Sensing behavior of acetone vapors on TiO2_2 nanostructures --- application of density functional theory

The electronic properties of TiO$_2$ nanostructure are explored using density functional theory. The adsorption properties of acetone on TiO$_2$ nanostructure are studied in terms of adsorption energy, average energy gap variation and Mulliken charge transfer. The density of states spectrum and the band structure clearly reveals the adsorption of acetone on TiO$_2$ nanostructures. The variation in the energy gap and changes in the density of charge are observed upon adsorption of acetone on n-type TiO$_2$ base material. The results of DOS spectrum reveal that the transfer of electrons takes place between acetone vapor and TiO$_2$ base material. The findings show that the adsorption property of acetone is more favorable on TiO$_2$ nanostructure. Suitable adsorption sites of acetone on TiO$_2$ nanostructure are identified at atomistic level. From the results, it is confirmed that TiO$_2$ nanostructure can be efficiently utilized as a sensing element for the detection of acetone vapor in a mixed environment.Comment: 13 pages, 14 figures, 3 table

Acetone in the Atmosphere of Hong Kong, Abundance, Sources and Photochemical Precursors

Intensive field measurements were carried out at a mountain site and an urban site at the foot of the mountain from September to November 2010 in Hong Kong. Acetone was monitored using both canister air samples and 2,4-dinitrophenylhydrazine cartridges. The spatiotemporal patterns of acetone showed no difference between the two sites (p > 0.05), and the mean acetone mixing ratios on O3 episode days were higher than those on non-O3 episode days at both sites (p < 0.05). The source contributions to ambient acetone at both sites were estimated using a receptor model i.e. Positive Matrix Factorization (PMF). The PMF results showed that vehicular emission and secondary formation made the most important contribution to ambient acetone, followed by the solvent use at both sites. However, the contribution of biogenic emission at the mountain site was significantly higher than that at the urban site, whereas biomass burning made more remarkable contribution at the urban site than that at the mountain site. The mechanism of oxidation formation of acetone was investigated using a photochemical box model. The results indicated that i-butene was the main precursor of secondary acetone at the mountain site, while the oxidation of i-butane was the major source of secondary acetone at the urban site.Department of Civil and Environmental Engineerin

Freon provides heat transfer for solid C02 calibration standard

Acetone and Freon as liquid heat transfer mediums bring a dry ice bath to, and keep it at, the temperature required when using solid carbon dioxide as a calibration standard. Although acetone gives better results, Freon TF is preferred since acetone reacts violently in the presence of liquid oxygen

Measurements of laminar flame speeds of acetone/methane/air mixtures

The effect of acetone on the laminar flame speed of methane/air mixtures is investigated over a range of stoichiometries at atmospheric pressure and room temperature. The liquid acetone is vaporised and seeded into the methane/air mixture at 5%, 9% and 20% of the total fuel by mole. The experiment is performed using the jet-wall stagnation flame configuration and the particle imaging velocimetry (PIV) technique. Laminar flame speeds are derived by extrapolating the reference flame speed back to zero strain rate. Experimental results are compared to numerically calculated values using a base methane chemical kinetic mechanism (GRI-Mech 3.0) extended with acetone oxidation and pyrolysis reactions from the literature. The experimental results show that acetone addition does not affect the laminar flame speed of methane significantly within the range of concentrations considered, with a stronger effect on the rich range than under fuel-lean conditions, and that the peak laminar flame speed of acetone in air is ~42.5 cm/s at ϕ = 1.2. Simulation results reveal that the most important reactions determining acetone laminar flame speeds are H + O2 → O + OH, OH + CO → H + CO2, HO2 + CH3 → OH + CH3O and H + O2 + H2O → HO2 + H2O. Comparison of the expected disappearance of acetone relative to methane shows that the former is a good fluorescent marker for the latter

Optimal operating conditions and characteristics of acetone/CaF_2 detector for inverse photoemission spectroscopy

Performance and characteristics of a band-pass photon detector using acetone gas and CaF_2 window (acetone/CaF_2) have been studied and compared with an ethanol/MgF_2 detector. The optimal operating conditions are found to be 4 mbar acetone pressure and 745+/-20 V anode voltage. The count rate obtained by us is about a factor of 3 higher than what has been reported earlier for the acetone detector. Unlike other gas filled detectors, this detector works in the proportional region with very small dead time (4 micro sec). A detector band-pass of 0.48+/-0.01 eV FWHM is obtained.Comment: Review of Scientific Instruments 76, 066102 (2005

Equilibrium in the Catalytic Condensation of Carboxylic Acids with Methyl Ketones to 1,3-Diketones and the Origin of the Reketonization Effect

