第04章--水污染与农业--2012-3-20--2012-5-3

1AquaticEnvironmentalChemistryandAgriculture0.04%(1)6.2m3(2)2.7m3(3)4.2m316%(4)0.82m3(5)2.8m32.7m30.83m32p.ppp35%507603001.3531990-20102Ca2+Mg2+Na+K+Cl-SO42-HCO3-CO32-ppbNPSiMnFeCuTDSTDS[Na++K++Ca2++Mg2++Cl-+SO42-+HCO3-]4-13Cu(OH)+,CuCO30.25CuMn2+8Mn2+,MnCl+0.2MnZn2+15Zn2+,Zn(OH)+4.9Zn3PbCO3,0.03PbNi2+0.5Ni2+,NiCO30.56Ni0.1HgCl42-,0.03Hg0.1CdCl20.11CdAs(,),0.5HAsO42-,3.7As(µg/L)(µg/L)X(g)?X(aq)[G(aq)]=KH·PGKH(mol/L·Pa)4O220.95%25oC3.167103PaO21.2610-8mol·L-1·Pa-1(25oC),O2O2Po2=(1.0133-0.03167)105Pa20.95%=2.057104PaO2O2[O2(aq)]=KHPo2=1.2610-8mol·L-1·Pa-12.057104Pa=2.610-4mol·L-1O232g·mol-1,=32g·mol-12.610-4mol·L-1=8.32g·L-1(Dissolvedoxygen)CO2CO20.0314%,250.03167105Pa,CO2KH3.3410-7mol/(L·Pa)(25),CO2:CO2(aq)+H2O=H++HCO3-K1=4.4510-7CO2CO2Pco2=(1.0130-0.031677)1053.1410-4=30.8Pa[CO2(aq)]=KHPCo2=3.3410-730.8=1.02810-5mol/LCO2(aq)+H2O=H++HCO3-H+HCO3-[H+]=[HCO3-]K1=[H+][HCO3-]/[CO2(aq)][H+]2/[CO2]=K1=4.4510-7[H+]=(1.02810-54.4510-7)1/2=2.1410-6mol/LCO2[CO2]+[HCO3-]=1.2410-5mol/L—CO2(aq)H2CO3HCO3-CO32-;—CO2(aq)H2CO3H2CO3*—H2CO3CO2?H2CO3*H2CO3H2O+CO2(g)H2CO3*pK0=1.46H2CO3*HCO3-+H+pK1=6.35K1=4.47*10-7HCO3-CO32-+H+pK2=10.33K2=4.68*10-11K0=[H2CO3*]/Pco2K1=[H+][HCO3-]/[H2CO3*]K2=[H+][CO32-]/[HCO3-]5o=[H2CO3*]/CT=[H2CO3*]/{[H2CO3*]+[HCO3-]+[CO32-]}=(1+K1/[H+]+K1K2/[H+]2)-11=[HCO3-]/CT=[HCO3-]/{[H2CO3*]+[HCO3-]+[CO32-]}=(1+[H+]/K1+K2/[H+])-12=[CO32-]/CT=[CO32-]/{[H2CO3*]+[HCO3-]+[CO32-]}=(1+[H+]2/K1K2+[H+]/K2)–1CTCO2+H2CO3HCO3-CO32-10080604020024681012pH3-1222222COH221COH022T-23COH1COH011T-3COH002TCOH2*32pK]H[KKpKC]CO[pK]H[KpKC]HCO[pK1/)]aq(CO[CpK)]aq(CO[]COH[⋅=⋅αα=α⋅=⋅=⋅αα=α⋅=⋅α=α=⋅=≈++[H2CO3*][CO2(aq)]=KHPCO2=10-5molL-1lgC—pHlg[H2CO3*]=-5[HCO3-]pK1=6.35[HCO3-]=lgC—pHlg[HCO3-]=pH-11.3[CO32-]pK2=10.33[CO32-]=lgC—pHlg[CO32-]=2pH-21.6][1010535.6+--×H2533.1035.6][101010+---××HlgCH+H2CO3*CO32-HCO3-OH-CTpK1=6.35pK2=10.33pH6,H2CO3*pH=6~10HCO3-pH10.3CO32-CTpH.HCO3-+H+H2CO3*6...][]][[*323COHHHCO+-7.635.61*3231010][][][--+-==HKCOHHCO124.21][][][3*32*32+=+-HCOCOHCOH[H2CO3*]=0CTC=0.31310-3molL-1=0.9310-3molL-1pH=6.70.9310-3molL-1H2CO3*0.9310-3molH+110-2molL-1VV=0.9310-3mol/(2110-2molL-1)=0.0465L=46.5mL46.5mLNaOHCa(OH)2NH3C6H5NH2Na2CO3NaHCO3HCO3-CO32-CO2(pH4.3)(pH3.1pH4.43.1-~4.4)=[HCO3-]+2[CO32-]+[OH-]-[H+]=CT(1+22)+KW/[H+]-[H+]CT=[H2CO3*]H2CO3*H2O-H++2H++H++H+HCO3-CO32-OH-H3O+pH=8.3OH-CO32-HCO3-=[CO32-]+[OH-]-[H2CO3*]-[H+]=CT(2-0)+KW/[H+]-[H+]8.28.2—10.010HCO3-H2O-H+-H+H2CO3H3O++H++H+CO32-OH-CO32--2H+-H+H2CO3HCO3-H2O-H+H3O++H+OH-=[OH-]-[HCO3-]-2[H2CO3*]-[H+]pH10.8pH=10.8=–CT(1+20)+KW/[H+]-[H+]7pHCO32-=2-CT=[CO32-][OH-]pH10-113CO2+H2O+hv(){CH2O}+O2HCO3-+H2O+hv(){CH2O}+OH-+O2CO2CO2HCO3-CO2pH101pH=8.001.0010-3mol/LH2CO3*HCO3-CO32-OH-[HCO3-]=[]=1.0010-3mol/L.