Search results for "CONSTANT"

Quantum Dynamics of the 17O + 32O2 Collision Process

2016

We report full quantum integral and differential cross sections and rate constants for the 17O + 32O2 reactive process. This constitutes the first quantum scattering study of the 17O16O16O system. We emphasize the comparison with the 18O + 32O2 collision in close connection to the mass-independent fractionation (hereafter referred to as MIF) puzzle for ozone in atmospheric chemistry. We find similar general trends in the cross sections and rate constants for both rare isotopes, but we note some singular behaviors peculiar to the use of 17O isotope, particularly at the lowest collision energies.

Oxoanion binding to a cyclic pseudopeptide containing 1,4-disubstituted 1,2,3-triazole moieties

2016

A macrocyclic pseudopeptide 3 is described featuring three amide groups and three 1,4-disubstituted 1,2,3-triazole units along the ring. This pseudopeptide was designed such that the amide NH groups and the triazole CH groups converge toward the cavity, thus creating an environment well suited for anion recognition. Conformational studies in solution combined with X-ray crystallography confirmed this preorganisation. Solubility of 3 restricted binding studies to organic media such as 5 vol% DMSO/acetone or DMSO/water mixtures with a water content up to 5 vol%. These binding studies demonstrated that 3 binds to a variety of inorganic anions in DMSO/acetone including chloride, nitrate, sulfat…

Nature of (C5Me5)2Mo2O5in water–methanol at pH 0–14. On the existence of (C5Me5)MoO2(OH) and (C5Me5)MoO2+: a stopped-flow kinetic analysis

2002

A stopped-flow analysis of compound Cp*2Mo2O5 (Cp* = η5-C5Me5) in 20% MeOH–H2O over the pH range 0–14 has provided the speciation of this molecule as well as the rate and mechanism of interconversion between the various species that are present in solution. The compound is a strong electrolyte in this solvent combination, producing the Cp*MoO2+ and Cp*MoO3− ions in equilibrium with a small amount of Cp*MoO2(OH), the latter attaining ca. 15% relative amount at pH 4. At low pH (  6. The acid dissociation constant of Cp*MoO2(OH) has been measured directly (pK = 3.65 ± 0.02) while the pK for the protonation equilibrium leading to Cp*MoO3H2+ is estimated as  5. The prevalent pathway at high pH i…

Computational Study of the Effect of Glyoxal–Sulfate Clustering on the Henry’s Law Coefficient of Glyoxal

2014

We have used quantum chemical methods to investigate the molecular mechanism behind the recently reported ( Kampf , C. J. ; Environ. Sci. Technol . 2013 , 47 , 4236 - 4244 ) strong dependence of the Henry's law coefficient of glyoxal (C2O2H2) on the sulfate concentration of the aqueous phase. Although the glyoxal molecule interacts only weakly with sulfate, its hydrated forms (C2O3H4 and C2O4H6) form strong complexes with sulfate, displacing water molecules from the solvation shell and increasing the uptake of glyoxal into sulfate-containing aqueous solutions, including sulfate-containing aerosol particles. This promotes the participation of glyoxal in reactions leading to secondary organic…

Lower mantle hydrogen partitioning between periclase and perovskite : a quantum chemical modelling

2016

Abstract Partitioning of hydrogen (often referred to as H2O) between periclase (pe) and perovskite (pvk) at lower mantle conditions (24–80 GPa) was investigated using quantum mechanics, equilibrium reaction thermodynamics and by monitoring two H-incorporation models. One of these (MSWV) was based on replacements provided by Mg2+ ↔ 2H+ and Si4+ ↔ 4H+; while the other (MSWA) relied upon substitutions in 2Mg2+ ↔ Al3+ + H+ and Si4+ ↔ Al3+ + H+. H2O partitioning in these phases was considered in the light of homogeneous (Bulk Silicate Earth; pvk: 75%–pe:16% model contents) and heterogeneous (Layered Mantle; pvk:78%–pe:14% modal contents) mantle geochemical models, which were configured for lower…

Determination of water speciation in hydrous haplogranitic glasses with partial Raman spectra

2020

Abstract We use a mathematical approach to decompose the Raman water band at 3000 cm−1 to 3750 cm−1 into two partial Raman spectra corresponding to the individual Raman activity of the two water species, i.e., molecular water (H2Om) and OH-groups, present in hydrous rhyolitic glasses. The approach is based on a least-squares optimization algorithm and the assumption that the water band can be expressed as a linear combination of two partial Raman spectra. Our model makes no assumptions regarding the shape of the partial Raman spectra. The model input consists of about 700 Raman spectra from hydrous haplogranitic (HPG8) compositions with total water contents from 0.6 to 3.1 wt% and with know…

2018

Rapid environmental fluctuations are ubiquitous in the wild, yet majority of experimental studies mostly consider effects of slow fluctuations on organism. To test the evolutionary consequences of fast fluctuations, we conducted nine independent experimental evolution experiments with bacteria. Experimental conditions were same for all species, and we allowed them to evolve either in fluctuating temperature alternating rapidly between 20°C and 40°C or at constant 30°C temperature. After experimental evolution, we tested the performance of the clones in both rapid fluctuation and in constant environments (20°C, 30°C and 40°C). Results from experiments on these nine species were combined meta…

Experimental approaches for testing if tolerance curves are useful for predicting fitness in fluctuating environments

2017

Most experimental studies on adaptation to stressful environments are performed under conditions that are rather constant and rarely ecologically relevant. Fluctuations in natural environmental conditions are ubiquitous and include for example variation in intensity and duration of temperature, droughts, parasite loads, and availability of nutrients, predators and competitors. The frequency and amplitude of many of these fluctuations are expected to increase with climate change. Tolerance curves are often used to describe fitness components across environmental gradients. Such curves can be obtained by assessing performance in a range of constant environmental conditions. In this perspectiv…

Harvesting‐induced population fluctuations?

2003

It has recently been shown that damped endogenous dynamics is a common feature in Finnish grouse species; In this paper, we demonstrate that time-variant harvesting may turn damped dynamics to quasi-periodic fluctuations. Exploited populations, e.g. grouse, may therefore fluctuate more than expected if we do not manage to keep the harvest fraction constant over time. However, the harvest fraction of Finnish grouse varies with the phase of the cycle. Such a harvesting strategy could potentially change the periodicity of the fluctuations, as can a threshold harvest strategy where a constant fraction is harvested above a density threshold. The two non-linear harvesting strategies investigated …

Comparative assessment of a foam-based method for ISCO of coal tar contaminated unsaturated soils

2019

Abstract In situ delivery of liquid reagents in vadose zone is limited by gravity and soil anisotropy. A new foam-based delivery method of persulfate (PS) solutions in unsaturated soils was previously shown to overcome these limitations. The goal of this paper is to demonstrate the efficiency of this method regarding contaminant removal. Hence, the comparative oxidation of 200 mg.kg−1 coal tar artificially contaminated soils with thermally activated PS was carried out after PS-delivery using foam, surfactant solution and pure water. The foam-based method was compared in unfavorable conditions to the reference methods. Especially, in the latter, soil and oxidant solutions were thoroughly mix…