第一节 概述 第二节 溶液中各级络合物型体的分布 第三节...
DESCRIPTION
第六章 络合滴定法 ( Complexometric Titration). —— 以络合反应为基础的滴定分析法. 第一节 概述 第二节 溶液中各级络合物型体的分布 第三节 络合滴定中的副反应 第四节 EDTA 滴定曲线 第五节 络合滴定指示剂 第六节 终点误差和准确滴定的条件 第七节 提高络合滴定选择性的方法 第八节 络合滴定的方式和应用. 1. 第一节 概述. 一、络合滴定中的滴定剂. 多核 络合物 简单络合物. 无机络合剂(单齿配位体). 络合剂. 有机络合剂(多齿配位体) 螯合物. - PowerPoint PPT PresentationTRANSCRIPT
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EDTA Complexometric Titration 1
-
2
-
:N-COO-CoNiZnCuCdHg EDTA 3
-
EDTA (H4Y, EDTA)Ethylene Diamine Tetra Acetic acid4
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EDTANa2H2Y2H2O EDTAS=11.1g/100mL0.3molL-1pH=4.4
-
H6Y2+H5Y+H4YH3Y-H2Y2-HY3-Y4-pKa1=0.90pKa2=1.60pKa3=2.00pKa4=2.67pKa5=6.16pKa6=10.26Ka1Ka6:10-0.9010-1.6010-2.00, 10-2.6710-6.1610-10.26 KH1KH6:1010.26106.16102.67102.00101.60100.90 EDTA7(P1536-1).
6
-
Y4- EDTA H2Y 2-HY 3-Y 4- pH < 0.9 H6Y2+2.676.16 H2Y2- >10.26 Y4-7
1
000.00000004280.0000239970.00281291950.11172678480.8854362559
000.00000025230.00008931130.00660550980.16554129280.8277636338
000.00000143790.00032116480.01498745830.23698889130.7477010476
000.00000780610.00110010230.03239165050.32317151740.6433289237
00.00000000010.00003967810.00352818490.06554677630.41262100930.5182643513
00.00000000110.00018528590.01039542680.12185471090.48399661440.3835679609
00.00000000710.00077975230.02760302280.20415341290.51163075710.2558330477
00.00000004210.00290374110.06485715490.30266199710.47858368950.1509933753
00.00000021610.00941356650.13266433760.39061974560.38972134510.0775807891
00.00000095470.0262349870.23328179790.43339196340.27282292060.0342673763
00.00000360340.06247543430.35051715950.41087458990.1631959150.012933298
00.00001164890.12743394650.45111278240.33364539350.08361518080.0041810478
00.00003258560.22491871120.50237218580.23443669290.03707025610.0011695683
00.00008009740.34883357150.49160724480.14474990070.01444169850.000287487
00.00017620520.48419326130.43054518920.07998687710.00503522340.0000632439
00.00035383940.61348812950.34419627340.04034652770.001602530.0000127001
00.00066156070.72371850060.25619442490.01894827480.00047486450.0000023745
0.00000000010.001172720.80945802830.18079829670.00843712210.00013341180.0000004209
0.00000000040.00200114740.87152345350.12282282410.00361642180.0000360810.0000000718
0.0000000010.00332578910.9138916340.08126334630.00150971410.00000950370.0000000119
0.00000000250.0054282230.94114747270.05280288850.0006189530.00000245840.0000000019
0.00000000640.00874914160.95711791310.03388171960.0002505910.0000006280.0000000003
0.00000001610.0139717710.96438724840.02154028570.00010051980.00000015890.0000000001
0.00000004040.02214017560.96423093440.01358879850.00004001120.00000003990
0.00000010060.03481440580.95666302160.00850665830.00001580370.00000000990
0.00000024850.05424336820.94047368710.00527650860.00000618510.00000000250
0.00000060620.08348412420.91327989140.00323298650.00000239110.00000000060
0.00000145340.12629717070.87175334310.00194712410.00000090860.00000000010
0.0000034020.18652274660.81232870860.00114480570.000000337100
0.00000770770.26664057540.73270007810.00065151770.00000012100
0.00001675220.36565442060.63397309620.00035568930.000000041700
0.00003466870.47746000520.52232041240.00018490.000000013700
0.00006807420.59153779360.40830293060.00009119740.000000004300
0.00012703390.69649735040.30333286610.00004274840.000000001300
0.00022670170.78425042080.21550371460.00001916260.000000000400
0.00039029060.8518988580.14770256460.00000828680.000000000100
0.00065407550.90079896030.09854347570.0000034884000
0.00107533720.93442545770.06449776450.0000014406000
0.00174472750.95659388580.04166079960.0000005871000
0.00280547790.97052527760.02666900740.0000002371000
0.00448315020.97855060510.01696614950.0000000952000
0.00713126580.98212468070.01074401550.000000038000
0.01129996680.98192239880.00677761920.0000000151000
