1、1.物料平衡物料平衡(质量平衡质量平衡)2.电荷平衡电荷平衡 求质子条件式的方法:求质子条件式的方法:32HHH OH OOH HHAcAc HOHAc OHOHOHHH23 CNHCNH34NHNHH3NHOHHCNH42POH H2H43POHHOH3H34POOHHOHPOPO2HPOHH344342OH224HPO 。KwHCaH242aaWCCKH(1 1)一元强酸(强碱)溶液)一元强酸(强碱)溶液 例:例:强酸强酸HA,浓度浓度Ca H+=强酸离解的强酸离解的H+水离解的水离解的H+5OH 1.0 10 mol/LbCpOH5.0pHppOH14.0-5.09.0wK 例:例:HK
2、HHAKaHWHKHHAKaHW0)(23WWKaKHKCaKaHKaHHHAKHaKaCaH0)(23WWKaKHKCaKaHKaHHKHHAKaHWWKOHH HKHHAKaHW5%WWaaaKKKHAK CHHAKHaHKHHAKaHW2HAKaH()Ka CaA()Ka CaH02KaCaHKaH242KaKaKaCaH 近似式K aC aHHHKaCaHKHHAKaHW条件条件 KaCa20Kw 忽略水的离解忽略水的离解 Ca/Ka 500 HACa,一一元元弱弱酸酸KaCa20KwCa/Ka 500Ca/Ka 500一一元元弱弱碱碱KbCb20KwCb/Kb 500KbCb20Kw
3、Cb/Kb 500KaCaH242KaCaKaKaHbbOHK C242bbbbKKK COH24H 2aaaaKKC K2102.710.04)102.7(102.74244(mol/L)102.8309.2pH aaHK CWbbbaKOHK CCK 242KaCaKaKaH242bbbbKKK COH 质子参考水准:质子参考水准:H2A,H2O H+=HA-+2A2-+OH-HA H+A2 H2A H+HA H2O H+OH H+=H2A离解离解H+HA-离解离解H+水离解水离解H+第一级离解第一级离解 第二级离解第二级离解 代入代入 经整理得精确式经整理得精确式2222121HKHAH
4、KKHAHKHWaaaaCAH02202112aaaHHKHK k WaaKHKAHKH)21(221aaCKH1Ca/Ka1 500211142KaKaKaCaHCa/Ka1 5001bbOHK C211142bbbbKKK COHCb/Kb1 500Cb/Kb1 50041114108.1106.5100.121awbKKK8714103.2102.4100.112awbKKKCO32-+H2O HCO3-+OH-HCO3-+H2O H2CO3+OH-wbbKKC20114580.10 1.8 101.8 10100 2.3 10bbCK500106.5108.110.0241bbKC(m
5、ol/L)102.4108.110.0OH341bbKC38.2pOH62.11pH 21HKwHHAKKHAHHaa121aWaKHAKHAKH一般两性物质的一般两性物质的Ka2和和Kb2较小,较小,HA-C 则若则若Ka2C20KW121aWaKCKCKH121aaKCCKH近似式近似式Ka2C20KW12aaKCCKH21aaKKH121aaKCCKH21aaKKH121aaKCCKHKa2C20KW,Ka2C20KW,近似式近似式 121aaKCCKH21aaKKH231aaKCCKH32aaKKH 5 5、缓冲溶液的、缓冲溶液的值计算值计算 baaaCCKAHAKHabaCCKlgppH例例 在在NH3-NH4Cl混合溶液中,若混合溶液中,若NH3 和和 NH4Cl 的浓度分别为的浓度分别为0.20和和0.10 mol/L,求该溶液的,求该溶液的pH值。(值。(NH3的的 Kb=1.810 5)解解 NH4+的的Ka=Kw/Kb=5.610 10)10.020.0lg106.5lglgppH10abaCCK94.8 COOHCOOk+NaOHCOONaCOOk+H2O