Simple derivation of the frequency dependent complex heat capacity

This paper gives a simple derivation of the well-known expression of the frequency dependent complex heat capacity in modulated temperature experiments. It aims at clarified again that the generalized calorimetric susceptibility is only due to the non-equilibrium behaviour occurring in the vicinity of thermodynamic equilibrium of slow internal degrees of freedom of a sample when the temperature oscillates at a well determined frequency

Kinetics of the glass transition of styrene-butadiene-rubber : Dielectric spectroscopy and fast differential scanning calorimetry

The glass transition is relevant for performance definition in rubber products. For extrapolation to high-frequency behavior, time–temperature superposition is usually assumed, although most complex rubber compounds might be outside of its area of validity. Fast differential scanning calorimetry (FDSC) with cooling rates up to 1500 K/s and broadband dielectric spectroscopy (BDS) with frequencies up to 20 MHz are applied here to directly access both kinetics and dynamics of glass formation in a wide frequency range. For the first-time, the relation between the thermal vitrification and the dielectric relaxation is studied on vulcanized styrene-butadiene rubber, showing that both cooling rate and frequency dependence of its glass transition can be described by one single Vogel-Fulcher-Tammann-Hesse equation. The results indicate the validity of the Frenkel-Kobeko-Reiner equation. Another focus is the sample preparation of vulcanized elastomers for FDSC and BDS as well as the temperature calibration below 0°C. © 2020 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals LLC

Macroscopic non-equilibrium thermodynamics in dynamic calorimetry

What is really measured in dynamic calorimetric experiments is still an open question. This paper is devoted to this question, which can be usefully envisaged by means of macroscopic non-equilibrium thermodynamics. From the pioneer work of De Donder on chemical reactions and with other authors along the 20th century, the question is tackled under an historical point of view. A special attention is paid about the notions of frequency dependent complex heat capacity and entropy production due to irreversible processes occurring during an experiment. This phenomenological approach based on thermodynamics, not widely spread in the literature of calorimetry, could open significant perspectives on the study of macro-systems undergoing physico-chemical transformations probed by dynamic calorimetry.Comment: review article (21 pages

Tropical montane cloud forest: Environmental drivers of vegetation structure and ecosystem function

Abstract:Tropical montane cloud forests (TMCF) are characterized by short trees, often twisted with multiple stems, with many stems per ground area, a large stem diameter to height ratio, and small, often thick leaves. These forests exhibit high root to shoot ratio, with a moderate leaf area index, low above-ground production, low leaf nutrient concentrations and often with luxuriant epiphytic growth. These traits of TMCF are caused by climatic conditions not geological substrate, and are particularly associated with frequent or persistent fog and low cloud. There are several reasons why fog might result in these features. Firstly, the fog and clouds reduce the amount of light received per unit area of ground and as closed-canopy forests absorb most of the light that reaches them the reduction in the total amount of light reduces growth. Secondly, the rate of photosynthesis per leaf area declines in comparison with that in the lowlands, which leads to less carbon fixation. Nitrogen supply limits growth in several of the few TMCFs where it has been investigated experimentally. High root : shoot biomass and production ratios are common in TMCF, and soils are often wet which may contribute to N limitation. Further study is needed to clarify the causes of several key features of TMCF ecosystems including high tree diameter : height ratio.This is the author accepted manuscript. The final version is available from Cambridge University Press via http://dx.doi.org/10.1017/S026646741500017

Floral odors and the interaction between pollinating Ceratopogonid midges and Cacao

Most plant species depend upon insect pollination services, including many cash and subsistence crops. Plants compete to attract those insects using visual cues and floral odor which pollinators associate with a reward. The cacao tree, Theobroma cacao, has a highly specialized floral morphology permitting pollination primarily by Ceratopogonid midges. However, these insects do not depend upon cacao flowers for their life cycle, and can use other sugar sources. To understand how floral cues mediate pollination in cacao we developed a method for rearing Ceratopogonidae through several complete lifecycles to provide material for bioassays. We carried out collection and analysis of cacao floral volatiles, and identified a bouquet made up exclusively of saturated and unsaturated, straight-chain hydrocarbons, which is unusual among floral odors. The most abundant components were tridecane, pentadecane, (Z)-7-pentadecene and (Z)-8-heptadecene with a heptadecadiene and heptadecatriene as minor components. We presented adult midges, Forcipomyia sp. (subgen. Forcipomyia), Culicoides paraensis and Dasyhelea borgmeieri, with natural and synthetic cacao flower odors in choice assays. Midges showed weak attraction to the complete natural floral odor in the assay, with no significant evidence of interspecific differences. This suggests that cacao floral volatiles play a role in pollinator behavior. Midges were not attracted to a synthetic blend of the above four major components of cacao flower odor, indicating that a more complete blend is required for attraction. Our findings indicate that cacao pollination is likely facilitated by the volatile blend released by flowers, and that the system involves a generalized odor response common to different species of Ceratopogonidae