1、+-AgCl sAgaq+Claq 溶解沉淀0 溶 解 度易溶电解质电解质难溶电解质:溶解度小于.01%的物质+-(Ag)/(Cl)/(AgCl)(AgCl)/ccccKcc+-(AgCl)(Ag)/(Cl)/spKccccspK+(A B)(A)/(B)/mnnmspmnKcccc 222(Cu S)(Cu)/(S)/spKcccc nmmnA BsmAaqnBaq 溶解沉淀通式:222Cu SCuSspKspKspKspKspKspK2s pKSs pSK34spKS34s pKS427spKS42 7s pKSspKspK10sp1298KAgClK1.8 10AgCl例:已知时,的为,
2、求的溶解度S。AgCl AgCl()Ag()Cl()saqaq 解:的电离平衡为1 c/mol L S S2+-K(AgCl)(Ag)/(Cl)/SPccccS c10551K(AgCl)1.8 101.3 10 1.3 10SPS cSmol L12245124 Ag CrO1.1 10Ag CrO6.6 10spKSmol LrmGspKspK2.303lgrmspGRTKlg2.303rmspGKRTspKspKspK50sp2(Ag S)6.3 10K NaCl +2NH3 Ag(NH3)2+spKspKspK22+(Mg)/(OH)/QccccspK (1)spQK当时,为饱和溶液,
3、达平衡状态。既不生成沉淀,沉淀也不溶解。(2)spQK当时,为不饱和溶液,无沉淀析出,若体系中有沉淀存在,沉淀将被溶解,直至饱和。(3)spQK当时,为过饱和溶液,有沉淀析出,直至饱和为止。spQK1124224410sp430.002Na SO0.02BaClBaSOSOKBaSO1.1 10mol Lmol L例:等体积混合的溶液和的溶液,是否有白色的沉淀生成?是否沉淀完全?已知213141 c SO0.002mol L1 10 mol L2 解:溶液等体积混合后,浓度减小一半,故21211 c Ba0.02mol L1 10 mol L2 2+22354 Q=(Ba)/(SO)/1 10
4、1 101 10cccc sp44QKBaSOBaSO ,所以溶液中有生成。24SO此时溶液中剩余的为2422111BaSOBaBaBa0.01mol L0.001mol L0.009mol L c析出沉淀后,溶液中还有过量的,达平衡状态时剩余的浓度为:10sp42432KBaSO1.1 10SO9 10Bacccc2814SO1.2 10 mol Lc24SO已沉淀完全。39sp3K(Fe(OH)2.79 103333sp3Fe OH(s)Fe(aq)3OH(aq)(Fe)/(OH)/K(Fe(OH)cccc 解:()开始沉淀时39sp333eq3131K(Fe(OH)2.79 10(OH)
5、/(Fe)/0.01(OH)6.5 10mol LcccccpH14pOH=14 12.191.81351 ()1.0 10 molc FeL沉淀完全时,则121 (OH)6.5 10mol L pH=14pOH2.81c3FepH1.81pH2.81 故开始沉淀时,溶液的为;沉淀完全时,溶液的为。39sp3333-5K(Fe(OH)2.79 10(OH)/(Fe)/1 10ccccspK1017(AgCl)1.8 10 (AgI)8.5 10 spspKKAgAg解:根据溶度积规则:离子积达到溶度积时所需浓度小的先析出沉淀。生成AgCl、AgI沉淀时所需的浓度分别为:101.8 10Ag0.
6、001ClspKccccAgCl71Ag1.8 10cmol L 178.5 10Ag0.001IspKccccAgI141Ag8.5 10cmol L371AgAgAgNOAg1.8 10Icmol L 由于生成AgI沉淀所需的浓度较生成AgCl沉淀时所需的浓度小,所以滴加后,先析出黄色AgI沉淀。当溶液中时,才有AgCl白色沉淀生成,此时溶液中残留的 浓度为:1778.5 10I1.8 10AgspKccccAgI 10151I4.7 101 10cmol Lmol L AgClI 可见:开始沉淀时,早已沉淀完全,利用分步沉淀可将二者分离。10(AgCl)1.8 10spK5(AgCl)1
7、.3 10S1224(Ag CrO)1.12 10spK524(Ag CrO)6.5 10SspKspK13+23+260.1mol LFeMgNaOHFeMgNaOH例:含有的和的溶液,用使其分离,即完全沉淀,而仍留在溶液中,的用量必须控制在什么范围内合适。3+FeOH解:欲使沉淀完全所需的最低平衡浓度为33sp3(Fe)/(OH)/K(Fe(OH)cccc 39sp3333-5K(Fe(OH)2.79 10(OH)/(Fe)/1.0 10cccc121(OH)6.5 10mol Lc2MgOH欲使沉淀所需的最低平衡浓度为12161NaOH6.5 10mol L7.5 10 mol L故用量
8、控制在22sp2(Mg)/(OH)/K(Mg(OH)cccc 12sp22K(Mg(OH)5.61 10(OH)/(Mg)/0.1cccc61(OH)7.5 10 mol LcspQK2224242242242C OCaC OCaC OC OHH 224224 2CaC OHCaH C O 总反应为22ZnS2HZnH S332Al(OH)3HAl3H O22+32+4222+322+4(Mg)(NH)(NH)(Mg)(NH)(OH)(NH)(OH)ccccKcccccccccccc 多重平衡常数为:21227Mg(OH)0.1,1 ()5.6 10spmolLKMg OH例:今有沉淀问需要多
9、大浓度的铵盐才能使之溶解。已知:222432Mg(OH)()222 0.1 0.2 0.1 0.2Mg OHsNHaqMgaqNHaqH O ln mol 解:溶于铵盐的竞争反应为24Mg(OH)NH根据多重平衡常数可算出完全溶解后,溶液中的平衡浓度:22+3422(Mg)(NH)0.10.2 1.7 1011ccccc NHcK 140.48c NHmol L2414140.1Mg(OH)0.20.480.68molmolNHNHmol LNHmol L由于溶解需用去(由多重平衡式可看出),平衡时溶液中的浓度为,所以共需为。12sp222523(Mg(OH)5.6 101.7 10(1.8 10)(NH)KKspQKspQK10171750172(AgCl)1.77 10(AgI)8.52 10 S=9.23 10(Ag S)6.3 10 S=2.5 10spspspKKKspKspKspK+=222444222333549()()()()()()()()4.9101.4103.410spspKCaSOc SOc SOc CaKc COc COc CaKCaCO10(AgCl)1.8 10spK1224(Ag CrO)1.1 10spK(3)(3)1210(AgSCN)1.0 10(AgCl)1.8 10spspKK smwmsFmwm