累积稳定常数与平衡浓度的关系nIg βn = Zlg K;多元络合物M+nL = MIi=1[ML,]K_(n-i+1)β, =IIK,MLi-1 +L= MLiKi=K[MLi-][L]j=1[ML;][ML.Mβ, = K, = KK2...KMIILIIMLTLITML-Lj=l[L]i[ML,]B[ML, ] = β,[M][L]’[M][L]重要公式质子络合物B+nH+ =H,B[H,B] = β,[B][H]
i i i [M][L] [ML ] = 累积稳定常数与平衡浓度的关系 i n i K K 1 −( − +1) = = = i j i K j 1 [ML ][L] [ML ] i-1 i MLi-1 + L = MLi Ki = [ML ][L] [ML ] . [ML][L] [ML ] [M][L] [ML] . 1 2 1 2 1 − = = = = i i i i j i K j K K K [L]i i i i [ML ] = [M][L] = = n i n Ki 1 lg lg 重要公式 多元络合物 MLn M + nL = 质子络合物 B + nH = Hn B + i i i [H B] = [B][H] 推导过程
质子化常数[H,B]Bn质子络合物：B+nH+=H,B[Hn-B][H]逐级质子化Stepwise protonation累积常数逐级质子化质子化常数酸离解常数[HB]KHKanB+H=HBβi = KHKH[B][H]一[H,B]K3KHH-B+H=HBa(n-i+1)KH B-IIKH[H,,B][Hj=1n[H,B]KalH,B+H-H,BKHβ, -IIkHKH[Hn-, B][H]ni=1
质子络合物： Stepwise protonation 质子化常数 B+ nH = Hn B + 逐级质子化 B+ H = HB H 1 1 K Kan = [B][H] H [HB] K1 = H 1 = K1 Hi-1 B+ H = Hi B . [H B][H] [H B] -1 H i i Ki = ( 1) H 1 i a n i K K − + = = = i j i K j 1 H 逐级质子化 质子化常数 酸离解常数 累积常数 [H B][H] [H B] n-1 n n = . 1 H 1 n a K K = = = n i n Ki 1 H Hn-1 B+ H = Hn B [H B][H] [H B] -1 H n n Kn =
4.1.3各级络合物的分布分数多元络合物M + nL = ML[ML;]分布分数定义; = x(ML;)CM据物料平衡：CM =[M] +[ML] +[ML2] + ....+[ML n]CM = [M]+ β,[M][L] + β,[M][L]2 +.... + β,[M][L]"nZβ,[L]')(1 +CM =[M]i-1[ML,]BIMILJ'S, = x(ML;)= f([L],β,)0[M](1+Zβ,[L])CM比较酸的分布分数：β,[L]S; = f(Ka,pH)(1+β,[L)
4.1.3各级络合物的分布分数 MLn 多元络合物 M + nL = 分布分数定义 M [ML ] (ML ) c x i i = i = 据物料平衡： [M] [ML] [ML ] . [ML ] M 2 n c = + + + + n n c [M] [M][L] [M][L] . [M][L] 2 M = + 1 + 2 + + （ i ） n i i c [M] 1 [L] 1 M = = + + = + = = (1 [L] ) [L] [M] (1 [L] ) [ML ] [M][L] M i i i i i i i i i i c (ML ) ([ ], ) i i L i = x = f f (K , pH ) i = a 比较酸的分布分数：
铜络合物各种型体的分布1. 02Cu(NH3),2+80.Cu(NH),2+分布分数0. 60. 4Cu(NH3)2+Cu(NH3)2+0. 20. 026531042.12.93.54.1IgKi-4pNH3
铜氨络合物各种型体的分布 0.0 0.2 0.4 0.6 0.8 1.0 6 5 4 3 2 1 0 pNH3 分布系数 Cu(NH3 ) 2+ Cu(NH3 )2 2+ Cu(NH3 )3 2+ Cu2+ Cu(NH3 )4 2+ lgK 4.1 3.5 2.9 2.1 1-4 分 布 分 数
4.2氨羧络合剂·4.2.1氨羧络合剂
4.2 氨羧络合剂 • 4.2.1 氨羧络合剂