Quantum Chemical Calculation and Evaluation of Partition Coefficients for Classical and Emerging Environmentally Relevant Organic Compounds

Salthammer, Tunga; Grimme, Stefan; Stahn, Marcel; Hohm, Uwe; Palm, Wolf-Ulrich

doi:10.1021/acs.est.1c06935

Cited by 23 publications

(34 citation statements)

References 125 publications

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“…The organic fraction of particles and surface films can be in equilibrium with air that ranges from very dry to very humid; therefore, the appropriate K OA will depend on RH and lie within the continuum between wet and dry 1‐octanol. For molecules with low to moderate water solubilities and negligible donor or acceptor properties, however, the differences in log K OA values for wet and dry 1‐octanol are small 51 …”

Section: The Thermodynamics Of Chemical Propertiesmentioning

confidence: 99%

“…Shiu and Mackay, 118 who evaluated literature data, give errors of 0.20–0.50 for their recommended values. Grimme et al 51 estimate errors of about 0.5 for logarithmic partition coefficients, but also state that the uncertainties increase with the number of possible conformers, that is, that the errors are larger for flexible molecules than for rigid molecules. The pp‐LFER method tends to lower values for log K OW .…”

Section: The Thermodynamics Of Chemical Propertiesmentioning

confidence: 99%

“…This made it possible to calculate a logarithmic partitioning coefficient (see Section 3.3) of 7.77 for n-hexadecane in itself, which corresponds to a vapor pressure of 0.15 Pa at 298 K when assuming ideal behavior. 51 The experimental value at 298 K is 0.20 Pa. 52…”

Section: Absolute and Relative Humiditymentioning

confidence: 99%

“…Grimme et al 50 use a semi‐empirical method for the computation of accurate conformer ensembles and refinement by density functional theory under consideration of solvation models. This made it possible to calculate a logarithmic partitioning coefficient (see Section 3.3) of 7.77 for n‐hexadecane in itself, which corresponds to a vapor pressure of 0.15 Pa at 298 K when assuming ideal behavior 51 52 …”

Section: The Thermodynamics Of Chemical Propertiesmentioning

confidence: 99%

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Temperature and indoor environments

Salthammer

Morrison

2022

Indoor Air

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From the thermodynamic perspective, the term temperature is clearly defined for ideal physical systems: A unique temperature can be assigned to each black body via its radiation spectrum, and the temperature of an ideal gas is given by the velocity distribution of the molecules. While the indoor environment is not an ideal system, fundamental physical and chemical processes, such as diffusion, partitioning equilibria, and chemical reactions, are predictably temperature‐dependent. For example, the logarithm of reaction rate and equilibria constants are proportional to the reciprocal of the absolute temperature. It is therefore possible to have non‐linear, very steep changes in chemical phenomena over a relatively small temperature range. On the contrary, transport processes are more influenced by spatial temperature, momentum, and pressure gradients as well as by the density, porosity, and composition of indoor materials. Consequently, emergent phenomena, such as emission rates or dynamic air concentrations, can be the result of complex temperature‐dependent relationships that require a more empirical approach. Indoor environmental conditions are further influenced by the thermal comfort needs of occupants. Not only do occupants have to create thermal conditions that serve to maintain their core body temperature, which is usually accomplished by wearing appropriate clothing, but also the surroundings must be adapted so that they feel comfortable. This includes the interaction of the living space with the ambient environment, which can vary greatly by region and season. Design of houses, apartments, commercial buildings, and schools is generally utility and comfort driven, requiring an appropriate energy balance, sometimes considering ventilation but rarely including the impact of temperature on indoor contaminant levels. In our article, we start with a review of fundamental thermodynamic variables and discuss their influence on typical indoor processes. Then, we describe the heat balance of people in their thermal environment. An extensive literature study is devoted to the thermal conditions in buildings, the temperature‐dependent release of indoor pollutants from materials and their distribution in the various interior compartments as well as aspects of indoor chemistry. Finally, we assess the need to consider temperature holistically with regard to the changes to be expected as a result of global emergencies such as climate change.

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Section: The Thermodynamics Of Chemical Propertiesmentioning

confidence: 99%

Section: The Thermodynamics Of Chemical Propertiesmentioning

confidence: 99%

Section: Absolute and Relative Humiditymentioning

confidence: 99%

Section: The Thermodynamics Of Chemical Propertiesmentioning

confidence: 99%

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Temperature and indoor environments

Salthammer

Morrison

2022

Indoor Air

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“… h Data (298 K) from Baskaran et al, 29 log K OA for benzophenone and TXIB calculated from SPARC, log K OA for DEHA from Salthammer et al 27 …”

Section: Model Architecture and Objectivesmentioning

confidence: 99%

A holistic modeling framework for estimating the influence of climate change on indoor air quality

et al. 2022

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The IPCC 2021 report predicts rising global temperatures and more frequent extreme weather events in the future, which will have different effects on the regional climate and concentrations of ambient air pollutants. Consequently, changes in heat and mass transfer between the inside and outside of buildings will also have an increasing impact on indoor air quality. It is therefore surprising that indoor spaces and occupant well‐being still play a subordinate role in the studies of climate change. To increase awareness for this topic, the Indoor Air Quality Climate Change (IAQCC) model system was developed, which allows short and long‐term predictions of the indoor climate with respect to outdoor conditions. The IAQCC is a holistic model that combines different scenarios in the form of submodels: building physics, indoor emissions, chemical–physical reaction and transformation, mold growth, and indoor exposure. IAQCC allows simulation of indoor gas and particle concentrations with outdoor influences, indoor materials and activity emissions, particle deposition and coagulation, gas reactions, and SVOC partitioning. These key processes are fundamentally linked to temperature and relative humidity. With the aid of the building physics model, the indoor temperature and humidity, and pollutant transport in building zones can be simulated. The exposure model refers to the calculated concentrations and provides evaluations of indoor thermal comfort and exposure to gaseous, particulate, and microbial pollutants.

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Enantio‐ and Diastereomerically Pure Titanocenes by Dynamic Conformational Locking

Hilche,

Krebs,

Weißbarth

et al. 2023

Chemistry A European J

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The synthesis of enantiomerically pure titanocenes is limited to cases with enantiomerically pure substituents at the cyclopentadienyl ligands and to ansa-titanocenes. For the latter complexes, the use of achiral ligands requires a resolution of enantiomers and frequently also a separation of the diastereoisomers obtained after metalation. Here, we introduce a new synthetic method that relies on the use of enantiomerically pure camphorsulfonate (CSA) ligands as control elements for the absolute and relative configuration of titanocene complexes. Starting from the conformationally flexible (RC 5 H 4 ) 2 TiCl 2 , the desired conformationally locked and hence enantio-and diastereomerically pure complexes (RC 5 H 4 ) 2 Ti(CSA) 2 are obtained in just two steps. According to X-ray crystallography the (RC 5 H 4 ) 2 Ti fragment is essentially C 2 -symmetric and nuclear magnetic resonance displays overall C 2 -symmetry. We applied density functional theory methods to unravel the dynamics of the complexes and the mechanisms and selectivities of their formation.

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Quantum Chemical Calculation and Evaluation of Partition Coefficients for Classical and Emerging Environmentally Relevant Organic Compounds

Cited by 23 publications

References 125 publications

Temperature and indoor environments

Temperature and indoor environments

A holistic modeling framework for estimating the influence of climate change on indoor air quality

Enantio‐ and Diastereomerically Pure Titanocenes by Dynamic Conformational Locking

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