Erratum: The Solubility of Nitrogen and Air in Liquids [J. Phys. Chem. Ref. Data 13, 563 (1984)]

Battino, Rubin; Rettich, Timothy R.; Tominaga, Toshihiro

doi:10.1063/1.4901082

Cited by 64 publications

(73 citation statements)

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“…15 min. The solubility of O 2 in THF at 25 °C and 1 atm is reported to be 10.0 m M (molar fraction χ = 8.16 × 10 –4 ),70 this value was used in the calculation of the O 2 concentrations. Since the system was closed and the solutions had no contact to the gas phase, no change in concentration was evident.…”

Section: Methodsmentioning

confidence: 99%

BOX Ligands in Biomimetic Copper‐Mediated Dioxygen Activation: A Hemocyanin Model

et al. 2014

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The μ‐η2:η2‐peroxodicopper(II) core found in the oxy forms of the active sites of type III dicopper proteins have been a key target for bioinorganic model studies. Here, it is shown that simple bis(oxazoline)s (BOXs), which are classified among the so‐called “privileged ligands”, provide a suitable scaffold for supporting such biomimetic copper/dioxygen chemistry. Three derivatives R,HBOX‐Me2 (R = H, Me, tBu) with different backbone substituents have been used. Their bis(oxazoline)‐copper(I) complexes bind dioxygen to yield biomimetic μ‐η2:η2‐peroxodicopper(II) species. O2 can be reversibly released upon an increase in temperature. Their formation kinetics have been studied under cryo‐stopped‐flow conditions for the tBu derivative, giving activation parameters ΔH‡on = (2.27 ± 0.18) kcal mol–1, ΔS‡on = (–46.3 ± 0.8) cal K–1 mol–1 for the binding event and ΔH‡off = (11.7 ± 1.9) kcal mol–1, ΔS‡off = (–16.1 ± 8.2) cal K–1 mol–1 for the release of O2, as well as thermodynamic parameters ΔH° = (–10.0 ± 1.7) kcal mol–1 and ΔS° = (–32.7 ± 7.4) cal K–1 mol–1 for this equilibrium. The μ‐η2:η2‐peroxodicopper(II) complexes have been isolated as surprisingly stable solids and investigated in depth by a variety of methods, both in solution and in the solid state. Resonance Raman spectroscopy revealed a characteristic isotope‐sensitive stretch $\tilde {\nu}$O–O = 731–742 cm–1 (Δ[18O2] ≈ –39 cm–1) and an intense feature around 280 cm–1 diagnostic for the fundamental symmetric Cu2O2 core vibration. A slight butterfly‐shape of the Cu2O2 core has been derived from EXAFS data and DFT calculations. SQUID magnetic data evidenced strong antiferromagnetic coupled CuII2 (–2J ≥ 1000 cm–1). Thermal degradation in solution yields bis(hydroxo)‐bridged [(tBu,HBOX‐Me2)(L)Cu(OH)]2(PF6)2 (L = H2O, MeCN or THF); whereas in the case of H,HBOX‐Me2, ligand oxygenation has been detected. Preliminary reactivity studies with the substrate 2,4‐di‐tert‐butylphenol indicate the formation of the C–C coupling product 3,3′,5,5′‐tetra‐tert‐butyl‐2,2′‐biphenol, whereas ortho‐hydroxylation was not observed. The copper(I) complex [(tBu,HBOX‐Me2)Cu(MeCN)]PF6 as well as two dicopper(II) complexes [(L)(tBu,HBOX‐Me2)Cu(OH)]2(PF6)2 have been characterised by single‐crystal X‐ray diffraction. Considering the vast number of known BOX derivatives, a rich and versatile Cu/O2 chemistry based on this platform is anticipated.

