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GES166/266,SoilChemistry
Winter2000

LectureSupplement4
OxidationandReduction(Redox)Reactions

The hydrogen ion (H+) and the availability of electrons (e) are the master
variablesofsoilchemicalreactions.UnlikeH+,electronsarenot'freeforming';theyare
contained within atoms or molecules. Thus, electrons are only transferred between
species.Redox,shortforreductionoxidation,isthetermedusedtodenotethetransfer
ofelectrons.Oxidationandreductionaredefinedas:

Reduction:Thegainofelectronsbyacompound

Oxidation:Thelossofelectronsbyacompound

Remember,oxidationandreductionMUSToccurtogether!Anelectroncannotexistas
an isolated entity; it is transferred from one species (the reductant) to another (the
oxidant). Individual oxidation or reduction reactions are termed halfreactions; half
reactionsmustbecoupledtogiveanoverallreaction.Whenanoxidationorreduction
reactioniswrittenindependently;forexample,thereductionofCO2
CO2+4e+4H+=CH2O+H2O (photosynthesis) [V.1]

orfortheoxidationofH2O

2H2O=O2+4e+4H+ [V.2].

afreeelectron(e)writtenintheequation.Anoverallredoxreactionswillneverhave
aneshown.Youcancouple[1]and[2]togetherforanoverallreaction:

CO2+H2O=CH2O+O2 [V.3]

Insoils,microorganismsplayakeyroleindrivingredoxreactions.Theydrive
redoxreactionsbyusingaspeciesasanelectrondonor(usuallyreducedcarbon)orasan
electronacceptor(usuallyoxygeninaerobicenvironments).Wecan,however,classify
compoundsaselectrondonorsoracceptors

ElectronDonors
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Byfarthe mostprevalent electron donoris organic carbon. Carbohydrate oxidation

servesasanexampleoforganiccarbonoxidationtocarbondioxide.

CH2O+H2O=CO2+4e

Thishalfreactioniswhatsuppliesenergytomicroorganismswithinsoils(wewillspeak
oftheelectronacceptortheyuseinamoment).Otherelectrondonorsthatoccurinsoils
and participate in chemical redox couples are compounds found in reduced (oxygen
limited)soils.Examplesinclude:

Mn(II)=Mn(IV)+2e

Fe(II)=Fe(III)+e

S2=SO42+8e

As(III)=As(V)+2e

allofwhichareusedmuchlessfrequentlythancarbonsources.Bacterialoxidationof
Fe(II)andsulfidearecommoninminespoilsandreducedsediment;sulfideisalsoused
asanelectrondonorbybacteriainhydrothermalmarinevents.

ElectronAcceptors

The most prevalent electron acceptor is O2 (g), and is the sole electron acceptor in
aeratedsystems(aerobicsystems).

O2+4e+4H+=2H2O [V.4]

Livingcompoundscreateenergybyoxidizingcarbohydratesandreducingoxygen.That
is, organisms take electrons from the organic carbon, run it through their metabolic
cycles,andthendumptheelectrontoanelectronacceptor.Whenoxygenisnotpresent,
microorganisms must seek alternate electron acceptors. The energy gain for the
organismsistheenergydifferencebetweenreducedcarbonandtheelectronacceptor.In
orderoffavorability,electronacceptorsare:

O2>NO3>Mn(VI)>Fe(III)>AsO43>SO42

Alackofoxygenleadstoananaerobicconditionandresultsinthebuildupof
reducedspecies:Mn(II),N2,Fe(II),As(III),andS2.Whenreducedspeciesarebuildup
inthesystem,itistermed"REDUCED".WhenO2ispresentwithreducedspeciessuch
asS2,Fe(II),Mn(II),orAs(III)itisenergeticallyfavorableforoxygentooxidizingthe
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previousspeciesandthusbecomereducedtowater.Thus,ifoxygenisintroducedtoa
reducedsystem,thereducedspeciesareoxidizesinoppositeorder:

SO42>AsO43>Fe(III)>Mn(VI)>NO3

Wewillspecifytheexactenergiesoftheseoverallreactionsshortly.

