Chloromethanes

Ohligschläger, André; Menzel, Katharina; Kate, Antoon ten; Martínez, Javier Rúiz; Frömbgen, Christoph; Arts, J.H.E.; McCulloch, Archie; Rossberg, Manfred; Lendle, Wilhelm; Pfleiderer, Gerhard; Tögel, Adolf; Torkelson, T. R.; Beutel, Klaus K.

doi:10.1002/14356007.a06_233.pub4

Cited by 6 publications

(9 citation statements)

References 48 publications

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“…The organochlorine compounds noted here are used as solvents or reactants for polymer precursors. As a solvent, the chloro-containing compounds are considered nonpolar and used across multiple applications due to their favorable intermediate polarity between water and alkanes . As polymer and material precursors, organochlorine compounds are used either because the chlorine atom is highly reactive and can react with less reactive substituents or because the chlorine atom imparts favorable properties.…”

Section: Resultsmentioning

confidence: 99%

Manufacturing Energy and Greenhouse Gas Emissions Associated with United States Consumption of Organic Petrochemicals

Nicholson

Rorrer

Uekert

et al. 2023

ACS Sustainable Chem. Eng.

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The production of commodity organic chemicals today is both primarily sourced from and powered by fossil carbon resources. Toward decarbonization of this key global economic sector, it is imperative to quantitatively understand the contributions to energy usage and greenhouse gas (GHG) emissions along the petrochemical manufacturing supply chain, which can inform judicious policy development and impactful technology options to improve or reimagine existing manufacturing practices. To that end, here we use the Materials Flows through Industry (MFI) tool to estimate the supply chain energy and GHG emissions for 51 organic petrochemicals and 6 intermediates that are globally produced at a capacity of at least 1 million metric tons (MMT) per year. This analysis focuses on supply chains in the United States, from which industrial data are readily sourced to obtain accurate energy and GHG emission estimates. Analysis for each chemical includes contributions from sourcing chemical feedstocks, electricity use, and fuel usage for transportation and manufacturing. This analysis predicts that process fuel, which is primarily used for heating, dominates GHG emissions in all cases except for chlorochemicals, where electricity is used extensively for the chloroalkali process and results in a large electricity GHG emission contribution ranging from 7 to 54% of total GHG emissions. Additionally, the contribution of electricity to GHG emissions ranges from 6 to 63%, representing the decarbonization potential in the transition toward renewable electricity with existing manufacturing processes. Taken together, these data serve as a critical baseline toward industrial decarbonization of the organic chemical sector, against which to compare changes to the electrical grid and industrial heat sources, improvements to existing technologies to manufacture the same chemicals, and new technologies to source alternative feedstocks to manufacture direct or functional replacement chemicals.

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Section: Resultsmentioning

confidence: 99%

Manufacturing Energy and Greenhouse Gas Emissions Associated with United States Consumption of Organic Petrochemicals

Nicholson

Rorrer

Uekert

et al. 2023

ACS Sustainable Chem. Eng.

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“…The two timeconstants may arise from the rotational diffusion around the three axes, as shown in Figure 5. Ariola et al obtained two time-constants 180 ps and 800 ps for a structurally similar BODIPY-col molecule from time-resolved emission anisotropy decay in dimethyl sulfoxide (η DMSO = 2 cP, at 293 K); [17] Because the viscosity of DCM (η DCM = 0.43 cP, at 293 K) [62] is ~5 times lower than the viscosity of DMSO, faster rotational relaxation time of 550 ps is obtained for the BODIPY-Ar-Chol molecule in DCM by TEA (Figure 4a) in this work. The better resolution of the TAA employed in this work enables us to resolve all three rotational relaxation times.…”

Section: Resultsmentioning

confidence: 99%

“…Additional references cited within the Supporting information (Ref. [2,25,40,41,58,62,67,[75][76][77][78][79][80][81][82][83][84][85][86]).…”

Section: Supporting Informationmentioning

confidence: 99%

A BODIPY‐Based Molecular Rotor in Giant Unilamellar Vesicles: A Case Study by Polarization‐Resolved Time‐Resolved Emission and Transient Absorption Spectroscopy

Jha,

Prabhakaran,

Spantzel

et al. 2023

ChemPhotoChem

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BODIPY and BODIPY‐derived systems are widely applied as fluorophores and as probes for viscosity detection in solvents and biological media. Their orientational and rotational dynamics in biological media are thus of vital mechanistic importance and extensively investigated. In this contribution, polarization‐resolved confocal microscopy is used to determine the orientation of an amphiphilic BODIPY‐cholesterol derivative in homogeneous giant unilamellar vesicles (GUV) made from 1,2‐dioleoyl‐sn‐glycero‐3‐phosphocholine (DOPC). The BODIPY‐moiety of the molecule is placed near the polar headgroups, and the cholesterol moiety is embedded in the membrane along the acyl chain of the lipids. The rotational relaxation of fluorophore is conventionally investigated by time‐resolved emission anisotropy (TEA); and this method is also used here. However, TEA depends on the emission of the fluorophore and may not be useful to probe rotational dynamics of the non‐emissive triplet states. Thus, we employ femtosecond transient absorption anisotropy (TAA), that relies on the absorption of the molecule to complement the studies of the amphiphilic BODIPY in DCM and GUV. The photoinduced anisotropy of the BODIPY molecule in DCM decays tri‐exponentially, the decay components (sub‐5 ps, 43 ps and 440 ps) of anisotropy are associated with the non‐spherical shape of the BODIPY molecule. However, the anisotropy decay in homogenous GUVs follows a biexponential decay; which arises from the wobbling‐in‐a‐cone motion of the non‐spherical molecule in the high viscous lipid bilayer media. The observations for the BODIPY‐chol molecule in the GUV environment by TAA will extend to the investigation of non‐emissive molecules in cellular environment since GUV structure and size resembles the membrane of a biological cell.

