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Lecture 36

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.

ENV 302 - Lectures

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