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本文研究了氧、温度和4-甲基-4-苯基-2-戊酮(Mpp)对乙醇辐解的影响。Mpp在实验使用的浓度范围内对乙醛的G值没有影响,G(2,3-丁二醇)值随Mpp浓度增加而下降,最后达0.9恒值。使用Mpp求得原初过程形成的G_(H_2)=1.9,动力学处理求得G_H=2.4,k_(12)/k_(11)=(11.9±1.8)×10~3。实验证明Mpp清除了体系中的H原子,抑制了CH_3CHOH自由基的形成,从而抑制了2,3-丁二醇的生成,但不影响乙醛的产额。这一研究否定了传统文献所述的在γ辐解乙醇时相当量的羟乙基自由基歧化反应生成乙醛。本文还对乙醇γ辐解机理进行了讨论,并求得了乙醇辐解的物料平衡。
The effects of oxygen, temperature and 4-methyl-4-phenyl-2-pentanone (Mpp) on ethanol radiolysis were studied. Mpp had no effect on the G value of acetaldehyde in the experimental concentration range. The value of G (2,3-butanediol) decreased with the increase of Mpp concentration and finally reached a constant value of 0.9. The initial value of G_ (H_2) = 1.9 was obtained by using Mpp and G_H = 2.4, k_ (12) / k_ (11) = (11.9 ± 1.8) × 10 ~ 3. Experiments show that Mpp eliminates H atoms in the system and inhibits the formation of CH_3CHOH free radicals, thereby inhibiting the production of 2,3-butanediol, but does not affect the yield of acetaldehyde. This study deny the traditional literature describes a considerable amount of hydroxyethyl radical disproportionation reaction to produce acetaldehyde in the case of gamma-irradiation of ethanol. The mechanism of ethanol γ-irradiation was also discussed, and the material balance of ethanol radiolysis was obtained.