• 作者： 吳榮泰 ; 卓靜哲
• 作者服務機構： 成功大學化學系
• 中文摘要： In aqueous H/sub 2/SO/sub 4/, Ce(IV) ion oxidizes rapidly Arnold's base ((p-Me/sub 2/NC/sub 6/H/sub 4/)/sub 2/CH/sub 2/, Ar/sub 2/CH/sub 2/) to the protonated species of Michler's hydrol ((p-Me/sub 2/NC/sub 6/H/sub 4/)/sub 2/CHOH, Ar/sub 2/CHOH) and Michler's hydrol blue((p-Me/sub 2/NC/sub 6/H/sub 4/)/sub 2/CH/sup +/, Ar/sub 2/CH/sup +/). With Ar/sub 2/CH/sub 2/ in excess, the rate law of the Ce(IV)-Ar/sub 2/CH/sub 2/ reaction in 0.100M H/sub 2/SO/sub 4/ is expressed-d(Ce(IV))/dt=k/sub app/(Ar/ sub 2/CH/sub 2/)/sub 0/(Ce(IV)) with k/sub app/=199.plmin.8M/sup -1/s/sup -1/ at 25.degree.C. When the consumption of Ce(IV) ion is nearly complete, the characteristic blue color of Ar/sub 2/CH/sup +/ ion starts to appear; later it fades relatively slowly. The electron transfer of this reaction takes place on the nitrogen atom rather than on the methylene carbon atom. The dissociation of the binuclear complex (Ce(III)ArCHArCe(III)) is responsible for the appearance of the Ar/sub 2/CH/sup +/ dye whereas the protonation reaction causes the dye to fade. In highly acidic solution, the rate law of the protonation reaction of Michler's hydrol blue is-d(Ar/sub 2/CH/sup +/)/dt=-d(Ar/sub 2/CH/sup +/)/dt=k/sub obs/(Ar/sub 2/CH/sup +/) where k/sub obs/=((ac+1)(H/sup +/)+bc(H/sup +/)/sup 2/)/(a+b(H/sup +/)+(in HClO/sub 4/) and k/sub obs/=((ac+1+e(HSO/sub 4//sup -/))(H/sup +/)+ bc(H/sup +/)/sup 2/+d(HSO/sub 4//sup -/)+ q(HSO/sub 4//sup -/)/sup 2//(H/sup +/))/(a+b(H/sup +/)+f(HSO/sub 4//sup -/)+ g(HSO/sub 4//sup -/)/sup 2//(H/sup +/))(in H/sub 2/SO/sub 4/), and at 25.degree.C and .mu.=0.1M, a=0,0870Ms, b=0.655s, c=0.202M/sup -1/s/sup -1/, d=0.110, e=0.0070M/sup -1/, f=0.156s, g=0.156s, and q=0.124. In highly basic solution, the rate law of the hydroxylation reaction of Michler's hydrol blue is-d(Ar/sub 2/CH/sup +/)/dt= k/sub OH/(OH/sup -/)/sub 0/(Ar/sub 2/CH/sup +/) with k/sub OH/=174.plmin.1M/sup -1/s/sup -1/ at 25.degree.C and .mu.=0.1M. The protonation reaction of Michler's hydrol blue takes place predominantly via hydrolysis whereas its hydroxylation occurs predominantly via the path of direct OH/sup -/ attack.
• 英文摘要： --
• 中文關鍵字： Cerium(Iv) Ion; Arnold's Base; Michler's Hydrol (Tetramethyldiaminobenz Hydrol); Oxidation; Kinetics; Protonation; Hydroxylation
• 英文關鍵字： 鈰離子；Arnold's鹼；四甲基二氨基二苯甲醇；氧化；動力學；質子化作用；水解作用