Andrew E. Pomerantz

Observation and interpretation of a time-delayed mechanism in the hydrogen exchange reaction

Extensive theoretical and experimental studies have shown the hydrogen exchange reaction H + H2 → H2 + H to occur predominantly through a ‘direct recoil’ mechanism: the H–H bonds break and form concertedly while the system passes straight over a collinear transition state, with recoil from the collision causing the H2 product molecules to scatter backward. Theoretical predictions agree well with experimental observations of this scattering process. Indirect exchange mechanisms involving H3 intermediates have been suggested to occur as well, but these are difficult to test because bimolecular reactions cannot be studied by the femtosecond spectroscopies used to monitor unimolecular reactions. Moreover, full quantum simulations of the time evolution of bimolecular reactions have not been performed. For the isotopic variant of the hydrogen exchange reaction, H + D2 → HD + D, forward scattering features observed in the product angular distribution have been attributed to possible scattering resonances associated with a quasibound collision complex. Here we extend these measurements to a wide range of collision energies and interpret the results using a full time-dependent quantum simulation of the reaction, thus showing that two different reaction mechanisms modulate the measured product angular distribution features. One of the mechanisms is direct and leads to backward scattering, the other is indirect and leads to forward scattering after a delay of about 25 femtoseconds.

Two-step laser mass spectrometry of asphaltenes.

Defined by their solubility in toluene and insolubility in n-heptane, asphaltenes are a highly aromatic, polydisperse mixture consisting of the heaviest and most polar fraction of crude oil. Although asphaltenes are critically important to the exploitation of conventional oil and are poised to rise in significance along with the exploitation of heavy oil, even as fundamental a quantity as their molecular weight distribution is unknown to within an order of magnitude. Laser desorption/ionization (LDI) mass spectra vary greatly with experimental parameters so are difficult to interpret: some groups favor high laser pulse energy measurements (yielding heavy molecular weights), arguing that high pulse energy is required to detect the heaviest components of this mixture; other groups favor low pulse energy measurements (yielding light molecular weights), arguing that low pulse energy is required to avoid aggregation in the plasma plume. Here we report asphaltene mass spectra recorded with two-step laser mass spectrometry (L2MS), in which desorption and ionization are decoupled and no plasma is produced. L2MS mass spectra of asphaltenes are insensitive to laser pulse energy and other parameters, demonstrating that the asphaltene molecular weight distribution can be measured without limitation from insufficient laser pulse energy or plasma-phase aggregation. These data resolve the controversy from LDI, showing that the asphaltene molecular weight distribution peaks near 600 Da and previous measurements reporting much heavier species suffered from aggregation effects.

Magnetic resonance in porous media: Recent progress

Recent years have seen significant progress in the NMR study of porous media from natural and industrial sources and of cultural significance such as paintings. This paper provides a brief outline of the recent technical development of NMR in this area. These advances are relevant for broad NMR applications in material characterization.

Minimization of Fragmentation and Aggregation by Laser Desorption Laser Ionization Mass Spectrometry

AbstractMeasuring average quantities in complex mixtures can be challenging for mass spectrometry, as it requires ionization and detection with nearly equivalent cross-section for all components, minimal matrix effect, and suppressed signal from fragments and aggregates. Fragments and aggregates are particularly troublesome for complex mixtures, where they can be incorrectly assigned as parent ions. Here we study fragmentation and aggregation in six aromatic model compounds as well as petroleum asphaltenes (a naturally occurring complex mixture) using two laser-based ionization techniques: surface assisted laser desorption ionization (SALDI), in which a single laser desorbs and ionizes solid analytes; and laser ionization laser desorption mass spectrometry (L2MS), in which desorption and ionization are separated spatially and temporally with independent lasers. Model compounds studied include molecules commonly used as matrices in single laser ionization techniques such as matrix assisted laser desorption ionization (MALDI). We find significant fragmentation and aggregation in SALDI, such that individual fragment and aggregate peaks are typically more intense than the parent peak. These fragment and aggregate peaks are expected in MALDI experiments employing these compounds as matrices. On the other hand, we observe no aggregation and only minimal fragmentation in L2MS. These results highlight some advantages of L2MS for analysis of complex mixtures such as asphaltenes. Figureᅟ

Analysis of petroleum compositional similarity using multiway principal components analysis (MPCA) with comprehensive two-dimensional gas chromatographic data

