h第八章 生物碱类药物分析.pptVIP

Theory Water behaves both as a weak acid and a weak base thus in an aqueous environment it can compete effectively with very weak acid and bases with regard to proton donation and acceptance as shown in Figure 1. The effect of this is that the inflection in the titration curves for very weak acids and very weak bases is small because they approach the pH limits in water of 14 and 0 respectively thus making end-point detection more difficult. A general rule is that H2O + H+ H3O+ Competes with RNH2 + H+ RNH3+ H2O + B OH- + BH+ Competes with ROH + B RO- + BH+ Fig.1 Competition of water with weak acid and bases for proton bases with pKa7 or acid with pKa7 cannot be determined accurately in aqueous solution. Various organic solvents may be used to replace water since they compete less effectively with the analyte for proton donation or acceptance. Non-aqueous titration of weak bases Acetic acid is a very weak proton acceptor and thus does not compete effectively with weak bases for protons. Only very strong acids will protonate acetic acid appreciably according to the equation shown below: CH3COOH + HA CH3COOH2+ + A- Perchloric acid is the strong of the common acids in acetic acid solution and the titration medium usually used for non-aqueous titration of bases is perchloric acid in acetic acid. Addition of acetic anhydride, which hydrolyses to acetic acid, is used to remove water from aqueous perchloric acid. Weak bases compete very effectively with acetic acid for protons. Crystal violet (very weak bases) or quinalidine red is used as the indicator in this type of titration. A typical analysis is shown in Figure 2 for L-DOPA. ＋ CH3COOH2+ ＋ CH3COOH Fig.2 Analysis of DOPA by non-aqueous When the bases is in the form of a salt of a weak acid, removal of an anionic counter ion prior to titrati