广义单核配合物化学平衡体系的Coates信号流图Coate

(271018)CoatesCoatesCoatesCoatesCoatesCoatesCoatesSignFlowGraphofChemicalEquilibriumSysteminBroadSenseMononuclearComplexesZhangYulei,XieXiezhong,SunSujuan(CollegeofHydraulicCivilEngineering,ShandongAgriculturalUniversity,Taian271018)AbstractThemathematicalmodelofcoatessignflowgraphofchemicalequilibriumsysteminbroadsensemononuclearcomplexesisproposed.Onthebasisofgeneralizingbasicalgorithmofthegraph,thesolutionwhichismixedbydicarboxylicacid(oritssalts),strongacidandstrongbaseistakenastheexampletoillustratetheprocessofcreatingtheflowgraphandtodeducechemicalequilibriumrelationshipbyusingthecalculatingrule.Ourresearchresultsshowthattheflowgraphisintuitionistic,clearandsimpleandcanelucidatetheequilibriumsystemofbroadsensemononuclearcomplexessystemicallyandgenerally.KeywordsIonequilibrium,Coatessignflowgraph,Mononuclearcomplexes,MathematicalmodelCoates[1]Coates40E-mail:[e-mail]2003-01-29[2]1CoatsTab.1RegulationofOperationonCoatesSignFlowGraphmm∑=mkka1m+1m(x0,xm)(x0,xm)∏=mkka1x0x0x0x01CoatesCoates11Fig.1Coatessignflowgraphofrelationinchemicalequilibriumphysicalchemistrycapacity(Q)epeplg(Q)=nqep-nep)Qlg(n1-ppqee=CoatesCoatesCoates22.1Coates22Fig.2Coatessignflowgraphofwaterchemicalequilibriumsystemofdicarboxylicacid11(a)(a)H+[H+]ΔHH2OΔHH2ACoates[H+](b)(b)()111[H2O]1KW/[H+]1H+(c)(c)H2AΔHH2AHA-A2-[H2A][HA-]ΔHH2A[H2A][HA-][A2-]ΔHH2ACoats[HA-][A2-]ΔHH2A[HA-]ΔHH2A2Ka2/[H+],(d)(d)[HA-]ΔHH2A12Ka2/[H+](e)(e)[H2A]ΔHH2A(f)(f)[H2A]c[H2A]c[H2A][HA-]c[H2A][HA-][A2-]c(g)(g)[H2A]cd0c[H2A]d0cH2Ac[H2A](h)(h)cΔHH2Ac[H+]+aOH-[H+](i)(i)[H+]abc[H+][H+]c2.223Coates233Fig.3Coatessignflowgraphofwaterchemicalequilibriumsystemofdicarboxylicacidanditssalts[H2A]0[H2A]c0[H2A][HA-]c0[H2A][HA-][A2-]c00)())][HKa1(][HKaA](1[HAHAAH2122=++-++++ccc)][HKa1(][HKa1)(]AH[21AHAAH22++++++=ccc[H+]3.20)2()][HKa21(][HKa]AH[HAHA212AH2=+-+=Δ++cc[H2A])2()][HKa21(][HKa)][HKa1(][HKa1HAHA2121AHAAH22AHccccc+-+++++=Δ++++2.3CoatsCoates2.3.1MLMLMLcCoates4cMLn[M][ML2][MLn]cMcML[ML]cMLK2[L]K1[L]Kn[L]2cL002n2n[L]cL-1cM00-14Fig.4CoatessignflowgraphofwaterchemicalequilibriumsystemofMononuclearComplexescM0cL0ML0ML[M][ML][ML][MLn]2.3.2M[H+][H+][H+][H+][H2Y][Y][MY]cY[HY]cK2[L]K1[L]KMY[M]cHY22-2MYcMH2Y-20c[M]M0c0-1Y0c-1-1[H+]H2Y[H+][OH-][H2O]1Kw/[H+]5Fig.5CoatessignflowgraphofwaterchemicalequilibriumsystemofacidradicalchelateligandComplexes2.3.3[Ox1][Red1][e]Z1K1z1cc1[e]1Ox1cRed10-1-z1OX10[Red2]Ox2[Ox2][e]Z2K2z2cc2[e]2cRed20-1-z2OX26Fig.6Coatessignflowgraphofcommonoxidation-reductionwaterchemicalequilibriumsystem2.3.4MnO4-/Mn2+Fe3+/Fe2+MnO4-/Mn2+Fe3+/Fe2+[H+][H+]a[H+][OH-]MnO4-/Mn2+[H+]Δ[H+]Mn[MnO4-][Mn2+][e]5[H+]8K15ccMn[e]1MnO4-cMn2+0-1-5[Fe3+][Fe2+][e]K2ccFe[e]2Fe3+cFe2+0-1-1OX20MnO4-[H+]Mn-88[H+][OH-][H2O]1aKw/[H+]7MnO4-/Mn2+Fe3+/Fe2+Fig.7CoatesSignFlowGraphofMnO4-/Mn2+Fe3+/Fe2+oxidation-reductionwaterchemicalequilibriumsystem2.3.5CaCO3H2O[H2O][CaCO3]11[H2O][CaCO3]0[Ca2+][H2CO3][CO3-][CO32-]CaCO311CaCO3[H2O][HO-]Kw/[H+][HCO3-][CO32-][H2CO3]Ka1/[H+]Ka2[H+]1-2Ksp/[Ca2+][CaCO3]10-1-12[Ca2+]/[H+]7CaCO3H2OCoatesFig.7CoatesSignFlowGraphofCaCO3H2Owaterchemicalequilibriumsystem3Coates[1],..:.1998,(8):210~216.[2],..:.1995,(8):152~158.