现代分析原理-第二章.pptVIP

* .Determine the composition of the compound and acid-base dissociation constant The determination of the composition of the compound 1.Mole ratio method We can determine the composition of the compound (complex ratio) and stability constant Suppose the complex reaction is :M + nR＝MRn Usually we fix the concentration of the metallic ion M , increase the concentration of the complexing agent gradually . ligand is R, obviously, R should be colorless or not remarkably absorbs in the designation wavelength range. Then dilute to the identical volume, obtains a series of solutions whose [ R ]/[ M ]is 1, 2, 3... ... ,preparing the corresponding reagent blank, under certain wave length, measuring its luminosity, then draw the curve, we can obtain the complexing ratio from the curve. * 典型的光度滴定曲线 依据滴定过程中溶液吸光度变化来确定终点的滴定分析方法。 Vsp 滴定剂吸收 Vsp 被滴物吸收 Vsp 滴定剂与待测物均吸收 Vsp 产物吸收 * 4. 络合物组成的测定 (1)摩尔比法: 固定cM ,改变cR 1:1 3:1 c(R)/c(M) A 1.0 2.0 3,0 * (2)等摩尔连续变化法: M:R=1:1 0.5 0.33 cM/c cM/c M:R=1:2 * 表观形成常数的测定 (设M、R均无吸收) 0.5 cM/c M:R=1:1 A0A c(M)=c(R)=c MmRn型 ? * 5.一元弱酸离解常数的测定 HL H＋＋L Ka＝[H+][L]/[HL] 高酸度下，几乎全部以HL存在，可测得AHL＝εHL·c(HL)； 低酸度下，几乎全部以L存在，可测得AL ＝εL·c(HL). 代入整理： [HL] [L] 或 配制一系列c相同,pH不同的溶液,测A. * Measuring the acid-base dissociation constant If there has monohydric weak acid, dissociation according to the following equations: HB =H+ + B- Ka=[B-][H+]/[HB] Preparing three kinds of solution whose analytical concentration c = [HB] + [B-] is equal, but its pH is different. pH of the first solution is near its pKa ,then in the solution HB and B- are coexist, measure its absorbance in 1cm absorption cell under some certain wavelength: * MO吸收曲线 Aa(HL) Ab (L) 1 2 3 4 5 6 Ab 6 5 4 3 2 1 Aa 350 400 450 500 550 600 ?/nm A 曲线 pH 1 1.10, 1.38 2 2.65 3 3.06 4 3.48 5 3.98 6 5.53,6.80 由每份溶液的一对pH、A，可求得一个Ka, 取平均值即可. * The second kind of solution is the acid solution whose pH is above