ABSTRACT
Being the lightest, most mobile atom that exists, hydrogen plays an important role in the chemistry of hydrocarbons, proteins and peptides and most biomolecules. Hydrogen can undergo transfer, exchange and migration processes, having considerable impact on the chemical behavior of these molecules. Although much has been learned about reaction dynamics involving one hydrogen atom, less is known about those processes where two or more hydrogen atoms participate. Here we show that single and double hydrogen migrations occurring in ethanol cations and dications take place within a few hundred fs to ps, using a 3D imaging and laser pump-probe technique. For double hydrogen migration, the hydrogens are not correlated, with the second hydrogen migration promoting the breakup of the C-O bond. The probability of double hydrogen migration is quite significant, suggesting that double hydrogen migration plays a more important role than generally assumed. The conclusions are supported by state-of-the-art molecular dynamics calculations.
ABSTRACT
In human biometeorology, the integration of several microclimatic variables as a combined index facilitates the understanding of how users perceive thermal environments. Indices, such as the physiological equivalent temperature (PET) index, translate the combined effects of meteorological variables on humans in terms of thermal stress or comfort and serve as important aids to climate-responsive urban and regional planning as well as heat stress and thermal comfort analyses. However, there is a need for adjusting proposed comfort/stress ranges of a given index when using it in different climatic contexts. The purpose of this study is to present a preliminary calibration procedure for the PET index for three different climatic regions: Curitiba, Brazil, a subtropical location; Rio de Janeiro, Brazil, a tropical city; and Glasgow, UK, a high-latitude location. Field studies have been carried out by the authors according to a similar protocol and using similar equipment, yielding actual thermal sensation votes and microclimate data, post-processed as PET data. The calibration procedure uses exclusively thermal sensation data as reported by pedestrians during outdoor comfort campaigns and concurrent microclimatic data recorded during the interviews. PET comfort/stress classes differ among the three locations and, in general, are less restrictive as in the original ranges proposed by the index developers.
Subject(s)
Climate , Thermosensing , Adult , Brazil , Calibration , Female , Humans , Male , Middle Aged , Scotland , TemperatureABSTRACT
Aimed at climate-responsive urban design for tropical areas, the paper attempts to answer the question whether the site-related context affects in some way the perceptual assessment of the microclimate by users of outdoor spaces. Our hypothesis was that visual cues resulting from urban design are important components of the outdoor thermal perception. Monitoring was carried out alongside the administration of standard comfort questionnaires throughout summer periods in 2012-2015 in pedestrian areas of downtown Rio de Janeiro (22° 54 10 S, 43° 12 27 W), Brazil. Campaigns took place at different points, pre-defined in respect of urban geometry attributes. For the measurements, a Davis Vantage Pro2 weather station was employed to which a gray globe thermometer was attached. Two thermal indices were used for assessing the overall meteorological conditions and comfort levels in the outdoor locations: physiological equivalent temperature (PET) and universal thermal climate index (UTCI). Our results suggest that thermal sensation in Rio depends to a large extent on the thermal environment as described by air temperature, PET, or UTCI, and that urban geometry (expressed by the sky-view factor (SVF)) may modify this relationship with increased building density associated to warmer sensation votes under moderate heat stress conditions. This relationship however reverses under strong heat stress with warmer sensations in less obstructed locations, and disappears completely under still higher heat stress, where meteorological conditions, and not the site's SVF, will drive thermal sensation.
