Mills Andrew, Lawrie Katherine, McFarlane Michael
Department of Pure & Applied Chemistry, University of Strathclyde, Glasgow, UKG1 1XL.
Photochem Photobiol Sci. 2009 Mar;8(3):421-5. doi: 10.1039/b821222h. Epub 2009 Jan 15.
The classic, non-photochemical blue bottle experiment involves the reaction of methylene blue (MB) with deprotonated glucose, to form a bleached form of the dye, leuco-methylene blue (LMB), and subsequent colour recovery by shaking with air. This reaction is a popular demonstrator of key principles in kinetics and reaction mechanisms. Here it is modified so as to highlight features of homogenous and heterogeneous photoinduced electron transfer (PET) (Pure Appl. Chem., 2007, 79, 293-465) reactions, i.e.blue bottle light experiments. The homogeneous blue bottle light experiment uses methylene blue, MB, as the photo-sensitizer and triethanolamine as the sacrificial electron donor. Visible light irradiation of this system leads to its rapid bleaching, followed by the ready restoration of its original colour upon shaking away from the light source. The heterogeneous blue bottle light experiment uses titania as the photo-sensitizer, MB as a redox indicator and glucose as the sacrificial electron donor. UVA light irradiation of this system leads to the rapid bleaching of the MB and the gradual restoration of its original colour with shaking and standing. The latter 'dark' step can be made facile and more demonstrator-friendly by using platinised titania particles. These two photochemical versions of the blue bottle experiment are used to explore the factors which underpin homogeneous and heterogeneous PET reactions and provide useful demonstrations of homogeneous and heterogeneous photochemistry.
经典的非光化学蓝瓶子实验涉及亚甲基蓝(MB)与去质子化葡萄糖的反应,形成染料的漂白形式——无色亚甲基蓝(LMB),随后通过与空气振荡实现颜色恢复。该反应是动力学和反应机理关键原理的一个广为人知的演示实验。在此对其进行改进,以突出均相和异相光致电子转移(PET)(《纯粹与应用化学》,2007年,79卷,293 - 465页)反应的特点,即蓝瓶子光实验。均相蓝瓶子光实验使用亚甲基蓝(MB)作为光敏剂,三乙醇胺作为牺牲电子供体。对该体系进行可见光照射会导致其迅速褪色,随后在远离光源振荡时又能迅速恢复其原始颜色。异相蓝瓶子光实验使用二氧化钛作为光敏剂,MB作为氧化还原指示剂,葡萄糖作为牺牲电子供体。对该体系进行紫外光A照射会导致MB迅速褪色,并在振荡和静置过程中逐渐恢复其原始颜色。通过使用镀铂二氧化钛颗粒,可使后者的“暗”步骤变得简便且更便于演示。这两个蓝瓶子实验的光化学版本用于探究支撑均相和异相PET反应的因素,并为均相和异相光化学提供有用的演示。