Enthalpies of interaction of hydroxylic solutes with organic solvents

Heats of solution of m-cresol, 1-butanol, 1-pentanol, t-amyl alcohol, and model compounds (toluene, ethyl ether, n-butyl methyl ether, t-butyl methyl ether) in 17 organic solvents (n-heptane, cyclohexane, carbon tetrachloride, 1,2-dichloroethane, α,α,α-trifluorotoluene, triethylamine, butyl ether, ethyl acetate, dimethylformamide, dimethyl sulfoxide, benzene, toluene, mesitylene, t-butyl alcohol, 1-octanol, methanol, 2,2,2-trifluoroethanol) have been combined with solute heats of vaporization to give solvation enthalpies (ΔH(v → S)). Dependencies of solute vs. model solvation enthalpy differences on solvent dipolarity–polarizability and hydrogen-bond-accepting basicity were determined via correlations with Taft–Kamlet solvatochromic parameters (π*, β, ξ).m-Cresol is a substantially stronger H-bond donor than 1-butanol, 1-pentanol, and t-amyl alcohol, and H-bonds to acceptor solvents including alcohols. Cresol acts as an H-bond acceptor with the strong H-bond donor solvent trifluoroethanol.

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Enthalpies of interaction of aromatic solutes with organic solvents

Canadian Journal of Chemistry ◽

10.1139/v85-418 ◽

1985 ◽

Vol 63 (9) ◽

pp. 2529-2534 ◽

Cited By ~ 31

Author(s):

W. Kirk Stephenson ◽

Richard Fuchs

Keyword(s):

Organic Solvents ◽

Butyl Alcohol ◽

Model Compounds ◽

Butyl Ether ◽

Enthalpies Of Transfer ◽

Benzene Toluene ◽

Polar Interactions ◽

S Model ◽

Heats Of Vaporization ◽

Butyl Methyl Ether

Heats of solution of several aromatic solutes (benzene, toluene, mesitylene, nitrobenzene, α,α,α-trifluorotoluene, anisole) and model compounds (n-butyl methyl ether, cyclohexane) in 17 organic solvents (n-heptane, cyclohexane, carbon tetrachloride, 1,2-dichloroethane, α,α,α-trifluorotoluene, triethylamine, butyl ether, ethyl acetate, dimethylformamide, dimethyl sulfoxide, benzene, toluene, mesitylene, t-butyl alcohol, 1-octanol, methanol, 2,2,2-trifluoroethanol) have been combined with solute heats of vaporization to give enthalpies of transfer from vapor to solvent (ΔH(v → S)). Differences between solute and model values (ΔΔH(v → S) = ΔH(v → S) (aromatic solute)–ΔH(v → S) (model) were used to evaluate aromatic solute–solvent polar interactions. Correlations of ΔΔH(v → S) with solvent dipolarity–polarizability (Taft–Kamlet π* parameter) have been determined.

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Enthalpies of interaction of nitrogen base solutes with organic solvents

Canadian Journal of Chemistry ◽

10.1139/v85-420 ◽

1985 ◽

Vol 63 (9) ◽

pp. 2540-2544 ◽

Cited By ~ 33

Author(s):

W. Kirk Stephenson ◽

Richard Fuchs

Keyword(s):