AHypotheticalThought:ElectronActivity(pe)

Althoughthisisnottrulycorrect,wecanthinkoftheavailabilityofelectronsinterms
ofanelectronactivity. Inthisway,electrons aretreatedjustlikeH +:Theyhavean
artificialACTIVITY(mol/l).Usually,electronactivityiswrittenaspe

log(e)=pe

Giventhisnotation,wecantreatelectronsjustasanyotherreactant. Letsconsidera
generalizedhalfreactiontoillustratethisconvention(anditsutility).

OX+ne=RED

K=(RED)/(OX)(e)n

logK=log(RED)/OXnloge

=log(RED)/OX+npe

logKnpe=log(RED)/(OX)

note:wecouldmeasurepeandknowtheratioofRED/OX

ElectrodePotential

Whilepeisaconvenientwayto'view'redoxreactions,itisnotreal.Sinceelectronsdo
notexistinsolutionweneedaseparatewayofmeasuringtheirreactivityinasystem.
Thisisdonewithanelectronpotential:Thepotentialforanelectrontoparticipateina
reaction.

DerivationoftheSystemPotential(Eh)
Grxn=Gro+RTlnQ(LewisEqn) [V.5]
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whereQisthereactionquotientandisanalogoustotheionactivityproduct(IAP)
wediscussedinthePrecipitationsection.

Gr=nFEorGro=nFEo [V.6]

wheren=#ofe(inmols)
andF=96,500C/mole or 23,061Cal/Vmole

substituting[2]into[1]yields

nFE=nFEo+RTlnQ
then
E=EoRT/nFlnQ

Forareaction: Oxid+e=Red

ThisthensimplifiestotheNernstEquation:

E=Eo0.059/nlog[Red/Oxid]

orwecouldsimplywriteamoregeneric,completereactionas

aA+bB=cC+dD

and
E=Eo0.059/nlog{[A]a[B]b/[C]c[D]d}

Ifweareatequilibrium,thenQ(IAP)=Keqand

Eo(V)=(0.059/n)logK

ConvertingbetweenEhandpe: Eh(mV)=59.2pe

ApplicationofpeandEh

MostsoilsmaintainapHbetween3.5and9;apeof6to+12(Eh:355to710mV);
andape+pHof218.
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peandEhRanges

Soilshavebeenbroadlyclassifiedinto3redoxstatesdependingontheirpevalues:

Oxic: pe>7 Eh>400mV

Suboxic pe27 100<Eh<400mV
Anoxic pe<2 Eh<100mV

butthisclassificationdoesnotincludeanecessaryconsiderationpH. Abetterwayto
classifytheredoxstatusistosimplystatethatsuboxiczonesarecharacterizedbythe
reductionofFeandMnoxides,butnotthereductionofsulfate. Anoxicsystemshave
beenloweredtowheresulfatebecomesanactiveelectronacceptor,yieldingS2orother
reducedsulfurspecies.Methane(CH3)isalsoproducedunderhighlyanoxicconditions.
Insoils,realizethattheremaybemicroenvironmentsthatareanoxicveryclosetoareas
thatareoxic.

Howdosoilsbecomeoxidizedorreduced,andhowaretheyoxidizingorreducing?

Theredoxpotentialisgovernedbytwoprimaryfactors:

1.Microbialactivity
2.Availabilityofelectronacceptors.

