlorinecycleandhybridsulfurcycleareunderresearchandintestingphaseto
producehydrogenandoxygenfromwaterandheatwithoutusingelectricity.[87]Anumberoflaboratories
(includinginFrance,Germany,Greece,Japan,andtheUSA)aredevelopingthermochemicalmethodsto
producehydrogenfromsolarenergyandwater.[88]
Anaerobiccorrosion
Underanaerobicconditions,ironandsteelalloysareslowlyoxidizedbytheprotonsofwaterconcomitantly
reducedinmolecularhydrogen(H2).Theanaerobiccorrosionofironleadsfirsttotheformationofferrous
hydroxide(greenrust)andcanbedescribedbythefollowingreaction:
Fe+2H2OFe(OH)2+H2
Initsturn,underanaerobicconditions,theferroushydroxide(Fe(OH)2)canbeoxidizedbytheprotonsof
watertoformmagnetiteandmolecularhydrogen.ThisprocessisdescribedbytheSchikorrreaction:
3Fe(OH)2Fe3O4+2H2O+H2
ferroushydroxidemagnetite+water+hydrogen
Thewellcrystallizedmagnetite(Fe3O4)isthermodynamicallymorestablethantheferroushydroxide
(Fe(OH)2).
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Thisprocessoccursduringtheanaerobiccorrosionofironandsteelinoxygenfreegroundwaterandin
reducingsoilsbelowthewatertable.
Geologicaloccurrence:theserpentinizationreaction
Intheabsenceofatmosphericoxygen(O2),indeepgeologicalconditionsprevailingfarawayfromEarth
atmosphere,hydrogen(H2)isproducedduringtheprocessofserpentinizationbytheanaerobicoxidationby
thewaterprotons(H+)oftheferrous(Fe2+)silicatepresentinthecrystallatticeofthefayalite(Fe2SiO4,the
olivineironendmember).Thecorrespondingreactionleadingtotheformationofmagnetite(Fe3O4),quartz
(SiO2)andhydrogen(H2)isthefollowing:
3Fe2SiO4+2H2O2Fe3O4+3SiO2+3H2
fayalite+watermagnetite+quartz+hydrogen
ThisreactioncloselyresemblestheSchikorrreactionobservedintheanaerobicoxidationoftheferrous
hydroxideincontactwithwater.
Formationintransformers
Fromallthefaultgasesformedinpowertransformers,hydrogenisthemostcommonandisgenerated
undermostfaultconditionsthus,formationofhydrogenisanearlyindicationofseriousproblemsinthe
transformer'slifecycle.[89]
Applications
Consumptioninprocesses
LargequantitiesofH2areneededinthepetroleumandchemicalindustries.ThelargestapplicationofH2is
fortheprocessing("upgrading")offossilfuels,andintheproductionofammonia.Thekeyconsumersof
H2inthepetrochemicalplantincludehydrodealkylation,hydrodesulfurization,andhydrocracking.H2has
severalotherimportantuses.H2isusedasahydrogenatingagent,particularlyinincreasingthelevelof
saturationofunsaturatedfatsandoils(foundinitemssuchasmargarine),andintheproductionof
methanol.Itissimilarlythesourceofhydrogeninthemanufactureofhydrochloricacid.H2isalsousedas
areducingagentofmetallicores.[90]
Hydrogenishighlysolubleinmanyrareearthandtransitionmetals[91]andissolubleinboth
nanocrystallineandamorphousmetals.[92]Hydrogensolubilityinmetalsisinfluencedbylocaldistortions
orimpuritiesinthecrystallattice.[93]Thesepropertiesmaybeusefulwhenhydrogenispurifiedbypassage
throughhotpalladiumdisks,butthegas'shighsolubilityisametallurgicalproblem,contributingtothe
embrittlementofmanymetals,[13]complicatingthedesignofpipelinesandstoragetanks.[14]
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Apartfromitsuseasareactant,H2haswideapplicationsinphysicsandengineering.Itisusedasa
shieldinggasinweldingmethodssuchasatomichydrogenwelding.[94][95]H2isusedastherotorcoolantin
electricalgeneratorsatpowerstations,becauseithasthehighestthermalconductivityofanygas.LiquidH2
isusedincryogenicresearch,includingsuperconductivitystudies.[96]BecauseH2islighterthanair,having
alittlemorethan114ofthedensityofair,itwasoncewidelyusedasaliftinggasinballoonsandairships.
