pHsp?14?6?0.72?8.72
?pH?pHep?pHsp?8.00?8.72??0.72TE%?10?0.72?10ep0.72KaKw??100cHB
5.251?00??0.0581.?8?100.05
?10.?1922. 用0.100mol?L0.100mol?L?1NaOH滴定0.100mol?L羟胺盐酸盐(
?1NH3OH?Cl??)和
NH4Cl的混合溶液。问a.化学计量点时溶液的pH为多少?b.在化学计
量点有百分之几的NH4Cl参加了反应? 解:(1) 已知NHSP?3OH?Cl? 和
4Ka?KwK?1.1?10?6
时,产物为
?3NH2OHNH4?
0 .0500/0.050[H]?KNH?OH?Cl??KNH??cNH?/cNH2OH4 (2) SP
?1.?1?61?0??5?.6/)1010?2.?5?81m0ol( LpH?7. 6时,
[H]?2.5?10??8mol/L
?10?10[NH3]??NH3?cNH??45.6?102.5?10?8?5.6?10?0.0500?1.1?10(mol/L)?3
?参加反应的NH4Cl百分数为:
2.2%1.?1
10?100?%0.0500?325.称取钢样1.000g,溶解后,将其中的磷沉淀为磷钼酸铵。用
20.00mL0.1000mol?L?1NaOH溶解沉淀,过量的NaOH用HNO3返滴定至酚酞刚好褪
色,耗去0.2000mol?L?1HNO37.50mL。计算钢中P和P2O5的质量分数。
1解:PP?(NH2O54)2HPO4?12MoO7?24NaOH?2
过量NaOH?0.2?7.5?10?3?1.5?10?3(mol)
用于滴定磷钼酸铵的NaOH?0.1?20?10?3?1.5?10?3?5.0?10?4(mol)
5.0含P物质的量为:24?10?4?2.1?10?5(mol)
P%?2.1?10?5?311?100?0.065 P2.1?10?52O5%??1421?2?100?0.15
28. 标定甲醇钠溶液时,称取苯甲酸0.4680g,消耗甲醇钠溶液25.50mL,求甲醇钠的浓度。 解:CH3ONa?C6H5COOH,令其浓度为c
c?0.468025.50?10?3?122?0.1500(mol/L)
第6章 络合滴定法
2.解: ?2?Cu(C2?1?????22O4)?1[C2O4]2[C2O24] ?104.5?0.10?108.9?(0.10)2?106.9 ??106.0?109.26?14?101.26Cu(OH?)?1??1[OH]?1? 又C?NH3[NH?[NH4][NH1?[H?]?2?[NH3]?0.10mol?L?13]?3]Ka?1 ??[NH25Cu(NH3)?1??1[NH3]??23]????5[NH3]?109.35 ?Cu??Cu(CO2????24)Cu(OH)??Cu(NH3)?109.36
4.解:用氨水调解时:
?M(NH?1?3)?1??1(0.010)??2(0.010)???122?102.02
?1[NH3]?M(NH3?10?2.0)122105.0?0.0083
?4.0?2??2[NH3]?M(NH107.032??10
?3?)122?0.083
?4?2??10?6.0122?0.0831010.0?10?8.0
122?0.83
?1 故主要存在形式是
M(NH3)4,其浓度为0.10?0.83?0.083mol?L
用氨水和NaOH调解时:
?M??M(OH4?)??M(NH3)?1?1?10?0.1?10?0.01???120?2?104811
?1?10?0.12?101411?5?10?9
?2?10?0.012?1015118?5?10?6
?1?3?10?0.0012?1011?0.5
?4??10?0.00012?1011?0.5 故主要存在形式是 6.解:
?1M(OH)3和
M(OH)42?,其浓度均为0.050mol?L
[T]?0.10mol?L,lg?Y(H)?4.65?Cd(T)?1??1(0.10)?10?Zn(T)?1?10?Y(Zn)?1?2.42.8?0.10?108.321.8?0.10?10?0.010?106.32KZnYCZn?Zn(T) ?Y(Cd)?1?KCdYCCd?Cd(T) lgK'CdY?16.46?lg?Cd(T)?lg(?Y(H)??Y(Zn))?6.48lgK'ZnY?16.5?lg?Zn(T)?lg(?Y(H)??Y(Cd))??2.48 8.解:PH=5.0时,
lgKZnY'?4.8?pZnep?4.8
lgK'ZnY?lglgKZnY?lg(?Y(H)??Y(Cd))lg?Y(H)?6.45lg?Y(Cd)?lgKCdYCCdsp?Cd(I)2.10 KCdY?10?104.4916.46 CCd?0.005mol?Lsp?1?Cd(I)?1?10?102.43?105.41?lg?Cd(I)?5.46?lg?Y(Cd)?8.70lgK'ZnY?16.50?lg(106.45?10sp8.70)?7.80pZnsp?0.5(lgK'ZnY?pCZn)?5.05??pZn??0.25Et?10?pZn?10??pZnspZn??0.22%
K'ZnYC
10.解:设Al3+浓度为0.010mol/L,则由Al(OH)3的Ksp计算可得Al3+发生水解时
pH=3.7。要想在加入EDTA时,Al3+不发生水解,pH应小于3.7。 ?Ac(H
??)?[HAc][Ac]CHAc??1?1??0.311.55[H]Ka??1?1010?5?4.74?1.55?1[Ac]??Ac(H)mol?L?1?0.2mol?L2?)12.解:a. ?Pb2?(Ac???1??1[Ac?]??2[Ac?]?1?10?6.451.9?0.2?103.8?0.04?102.43 lg?Y(H
b.
)lgK'PbY?lgKPbY?lg?Pb2?(Ac?)?lg?Y(H?)?18.04?2.43?6.45?9.16pPb'sp?6.08 pPbep?7.0 pPb'ep?7.0?2.43?4.57?pPb'??pPb??1.51 Et?10?pPb?10??pPbspPb??2.7%K'PbYClgK'PbY?lgKPbY?lg?Y(H)?18.04?6.45?11.59pPbsp?Et?1011.59?32?10spPb?7.30 pPbep?7.0 ?pPb??0.30??0.007%?pPb??pPbK'PbYC
15. 解: 由Ksp ,测Th时pH<3.2,测La时pH<8.4,查酸效应曲线(数据)可知,测Th时 pH?2较好,为消除La的干扰,宜选pH<2.5,因此侧Th可在稀酸中进行;侧La在pH5-6较合适,可选在六亚甲基四胺缓冲溶液中进行。 18. 解: 由题意可知
?Sn?0.03?35?118.690.2?1000?100%?62.31%
?100%?37.29%
?Pb?(0.03?50?0.03?3.0?0.03?35)?207.20.2000?1000
21. 解: 据题中计量关系得:
???0.025?0.03?0.0036?0.001?10??254.2?20.2014?100%?98.45%
24. 解: 据题中计量关系得:
?Ni?0.05831?0.02614?58.6930.7176?100%?63.33%
?100%?Fe?(0.03544?0.05831?0.02614?0.05831)?5?55.8450.7176
=21.10%
?Cr?(0.05?0.05831?0.00621?0.06316?0.03544?0.05831)?5?51.9960.7176 ?10
0%=16.55%)
第 7 章 氧化还原滴定法
1. 解:查表得:lgK(NH3) =9.46
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