Intheoxygensupplyisthedominantfactorcontrollingtheredoxstatusofasoil;when
oxygenislimitedotherterminalelectronacceptorsbecomeimportant.
Chemicalspeciesalsoinfluencetheredoxstatusofsystems,butinthepresenceof
microbial activity they are a small consideration compared to the microorganisms
themselves.Letsaskanotherimportantquestionregardingtheredoxstatusofasoil.
WhydoesthepresenceofO2increasetheredoxpotentialofthesystemandmakeit
moreoxidized?Theansweristhatcouplingoxygensreductionhalfreactionwithany
redox couple having a lower Eh value will result in an energetically favor redox
reaction. ThisleadstothereductionofO2 andoxidationoftheoriginallyreduced
compound.
Forexample,considerFe(II)comingincontactwithmolecularoxygen(O2):
H++1/4O2+e=1/2H2O 1.229
Fe2+=Fe3++e 0.711V

so Fe2++1/2O2+H+=Fe3++1/2H2O 0.518

ApositiveEh,orEhrxn,meansthatthereactionisthermodynamicallyfavorable.Thus,
ifkineticconstraintsarenotlimitingoxygenwilloxidizeeverythingwithalowerE(h)
valueandcausethesystemtohavea'lowelectronactivity'(orhighredoxpotential).
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Microorganisms

Microorganismsareprobablythemostimportantfactorcontrollingtheredoxstatusof
soils:
theyreducecarbontostoreenergy
theyoxidizeittoreleaseenergy
theyuseoxygenorothermoleculesaselectronacceptors,thusformingreduced
speciesunderoxygenlimitingconditions.

Microorganisms control the redox potential along with the redox couple of the
electronacceptor.Oxygenisthepreferredacceptorbecauseitismosteasilyreduced
towateroftheavailableacceptors.Thisleavesthegreatestenergyfromrespiration.
Initsabsence,otherredoxcouplesmustbeusedtoputelectronsliberatedfromthe
oxidationofcarboncompounds.

photosynthesisstoresenergybyreducingC

Red.ofC CO2+4e+4H+=>CH2O+H2O 0.21V

balancer 2H2O=2O2 +4e+4H+ 1.21V

overall CO2+H2O=CH2O+O2 1.00V

ToacquirethestoredenergytheCsourceisoxidized

OxidofC CH2O+H2O =>CO2+4e+4H+

RedofO2 2O2+4e+4H+=>2H2O

Overall CH2O+O2=>CO2+H2O +1.00

Alternateelectronacceptors,inorderofpreference(basedonEvalues):

NO3>N2(orotherreducedNforms)
Mn(IV)>Mn(II)
Fe(III)>Fe(II)
SO42>S2(orH2S)
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Theorderoftheirpreferenceisduetotheirredoxpotentialsforthehalfreactions(see
Table7.1inEnvironmentalChemistryofSoilsbyM.B.McBride).NotethatO2has
the highest redox potential, followed by NO3>Mn(IV)>Fe(III)>SO42. The reverse
orderwillapplyuponoxidation. Sulfidewillgofirst,followedbyFe(II),andthen
Mn(II).Alsonotethatifareducedspecieswithalowredoxpotentialispresentwitha
speciesintheoxidizedformwhichhasahigherredoxpotential,thenthereisahigh
probabilityforoxidationofthereducedspeciesandreductionoftheoxidizedspecies.

Example,ifS2andMnO2werepresenttogether.

1/8H2S+1/2H2O=1/8SO42+5/4H++e 0.303
1/2MnO2(s)+2H++e=1/2Mn2++H2O 1.23

1/8H2S+1/2MnO2(s)+1/2H2O+3/4H+=1/8SO42+1/2Mn2++1/2H2O 0.927

Theselectivityoftheterminalelectronacceptoralsoleadstothesoilbeing'Poised'at
acertainredoxpotential.Thismeansthatasasoilbecomesreduceditdoesnothavea
smoothlydecreasingpotential. Rathertheredoxpotentialmovesinstepsfromthe
potentialofoneredoxpotentialtoanotheralongthesequencediscussedabove.

pHChanges

Assoilsorsedimentsbecomereduced,theirpHtendstomovetowardneutrality.
Thatis,ifthepHofthesystemisacidicthenthepHwillincreasewhilesoilswithpH
valuesabove7tendtohavedecreasingpHvalues.