[97]
Inmorerecentapplications,hydrogenisusedpureormixedwithnitrogen(sometimescalledforminggas)
asatracergasforminuteleakdetection.Applicationscanbefoundintheautomotive,chemical,power
generation,aerospace,andtelecommunicationsindustries.[98]Hydrogenisanauthorizedfoodadditive(E
949)thatallowsfoodpackageleaktestingamongotherantioxidizingproperties.[99]
Hydrogen'srarerisotopesalsoeachhavespecificapplications.Deuterium(hydrogen2)isusedinnuclear
fissionapplicationsasamoderatortoslowneutrons,andinnuclearfusionreactions.[7]Deuterium
compoundshaveapplicationsinchemistryandbiologyinstudiesofreactionisotopeeffects.[100]Tritium
(hydrogen3),producedinnuclearreactors,isusedintheproductionofhydrogenbombs,[101]asanisotopic
labelinthebiosciences,[56]andasaradiationsourceinluminouspaints.[102]
ThetriplepointtemperatureofequilibriumhydrogenisadefiningfixedpointontheITS90temperature
scaleat13.8033kelvins.[103]
Coolant
Mainarticle:Hydrogencooledturbogenerator
Hydrogeniscommonlyusedinpowerstationsasacoolantingeneratorsduetoanumberoffavorable
propertiesthatareadirectresultofitslightdiatomicmolecules.Theseincludelowdensity,lowviscosity,
andthehighestspecificheatandthermalconductivityofallgases.
Energycarrier
Seealso:HydrogeneconomyandHydrogeninfrastructure
Hydrogenisnotanenergyresource,[104]exceptinthehypotheticalcontextofcommercialnuclearfusion
powerplantsusingdeuteriumortritium,atechnologypresentlyfarfromdevelopment.[105]TheSun's
energycomesfromnuclearfusionofhydrogen,butthisprocessisdifficulttoachievecontrollablyonEarth.
[106]Elementalhydrogenfromsolar,biological,orelectricalsourcesrequiremoreenergytomakeitthanis
obtainedbyburningit,sointhesecaseshydrogenfunctionsasanenergycarrier,likeabattery.Hydrogen
maybeobtainedfromfossilsources(suchasmethane),butthesesourcesareunsustainable.[104]
Theenergydensityperunitvolumeofbothliquidhydrogenandcompressedhydrogengasatany
practicablepressureissignificantlylessthanthatoftraditionalfuelsources,althoughtheenergydensityper
unitfuelmassishigher.[104]Nevertheless,elementalhydrogenhasbeenwidelydiscussedinthecontextof
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energy,asapossiblefuturecarrierofenergyonaneconomywidescale.[107]Forexample,CO2
sequestrationfollowedbycarboncaptureandstoragecouldbeconductedatthepointofH2production
fromfossilfuels.[108]Hydrogenusedintransportationwouldburnrelativelycleanly,withsomeNOx
emissions,[109]butwithoutcarbonemissions.[108]However,theinfrastructurecostsassociatedwithfull
conversiontoahydrogeneconomywouldbesubstantial.[110]Fuelcellscanconverthydrogenandoxygen
directlytoelectricitymoreefficientlythaninternalcombustionengines.[111]
Semiconductorindustry
Hydrogenisemployedtosaturatebroken("dangling")bondsofamorphoussiliconandamorphouscarbon
thathelpsstabilizingmaterialproperties.[112]Itisalsoapotentialelectrondonorinvariousoxidematerials,
includingZnO,[113][114]SnO2,CdO,MgO,[115]ZrO2,HfO2,La2O3,Y2O3,TiO2,SrTiO3,LaAlO3,SiO2,
Al2O3,ZrSiO4,HfSiO4,andSrZrO3.[116]
Biologicalreactions
Furtherinformation:BiohydrogenandBiologicalhydrogenproduction(Algae)
H2isaproductofsometypesofanaerobicmetabolismandisproducedbyseveralmicroorganisms,usually