[H2CO3*]=[H+][HCO3-]/K1=1.0010-81.0010-3/4.4510-7=2.2510-5mol/L[CO32-]=K2[HCO3-]/[H+]=4.6910-111.0010-3/1.0010-8=4.6910-6mol/L=[HCO3-]+2[CO32-]+[OH-]-[H+].8H+H2CO3*HCO3-.CO2H2CO3FeCl3OH-+H+?H2OOH-+H2CO3*?HCO3-+H2OOH-+HCO3-?CO32-+H2O.,H+H+pH=10.8,=[H+]+[HCO3-]+2[H2CO3*]-[OH-]=CT(1+20)+[H+]-Kw/[H+]=2CO2-=CT(0-2)+[H+]-Kw/[H+]=-CT(1+22)+[H+]-Kw/[H+]9pH][]/[)2(21++-++HHKcwTaa][]/[)(02++-+-HHKcwTaa]H[]H/[K)2(cw01T++-+α+α-]/[][)2(01++-++HKHcwTaa]/[][)(20++-+-HKHcwTaa]/[][)2(21++-++-HKHcwTaaCO2+H2CO3HCO3-CO32-10080604020024681012pH3-1lgCH+H2CO3*CO32-HCO3-OH-CTpK1=6.35pK2=10.33pH6,H2CO3*pH=6~10HCO3-pH10.3CO32-CTpH3pH=7.8100mL0.02molL-1HCl13.7mLCT=CT(1+22)+Kw/[H+]-[H+]=(13.710-3L0.02molL-1)/(10010-3L)=2.7410-3molL-1pH=7.8HCO3-H2CO3*0=0.0342;1=0.9657;20.002.7410-3=CT1+10-14/10-7.8-10-7.8=CT0.9657+10-6.2-10-7.8CT=2.8410-3molL-1122110)]H[kk]H[k1(-++++=α1211)][][1(-++++=HkkHa122122)][][1(-++++=kHkkHaCO2+H2CO3HCO3-CO32-10080604020024681012pH3-110=CT(1+22)+Kw/[H+]-[H+](1+22){+[H+]-Kw/[H+]}pH5-9[]10-3mol/LpH6-8[]10-4mol/L[H+][OH-]1=0.816,2=3.8310-4,=1.71mmol/L,pH6.0CT(1+22)3.25[]=1.71/3.25=0.526mmol/LA=1.4-0.526=0.874mmol/L3pH6-9pHpHpH8.3pHCO2+H2CO3HCO3-CO32-10080604020024681012pH3-15pH6.51.6mmol/LNaOHpH8.0?pH=8-6.5=1.5,pH=6.5,=1.6mmol/LB=[][10pH-1]/(1+K110pH+pH)=1.6(101.5-1)/(1+10-6.35106.5+1.5)=1.6(101.5-1)/45.668=1.08mmol/LAA4111K1K2pHH2CO3*-HCO3--CO32-2pH6[H2CO3*]pH=6~10.3[HCO3-]pH10.3[CO32-]CTCTpH3pH4pH9pH=7.8100mL0.02molL-1HCl13.7mLCT10pH8.001.0010-3mol/L[HCO3-][H2CO3*][CO32-]11pH7.01.4mmol/LpH6.012ZPCZeroPointofChargepHpHZPC–H++H+pH=6~9.~.~[SiO2]+Al()[AlO2-]+Si()213m4HenryFreundlichLangmuirHFLHenryQ=kCkQCHFreundlichQ=kC1/nlogQ=logk+1/nlogCCQFFlgQlgCQmbQm1/bCL1/Q1/CeLLangmuirQmbCe1+bCeQ=1111QQmQmbCe=+Qm214SOH2+SOH+H+Ksa1={SOH}[H+]/{SOH2+}SOHSO-+H+Ksa2={SO-}[H+]/{SOH}SOH+MZ+SOM(Z-1)++H+*K1sSOH+AZ-SA(Z-1)-+OH-K1sSOHpHpHH+——————DLVODerjguinLandauVerweyOverbeekDLVO——DLVO1521JS94H-234“”””””5“”“”Ksp=[Men+][OH-]n[Men+]=Ksp/[OH-]n=Ksp[H+]n/Kwn-lg[Men+]=-lgKsp-nlg[H+]+nlgKwpC=pKsp–npKw+npHMe(OH)n(s)Men++nOH-pC=pKsp–npKw+npHC=1.0mol/L:pH=14-(1/n)pKsp16∑-++=n1nznzT]Me(OH)[][MeMePbO(s)+2H+Pb2++H2OlgKs0=12.7PbO(s)+H+Pb(OH)+lgKs1=5.0PbO(s)+H2OPb(OH)2lgKs2=-4.4PbO(s)+2H2OPb(OH)3-+H+lgKs3=-15.4[Pb(II)T]=Ks0[H+]2+Ks1[H+]+Ks2+Ks3[H+]-1pHlgC-pHlgCPb(OH)2OH-Pb(OH)3+Pb(OH)+Pb2+PbTH+PbPbO(s)0.01mg/L0.1mg