At currently achievable Fourier transform ion cyclotron resonance broadband mass spectrometry resolving power (m/Δm50% > 350 000 for 200 < m/z 1000), it would be necessary to spread out a conventional spectrum over ∼200 m in order provide visual resolution of the most closely resolved peaks. Fortunately, there are natural gaps typical spectrum, spaced 1 Da apart, because virtually no commonly encountered elemental compositions yield masses at those values. Thus, is possible break into 1-Da...

Although crude acids are minor constituents in petroleum, they have significant implications for oil geochemistry, corrosion, and commerce. We previously demonstrated that a single positive-ion electrospray ionization (ESI) high-field Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) experiment can resolve identify 3000 chemically different elemental compositions of bases (basic nitrogen compounds) oil. Here, we show negative-ion ESI FT-ICR MS selectively ionize...

Extra heavy petroleum crude oil (50% of the mixture boils at >566 °C) has been analyzed directly, without prior fractionation, by a high-field (9.4 T) Fourier transform ion cyclotron resonance mass spectrometer coupled to an external micro-electrospray source. At average resolving power, (m/Δm50% ≈ 50 000), single wideband (250−1250 Da) spectrum exhibited ∼5000 resolved peaks with 617 Da (e.g., up 7−10 each nominal mass). Their elemental compositions were positively identified accurate...

We report here an examination of the mass spectrometric fragmentation behavior molecular ions generated (and excited) by electron ionization (EI) from several asphaltene model compounds simulating both island and archipelago structural models. This is compared to that protonated molecules same atmospheric pressure chemical (APCI) excited collision-activated dissociation (CAD). The surprisingly similar. Both types yielded distinct patterns for compounds. Ions derived island-type fragment...

Laser-induced acoustic desorption (LIAD)/electron ionization (EI) was used to study asphaltene model compounds and asphaltenes derived from North American crude oil in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer (MS). Successful by LIAD of all (including polyphenylated vanadoyl porphyrin) as intact neutral molecules into the indicates that this method allows evaporation most if not components spectrometers for further characterization. Electron is universal ionizes...

Field desorption (FD) ionization is studied for the measurement of molecular weight distribution heavy petroleum, vacuum residua, and asphaltene derived from them. Hydrocarbon polymers, petroleum distillation cuts, chemical solubility fractions petroleums were examined to determine efficiency. FD showed effective molecules a wide range (300−5000 Da) with different compositions (saturates versus aromatics) (maltene asphaltene) properties. Electrospray (ESI) was explored compared FD. Previous...

Abstract Vanadyl (VO) porphyrins and sulfur‐containing vanadyl (VOS) of a wide carbon number range (C 26 to C 52 ) Z‐number (−28 −54) were detected identified in petroleum asphaltene by atmospheric pressure photonionization (APPI) Fourier transform ion cyclotron resonance mass spectrometry (FTICR‐MS). APPI provides soft ionization molecules (including VO VOS porphyrins), generating primarily molecular ions (M +. ). The ultra‐high resolving power (m/Δm FWHM ∼500 K) FTICR‐MS enabled resolution...

Thin film pyrolysis was used to thermally crack asphaltene molecules into their constituent building blocks at 500 °C. By using a thin of liquid ca. 20 μm, the cracked products were rapidly released much colder sweep gas stream quench reactions and minimize further decomposition. The condensed collected, with over 91% material balance on recovery gas, liquid, coke product. Simulated distillation showed wide range compounds boiling points up more than 700 °C produced in various stages...

We report here the first high resolution mass spectrometric evidence of nickel porphyrins in petroleum. A petroleum asphaltene sample is fractionated by a silica-gel cyclograph. Nickel content enriched approximately 3 fold one cyclograph fractions. The fraction subsequently analyzed atmospheric pressure photoionization (APPI) Fourier transform ion cyclotron resonance spectrometry (FTICR MS) with an average resolving power over 500 K (M/DeltaM(fwhm)). Similar to vanadyl porphyrins,...

