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Hydrogen Bond Induced Nonmonotonic Composition Behavior of the Glass Transition in Aqueous Binary Mixtures

Sjöström, Johan, 1978 (författare)
Chalmers tekniska högskola,Chalmers University of Technology
Mattsson, Johan, 1969 (författare)
Chalmers tekniska högskola,Chalmers University of Technology
Bergman, Rikard, 1966 (författare)
Chalmers tekniska högskola,Chalmers University of Technology
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Swenson, Jan, 1966 (författare)
Chalmers tekniska högskola,Chalmers University of Technology
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 (creator_code:org_t)
2011-08-02
2011
Engelska.
Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-5207 .- 1520-6106. ; 115:33, s. 10013-10017
  • Tidskriftsartikel (refereegranskat)
Abstract Ämnesord
Stäng  
  • The glass transition temperature, T(g), of a binary mixture commonly varies monotonically between the T(g)s of its two components. However, mixtures of strongly associating liquids can instead exhibit a nonmonotonic T(g) variation. The origins of such nonideal mixing behavior have often been correlated with composition dependent structural variations. For binary mixtures between a hydrogen- (H-) bonded liquid and water, however, such behavior is generally not well understood. The ubiquity and importance of aqueous mixtures both in nature and in man-made applications stresses the needed for a better understanding. We here demonstrate nonmonotonic T(g) variations in binary mixtures of n-propylene glycol monomethyl ethers (nPGMEs) and water, where the composition dependent T(g) show maxima within an intermediate composition range. We show that these T(g) maxima correspond to crossovers in the composition dependence of the step amplitude in the isobaric heat capacity at T(g). We further demonstrate that the observed effects are caused by H-bond interactions involving the nPGME hydroxyl group. We can account for our obervations using a simple model based on two effects due to the added water: (i) an H-bond induced formation of effective relaxing entities and (ii) a plasticizing effect at high water contents.

Ämnesord

NATURVETENSKAP  -- Fysik (hsv//swe)
NATURAL SCIENCES  -- Physical Sciences (hsv//eng)

Nyckelord

1993
entropy
relaxation
former
v65
water solutions
estrelski sj
temperature
dynamics
liquid transition
p661
vapor
alcohols

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