Hydrogen Bond ◽

Organic Solvents ◽

Butyl Alcohol ◽

Hydrogen Bond Donor ◽

Butyl Ether ◽

Hydrogen Bond Acceptor ◽

Nitrogen Base ◽

Benzene Toluene ◽

Polar Interactions ◽

S Model

Heats of solution of triethylamine, aniline, pyridine, and model compounds (3-ethylpentane, benzene) in 17 organic solvents (n-heptane, cyclohexane, carbon tetrachloride, 1,2-dichloroethane, α,α,α-trifluorotoluene, triethylamine, butyl ether, ethyl acetate, dimethylformamide, dimethyl sulfoxide, benzene, toluene, mesitylene, t-butyl alcohol, 1-octanol, methanol, 2,2,2-trifluoroethanol) have been combined with solute heats of vaporization to give enthalpies of transfer from vapor to solvent (ΔH(v → s)). Differences between solute and model values (ΔΔH(v → s) = ΔH(v → s) (solute) – ΔH(v → s) (model)) were used to evaluate nitrogen base solute–solvent polar interactions. Correlations of ΔΔH(v → s) with Taft–Kamlet solvatochromic parameters (π*, α, β) have been determined.Aniline was found to be a better hydrogen bond donor acid than hydrogen bond acceptor base. Nevertheless, alcohols donate H-bonds to aniline. Triethylamine and pyridine are stronger HBA bases than aniline. The π* (dipolarity–polarizability) parameter of aniline (as a solute) is calculated to be 1.10.

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Enthalpies of interaction of ketones with organic solvents

Canadian Journal of Chemistry ◽

10.1139/v85-057 ◽

1985 ◽

Vol 63 (2) ◽

pp. 336-341 ◽

Cited By ~ 30

Author(s):

W. Kirk Stephenson ◽

Richard Fuchs

Keyword(s):

Organic Solvents ◽

Bond Formation ◽

Butyl Alcohol ◽

Enthalpies Of Solution ◽

Butyl Ether ◽

Hydrogen Bond Formation ◽

Linear Relationships ◽

Benzene Toluene ◽

Polar Interactions ◽

Alcohol Solvents

Enthalpies of solution (ΔHS) of a series of ketones (acetone, 2-butanone, 2-heptanone, 2-nonanone, 5-nonanone, 2,2,4,4-tetramethyl-3-pentanone, cyclohexanone) and alkane model compounds (n-heptane, n-nonane, 2,2,4,4-tetramethylpentane, cyclohexane) have been determined in 17 organic solvents (n-heptane, cyclohexane, CCl4, α,α,α,-trifluorotoluene, 1,2-dichloroethane, triethylamine, butyl ether, ethyl acetate, DMF, DMSO, benzene, toluene, mesitylene, 1-octanol, methanol, t-butyl alcohol, 2,2,2-trifluoroethanol), and combined with heats of vaporization to give enthalpies of transfer from vapor to solvent (ΔH(v → S)). These values have been used to evaluate ketone–solvent polar interactions (ΔΔH(v → S) = ΔH(v → S)(ketone) − ΔH(v → S)(alkane)). The linear relationships between ΔΔH(v → S) and solvent dipolarity-polarizability (Taft-Kamlet π* parameters) are derived. Based on the deviations from these correlations, ketone–CF3CH2OH enthalpies of hydrogen bond formation have been evaluated. The other alcohol solvents show no evidence of exothermic H-bond formation with ketones.

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Biodegradation of Methyl tert-Butyl Ether and Other Fuel Oxygenates by a New Strain, Mycobacterium austroafricanum IFP 2012

Applied and Environmental Microbiology ◽

10.1128/aem.68.6.2754-2762.2002 ◽

2002 ◽

Vol 68 (6) ◽

pp. 2754-2762 ◽

Cited By ~ 95

Author(s):

Alan François ◽

Hugues Mathis ◽

Davy Godefroy ◽

Pascal Piveteau ◽

Françoise Fayolle ◽

...