0.01783596970.97790513140.0042588930.000000006000
0.02801983930.96931657890.00266357940.0000000024000
0.04373469180.95461020030.0016551070.0000000009000
0.06762623440.93135490360.00101886160.0000000004000
0.1031395450.89624183310.00061862180.0000000001000
0.15419826060.8454335430.00036819630.0000000001000
0.2241979350.77558894140.00021312360000
0.31415832850.68572278060.00011889090000
0.42063463060.57930199630.00006337310000
0.53503963650.46492827230.00003209120000
0.64586931180.3541152660.00001542210000
0.74297026580.25702267150.00000706270000
0.82083153850.17916535520.00000310640000
0.87894898880.1210496870.00000132420000
0.92005068440.07994876380.00000055180000
0.94802191580.05197785790.00000022640000
0.96656269830.03343720980.00000009190000
0.97863891860.02136104440.0000000370000
0.98641498460.01358500060.00000001490000
0.99138524850.00861474550.00000000590000
0.99454712480.00545287280.00000000240000
0.99655253140.00344746760.00000000090000
0.99782202360.0021779760.00000000040000
0.99862468450.00137531540.00000000020000
0.99913179390.0008682060.00000000010000
0.99945202350.000547976500000
0.99965418020.000345819700000
0.99978177460.000218225400000
pH
Sheet1
0.12589254120.0010.99770006381.1138910102000.00000004280.0000239970.00281291950.11172678480.8854362559
0.02511886430.2010.62950618290.0751785002000.00000025230.00008931130.00660550980.16554129280.8277636338
0.00851138040.4010.39719154950.0052513626000.00000143790.00032116480.01498745830.23698889130.7477010476
0.00177827940.6010.25061092530.0003850942000.00000780610.00110010230.03239165050.32317151740.6433289237
0.00000057540.8010.15812480390.000030161200.00000000010.00003967810.00352818490.06554677630.41262100930.5182643513
01.0010.09977000640.000002571300.00000000110.00018528590.01039542680.12185471090.48399661440.3835679609
01.2010.06295061830.000000243200.00000000710.00077975230.02760302280.20415341290.51163075710.2558330477
01.4010.03971915490.00000002600.00000004210.00290374110.06485715490.30266199710.47858368950.1509933753
0.00000004791.6010.02506109250.000000003200.00000021610.00941356650.13266433760.39061974560.38972134510.0775807891
0.00002691531.8010.01581248040.000000000500.00000095470.0262349870.23328179790.43339196340.27282292060.0342673763
0.00316227772.0010.00997700060.000000000100.00000360340.06247543430.35051715950.41087458990.1631959150.012933298
0.12589254122.2010.0062950618000.00001164890.12743394650.45111278240.33364539350.08361518080.0041810478
2.4010.0039719155000.00003258560.22491871120.50237218580.23443669290.03707025610.0011695683
2.6010.0025061093000.00008009740.34883357150.49160724480.14474990070.01444169850.000287487
2.8010.001581248000.00017620520.48419326130.43054518920.07998687710.00503522340.0000632439
3.0010.0009977001000.00035383940.61348812950.34419627340.04034652770.001602530.0000127001
3.2010.0006295062000.00066156070.72371850060.25619442490.01894827480.00047486450.0000023745
3.4010.000397191500.00000000010.001172720.80945802830.18079829670.00843712210.00013341180.0000004209
3.6010.000250610900.00000000040.00200114740.87152345350.12282282410.00361642180.0000360810.0000000718
3.8010.000158124800.0000000010.00332578910.9138916340.08126334630.00150971410.00000950370.0000000119
4.0010.0000997700.00000000250.0054282230.94114747270.05280288850.0006189530.00000245840.0000000019
4.2010.000062950600.00000000640.00874914160.95711791310.03388171960.0002505910.0000006280.0000000003
4.4010.000039719200.00000001610.0139717710.96438724840.02154028570.00010051980.00000015890.0000000001
4.6010.000025061100.00000004040.02214017560.96423093440.01358879850.00004001120.00000003990
4.8010.000015812500.00000010060.03481440580.95666302160.00850665830.00001580370.00000000990
5.0010.00000997700.00000024850.05424336820.94047368710.00527650860.00000618510.00000000250
