Research on the volatility, phase transitions and thermodynamic stability of five organochlorine compounds.

The present investigation describes the experimental evaluation of relevant physicochemical properties of five organochlorine compounds (OCs), including some that are related to their environmental mobility. The vapor pressures of (2,4'-Dichlorodiphenyl)dichloroethane (2,4'-DDD, CASN:53-19-0), 1,1-Dichloro-2,2-bis(4-chlorophenyl)ethane (4,4'-DDD, CASN:72-54-8) and 2,2-Bis(4-chlorophenyl)acetic acid (4,4'-DDA, CASN:83-05-6), as well as of the bactericide Nitrapyrin (CASN:1929-82-4) and of the rodenticide Crimidine (CASN:535-89-7) were determined at different temperatures. The Knudsen mass-loss effusion technique was employed to determine the sublimation vapor pressures of the referred compounds, apart from Crimidine. For the latter compound, a static method using a capacitance diaphragm manometer enabled the measurement of vapor pressures of both condensed (crystalline and liquid) phases. This technique was also used to measure the vapor pressures of the crystalline phase of Nitrapyrin over a larger temperature range, as well as its vaporization vapor pressures. The results of the standard molar enthalpies, entropies, and Gibbs energies of sublimation for all five compounds and of vaporization for Crimidine and Nitrapyrin, at reference temperatures, were derived. For these two compounds the phase diagram representations of the (p,T) results, in the vicinity of the triple point, were obtained. DSC analysis enabled the determination of the crystalline heat capacities of the five OCs studied and also of their temperatures and enthalpies of fusion. Gas-phase thermodynamic properties were estimated using quantum chemical calculations. The thermodynamic stability of the compounds studied was evaluated and compared in the crystalline and gaseous phases, at 298.15 K, in consideration with estimated results of the standard Gibbs energies of formation. Combined with other physical and chemical properties, the results derived from this study can be used to predict the mobility, and environmental fate of these pollutants.

Phase Transitions Equilibria of Five Dichlorinated Substituted Benzenes.

This work reports an experimental study aiming to determine the thermodynamic properties of five chlorinated compounds with environmental impact. The vapor pressures of the crystalline phases of three isomers of dichlorobenzoic acid (2,4-, 2,5-, and 2,6-) and 2,6-dichlorobenzonitrile were measured at several temperatures using the Knudsen effusion technique. Another technique (a static method based on capacitance diaphragm manometers) allowed the measurement of the vapor pressures of both the crystalline and liquid phases of 2,4-dichlorobenzonitrile between 303.0 and 380.0 K. This latter technique also enabled the measurement of sublimation vapor pressures of 2,6-dichlorobenzonitrile over a larger range interval of temperatures, T = 328.7 and 391.8 K. The standard molar enthalpy, entropy, and Gibbs energy of sublimation (for all the compounds studied) and vaporization (for 2,4-dichlorobenzonitrile) were derived, at reference temperatures, from the experimental vapor pressure results. The temperatures and enthalpies of fusion and the isobaric heat capacities of the five crystalline-substituted benzenes were determined using differential scanning calorimetry. The contributions of the three substituents (-COOH, -CN, and -Cl) to the sublimation thermodynamic properties of the compounds studied were discussed.

Thermodynamic Stability of Fenclorim and Clopyralid.

The present work reports an experimental thermodynamic study of two nitrogen heterocyclic organic compounds, fenclorim and clopyralid, that have been used as herbicides. The sublimation vapor pressures of fenclorim (4,6-dichloro-2-phenylpyrimidine) and of clopyralid (3,6-dichloro-2-pyridinecarboxylic acid) were measured, at different temperatures, using a Knudsen mass-loss effusion technique. The vapor pressures of both crystalline and liquid (including supercooled liquid) phases of fenclorim were also determined using a static method based on capacitance diaphragm manometers. The experimental results enabled accurate determination of the standard molar enthalpies, entropies and Gibbs energies of sublimation for both compounds and of vaporization for fenclorim, allowing a phase diagram representation of the (p,T) results, in the neighborhood of the triple point of this compound. The temperatures and molar enthalpies of fusion of the two compounds studied were determined using differential scanning calorimetry. The standard isobaric molar heat capacities of the two crystalline compounds were determined at 298.15 K, using drop calorimetry. The gas phase thermodynamic properties of the two compounds were estimated through ab initio calculations, at the G3(MP2)//B3LYP level, and their thermodynamic stability was evaluated in the gaseous and crystalline phases, considering the calculated values of the standard Gibbs energies of formation, at 298.15 K. All these data, together with other physical and chemical properties, will be useful to predict the mobility and environmental distribution of these two compounds.