Reasons:
When the pH is initially low, H+ consumption in the reduction reactions
increasesthepH.
Forexample:MnO2(s)+4H++2e=Mn2++2H2O

IfthepHisinitiallybasic,thentheliberationandreprecipitationofmetalions
suchasFeandMnashydroxides,carbonates,orsulfidestendstolowerthepH.
Forexample:Fe2++2H2O=Fe(OH)2+2H+
Fe2++HCO3=FeCO3+H+

Soilsthatundergoseasonalfloodinganddryingtendtobecomemoreacidic.Basedon
reversiblereactionsuchasthatforsulfatesulfideyouwouldnotexpectthis.
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1/8SO42+5/4H++e=1/8H2S+1/2H2O

However,ifsulfateisleachedfromthesystemthentheaciditygeneratedintheoxidation
directionwillnotberemovedbyreduction.Thisthenleadstoagradualacidificationof
thesoil.

SpecificCycles

IronCycles:

Irongoesthroughpronouncedchangeswithredoxpotentialchanges.
Fe(III)oxidesaredominantinoxidizedsystems
suboxicsoilsresultinhighFe(II)concentrations
*Fe(II)canprecipitateasFeCO 3(siderite)
inanoxicsystems,Fe(II)mayprecipitateasFeS/FeS 2(pyrite)
uponaeration,thereducedFeformsareoxidizedquickly

O2

Oxic precipitation
oxidation
Fe 2+ Fe 3+ + 3H2O = Fe(OH)3 + 3H+
zone

diffusion
Suboxic Fe(OH)3 = Fe2+ + 3OH-
zone Fe 2+ reductivedissolution
Fe 2+ +CO 3 2 =FeCO 3
Anoxic Fecarbonateprecipitation
zone Fe 2+ +S 2 =FeS
pryiteprecipitation
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ManganeseCycles:

LikeFe,Mngoesthroughextensivechangeswithredoxpotentialchanges.
Mnoxidesdominateinaeratedsystems
Mn(II)isformeduponreduction
MnCO3 formsinreduced(suboxic)systems,lesslikelyareMnSbuttheydo
form
oxidationismuchslowerthanforFe(II)exceptatmineralsurfaces

O2

Oxic oxidation precipitation

Mn2+ Mn2+ + O2 = MnO 2
zone

diffusion
Suboxic MnO2 + 4H+ = Mn2+ + 2H2 O
zone Mn2+ reductivedissolution
Mn2+ +CO 3 2 =MnCO 3
Anoxic Fecarbonateprecipitation
zone

NitrogenCycles

OxidationofN2doesnotoccurexceptinafeworganisms
ReductionofNO3toreducedNformsaccountsfordenitrificationinsoils
NO3toNH4+istermedmineralizationandonlyoccursinlivingorganisms
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Gaseous Nitrogen Evolution

Oxic NO3 -
zone
NO2 -
NO
Suboxic N2 O
N2
zone
N-mineralization
Organic-N NH3
Nfixation

SulfurCycles

Sulfurgoesthroughdramaticchangesinredoxcycling.Itcoversafull8electron
transfersequencewithmostintermediatesbeingpossible.
We usually only consider sulfate and sulfide, but we should look at the other
possibleoxidationstates.
Sulfatedominatesinoxidizedenvironments
anoxicconditionsleadstotheformationofsulfidesandotherreducedSforms
planttissuedegradationleavesmanyintermediateSoxidationstates
sulfidetendstoformstrong,insolublecomplexeswithsofttointermediateacids:
Fe(II),Cd,Cu,Pb,Hg,...
oxidationofsulfideleadstoacidificationofmanysystems(acidminedrainage)
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O2

Oxic SO42-
zone

Suboxic zone

H2 S
Anoxic
zone S 2
Fe 2+ +S 2 =FeS
pyriteprecipitation