Irradiation of 3-methyl-2-phenyl-2H-azirine (1) at 254 nm in argon matrices results in ylide 6. Similarly, laser flash photolysis (λ = 266 nm) of azirine 1 in acetonitrile yields ylide 6, which has a transient absorption with λmax at ~340 nm and a lifetime of 14 μs. Density functional theory calculations were preformed to support the characterisation of ylide 6 in solution and argon matrices. Irradiation of azirine 1 above 300 nm has previously been reported (J. Org. Chem. 2014, 79, 653) to yield triplet vinylnitrene in solution and ketenimine in cryogenic argon matrices. Thus, the photochemistry of azirine 1 is dependent on the irradiation wavelength.
The thermal reaction of ozone with trimethyl aluminum was explored using twin jet, concentric jet, and merged jet deposition into cryogenic matrixes. Infrared spectroscopy and density functional theory calculations were employed to identify and characterize the products formed in each case. Together, these deposition techniques provide information over the essentially full course of the gas-phase reaction. At short times with twin jet deposition, the primary product is the O atom insertion product (CH)AlOCH. With merged jet deposition and longer gas-phase mixing times, the methyl peroxy radical HCOO· was seen in good yield along with final stable products HCO, HCOH, and CH. Production of AlO and its deposition onto the walls of the reaction tube as a powdery film was noted as well. All of these outcomes were combined to propose a reaction mechanism for this system. Of particular note, the observation of HCOO· provides clear evidence for a free radical component to the overall mechanism.
Laser flash photolysis of 2-methyl-1-phenylbut-3-en-1-one (1) conducted at irradiation wavelengths of 266 and 308 nm results in the formation of triplet 1,2-biradical 2 that has λmax at 370 and 480 nm. Biradical 2 is formed with a rate constant of 1.1 × 107 s–1 and decays with a rate constant of 2.3 × 105 s–1. Isoprene-quenching studies support the notion that biradical 2 is formed by energy transfer from the triplet-excited state of the ketone chromophore of 1. Density functional theory calculations were used to verify the characterization of triplet biradical 2 and validate the mechanism for its formation. Thus, it has been demonstrated that intramolecular sensitization of simple alkenes can be used to form triplet 1,2-biradicals with the two radical centres localized on the adjacent carbon atoms.
Broadband irradiation of 3,5‐diphenylisoxazole 1 in an argon matrix results in formation of azirine 3. Further irradiation of the matrix reduces the amount of azirine 3 with concurrent formation of ylide 4. Thus, it is theorized that the conversion of isoxazole 1 to azirine 3 goes through a triplet vinylnitrene 2 that does not intersystem cross to ketenimine 6. Hence, the reactivity of triplet vinylnitrene 2 is different from similar vinylnitrene intermediates with α‐methyl substituents that intersystem cross to form corresponding ketenimines. Density functional theory calculations support the notion that the conjugation of the α‐phenyl group to the vinylnitrene moiety in vinylnitrene 2 renders it more flexible than vinylnitrenes with α‐methyl substituents, and therefore, vinylnitrene 2 intersystem crosses to azirine 3, rather than ketenimine 6. Copyright © 2016 John Wiley & Sons, Ltd.
The thermal and photochemical reactions of (CH3)3Ga and O3 have been explored using a combination of matrix isolation, infrared spectroscopy, and theoretical calculations. Experimental data using twin jet deposition and theoretical calculations demonstrate the formation of multiple product species after deposition, annealing to 35 K, and UV irradiation of the matrices. The products were identified as (CH3)2GaOCH3, (CH3)2GaCH2OH, (CH3)(CH3O)Ga(OCH3), (CH3)2GaCHO, and (CH3)Ga(OCH3)(CH2OH). Product identifications were confirmed by annealing and irradiation behavior, (18)O substitution experiments, and high level theoretical calculations. Merged jet deposition led to a number of stable late reaction products, including C2H6, CH3OH, and H2CO. A white solid film was also noted on the walls of the merged (flow reactor) region of the deposition system, likely due to the formation of Ga2O3.