A flexible cell for in situ combined XAS-DRIFTS-MS experiments.

A new cell for in situ combined X-ray absorption, diffuse reflectance IR Fourier transform and mass spectroscopies (XAS-DRIFTS-MS) is presented. The cell stands out among others for its achievements and flexibility. It is possible to perform XAS measurements in transmission or fluorescence modes, and the cell is compatible with external devices like UV-light and Raman probes. It includes different sample holders compatible with the different XAS detection modes, different sample forms (free powder or self-supporting pellet) and different sample loading/total absorption. Additionally, it has a small dead volume and can operate over a wide range of temperature (up to 600°C) and pressure (up to 5 bar). Three research examples will be shown to illustrate the versatility of the cell. This cell covers a wider range of applications than any other cell currently known for this type of study.

Coupled X-ray Absorption/UV-vis Monitoring of Fast Oxidation Reactions Involving a Nonheme Iron-Oxo Complex.

Time-resolved X-ray absorption (XAS) and UV-vis spectroscopies with millisecond resolution are used simultaneously to investigate oxidation reactions of organic substrates by nonheme iron activated species. In particular, the oxidation processes of arylsulfides and benzyl alcohols by a nonheme iron-oxo complex have been studied. We show for the first time that the pseudo-first-order rate constants of fast bimolecular processes in solution (milliseconds and above) can be determined by time-resolved XAS technique. By following the Fe K-edge energy shift, it is possible to detect the rate of iron oxidation state evolution that matches that of the bimolecular reaction in solution. The kinetic constant values obtained by XAS are in perfect agreement with those obtained by means of the concomitant UV-vis detection. This combined approach has the potential to provide unique insights into reaction mechanisms in the liquid phase that involve changes of the oxidation state of a metal center, and it is particularly useful in complex chemical systems where possible interferences from species present in solution could make it impossible to use other detection techniques.

Estimations of the thermodynamic properties of halogenated benzenes as they relate to their environment mobility.

In this work, several simple new equations for predicting important environmental mobility properties, at T = 298.15 K, were derived for halogenated benzenes: standard Gibbs energy of hydration, aqueous solubility, octanol-water partition coefficients, and Henry's law constants. A discussion on our previous estimates of other related properties (standard Gibbs energy and vapor pressure of sublimation and of vaporization) and their relation with entropy of fusion is also presented. As we aimed to estimate these properties for any of the ca. 1500 halogenated benzenes that may exist theoretically, an equation for estimating the temperature of fusion was also derived, since some of the proposed predictive equations (solubility of solids and Gibbs energy of sublimation) require its knowledge. For the other estimated properties just the number of each halogen that replaces hydrogen atoms in the halogenated benzene is needed. It was found that the coefficients that multiply the number of halogen atoms in the predictive equations vary linearly with the volume of the halogen atom.

Following a Chemical Reaction on the Millisecond Time Scale by Simultaneous X-ray and UV/Vis Spectroscopy.

An innovative approach aimed at disclosing the mechanism of chemical reactions occurring in solution on the millisecond time scale is presented. Time-resolved energy dispersive X-ray absorption and UV/vis spectroscopies with millisecond resolution are used simultaneously to directly follow the evolution of both the oxidation state and the local structure of the metal center in an iron complex. Two redox reactions are studied, the former involving the transformation of FeII into two subsequent FeIII species and the latter involving the more complex FeII-FeIII-FeIV-FeIII sequence. The structural modifications occurring around the iron center are correlated to the reaction mechanisms. This combined approach has the potential to provide unique insights into reaction mechanisms in the liquid phase and represents a new powerful tool to characterize short-lived intermediates that are silent to common spectroscopic techniques.

Structure of Nano-sized CeO2 Materials: Combined Scattering and Spectroscopic Investigations.

The structure of several nano-sized ceria, CeO2 , systems was investigated using neutron and X-ray diffraction and X-ray absorption spectroscopy. Whilst both diffraction and total pair distribution functions (PDFs) revealed that in all of the samples the occupancy of both Ce4+ and O2- are very close to the ideal stoichiometry, the analysis using Reverse Monte Carlo technique revealed significant disorder around oxygen atoms in the nano-sized ceria samples in comparison to the highly crystalline NIST standard. In addition, the analysis revealed that the main differences observed in the pair correlations from various X-ray and neutron diffraction techniques were attributable to the particle size of the CeO2 prepared by the reported three methods. Furthermore, detailed analysis of the Ce L3 - and K-edge EXAFS data support this finding; in particular the decrease in higher shell coordination numbers with respect to the NIST standard, is attributed to differences in particle size.