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“…To do this, we first consider the conditions in which these methyl groups were likely formed. Methanol is the principal source of methyl groups for the industrial synthesis of methyl halogens and organic monomers (Cheng, 1994;Ott et al, 2012;Siegemund et al, 2016;Ohligschläger et al, 2019). Since the 1960s, industrial methanol has been produced by the reaction of H 2 , CO 2 , and CO on Cu-ZnO-Al 2 O 3 catalysts at temperatures between 200 and 300°C.…”

Section: Sources Of D13 Ch 2 D and D12 Chd 2 Values In Methyl Groups In Commercial Materialsmentioning

confidence: 99%

“…Methylation reactions occur in the biosynthesis of major compound classes including lipids, sugars, nucleotides, and amino acids, as well as plant structural biopolymers such as lignin and pectin (e.g., Robertson, 2005;Roje, 2006;Landgraf et al, 2016;Rahikainen et al, 2018). Additionally, methylated compounds such as methanol (CH 3 OH), methyl tert-butyl ether, and various halomethanes (e.g., chloromethane (CH 3 Cl) and fluoromethane (CH 3 F)), have industrial applications (e.g., Cheng, 1994;Ott et al, 2012, Ohligschläger et al, 2019 or, in the case of methylated mercury compounds, are significant environmental biotoxins (Selin, 2009). The stable isotopic composition (i.e., 13 C/ 12 C and D/H ratios) of methyl groups are used as tracers for their formational and removal pathways in environmental and industrial applications.…”

Section: Introductionmentioning

confidence: 99%

Clumped 13CH2D and 12CHD2 compositions of methyl groups from wood and synthetic monomers: Methods, experimental and theoretical calibrations, and initial results

Lloyd

Eldridge

Stolper

2021

Geochimica et Cosmochimica Acta

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Methyl groups are found in numerous biogenic and synthetic materials including geologically preserved materials such as wood. The carbon and hydrogen isotope compositions of methyl groups are used as tracers in biogeochemical cycles, as paleothermometers, and to determine the hydrogen isotopic composition of ancient rain. Here we present analyses of resolved 13 C-D ( 13 CH 2 D) and D-D ( 12 CHD 2 ) clumped isotope compositions of methyl groups as new variables for the study of methyl groups in the present and past. We first present chemical methods to extract, purify, and derivatize methyl groups from methoxyl (R-O-CH 3 ) groups as CH 3 F and CH 3 Cl, and high-resolution mass spectrometric techniques to determine the clumped isotope compositions of these species. We achieve precisions for 13 C-D clumping of ±0.25‰ and D-D clumping of ±2.5‰. We anchor our clumped isotopic measurements to a thermodynamic reference frame by first calculating the theoretical temperature dependences of 13 C-D and D-D clumping in CH 3 Cl, then placing our measurements onto this reference frame through experimental internal isotopic equilibration of CH 3 Cl at 200°C. Finally, we provide and analyze an initial dataset of clumped 13 C-D and D-D compositions of methyl groups from various commercial/synthetic monomers and environmental woods. We observe ranges in clumped isotope compositions of $11‰ in 13 C-D and $48‰ in D-D, and systematic differences within these ranges between methyl groups from commercial monomers and wood. Specifically, commercial clumped 13 C-D compositions are between 0 and 3‰, which correspond to apparent equilibrium temperatures between 170°C and the infinite temperature limit. In contrast, the clumped 13 C-D compositions of wood methoxyl groups are distinctively high (9.50-11.25‰) and 3-6‰ higher than would be expected if formed in internal isotopic equilibrium at Earth-surface temperatures. Commercial/synthetic methyl and wood methoxyl clumped D-D compositions are also distinct: À5 to +13‰ in commercial monomers vs. À35 to À8‰ in wood-such negative values cannot result from formation in isotopic equilibrium and require kinetic processes to have occurred. These results indicate that wood methoxyl groups are formed out of isotopic equilibrium and that clumped isotope compositions of methyl groups may be useful tracers of methyl group sources and sinks in the environment. For instance, isotopic clumping in methyl groups may be useful for understanding controls on isotopic clumping in methane produced by methylotrophic methanogens.

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Chloromethanes

Cited by 6 publications

References 48 publications

Manufacturing Energy and Greenhouse Gas Emissions Associated with United States Consumption of Organic Petrochemicals

Manufacturing Energy and Greenhouse Gas Emissions Associated with United States Consumption of Organic Petrochemicals

A BODIPY‐Based Molecular Rotor in Giant Unilamellar Vesicles: A Case Study by Polarization‐Resolved Time‐Resolved Emission and Transient Absorption Spectroscopy

Clumped 13CH2D and 12CHD2 compositions of methyl groups from wood and synthetic monomers: Methods, experimental and theoretical calibrations, and initial results

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