Enthalpies of interaction of ketones with organic solvents

1985 ◽  
Vol 63 (2) ◽  
pp. 336-341 ◽  
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.

Enthalpies of interaction of nitrogen base solutes with organic solvents

1985 ◽  
Vol 63 (9) ◽  
pp. 2540-2544 ◽  
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.

Enthalpies of hydrogen bond formation of 1-octanol with aprotic organic solvents. A comparison of the solvation enthalpy, pure base, and non-hydrogen-bonding baseline methods

1985 ◽  
Vol 63 (2) ◽  
pp. 342-348 ◽  
Author(s):  
W. Kirk Stephenson ◽  
Richard Fuchs
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Bond Formation ◽  
Enthalpies Of Solution ◽  
Dispersion Interactions ◽  
Butyl Ether ◽  
Hydrogen Bond Formation ◽  
Solvation Enthalpy ◽  
Benzene Toluene ◽  
Good Agreement

Enthalpies of solution (ΔHs) of 1-octanol and five model compounds (di-n-butyl ether, n-heptyl methyl ether, 1-fluoro-octane, 1-chlorooctane, and n-octane) have been determined in 13 solvents (heptane, cyclohexane, CCl4, 1,1,1-trichloro-ethane, 1,2-dichloroethane, triethylamine, butyl ether, ethyl acetate, DMF, DMSO, benzene, toluene, mesitylene), and combined with heats of vaporization to give enthalpies of transfer from vapor to solvent (ΔH(v → S)). These values have been used to calculate the enthalpy of hydrogen bond formation (ΔHh) of 1-octanol with each solvent, using the pure base (PB), solvation enthalpy (SE), and non-hydrogen-bonding baseline (NHBB) methods. Evidence is presented suggesting that (a) the SE method is susceptible to mismatches of the 1-octanol vs. model polar and dispersion interactions, (b) the PB method is sensitive to polar interaction mismatches, whereas (c) the NHBB method compensates for both polar and dispersion interactions mismatches. The (apparent) ΔHh values determined by the SE and PB methods may be as much as several kcal/mol (nearly 50%) too large, because of the inclusion of other polar and dispersion interactions. The NHBB method is therefore preferred for determining enthalpies of H-bond formation from calorimetric data. However, apparent ΔHh values from the SE and PB methods can be incorporated into total solvatochromic equations using Taft–Kamiet π*, β, and ξ parameters, to provide enthalpies of H-bond formation in good agreement with ΔHh (NHBB).

Enthalpies of interaction of aromatic solutes with organic solvents

1985 ◽  
Vol 63 (9) ◽  
pp. 2529-2534 ◽  
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.

Enthalpies of interaction of hydroxylic solutes with organic solvents

1985 ◽  
Vol 63 (9) ◽  
pp. 2535-2539 ◽  
Author(s):  
W. Kirk Stephenson ◽  
Richard Fuchs
Keyword(s):  
Organic Solvents ◽  
Methyl Ether ◽  
Butyl Alcohol ◽  
Amyl Alcohol ◽  
Solvatochromic Parameters ◽  
Model Compounds ◽  
Butyl Ether ◽  
Donor Solvent ◽  
Benzene Toluene ◽  
Butyl Methyl Ether

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.

Hydrogen bonding and other polar interactions of 1-, 2-, and 4-octyne with organic solvents

1983 ◽  
Vol 61 (9) ◽  
pp. 2044-2047 ◽  
Author(s):  
John H. Hallman ◽  
W. Kirk Stephenson ◽  
Richard Fuchs
Keyword(s):  
Hydrogen Bond ◽  
Bond Formation ◽  
Butyl Ether ◽  
Hexamethylphosphoric Triamide ◽  
Hydrogen Bond Formation ◽  
Enthalpies Of Transfer ◽  
Induced Dipole ◽  
Base Method ◽  
Polar Interactions ◽  
Heats Of Vaporization