Study on the volatility of halogenated fluorenes.

This work reports the experimental determination of relevant thermophysical properties of five halogenated fluorenes. The vapor pressures of the compounds studied were measured at different temperatures using two different experimental techniques. The static method was used for studying 2-fluorofluorene (liquid and crystal vapor pressures between 321.04 K and 411.88 K), 2-iodofluorene (liquid and crystal vapor pressures between 362.63 K and 413.86 K), and 2,7-dichlorofluorene (crystal vapor pressures between 364.64 K and 394.22 K). The Knudsen effusion method was employed to determine the vapor pressures of 2,7-difluorofluorene (crystal vapor pressures between 299.17 K and 321.19 K), 2,7-diiodofluorene (crystal vapor pressures between 393.19 K and 415.14 K), and (again) 2-iodofluorene (crystal vapor pressures between 341.16 K and 361.12 K). The temperatures and the molar enthalpies of fusion of the five compounds were determined using differential scanning calorimetry. The application to halogenated fluorenes of recently developed methods for predicting vapor pressures and enthalpies of sublimation and vaporization of substituted benzenes is also discussed.

Vapor pressures, thermodynamic stability, and fluorescence properties of three 2,6-alkyl naphthalenes.

This work reports the experimental determination of relevant thermodynamic properties and the characterization of luminescence properties of the following polycyclic aromatic hydrocarbons (PAHs): 2,6-diethylnaphthalene, 2,6-diisopropylnaphthalene and 2,6-di-tert-butylnaphthalene. The standard (p(o) = 0.1 MPa) molar enthalpies of combustion, ΔcHm(o), of the three compounds were determined using static bomb combustion calorimetry. The vapor pressures of the crystalline phase of 2,6-diisopropylnaphthalene and 2,6-di-tert-butylnaphthalene were measured at different temperatures using the Knudsen effusion method and the vapor pressures of both liquid and crystalline phases of 2,6-diethylnaphthalene were measured by means of a static method. The temperatures and the molar enthalpies of fusion of the three compounds were determined using differential scanning calorimetry. The gas-phase molar heat capacities and absolute entropies of the three 2,6-dialkylnaphthalenes studied were determined computationally. The thermodynamic stability of the compounds in both the crystalline and gaseous phases was evaluated by the determination of the Gibbs energies of formation and compared with the ones reported in the literature for 2,6-dimethylnaphthalene. From fluorescence spectroscopy measurements, the optical properties of the compounds studied and of naphthalene were evaluated in solution and in the solid state.

Near-ambient XPS characterization of interfacial copper species in ceria-supported copper catalysts.

Catalysts based on combinations of copper and cerium oxides are interesting alternatives to noble metal ones for processes involved in the production/purification of hydrogen produced from hydrocarbons or biomass like the water-gas shift or the preferential oxidation of CO reactions. Active sites for such processes have been proposed to correspond to reduced species formed at the interface between both oxides. The present work provides direct evidence of reduced copper species located at the interface and observed during the course of near-ambient XPS experiments performed over samples of copper oxide supported on ceria nanospheres and nanocubes subjected to interaction with CO at different temperatures. The analysis of XPS results is based on DFT+U calculations employed as a complementary method for the analysis of redox properties of the catalysts and core-level shifts produced upon such redox changes. Differences observed in interfacial redox properties as a function of the ceria support morphology appear to be most useful to explain catalytic properties of this type of system for mentioned processes.

Modeling Interactions between an Amino Acid and a Metal Dication: Cysteine-Calcium(II) Reactions in the Gas Phase.

