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Ultraviolet absorption study of aqueous mixtures of monohydric alcohols: Water structural effects

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Il Nuovo Cimento D

Summary

The ultraviolet absorption spectra of aqueous mixtures of methanol, ethanol, 1- and 2-propanol in the spectral region (190÷210) nm were measured as a function of alcohol concentration in the entire cosolvent mole fraction. The ultraviolet absorption coefficient exhibits, for all the systems investigated, an anomalous behaviour which occurs in the water-rich region (mole fraction of cosolventx 2<0.1) and which for each alcohol shows the existence of a solvent composition,x 2 *, corresponding to which the association state of the alcohol molecules changes. This behaviour is in line with the prediction of a liquid-clathrate-hydrate model and with the conclusions drawn from recent results on compressibility data.

Riassunto

È stato misurato lo spettro di assorbimento di soluzioni acquose di metanolo, etanolo, 1-e 2-propanolo, nell'intervallo spettrale (190÷210) nm, in funzione della temperatura e della frazione molare,x 2, di cosolvente. L'assorbanza delle miscele esaminate mostra un comportamento anomalo nella regione ricca in acqua (x 2<0.1). In questo modo si individua, per ciascun alcool, un valorex 2 * della frazione molare in corrispondenza del quale cambia lo stato di associazione delle molecole di alcool. Tale comportamento è in accordo con le conclusioni tratte da un recente studio sulla compressibilità di miscele acqua-alcool etilico e con l'ipotesi dell'esistenza nelle miscele esaminate di strutture locali simili a quelle di un clatrato idrato.

Резюме

Измеряются ультрафиолетовые спектры поглощения в водных смесях метанола, этанола, 1- и 2-пропанола в спектральной области (190÷210) нм, как функция температуры и молярной доли,x 2, сорастворителя. Коэффициент ультрафиолетового поглощения для всех исследованных систем обнаруживает аномальное поведение, которое имеет место в области с большим слдержанием воды (мольная доля сорастворителяx 2<0.1) и которое для каждого из спиртов указывает на существование значения молярной долиx 2 * растворителя, при котором происходит изменение состояния связи молекул спирта. Это поведение согласуется с предсказаниями о существовании локальной структуры в исследованных смесях и с выводами из недавних исследований сжимаем ости водных смесей спиртов.

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Authors and Affiliations

  1. Dipartimento di Fisica, Università degli Studi-via Elce di Sotto, 06100, Perugia, Italia

    G. Onori

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  1. G. Onori
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Onori, G. Ultraviolet absorption study of aqueous mixtures of monohydric alcohols: Water structural effects. Il Nuovo Cimento D 9, 507–515 (1987). https://doi.org/10.1007/BF02667946

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  • DOI: https://doi.org/10.1007/BF02667946

PACS. 61.25

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