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Chemical Reactions
Fetter10
Therearemanyreactionsthatoperatetotransfermassamongfluids,gasesandsolids.
1)AcidBasereactions
InfluencethepHandionchemistryofwater
pHcontrolsmanychemicalsystems
pH=log[H+]
Acidasubstancethatlosesaproton
Baseasubstancethatgainsaproton
example:
HCO3+H2OH3O+
acid+baseacid+base
ImportantnaturalacidbasesystemsincludeCO2waterandalkalinity
Thefollowingreactionsareimportantincarbonateequilibriasystems
1)Dissolutionofcarbondioxideinwatertoformcarbonicacid.
H20+CO2H2CO3
2)Thedissolutionofcarbonicacidinwatertoformthebicarbonateion.
H2CO3H++HCO3
3)Thebicarbonateionthendissolvesinwatertoformcarbonate.
HCO3H++
4)Andfinally,thedissolutionofcalcite/aragoniteinwatertoform
calciumandcarbonate.
CaCO3Ca2++
Thisinformationcanbegraphedtoshowthedistributionofthedifferent
ionicspecieswithaspecifictotalcarbonateactivityatdifferentpH.
atpH=6.38,50%H2CO3and50%HCO3
atpH=10.38,50%HCO3and50%CO3
atpH=8.3,~100%HCO3
Figure10.1Distributionofmajorspeciesofdissolvedinorganiccarbonat20
oC.
2)Solution,Volatilization,andPrecipitation
Wateriscapableofdissolvinggases,liquidsandsolids
Thesereactionsareresponsibleformuchofthenaturalloadingof
chemicalspeciestoaquifers.
APL'saqueousphaseliquids
organiccompoundscapableofdissolvinginwater
Ruleofthumb:thesmallertheorganiccompound,themoresolubleitisinwater.
Compound
Molecularweight
Solubility
(g/mol)
(g/m3)
Benzene(C6H6)
78.0
1,780
Biphenyl(C12H10)
154.0
7.48
Smallercompoundfindspaceinthestructureofwatermoreeasilythandolarger
compounds.
3)Complexationreactions
Complexationfacilitatesthetransportofmanypotentiallytoxic
metalssuchascopper,cadmiumandlead.
Acomplexisformedbycombiningsimplecations,anions
andsometimesorganicmolecules.
Forexample:Cr(OH)2+,PbCl3,MEDTA
(ethylenediaminetetraaceticacid,adetergent)
Theformationofcomplexesmayallowcertainsolutestotravelmuch
furtherandfasterthanotherwisepredicted.
4)Surfacereactions
Reactionsbetweensolutesandthesurfacesofsolidsthatare
capableofremovingsolutesfromsolution.
Sorptionisthelumpedtermforprocessesthatincludeadsorption,
chemisorption,absorption,andionexchange.
5)Oxidationreductionreactions
Reactionsthataregenerallymediatedbymicroorganisms.Thebugsspeedupthe
reactions.
Oxidationremovalofanelectrontoincreasetheoxidationnumber
Fe2+=Fe3++e
Reductionadditionofanelectrontoloweroxidationnumber
Cr4++e=Cr3+
Redoxreactionsinfluencethemobilityofmetalsinsolution.Somemetals
mayhavedifferentmobilitiesindifferentpHandEhsolutions.(Ehistheredox
potential)
Unfortunately,Ehisaverytenuousparametertomeasureinthefield.
Biodegradationreactionsareredoxreactionsthatinvolvetheoxidationof
organiccompoundsintosimplerforms.
EhpHdiagramscanbeusefultodeterminewhatspeciesarepotentiallystable.
6)Hydrolysis
Reactionsbetweenanorganicmoleculeandwateroracomponentionofwater.
Forinstance,ahydroxylgroup(OH)maybeaddedtoanorganic
compoundmakingitmoresolubleandpotentiallymoresusceptibletobiodegradation.
CH3CH2CH2Br+H2O=CH3CH2CH2OH+HBr
Resistanttohydrolysis
(DomenicoandSchwartz,1990)
Alkanes
Alkenes
Benzene
PAHs
Alcohols
DDT
Phenols
Susceptibletohydrolysis
Amides
Carbamates
Trazines
7)Isotopicprocesses
Radioactivedecayofisotopesofcertainchemicalspecies.
Someelementshaveisotopeswiththesameatomicnumber,but
varyingnumbersofneutronsinthenucleus.
Forinstance,Oxygenhasthreeisotopes,allstable
Isotopes
Averageabundance
99.76
0.037
0.10
Sulfonicacidesters
Radioactivedecayoccursbyemissionof
particle
particleelectron
Radioactivedecayisirreversible.
Decayfollowsafirstorderratelaw.
Halflifeisthetimerequiredtoreducethenumberofparentatomsbyonehalf.
Radon3.8days
Uranium4.5x109years
238
Carbon5,000years
14
Theisotopesofhydrogen,oxygen,carbon,sulfur,CFC's,krypton,andnitrogen
areusefulformanyenvironmentalstudies.
Theenvironmentalisotopesareusedforsuchapplicationsasagedatingwater
anddeterminingrates/degreesofmixing.