The heats of vaporization of 1-octyne (10.11 ± 0.02 kcal/mol), 2-octyne (10.63 ± 0.03 kcal/mol), and 4-octyne (10.21 ± 0.02 kcal/mol) have been determined. Heats of solution of the liquid octynes and n-octane have been measured in heptane, cyclohexane, 1,2-dichloroethane, n-butyl ether, ethanol, triethylamine, dimethyl sulfoxide, butyrolactone, dimethylformamide, and hexamethylphosphoric triamide. Enthalpies of transfer from vapor to each solvent have been calculated. Enthalpies of hydrogen bond formation, calculated by the pure base method, become more exothermic in the above solvent order. Correlations with the Taft–Kamlet solvent parameters π* and β indicate that other polar interactions (presumably dipole – induced dipole) are appreciably larger for 1-octyne than for 2- and 4-octyne.

scholarly journals Proton transfer equilibria, temperature and substituent effects on hydrogen bonded complexes between chloranilic acid and anilines

2000 ◽  
Vol 14 (3) ◽  
pp. 99-107 ◽  
Author(s):  
Gamal A. Gohar ◽  
Moustafa M. Habeeb
Keyword(s):  
Hydrogen Bond ◽  
Complex Formation ◽  
Proton Transfer ◽  
Equilibrium Constants ◽  
Bond Formation ◽  
Substituent Effects ◽  
Substituted Anilines ◽  
Chloranilic Acid ◽  
Hydrogen Bond Formation ◽  
Linear Relationships

The proton transfer equilibrium constants (KPT) for 1 : 1 complex formation between Chloranilic Acid (CA) and a series ofp- andm‒substituted anilines have been measured in 1,4-dioxane spectrophotometrically. The results supported the concept of amine-solvent hydrogen bond formation (short range solvation effect). Beside, this effect, theKPTvalues were apparently affected by the electron donation power of the aniline ring substituent, which was transmitted to the interaction center via resonance and inductive effects. Linear relationships betweenKPTand σ-Hammett substituent constants, or pKvalues formandpanilines,were obtained verifying the above conclusions. The solute-solvent hydrogen bond formation might increase the reactivity of the aniline nitrogen than would the inductive effect of the alkyl group, in case of CA-N-alkyl aniline complexes. The thermodynamic parameters for the proton transfer complex formation were estimated and it was indicated that the solvent–aniline hydrogen bond formation was preferred in the case ofp-substituted aniline complexes more than in the case of the correspondingm‒isomer. It has been found that the proton transfer process was enthalpy and entropy controlled.

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

2009 ◽  
Vol 75 (24) ◽  
pp. 7774-7782 ◽  
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.

Enthalpies of solution of naphthalene, N,N-dimethyl-1-naphthylamine, and 1,8-bis(dimethylamino)naphthalene in 16 organic solvents

1992 ◽  
Vol 70 (6) ◽  
pp. 1586-1589 ◽  
Author(s):  
Daniel Figeys ◽  
Maegorzata Koschmidder ◽  
Robert L. Benoit
Keyword(s):  
Carbon Tetrachloride ◽  
Ethyl Acetate ◽  
Dimethyl Sulfoxide ◽  
Organic Solvents ◽  
Enthalpies Of Solution ◽  
Proton Sponge ◽  
Solvent Interactions ◽  
Linear Relationships

The enthalpies of solution of naphthalene, N,N-dimethyl-1-naphthylamine, and 1,8-bis(dimethylamino)naphthalene (proton sponge) were determined at 298.15 K in 16 organic solvents (n-hexane, cyclohexane, carbon tetrachloride, chloroform, 1,2-dichloroethane, benzene, chlorobenzene, dimethyl sulfoxide, N,N-dimethylformamide, ethyl acetate, 1,4-dioxane, anisole, nitrobenzene, benzonitrile, methanol, ethanol). Additional determinations were made with benzene. Useful linear relationships are observed between the molar enthalpies of solution of the four compounds in the solvents. The molar enthalpies of solution were correlated with the solvatochromic parameter of the solvents. The presence of N(CH3)2 groups on naphthalene does not significantly contribute to the solute–solvent interactions.

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