Pourbaix基础理论及计算.pptVIP

1THEGEOCHEMISTRYOFNATURALWATERSREDOXREACTIONSANDPROCESSES-IICHAPTER5-Kehew(2001)N-O2-H2OSYSTEM

2N-O2-H2OSYSTEM

3Preliminarymappingofspeciesinpe-pHspacefortheN-O2-H2Osystem.Moreoxidizedspeciesareathighpeandmorereducedspeciesatlowpe.Nitrite(NO2-)isametastablespecies.

4NH30/NH4+BOUNDARYAsbefore,wewriteareactionbetweenthespeciesNH3°+H+?NH4+Bydefinition,theboundarybetweenthesetwospeciesiswhereso

5?Gr°=?Gf°NH4+-?Gf°NH3o?Gr°=(-79.4)-(-26.5)=-52.9kJmol-1SothisisaverticallineatpH=9.27.

6Weplotthefirstboundaryfromuppertolowerwaterstabilitylimit,becauseatthispoint,wedonotknowwheretheotherboundarieswillintersectit.

7N2(g)/NH4+BOUNDARYWewritethereaction?N2+4H++3e-?NH4+Toplotthisboundary,wehavetofixboth?Naq?mNH4+andpN2.For?Naqwechoose10-3molL-1,whichisnearthedrinkingwaterstandardfornitratenitrogen.ForpN2wechoosetheatmosphericvalueof0.77atm.

8?Gr°=?Gf°NH4+-??Gf°N2?Gr°=(-79.4)-?(0)=-79.4kJmol-1

9TheN2/NH4+boundaryintersectstheNH4+/NH3°boundaryatpe=-6.78andpH=9.27.ThefieldofNH4+isnowtotallyenclosedbyboundariesintersectingatangles180°.ThenextlogicalboundarytocalculateistheN2/NH3°boundary.

10N2(g)/NH3oBOUNDARYWenowwritethereaction?N2+3H++3e-?NH3°Wechoose?Naq?mNH3°=10-3molL-1andpN2=0.77atmasbefore.

11?Gr°=?Gf°NH3°-??Gf°N2?Gr°=(-26.5)-?(0)=-26.5kJmol-1

12NowtheNH3°fieldistotallyenclosed.WewouldsuspectthatthenextboundarytocalculateistheN2(g)/NO3-boundary.

13N2(g)/NO3-BOUNDARYStartingwiththereactionNO3-+6H++5e-??N2+3H2OTobeconsistent,wechoose?Naq?mNO3-=10-3molL-1andpN2=0.77atmasbefore.

14?Gr°=3?Gf°H3O+??Gf°N2-?Gf°NO3-?Gr°=3(-237.1)+?(0)-(-110.8)=-600.5kJmol-1

15FinalEh-pHdiagramfortheN-O2-H2Osystem.NotethatNO3-shouldbepresentinsignificantquantitiesonlyin