The kinetic isotope effects in the reactions of CH₃Cl, ¹³CH₃Cl and CD₃Cl with OH radicals and Cl atoms were studied in relative rate experiments at 298±2 K and 1013±10 mbar. The reactions were carried out in a smog chamber using long path FTIR detection and the spectroscopic data analyzed employing a non-linear least squares spectral fitting method using measured high-resolution infrared spectra as well as absorption cross sections from the HITRAN database. The reaction rates of ¹³CH₃Cl and CD₃Cl with OH and Cl were determined relative to CH₃Cl as: k_OH+CH3Clk_OH+CH3Cl/k_OH+13CH3Cl}k_OH+13CH3Cl=1.059±0.008, k_OH+CH3Clk_OH+CH3Cl/k_OH+CD3Clk_OH+CD3Cl=3.9±0.4, k_Cl+CH3Clk_Cl+CH3Cl/k_Cl+13CH3Clk_Cl+13CH3Cl =1.070±0.010 and k_Cl+CH3Clk_Cl+CH3Cl/k_Cl+CD3Clk_Cl+CD3Cl=4.91±0.07. The uncertainties given are 2σ from the statistical analyses and do not include possible systematic errors. The unexpectedly large ¹³C kinetic isotope effect in the OH reaction of CH₃Cl has important implications for the global emission inventory of CH₃Cl.

We present a systematic study of crude oil–brine–rock interactions in tight chalk cores at reservoir conditions. Flooding experiments are performed on outcrops (Stevns Klint) as well as on reservoir core plugs from Dan field, the Ekofisk and Tor formations. These studies are carried out in core plugs with reduced pore volumes, i.e., short core samples and aged with a dynamic ageing method. The method was evaluated by three different oil compositions. A series of synthetic multicomponent brines and designed fluid injection scenarios are investigated; injection flow rates are optimized to ensure that a capillary-dominant regime is maintained. Changes in brine compositions and fluid distribution in the core plugs are characterized using ion chromatography and X-ray computed tomography, respectively. First, we show that polar components in the oil phase play a major role in wettability alteration during ageing; this controls the oil production behavior. We also show that, compared to seawater, both formation water and ten-times-diluted seawater are better candidates for enhanced oil recovery in the Dan field. Finally, we show that the modified flow zone indicator, a measure of rock quality, is likely the main variable responsible for the higher oil recoveries observed in Tor core samples.

The specific far-infrared spectral signatures associated with highly localized large-amplitude out-of-plane librational motion of water molecules have recently been demonstrated to provide sensitive spectroscopic probes for the micro-solvation of organic molecules [Mihrin et al., Phys. Chem. Chem. Phys. 21(4), 1717 (2019)]. The present work employs this direct far-infrared spectroscopic approach to investigate the non-covalent intermolecular forces involved in the micro-solvation of a selection of seven ether molecules with systematically varied alkyl substituents: dimethyl ether, diethyl ether, diisopropyl ether, ethyl methyl ether, t-butyl methyl ether, and t-butyl ethyl ether. The ranking of the observed out-of-plane water librational band signatures for this selected series of ether–water complexes embedded in inert neon matrices at 4 K reveals information about the interplay of directional intermolecular hydrogen bond motifs and non-directional and long-range dispersion interactions for the micro-solvated structures. These far-infrared observables differentiate minor subtle effects introduced by specific alkyl substituents and serve as rigorous experimental benchmarks for modern quantum chemical methodologies of various levels of scalability, which often fail to accurately predict the structural variations and corresponding vibrational signatures of the closely related systems. The accurate interaction energies of the series of ether–water complexes have been predicted by the domain based local pair natural orbital coupled cluster theory with single-, double-, and perturbative triple excitations, followed by a local energy decomposition analysis of the energy components. In some cases, the secondary dispersion forces are in direct competition with the primary intermolecular hydrogen bonds as witnessed by the specific out-of-plane librational signatures.

Multi‐exponential decay is prevalent in magnetic resonance spectroscopy, relaxation, and imaging. This paper describes simple MATLAB and Python functions and scripts for regularized multi‐exponential analysis methods for 1D and 2D data and example test problems and experiments. Regularized least‐squares solutions provide production‐quality outputs with robust stopping rules in ~5 and ~20 lines of code for 1D and 2D inversions, respectively. The software provides an open‐architecture simple solution for transforming exponential decay data to the distribution of their decay lifetimes. Examples from magnetic resonance relaxation of a complex fluid, a Danish North Sea crude oil, and fluid mixtures in porous materials—brine/crude oil mixture in North Sea reservoir chalk—are presented. Developed codes may be incorporated in other software or directly used by other researchers, in magnetic resonance relaxation, diffusion, and imaging or other physical phenomena that require multi‐exponential analysis.