Keyword(s):

Polyacrylamide Gel Electrophoresis ◽

Sodium Dodecyl ◽

Dry Weight ◽

Butyl Alcohol ◽

Amyl Alcohol ◽

Methyl Tert Butyl Ether ◽

Methylotrophic Bacterium ◽

Specific Rate ◽

Butyl Ether ◽

Mycobacterium Austroafricanum

ABSTRACT A strain that efficiently degraded methyl tert-butyl ether (MTBE) was obtained by initial selection on the recalcitrant compound tert-butyl alcohol (TBA). This strain, a gram-positive methylotrophic bacterium identified as Mycobacterium austroafricanum IFP 2012, was also able to degrade tert-amyl methyl ether and tert-amyl alcohol. Ethyl tert-butyl ether was weakly degraded. tert-Butyl formate and 2-hydroxy isobutyrate (HIBA), two intermediates in the MTBE catabolism pathway, were detected during growth on MTBE. A positive effect of Co2+ during growth of M. austroafricanum IFP 2012 on HIBA was demonstrated. The specific rate of MTBE degradation was 0.6 mmol/h/g (dry weight) of cells, and the biomass yield on MTBE was 0.44 g (dry weight) per g of MTBE. MTBE, TBA, and HIBA degradation activities were induced by MTBE and TBA, and TBA was a good inducer. Involvement of at least one monooxygenase during degradation of MTBE and TBA was shown by (i) the requirement for oxygen, (ii) the production of propylene epoxide from propylene by MTBE- or TBA- grown cells, and (iii) the inhibition of MTBE or TBA degradation and of propylene epoxide production by acetylene. No cytochrome P-450 was detected in MTBE- or TBA-grown cells. Similar protein profiles were obtained after sodium dodecyl sulfate-polyacrylamide gel electrophoresis of crude extracts from MTBE- and TBA-grown cells. Among the polypeptides induced by these substrates, two polypeptides (66 and 27 kDa) exhibited strong similarities with known oxidoreductases.

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Oxidation of Methyl tert-Butyl Ether by Alkane Hydroxylase in Dicyclopropylketone-Induced and n-Octane-Grown Pseudomonas putida GPo1

Applied and Environmental Microbiology ◽

10.1128/aem.70.8.4544-4550.2004 ◽

2004 ◽

Vol 70 (8) ◽

pp. 4544-4550 ◽

Cited By ~ 43

Author(s):

Christy A. Smith ◽

Michael R. Hyman

Keyword(s):

Pseudomonas Putida ◽

Kinetic Studies ◽

Butyl Alcohol ◽

Amyl Alcohol ◽

Methyl Tert Butyl Ether ◽

Rich Medium ◽

Hydroxylase Activity ◽

Alkane Hydroxylase ◽

Butyl Ether ◽

Putative Mechanism

ABSTRACT The alkane hydroxylase enzyme system in Pseudomonas putida GPo1 has previously been reported to be unreactive toward the gasoline oxygenate methyl tert-butyl ether (MTBE). We have reexamined this finding by using cells of strain GPo1 grown in rich medium containing dicyclopropylketone (DCPK), a potent gratuitous inducer of alkane hydroxylase activity. Cells grown with DCPK oxidized MTBE and generated stoichiometric quantities of tert-butyl alcohol (TBA). Cells grown in the presence of DCPK also oxidized tert-amyl methyl ether but did not appear to oxidize either TBA, ethyl tert-butyl ether, or tert-amyl alcohol. Evidence linking MTBE oxidation to alkane hydroxylase activity was obtained through several approaches. First, no TBA production from MTBE was observed with cells of strain GPo1 grown on rich medium without DCPK. Second, no TBA production from MTBE was observed in DCPK-treated cells of P. putida GPo12, a strain that lacks the alkane-hydroxylase-encoding OCT plasmid. Third, all n-alkanes that support the growth of strain GPo1 inhibited MTBE oxidation by DCPK-treated cells. Fourth, two non-growth-supporting n-alkanes (propane and n-butane) inhibited MTBE oxidation in a saturable, concentration-dependent process. Fifth, 1,7-octadiyne, a putative mechanism-based inactivator of alkane hydroxylase, fully inhibited TBA production from MTBE. Sixth, MTBE-oxidizing activity was also observed in n-octane-grown cells. Kinetic studies with strain GPo1 grown on n-octane or rich medium with DCPK suggest that MTBE-oxidizing activity may have previously gone undetected in n-octane-grown cells because of the unusually high Ks value (20 to 40 mM) for MTBE.

