pH=3.80,因此,为防止Al3+发生水解选择pH=3左右比较合适。
8-21 量取含Bi3+、Pb2+、Cd2+的试液25.00mL,以二甲酚橙为指示剂,在pH=1.0时用0.02015mol·L-1EDTA溶液滴定,用去20.28mL。调节pH至5.5,用此EDTA滴定时又消耗28.86mL。加入邻二氮菲,破坏CdY2-,释放出的EDTA用0.01202mol·L-1Pb2+溶液滴定,用去18.05mL。计算溶液中的Bi3+、Pb2+、Cd2+的浓度。
???lgKlgK-lgK2?BiY=27.94, PbY=18.04,Cd2?Y=16.46, 解:查表得:
pH=1.0时,lgαpH=5.5时,lgα
Y(H)=18.01; Y(H)=5.69
??lgKMY由判据c(M) >6知,pH=1时只能测定Bi3+离子, pH=5.5时可测定Pb2+,Cd2+离子。
而由CdY2-释放出来的EDTA消耗的Pb2+量相当于Cd2+的量,则有: c(Bi3+)=c(EDTA)V(EDTA) /V(Bi3+)=20.28×0.02015/25.00=0.01635 mol·L-1 c(Cd2+)=c(Pb2+)V(Pb2+) /V(Cd2+)=0.01202×18.05/25.00=0.008678 mol·L-1
c(Pb2+)=[ c(EDTA)V(EDTA)-c(Pb2+)V(Pb2+)]/V (Pb2+)=(0.02015×28.86-18.05×0.01202)/25.00 =0.01458 mol·L-1
8-22 在25.00mL含Ni2+、Zn2+的溶液中加入50.00mL 0.01500mol·L-1EDTA溶液,用0.01000mol·L-1Mg2+返滴定过量的EDTA,用去17.52mL,然后加入二巯基丙醇解蔽Zn2+,释放出EDTA,再用去22.00mL Mg2+溶液滴定。计算原试液中Ni2+、Zn2+的浓度。 解: c(Zn 2+)= 0.01000×22.00/25.00 = 0.008800mol·L-1 ?c(Ni 2+) =(0.01500×50.00-0.01000×17.52)/25.00 =0.01419mol·L-1
8-23 间接法测定
2?SO4时,称取3.000g试样溶解后,稀释至250.00mL。在25.00mL试液
中加入25.00mL0.05000mol·L-1BaC12溶液,过滤BaSO4沉淀后,滴定剩余Ba2+用去29.15mL0.02002mol·L-1EDTA。试计算SO4的质量分数。
2?解:n(SO42-)=[n(Ba2+)-n(EDTA)]×250.00/25.00
ω(SO42-)=[(0.05000×25.00-0.02002×29.15)×10-3×10×M(SO42-)]/3.000 =0.2133
8-24 称取硫酸镁样品0.2500g,以适当方式溶解后,以0.02115 mol·L-1EDTA标准溶液滴定,用去24.90mL,计算EDTA溶液对MgSO4·7H2O的滴定度及样品中MgSO4的质量分数。
?3?1T?0.02155?246.47?10?0.005203g?L解:MgSO4?7H2O/EDTA
0.02155?24.90?10?3?120.4?(MgSO4)??0.25360.2500
8-25 分析铜、锌、镁合金时,称取试样0.5000g,溶解后稀释至200.00mL。取25.00mL调至pH=6,用PAN作指示剂,用0.03080 mol·L-1EDTA溶液滴定,用去30.30ml。另取25.00mL试液,调至pH=10,加入KCN掩蔽铜、锌,用同浓度EDTA滴定,用去3.40mL,然后滴加甲醛解蔽剂,再用该EDTA溶液滴定,用去8.85mL。计算试样中铜、锌、镁的质量分数。
?lgKZnY2?解:查表得:=16.50,
?lgKMgY2?=8.7,
?lgKCuY2?=18.80,
pH=6时,lgαY(H)=4.65; Y(H)=0.45;
pH=10.0时lgα
由准确滴定的判据可知pH=6时,可滴定Cu2+和Zn2+,消耗EDTA体积为30.30mL。 pH=10.0时,加KCN掩蔽Cu2+和Zn2+,则滴定Mg2+消耗3.40mLEDTA。 甲醛解蔽后,用去EDTA体积为8.85mL为滴定Cu2+所消耗的量。则有: ω(M)= c(EDTA)V(EDTA)×M/G×(25.00/200.00) ω(Mg2+)=3.40×0.03080×24.30×10-3/(1/8)×0.5000
=0.04070
ω(Zn2+) =8.85×0.03080×65.39×10-3/(1/8)×0.5000
=0.2852
ω(Cu2+) =(30.30-8.85)×0.03080×63.55×10-3/(1/8)×0.5000
=0.6718
8-26 A 100mL sample of water is titrated with 12.24mL of the EDTA solution(0.02040mol·L-1). Calculate the degree of hardness of the water in parts per million of CaCO3.
解:水的总硬度(ppmCaCO3)=c(EDTA)V(EDTA)M(CaCO3)×1000/100 =0.02040×12.24×100.09×1000/100=249.9(mg·L-1)
8-27 A 25.00 mL sample of unknown Fe3+ and Cu2+ required 16.06mL of 0.05083 mol·L-1 EDTA for complete titraition. A 50.00 mL sample of unknown was treated with NH4F to protect the Fe3+ .Then the Cu2+ was reduced and masked by addition of thiourea.Upon addition of 25.00 mL of 0.05083 mol·L-1 EDTA,the Fe3+ was liberated from is fluoride complex and formed an EDTA complex.The excess EDTA required 19.77mL of 0.01883 mol·L-1 Pb2+ to reach an endpoint using xylenol orange. Find the concentration of Cu2+ in the unknown.
解:与Fe3+反应的EDTA为(25.00×0.05083-19.77×0.01883)mmol 则Cu2+的物质的量浓度
16.06?0.05083?c(Cu2?)? =0.01468mol·L-1
25?(25.00?0.05083?19.77?0.01883)5025