5.2010.000006295100.00000060620.08348412420.91327989140.00323298650.00000239110.00000000060
5.4010.000003971900.00000145340.12629717070.87175334310.00194712410.00000090860.00000000010
5.6010.000002506100.0000034020.18652274660.81232870860.00114480570.000000337100
5.8010.000001581200.00000770770.26664057540.73270007810.00065151770.00000012100
6.0010.000000997700.00001675220.36565442060.63397309620.00035568930.000000041700
6.2010.000000629500.00003466870.47746000520.52232041240.00018490.000000013700
6.4010.000000397200.00006807420.59153779360.40830293060.00009119740.000000004300
6.6010.000000250600.00012703390.69649735040.30333286610.00004274840.000000001300
6.8010.000000158100.00022670170.78425042080.21550371460.00001916260.000000000400
7.0010.000000099800.00039029060.8518988580.14770256460.00000828680.000000000100
7.2010.00000006300.00065407550.90079896030.09854347570.0000034884000
7.4010.000000039700.00107533720.93442545770.06449776450.0000014406000
7.6010.000000025100.00174472750.95659388580.04166079960.0000005871000
7.8010.000000015800.00280547790.97052527760.02666900740.0000002371000
8.0010.0000000100.00448315020.97855060510.01696614950.0000000952000
8.2010.000000006300.00713126580.98212468070.01074401550.000000038000
8.4010.00000000400.01129996680.98192239880.00677761920.0000000151000
8.6010.000000002500.01783596970.97790513140.0042588930.000000006000
8.8010.000000001600.02801983930.96931657890.00266357940.0000000024000
9.0010.00000000100.04373469180.95461020030.0016551070.0000000009000
9.2010.000000000600.06762623440.93135490360.00101886160.0000000004000
9.4010.000000000400.1031395450.89624183310.00061862180.0000000001000
9.6010.000000000300.15419826060.8454335430.00036819630.0000000001000
9.8010.000000000200.2241979350.77558894140.00021312360000
10.0010.000000000100.31415832850.68572278060.00011889090000
10.2010.000000000100.42063463060.57930199630.00006337310000
10.401000.53503963650.46492827230.00003209120000
10.601000.64586931180.3541152660.00001542210000
10.801000.74297026580.25702267150.00000706270000
11.001000.82083153850.17916535520.00000310640000
11.201000.87894898880.1210496870.00000132420000
11.401000.92005068440.07994876380.00000055180000
11.601000.94802191580.05197785790.00000022640000
11.801000.96656269830.03343720980.00000009190000
12.001000.97863891860.02136104440.0000000370000
12.201000.98641498460.01358500060.00000001490000
12.401000.99138524850.00861474550.00000000590000
12.601000.99454712480.00545287280.00000000240000
12.801000.99655253140.00344746760.00000000090000
13.001000.99782202360.0021779760.00000000040000
13.201000.99862468450.00137531540.00000000020000
13.401000.99913179390.0008682060.00000000010000
13.601000.99945202350.000547976500000
13.801000.99965418020.000345819700000
14.001000.99978177460.000218225400000
Sheet1
pH
Sheet2
Sheet3
-
-EDTA(M-Y):1.2.1:13.MHYMOHY,,1:14.MY(P155)8
-
MY H+pHpM9
-
10
-
(KMYEt)11
-
M + L = MLML + L = ML2
MLn-1+L=MLn[MLn]=n[M][L]n12
-
M + L = ML(1) M + L = ML ML + L = ML2
M+2L=ML21 [ML]= 1[M][L]1 [ML2]=2[M][L]21. ML(1:1) 2. MLn(1:n) 1:1 13
-
(2) M + L = ML ML + L = ML2
ML2+ L=ML3 M + 3L=ML3[ML3]=3[M][L]314
-
(3) M + L = ML ML + L = ML2
ML2+L=ML3
MLn-1 + L=MLn
:M+nL=MLnn=K1K2Kn=[MLn]=n[M][L]n15
-
MLn MLn=MLn-1+L MLn-1=MLn-2+L
ML= M + L
: MLn =M+nL MLn(K)(K)nn-1n 16
-
[H+] 17
-
18
-
19
-
6-1[NH3]=0.10molL-1,CZn2+=10-1.70molL-15a-b210a+10b10a20
-
24
Cu2+ + NH3Cu(NH3)2+ K1 = 104.18
Cu(NH3)2+ + NH3 Cu(NH3)22+ K2 = 103.48
Cu(NH3)22+ + NH3 Cu(NH3)32+ K3 = 102.87
Cu(NH3)32+ + NH3 Cu(NH3)42+ K4 = 102.11
: Cu2++4NH3Cu(NH3)42+
(K=K1K2K3K4=1012.6
-
23
1:4
0
12.6
1:2
2
19.6
1:1
3
20.6
-
25
Cu2+ + en Cu(en)2+ K1 = 1010.67
Cu(en)2+ + en Cu(en)22+ K2 = 108.93
Cu2++2enCu(en)22+ (=K1K2=1019.6
-
26
Cu2+ + tn Cu(tn)2+ (K1 = 1020.6
-
2 127
1.
2.
3.
-
2128
1.
2.
3.n
EDTA
-
29
-
30
Ca2+ CaY
-
31
3