Saturated nonfunctionalized hydrocarbons can be oxidized in situ by initiating an electrical discharge during desorption electrospray ionization (DESI) to generate the corresponding alchohols and ketones. This form of reactive DESI experiment utilized as derivatization method for rapid direct analysis alkanes at atmospheric pressure without sample preparation. Betaine aldehyde was incorporated into spray solution improve sensitivity detecting long-chain alcohol oxidation products. The limit...

Collision-induced dissociation Fourier Transform ion cyclotron resonance mass spectrometry (CID-FTICR MS) was developed to determine structural building blocks in heavy petroleum systems. Model compounds with both single core and multicore configurations were synthesized study the fragmentation pattern response factors CID reactions. Dealkylation is found be most prevalent reaction pathway CID. Single molecules exhibit primarily molecular weight reduction no change total unsaturation of...

Petroporphyrin compositional analysis of a heavy crude oil has been realized by isolation and subsequent ESI-FT-ICR mass spectrometric the porphyrin-containing fractions. Vanadium octaethyl (V=O(II)OEP) nickel (Ni(II)OEP) porphyrin standards were analyzed to determine favorable electrospray ionization conditions provide insight as molecular species present (e.g., adducts, multimers). Standard V=O(II)OEP Ni(II)OEP solutions revealed presence both monomer dimer with greater relative abundance...

The chemical building blocks that comprise petroleum asphaltene molecules were determined by thermal cracking of samples under conditions minimized alterations to aromatic and cycloalkyl groups. Favorable hydrogenation used tetralin as a hydrogen-donor solvent an iron-based catalyst allowed asphaltenes derived from different crude oils yield approximately 50–60 wt % distillates (<538 °C fraction), with coke yields below 10 %, reach conversions the vacuum residue fraction between 65 75 %....

Determination of the molecular structures petroporphyrins has been crucial to understand diagenetic pathways and maturation petroleum. However, these studies have hampered by their structural complexity challenges associated with isolation. In comparison skeletal macrocyclic structures, much less is known about substitutions, which are more sensitive diagenesis pathways. While isolated vanadyl largely consist etioporphyrin deoxophylloerythroetioporphyrin as expected, surprisingly, we find...

Comprehensive two-dimensional gas chromatography can be viewed as a traditional with sophisticated "elution-resolved" flame ionization detector (GC/FID) or separation capability. The concept of multidimensional extended to other detectors that also have capability, such ultraviolet, infrared, and mass spectrometer. Mass spectrometry, combined chromatography, GC/MS, has been powerful separation/identification device for many years. However, if one applies the this combination nonfragmentation...

We report the first field desorption ionization broadband high-resolution (m/Δm50% ≈ 65 000) mass spectra. have interfaced a ionization/field source to home-built 9.4-T FT-ICR spectrometer. The instrumental configuration employs convenient sample introduction (in-source liquid injection) and external ion accumulation. demonstrate utility of this by generating positive-ion spectra C60 midboiling crude oil distillate. latter contains species not accessible common soft-ionization methods, for...

We present continuous flow field desorption ionization Fourier transform ion cyclotron resonance mass spectrometry (FD FT-ICR MS) as a method for detailed speciation of aromatic compounds in fractionated crude oils and petroleum refinery process streams. The high efficiency nonpolar molecules combined with the unparalleled resolving power accuracy MS enable unequivocal elemental composition assignment ∼700−1400 species each four samples analysis. On basis assignments, we complete class type...

We report a new method for rapid measurement of total acid number (TAN) and TAN boiling point (BP) distribution petroleum crude products. The technology is based on negative ion electrospray ionization mass spectrometry (ESI-MS) selective quantification structures molecular weight distributions. A chip-based nanoelectrospray system enables microscale (<200 mg) higher throughput (20 samples/h) measurement. Naphthenic were assigned nominal masses set predefined structures. Stearic used as an...

Laser desorption ionization (LDI) and ion mobility mass spectrometry (IM-MS) are applied to study molecular weight distribution cross sections of petroleum asphaltene (ASPH) deasphaltened oils (DAO). Ion data confirmed the presence gas-phase aggregation in LDI experiments. Most molecules with MW > 3000 g/mol result from aggregation. Two-dimensional (2D) IM-MS trend lines compared model polymer systems confirm order (polywax polystyrene ≫ DAO ASPH fullerenes), these illustrate that has a more...