The accurate establishment of oil similarity is a longstanding problem in petroleum geochemistry and a necessary component for resolving the architecture of an oil reservoir. Past limitations have included the excessive reliance on a relatively small number of biomarkers to characterize such complex fluids as crude oils. Here we use multiway principal components analysis (MPCA) on large numbers of specific chemical components resolved with comprehensive two-dimensional gas chromatography-flame ionization detection (GC×GC-FID) to determine the molecular relatedness of eight different maltene fractions of crude oils. MPCA works such that every compound eluting within the same first and second dimension retention time is quantitatively compared with what elutes at that same retention times within the other maltene fractions. Each maltene fraction and corresponding MPCA analysis contains upwards of 3500 quantified components. Reservoir analysis included crude oil sample pairs from around the world that were collected sequentially at depth within a single well, collected from multiple depths in the same well, and from different depths and different wells but thought to be intersected by the same permeable strata. Furthermore, three different regions of each GC×GC-FID chromatograms were analysed to evaluate the effectiveness of MPCA to resolve compositional changes related to the source of the oil generating sediments and its exposure to biological and/or physical weathering processes. Compositional and instrumental artefacts introduced during sampling and processing were also quantitatively evaluated. We demonstrate that MPCA can resolve multi-molecular differences between oil samples as well as provide insight into the overall molecular relatedness between various crude oils.

Downhole Fluid Analysis and Asphaltene Science for Petroleum Reservoir Evaluation

Petroleum reservoirs are enshrouded in mysteries associated with all manner of geologic and fluid complexities that Mother Nature can inspire. Efficient exploitation of petroleum reservoirs mandates elucidation of these complexities; downhole fluid analysis (DFA) has proven to be indispensable for understanding both fluids and reservoir architecture. Crude oil consists of dissolved gases, liquids, and dissolved solids, known as the asphaltenes. These different fluid components exhibit fluid gradients vertically and laterally, which are best revealed by DFA, with its excellent precision and accuracy. Compositional gradient analysis falls within the purview of thermodynamics. Gas-liquid equilibria can be treated with a cubic equation of state (EoS), such as the Peng-Robinson EoS, a modified van der Waals EoS. In contrast, the first EoS for asphaltene gradients, the Flory-Huggins-Zuo (FHZ) EoS, was developed only recently. The resolution of the asphaltene molecular and nanocolloidal species in crude oil, which is codified in the Yen-Mullins model of asphaltenes, enabled the development of this EoS. The combination of DFA characterization of gradients of reservoir crude oil with the cubic EoS and FHZ EoS analyses brings into view wide-ranging reservoir concerns, such as reservoir connectivity, fault-block migration, heavy oil gradients, tar mat formation, huge disequilibrium fluid gradients, and even stochastic variations of reservoir fluids. New petroleum science and DFA technology are helping to offset the increasing costs and technical difficulties of exploiting ever-more-remote petroleum reservoirs.

Construction and calibration of an instrument for three-dimensional ion imaging

We describe a new instrument based on a delay-line detector for imaging the complete three-dimensional velocity distribution of photoionized products from photoinitiated reactions. Doppler-free [2+1] resonantly enhanced multiphoton ionization (REMPI) of H and D atoms formed upon photolysis of HBr and DBr in the range 203 nm < or = lambda photolysis < or = 243 nm yields radial speeds measured to be accurate within 1% of those calculated. The relative speed resolution is about 5% and limited by photoionization recoil broadening. A relative speed resolution of 3.4% is obtained for [3+1] REMPI, which minimizes the ionization recoil. We also determine the branching ratio between ground-state and spin-orbit-excited product channels and their associated anisotropies. We find that DBr photolysis dynamics differs slightly from its HBr counterpart.

Measurement of the cross section for H+D2→HD(v′=3,j′=0)+D as a function of angle and energy

Scattering of the HD(v′=3,j′=0) product from the H+D2 reaction is measured as a function of angle and collision energy from 1.39 to 1.85 eV. The plot of the cross section vs angle and energy is believed to be the first fully experimental plot of its kind reported for this benchmark reaction. Changes in the differential cross section (DCS) are observed in this collision energy range, including a forward-scattering component that peaks at about 1.64 eV and is a strong function of collision energy. This feature has been assigned to result from a barrier resonance, but its full interpretation is presently unsettled. These changes in the DCS do not manifest themselves as variations in the integral cross section (ICS), which varies less than 25% over the energy range measured. Comparisons of the DCSs and the ICS with quantum mechanical calculations show quantitative agreement, although some aspects of the DCS near 1.54 eV are not fully satisfactory.

Doppler-free multi-photon ionization: a proposal for enhancing ion images

Abstract We report on the use of Doppler-free 2+1 resonance enhanced multi-photon ionization (REMPI) to probe H atoms resulting from HBr photolysis at 243 nm. The Doppler-free technique allows almost all H atoms to be ionized at a single probe wavelength, regardless of their lab-frame velocities. This technique yields a significant enhancement in ionization efficiency of the product while leaving the background ionization essentially unaffected. We point out the utility of this technique for the ion imaging of reaction products.

A non-empirical gas slippage model for low to moderate Knudsen numbers

In this study, we present a novel derivation of the gas slip flow boundary condition within micro- and nano-flow channels. The newly derived boundary condition is of second order. Our model is based on the kinetic theory of gases. The slippage condition is obtained via the calculation of the shear stress in a confined micro-channel. We have benchmarked the mass transfer rate predicted by our model with existing numerical and physical experimental data, and the new model matches experiments within 10%.