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Section: Methodsmentioning

confidence: 99%

BOX Ligands in Biomimetic Copper‐Mediated Dioxygen Activation: A Hemocyanin Model

et al. 2014

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“…[85] ln x 1 ¼ 43:0160 þ 48:5244=t þ 13:9321 ln t þ 0:97004 ln P À 0:00048296P ð1Þ At 120, 140, and 170 8C, the dynamic viscosity of water is 0.230, 0.204, and 0.163 cP, respectively.…”

Section: Effect Of Temperature and Pressurementioning

confidence: 99%

A One‐Pot Method for the Selective Conversion of Hemicellulose from Crop Waste into C5 Sugars and Furfural by Using Solid Acid Catalysts

2012

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We present a solid-acid catalyzed one-pot method for the selective conversion of solid hemicellulose without its separation from other lignocellulosic components, such as cellulose and lignin. The reactions were carried out in aqueous and biphasic media to yield xylose, arabinose, and furfural. To overcome the drawbacks posed by mineral acid methods in converting hemicelllulose, we used heterogeneous catalysts that work at neutral pH. In a batch reactor, these heterogeneous catalysts, such as solid acids (zeolites, clays, metal oxides etc.), resulted in >90 % conversion of hemicellulose. It has been shown that the selectivity for the products can be tuned by changing the reaction conditions, for example, a reaction carried out in water at 170 °C for 1 h with HBeta (Si/Al=19) and HUSY (Si/Al=15) catalysts gave yields of 62 and 56 % for xylose and arabinose, respectively. With increased reaction time (6 h) and in presence of only water, HUSY resulted in yields of 30 % xylose + arabinose and 18 % furfural. However, in a biphasic reaction system (water + p-xylene, 170 °C, 6 h) yields of 56 % furfural with 17 % xylose+arabinose could be achieved. It was shown that with the addition of organic solvent the furfural yield could be increased from 18 to 56 %. Under optimized reaction conditions, >90 % carbon balance was observed. The study revealed that catalysts were recyclable with a 20 % drop in activity for each subsequent run. It was observed that temperature, pressure, reaction time, substrate to catalyst ratio, solvent, and so forth had an effect on product formation. The catalysts were characterized by means of X-ray diffraction, temperature-programmed desorption of NH(3), inductively coupled plasma spectroscopy, elemental analysis, and solid-state NMR ((29)Si, (27)Al) spectroscopy techniques.

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“…In addition, the gas content of the oil is reported to be significantly greater than water. Battino et al reported that the mole fraction of nitrogen in olive oil is 2.82 x 10 -3 whereas in water it is reported as 1.18 x 10 -5 under the same conditions 44 . The significant differences in gas solubility and viscosity as well as …”

Section: Please Do Not Adjust Margins Please Do Not Adjust Marginsmentioning

confidence: 99%

Cavitation clusters in lipid systems – surface effects, local heating and streamer formation

Birkin

Foley

Truscott

et al. 2017

Phys. Chem. Chem. Phys.

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Cavitation clusters and streamers are characterised in lipid materials (specifically sunflower oil) and compared to water systems. The lipid systems, which are important in food processing, are studied with high-speed camera imaging, laser scattering and pressure measurements. In these oils, clusters formed at an aged (roughened) tip of the sound source (a piston like emitter, PLE) are shown to collapse with varied periodicity in relation to the drive amplitude employed. A distinct streamer (an area of increased flow emanating from the cavitation cluster) is seen in the lipid media which is collimated directly away from the tip of the PLE source whereas in water the cavitation plume is visually less distinct. The velocity of bubbles in the lipid streamer near the cluster on the order of 10 m s -1. Local heating effects, within the streamer, are detected using a dual thermocouple measurement at extended distances. Viscosity, temperature and the outgassing within the oils are suggested to play a key role in the streamer formation in these systems.

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Erratum: The Solubility of Nitrogen and Air in Liquids [J. Phys. Chem. Ref. Data 13, 563 (1984)]

Cited by 64 publications

References 1 publication

BOX Ligands in Biomimetic Copper‐Mediated Dioxygen Activation: A Hemocyanin Model

BOX Ligands in Biomimetic Copper‐Mediated Dioxygen Activation: A Hemocyanin Model

A One‐Pot Method for the Selective Conversion of Hemicellulose from Crop Waste into C5 Sugars and Furfural by Using Solid Acid Catalysts

Cavitation clusters in lipid systems – surface effects, local heating and streamer formation

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