Acetone is the expected ketone product of an acetic acid decarboxylative ketonization reaction with metal oxide catalysts used in the industrial production of ketones and for biofuel upgrade. Decarboxylative cross-ketonization of a mixture of acetic and isobutyric acids yields highly valued unsymmetrical methyl isopropyl ketone (MIPK) along with two less valuable symmetrical ketones, acetone and diisopropyl ketone (DIPK). We describe a side reaction of isobutyric acid with acetone yielding the cross-ketone MIPK with monoclinic zirconia and anatase titania catalysts in the absence of acetic acid. We call it a reketonization reaction because acetone is deconstructed and used for the construction of MIPK. Isotopic labeling of the isobutyric acid’s carboxyl group shows that it is the exclusive supplier of the carbonyl group of MIPK, while acetone provides only methyl group for MIPK construction. More branched ketones, MIPK or DIPK, are less reactive in their reketonization with carboxylic acids. The proposed mechanism of reketonization supported by density functional theory (DFT) computations starts with acetone enolization and proceeds via its condensation with surface isobutyrate to a β-diketone similar to β-keto acid formation in the decarboxylative ketonization of acids. Decomposition of unsymmetrical β-diketones with water (or methanol) by the retrocondensation reaction under the same conditions over metal oxides yields two pairs of ketones and acids (or esters in the case of methanol) and proceeds much faster compared to their formation. The major direction yields thermodynamically more stable products—more substituted ketones. DFT calculations predict even a larger fraction of the thermodynamically preferred pair of products. The difference is explained by some degree of a kinetic control in the opposite direction. Reketonization has lower reaction rates compared to regular ketonization. Still, a high extent of reketonization occurs unnoticeably during the decarboxylative ketonization of acetic acid as the result of the acetone reaction with acetic acid. This degenerate reaction is the major cause of the inhibition by acetone of its own rate of formation from acetic acid at high conversions

Purification of Curcumin from Ternary Extract-Similar Mixtures of Curcuminoids in a Single Crystallization Step

Crystallization-based separation of curcumin from ternary mixtures of curcuminoids having compositions comparable to commercial extracts was studied experimentally. Based on solubility and supersolubility data of both, pure curcumin and curcumin in presence of the two major impurities demethoxycurcumin (DMC) and bis(demethoxy)curcumin (BDMC), seeded cooling crystallization procedures were derived using acetone, acetonitrile and 50/50 (wt/wt) mixtures of acetone/2-propanol and acetone/acetonitrile as solvents. Starting from initial curcumin contents of 67–75% in the curcuminoid mixtures single step crystallization processes provided crystalline curcumin free of BDMC at residual DMC contents of 0.6–9.9%. Curcumin at highest purity of 99.4% was obtained from a 50/50 (wt/wt) acetone/2-propanol solution in a single crystallization step. It is demonstrated that the total product yield can be significantly enhanced via addition of water, 2-propanol and acetonitrile as anti-solvents at the end of a cooling crystallization process

Photochemical Studies in Flash Photolysis. I. Photolysis of Acetone

The high-intensity flash photolysis of acetone was investigated using an exploding wire as a light source. Experiments were conducted with the unfiltered light of the flash, containing light in the near as well as in the far ultraviolet region of the spectrum. The results show that the C2H6/CO ratio in the reaction products is about 1.25 and is fairly insensitive to variation in acetone pressure. Addition of small amounts of biacetyl lowers the ratio still further. This is attributed to the deactivation of a long-lived excited acetone molecule formed in the ultraviolet region below 210 mµ. Addition of butane lowers the ratio far below unity. The CH4/CO ratio has the constant value of 0.1 for various light intensities, acetone pressures, pressures of added butane or of carbon dioxide. A convenient way of separating small amounts of ethane from very large amounts of carbon dioxide is described

Spectral characterisation of red pigment in Italian-type dry-cured ham. Increasing lipophilicity druing processing and maturation

Spectroscopic studies of Parma ham during processing revealed a gradual transformation of muscle myoglobin, initiated by salting and continuing during ageing. Electron spin resonance spectra did, however, conclusively show that the pigment in dry-cured Parma ham at no stage is a nitrosyl complex of ferrous myoglobin as found in brine-cured ham and Spanish Serrano hams. Both near-infra red reflectance spectra of sliced ham and UV/visible absorption spectra of extract of hams, obtained with aqueous buffer or acetone, showed the presence of different red pigments at varying processing stages for both solvents. Especially, the pigment extracted with aqueous buffer exhibited unique spectral features different from those of well-known myoglobin derivatives. At the end of processing, the pigment(s) becomes less water extractable, while the fraction of red pigment(s) extractable with acetone/water (75%/25%) increases throughout the processing time up to full maturation at 18 months. The chemical identity of the 6th ligand of myoglobin could not be conclusively established, but possible candidates are discussed. The partition of the pigment(s) between pentane and acetone/water showed a strong preference for pentane, suggesting that only the heme moiety is present in the acetone/water extract, and that Parma ham pigment is gradually transformed from a myoglobin derivative into a non-protein heme complex, which was found to be thermally stable in acetone/water solutio