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Physicochemical measurements by gas chromatography.

McGill, Robert Andrew. (1988) Physicochemical measurements by gas chromatography. Doctoral thesis, University of Surrey (United Kingdom)..

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Abstract

First the method of gas-liquid chromatography (GLC) has been used to obtain partition coefficients, K, at infinite dilution on polymeric and non-polymeric phases. About 30-40 solutes were studied per stationary phase. Secondly the method of gas-solid chromatography has been used to obtain adsorption isotherms for a series of adsorbents by the technique of elution by characteristic point (ECP). A single injection of a gas or vapour suffices to obtain the isotherm, and then the limiting Henry's law constant, Kh, for adsorption at low surface coverage. About 20-30 solutes were studied per adsorbent. Experiments were carried out at several levels of relative humidity (RH) 0%, 31% and 53%. The solute compounds used were chosen so as to have a wide range of properties such as polarity (pi*2), hydrogen-bond acidity (alpha[H]2), and hydrogen-bond basicity (beta[H]2). The results as log partition coefficients or -log Henry's constants were analysed by multiple linear regression analysis using equations such as: -LogK[H] or LogK = SPo + s.pi* 2 + a.alpha[H]2 + b.beta[H]2 + 1. LogL[18] where L[18] is the solute Ostwald absorption coefficient on n-hexadecane. In this way, the selectivity of the liquid polymeric phase or solid adsorbent towards classes of compound was investigated and equations for the prediction of further values of LogK or LogK[H] formulated. In parallel with the measurement of partition coefficients on liquid polymeric phases by GLC in this work, partition coefficients for the polymers have been determined using surface acoustic wave (SAW) devices by coworkers at the Naval Research Laboratory, Washington. The results for a series of 8-9 solutes in six polymeric phases show that partition coefficients and patterns of responses predicted through GLC experiments are the same as those found experimentally using coated SAW devices. Hence GLC can be used to evaluate possible coating materials, and by the technique of multiple linear regression analysis, to predict SAW responses for a multitude of vapours.

Item Type: Thesis (Doctoral)
Divisions : Theses
Authors :
NameEmailORCID
McGill, Robert Andrew.
Date : 1988
Contributors :
ContributionNameEmailORCID
http://www.loc.gov/loc.terms/relators/THS
Additional Information : Thesis (Ph.D.)--University of Surrey (United Kingdom), 1988.
Depositing User : EPrints Services
Date Deposited : 22 Jun 2018 14:24
Last Modified : 06 Nov 2018 16:53
URI: http://epubs.surrey.ac.uk/id/eprint/847792

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