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Degradation of a Mixture of Hydrocarbons, Gasoline, and Diesel Oil Additives by Rhodococcus aetherivorans and Rhodococcus wratislaviensis

Applied and Environmental Microbiology ◽

10.1128/aem.01117-09 ◽

2009 ◽

Vol 75 (24) ◽

pp. 7774-7782 ◽

Cited By ~ 63

Author(s):

Marc Auffret ◽

Diane Labbé ◽

Gérald Thouand ◽

Charles W. Greer ◽

Françoise Fayolle-Guichard

Keyword(s):

Detrimental Effect ◽

Dry Weight ◽

Diesel Oil ◽

Butyl Alcohol ◽

Butyl Ether ◽

Oil Additives ◽

Degradation Rates ◽

Benzene Toluene ◽

Rhodococcus Wratislaviensis ◽

Positive Effect

ABSTRACT Two strains, identified as Rhodococcus wratislaviensis IFP 2016 and Rhodococcus aetherivorans IFP 2017, were isolated from a microbial consortium that degraded 15 petroleum compounds or additives when provided in a mixture containing 16 compounds (benzene, toluene, ethylbenzene, m-xylene, p-xylene, o-xylene, octane, hexadecane, 2,2,4-trimethylpentane [isooctane], cyclohexane, cyclohexanol, naphthalene, methyl tert-butyl ether [MTBE], ethyl tert-butyl ether [ETBE], tert-butyl alcohol [TBA], and 2-ethylhexyl nitrate [2-EHN]). The strains had broad degradation capacities toward the compounds, including the more recalcitrant ones, MTBE, ETBE, isooctane, cyclohexane, and 2-EHN. R. wratislaviensis IFP 2016 degraded and mineralized to different extents 11 of the compounds when provided individually, sometimes requiring 2,2,4,4,6,8,8-heptamethylnonane (HMN) as a cosolvent. R. aetherivorans IFP 2017 degraded a reduced spectrum of substrates. The coculture of the two strains degraded completely 13 compounds, isooctane and 2-EHN were partially degraded (30% and 73%, respectively), and only TBA was not degraded. Significant MTBE and ETBE degradation rates, 14.3 and 116.1 μmol of ether degraded h−1 g−1 (dry weight), respectively, were measured for R. aetherivorans IFP 2017. The presence of benzene, toluene, ethylbenzene, and xylenes (BTEXs) had a detrimental effect on ETBE and MTBE biodegradation, whereas octane had a positive effect on the MTBE biodegradation by R. wratislaviensis IFP 2016. BTEXs had either beneficial or detrimental effects on their own degradation by R. wratislaviensis IFP 2016. Potential genes involved in hydrocarbon degradation in the two strains were identified and partially sequenced.

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Surface and Interfacial Tensions Along the Binodal Curve in the tert-Butyl Methyl Ether-Water-Alcohol Ternary Systems at 25 °C

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc20001487 ◽

2000 ◽

Vol 65 (9) ◽

pp. 1487-1496 ◽

Cited By ~ 5

Author(s):

Lidmila Bartovská ◽

Markéta Čechová ◽

Jaroslav Matouš ◽

Josef P. Novák

Keyword(s):

Methyl Ether ◽

Ternary Systems ◽

Butyl Alcohol ◽

Binodal Curve ◽

Miscibility Gap ◽

Surface Tensions ◽

Interfacial Tensions ◽

Tert Butyl ◽

Water Alcohol ◽

Butyl Methyl Ether

The surface tensions, interfacial tensions, and densities of conjugate solutions of compositions lying in the miscibility gap were measured for three ternary systems, viz. tert-butyl methyl ether-water-ethanol, tert-butyl methyl ether-water-tert-butyl alcohol, and tert-butyl methyl ether-water-butan-1-ol, at 25 °C.

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