viareactionscatalyzedbyironornickelcontainingenzymescalledhydrogenases.Theseenzymescatalyze
thereversibleredoxreactionbetweenH2anditscomponenttwoprotonsandtwoelectrons.Creationof
hydrogengasoccursinthetransferofreducingequivalentsproducedduringpyruvatefermentationto
water.[117]Thenaturalcycleofhydrogenproductionandconsumptionbyorganismsiscalledthehydrogen
cycle.[118]
Watersplitting,inwhichwaterisdecomposedintoitscomponentprotons,electrons,andoxygen,occursin
thelightreactionsinallphotosyntheticorganisms.Somesuchorganisms,includingthealga
Chlamydomonasreinhardtiiandcyanobacteria,haveevolvedasecondstepinthedarkreactionsinwhich
protonsandelectronsarereducedtoformH2gasbyspecializedhydrogenasesinthechloroplast.[119]
Effortshavebeenundertakentogeneticallymodifycyanobacterialhydrogenasestoefficientlysynthesize
H2gaseveninthepresenceofoxygen.[120]Effortshavealsobeenundertakenwithgeneticallymodified
algainabioreactor.[121]
Safetyandprecautions
Mainarticle:Hydrogensafety
Hydrogenposesanumberofhazardstohumansafety,frompotentialdetonationsandfireswhenmixed
withairtobeinganasphyxiantinitspure,oxygenfreeform.[122]Inaddition,liquidhydrogenisacryogen
andpresentsdangers(suchasfrostbite)associatedwithverycoldliquids.[123]Hydrogendissolvesinmany
metals,and,inadditiontoleakingout,mayhaveadverseeffectsonthem,suchashydrogenembrittlement,
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[124]leadingtocracksandexplosions.[125]Hydrogengasleakingintoexternalairmayspontaneouslyignite.
Moreover,hydrogenfire,whilebeingextremelyhot,isalmostinvisible,andthuscanleadtoaccidental
burns.[126]
Eveninterpretingthehydrogendata(includingsafetydata)isconfoundedbyanumberofphenomena.
Manyphysicalandchemicalpropertiesofhydrogendependontheparahydrogen/orthohydrogenratio(it
oftentakesdaysorweeksatagiventemperaturetoreachtheequilibriumratio,forwhichthedataisusually
given).Hydrogendetonationparameters,suchascriticaldetonationpressureandtemperature,strongly
dependonthecontainergeometry.[122]
Notes
1. However,mostoftheuniverse'smassisnotintheformofbaryonsorchemicalelements.Seedarkmatterand
darkenergy.
2. 286kJ/mol:energypermoleofthecombustiblematerial(molecularhydrogen)
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8/21/2015
2010.ISBN9780984365302.
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UniversityPress.ISBN0531125017.
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Climate.IslandPress.ISBN155963703X.
Scerri,Eric(2007).ThePeriodicSystem,ItsStoryandItsSignificance.NewYork:Oxford
UniversityPress.ISBN0195305736.
Externallinks
BasicHydrogenCalculationsofQuantumMechanics
(http://www.physics.drexel.edu/~tim/open/hydrofin/)
Hydrogen(http://www.periodicvideos.com/videos/001.htm)atThePeriodicTableofVideos
(UniversityofNottingham)
Hightemperaturehydrogenphasediagram(http://militzer.berkeley.edu/diss/node5.html)
Wavefunctionofhydrogen(http://hyperphysics.phyastr.gsu.edu/Hbase/quantum/hydwf.html#c3)
Retrievedfrom"https://en.wikipedia.org/w/index.php?title=Hydrogen&oldid=676683637"
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