The gas-phase interactions between Ca2+ and cysteine (Cys) have been investigated through the use of electrospray ionization/mass spectrometry techniques and B3LYP/6-311++ G(3df,2p)//B3LYP/6-311+G(d,p) density functional theory computations. The unimolecular collision-activated decomposition of [Ca(Cys)]2+ is dominated by the loss of ammonia, a Coulomb explosion yielding NH4 + and [CaC3 H3 O2 S]+ , and the loss of H2 S. The detection of lighter [C3 H3 OS]+ monocations indicates that the [CaC3 H4 O2 S]2+ doubly charged species produced by the loss of ammonia undergo a subsequent Coulomb explosion yielding [C3 H3 OS]+ +CaOH+ . This [C3 H3 OS]+ cation finally decomposes into [C2 H3 S]+ +CO. Alternatively, the aforementioned [CaC3 H4 O2 S]2+ dications may also lead to lighter [CaCO2 ]2+ and [CaC2 H4 S]2+ dications by the loss of C2 H4 S and CO2 , respectively. A detailed theoretical exploration of the Ca2+ /Cys potential-energy surface indicates that the salt-bridge structures, in which the metal dication interacts with the carboxylate group of the zwitterionic form of cysteine, are at the origin of the different reaction pathways leading to the observed product ions, even though they lie higher in energy than the charge-solvated adduct in which the metal interacts simultaneously with the carbonyl oxygen, the amino, and the SH group of its canonical form. The interaction between the metal cation and the base is essentially electrostatic, with a calculated binding energy of 560 kJ mol-1 .

Energetic study applied to the knowledge of the structural and electronic properties of monofluorobenzonitriles.

The present work reports an energetic and structural study of 2-fluoro-, 3-fluoro-, and 4-fluorobenzonitrile. The standard molar enthalpies of formation, in the condensed phase, of the three isomers were derived from the standard molar energies of combustion, in oxygen, at T = 298.15 K. The standard molar enthalpies of vaporization or sublimation (for 4-fluorobenzonitrile), at T = 298.15 K, were measured using high-temperature Calvet microcalorimetry. The combination of these two parameters yields the standard molar enthalpies of formation in the gaseous phase. The vapor-pressure study of the referred compounds was performed by a static method, and the enthalpies of phase transition derived from the application of the Clarke and Glew equation. Theoretically estimated gas-phase enthalpies of formation, basicities, proton and electron affinities, and adiabatic ionization enthalpies were calculated from the G3MP2B3 level of theory. In order to evaluate the electronic properties, the geometries were reoptimized at MP2/cc-pVTZ level, and the QTAIM and NICS were computed. On the basis of the donor-acceptor system, another approach for evaluating the electronic effect for these compounds, using the NBO is suggested. The UV-vis spectroscopy study for the three isomers was performed. The intensities and the band positions were correlated with the thermodynamic properties calculated computationally.

A combined experimental and computational thermodynamic study of difluoronitrobenzene isomers.

This work reports the experimental and computational thermochemical study performed on three difluorinated nitrobenzene isomers: 2,4-difluoronitrobenzene (2,4-DFNB), 2,5-difluoronitrobenzene (2,5-DFNB), and 3,4-difluoronitrobenzene (3,4-DFNB). The standard (p° = 0.1 MPa) molar enthalpies of formation in the liquid phase of these compounds were derived from the standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by rotating bomb combustion calorimetry. A static method was used to perform the vapor pressure study of the referred compounds allowing the construction of the phase diagrams and determination of the respective triple point coordinates, as well as the standard molar enthalpies of vaporization, sublimation, and fusion for two of the isomers (2,4-DFNB and 3,4-DFNB). For 2,5-difluoronitrobenzene, only liquid vapor pressures were measured enabling the determination of the standard molar enthalpies of vaporization. Combining the thermodynamic parameters of the compounds studied, the following standard (p° = 0.1 MPa) molar enthalpies of formation in the gaseous phase, at T = 298.15 K, were derived: Δ(f)H(m)° (2,4-DFNB, g) = -(296.3 ± 1.8) kJ · mol⁻¹, Δ(f)H(m)° (2,5-DFNB, g) = -(288.2 ± 2.1) kJ · mol⁻¹, and Δ(f)H(m)° (3,4-DFNB, g) = -(302.4 ± 2.1) kJ · mol⁻¹. Using the empirical scheme developed by Cox, several approaches were evaluated in order to identify the best method for estimating the standard molar gas phase enthalpies of formation of these compounds. The estimated values were compared to the ones obtained experimentally, and the approach providing the best comparison with experiment was used to estimate the thermodynamic behavior of the other difluorinated nitrobenzene isomers not included in this study. Additionally, the enthalpies of formation of these compounds along with the enthalpies of formation of the other isomers not studied experimentally, i.e., 2,3-DFNB, 2,6-DFNB, and 3,5-DFNB, were estimated using the composite G3MP2B3 approach together with adequate gas-phase working reactions. Furthermore, we also used this computational approach to calculate the gas-phase basicities, proton and electron affinities, and, finally, adiabatic ionization enthalpies.

A calorimetric and computational study of aminomethoxybenzoic acids.