Photolysis of 2,3-diazidonaphthalene-1,4-dione (1) in methyltetrahydrofuran matrices forms 2-(λ 1 -azaneyl)-3-azidonaphthalene-1,4-dione (vinylnitrene 3 2), as confirmed by electron paramagnetic resonance spectroscopy. The zero-field splitting (zfs) parameters for 3 2 (D/hc = 0.5338 cm −1 , and E/hc = 0.0038 cm −1 ) reveal significant 1,3biradical character. Irradiating 3 2 yields 2-(λ 1 -azaneyl)-1,3-dioxo-2,3dihydro-1H-indene-2-carbonitrile (alkylnitrene 3 3), which has zfs parameters typical of a cycloalkylnitrene (D/hc = 1.57 cm −1 , and E/hc = 0.00071 cm −1 ). Photolysis of 1 in argon matrices verifies that 3 2 forms 3 3.
Silica is ubiquitous in oil and gas production water because of quartz and clay dissolution from rock formations. Furthermore, the produced water from unconventional production often contains high Ca2+, Mg2+ and Fe2+ concentrations. These common cations, especially iron, can form aqueous or surface complexes with silica and affect the nucleation inhibition of other scales such as barite. Thus, it is important to investigate the silica matrix ion effects on barite scale inhibitors efficiency to evaluate inhibitor compatibility with silica and common cations in produced waters. In this study, experimental conditions were varied from 50 mg/L to 160 mg/L SiO2 in the presence of Ca2+ (1,000 and 16,000 mg/L), Mg2+ (2,000 mg/L) and Fe2+ (10 mg/L) at 70°C and neutral pH conditions, all with a background of 1 M NaCl. Our laser scattering apparatus was used to study the effect of silica matrix ions on barite nucleation inhibition [Yan et al., 2015]. For the experiments with redox-sensitive cations (such as Fe2+), a novel anoxic apparatus along with laser scattering apparatus was used. Phosphonate, carboxylate and sulfonate inhibitors were tested. All inhibitors tolerated the experimental conditions with silica. The inhibition efficiency of phosphonate inhibitor DTPMP was impaired by high Ca2+ and Mg2+, and the addition of silica would not affect this result. The polycarboxylic acid inhibitor PPCA tolerated high Ca2+ and Mg2+ conditions, and adding silica did not have influence on this behavior. The polymeric inhibitors, such as PVS and PPCA, also tolerated the experimental conditions with Fe2+ and Fe-silica. Fe2+ significantly impaired the inhibition performance of DTPMP. This may be due to the formation of an Fe(II)-DTPMP precipitate. The detrimental effect of Fe2+ on DTPMP could be reduced, to some extent, by adding silica, which might be due to the formation of Fe-silica complex and the reduction of Fe2+ impact on phosphonate.
Calcium carbonate deposition experiments were carried out by pumping a brine solution through PTFE plastic, carbon steel, and 316 stainless steel tubing at 150°C and at a maximum SICaCO3 of 1.36. The kinetics of deposition were inferred from the variation of HCO3- concentration in the effluent with changing flow rate. The inhibition kinetics were determined before, during, and after the addition of NTMP inhibitor into the system. On the metal surfaces, deposition occurred within 10 minutes of the start of the experiment and had similar behavior with changing flow rate, whereas deposition did not begin on the PTFE surface until 30 minutes had passed. No more than 1ppm of NTMP was sufficient to completely halt deposition in the PTFE and stainless steel experiments, whereas up to 2 ppm of NTMP was required in the carbon steel experiment. The deposition kinetics were indistinguishable between the metal surfaces, and were ultimately similar on the smoother hydrophobic PTFE surface once an initial coating of scale had developed. The inhibition efficiency of the NTMP was negatively affected by the corrosion products produced in the carbon steel experiments, assumed to be primarily dissolved Fe (II). Inhibitor retention was higher in the metal surfaces than in the PTFE, possibly due to the preferential adsorption of the NTMP to the surface of the Fe rich steel tubing. Our results suggest that it is the hydrodynamics of brine in the tubing, controlled by flow rate, and the SI that are the main factors controlling scale deposition. Calcium carbonate scale attachment occurs via heterogenous nucleation directly onto the surface of the tube when the brine solution approaches oversaturation from a state of equilibrium with respect to calcium carbonate. The mechanism of inhibition in our system is likely to proceed through the formation of Ca- and Fe-NTMP complexes that either poison the growth surfaces of the scale, or drop the SI of the calcium carbonate by reducing the acitivity of free Ca in the brine.
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