The standard (p(0) = 0.1 MPa) molar enthalpies of formation, in the crystalline phase, of five aminomethoxybenzoic acids, at T = 298.15 K, were derived from the standard molar energies of combustion in oxygen, measured by static-bomb combustion calorimetry. Combining these results with literature results of the standard molar enthalpies of sublimation, at T = 298.15 K, the standard molar enthalpies of formation, in the gaseous phase, were derived. Additionally, the enthalpies of formation of the ten possible isomers of aminomethoxybenzoic acid were estimated using accurate Double Hybrid Density Functional Theory (DHDFT) computational methods. The good agreement between the experimental and estimated values of the enthalpies of formation of the five isomers studied experimentally allows us to be confident on the estimated values for the other five isomers. A quantitative evaluation and analysis of the aromatic character of all the studied isomers based on the calculation of Nucleus Independent Chemical Shifts (NICS) was also conducted.

Experimental and computational thermodynamic study of three monofluoronitrobenzene isomers.

The present work reports the thermodynamic study performed on three monofluorinated nitrobenzene derivatives by a combination of experimental techniques and computational approaches. The standard (p degrees = 0.1 MPa) molar enthalpies of formation in the liquid phase of the three isomers of fluoronitrobenzene were derived from the standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by rotating bomb combustion calorimetry. The vapor pressure study of the referred compounds was done by a static method and, from the obtained results, the phase diagrams were elaborated, and the respective triple point coordinates, as well as the standard molar enthalpies of vaporization, sublimation and fusion, at T = 298.15 K, were determined. The combination of some of the referred thermodynamic parameters yielded the standard (p degrees = 0.1 MPa) molar enthalpies of formation in the gaseous phase, at T = 298.15 K, of the studied compounds: Delta(f)H(m)(o) (2-fluoronitrobenzene, g) = -(102.4 +/- 1.5) kJ x mol(-1), Delta(f)H(m)(o) (3-fluoronitrobenzene, g) = -(128.0 +/- 1.7) kJ x mol(-1), and Delta(f)H(m)(o) (4-fluoronitrobenzene, g) = -(133.9 +/- 1.4) kJ x mol(-1). Using the empirical scheme developed by Cox, values of standard molar enthalpies of formation in the gaseous phase were estimated and afterwards compared with the ones obtained experimentally, and both were interpreted in terms of the molecular structure of the compounds. The theoretically estimated gas-phase enthalpies of formation were calculated from high-level ab initio molecular orbital calculations at the G3(MP2)//B3LYP level of theory. The computed values compare very well with the experimental results obtained in this work and show that 4-fluoronitrobenzene is the most stable isomer from the thermodynamic point of view. Furthermore, this composite approach was also used to obtain information about the gas-phase basicities, proton and electron affinities and, finally, adiabatic ionization enthalpies.

Energetic studies and phase diagram of thioxanthene.

The molecular stability of thioxanthene, a key species from which very important compounds with industrial relevance are derived, has been studied by a combination of several experimental techniques and computational approaches. The standard (p degrees = 0.1 MPa) molar enthalpy of formation of crystalline thioxanthene (117.4 +/- 4.1 kJ x mol(-1)) was determined from the experimental standard molar energy of combustion, in oxygen, measured by rotating-bomb combustion calorimetry at T = 298.15 K. The enthalpy of sublimation was determined by a direct method, using the vacuum drop microcalorimetric technique, and also by an indirect method, using a static apparatus, where the vapor pressures at different temperatures were measured. The latter technique was used for both crystalline and undercooled liquid samples, and the phase diagram of thioxanthene near the triple point was obtained (triple point coordinates T = 402.71 K and p = 144.7 Pa). From the two methods, a mean value for the standard (p degrees = 0.1 MPa) molar enthalpy of sublimation, at T = 298.15 K (101.3 +/- 0.8 kJ x mol(-1)), was derived. From the latter value and from the enthalpy of formation of the solid, the standard (p degrees = 0.1 MPa) enthalpy of formation of gaseous thioxanthene was calculated as 218.7 +/- 4.2 kJ x mol(-1). Standard ab initio molecular orbital calculations were performed using the G3(MP2)//B3LYP composite procedure and several homodesmotic reactions in order to derive the standard molar enthalpy of formation of thioxanthene. The ab initio results are in excellent agreement with the experimental data.

Calorimetric and computational study of indanones.

Condensed phase standard (p degrees = 0.1 MPa) molar enthalpies of formation for 1-indanone, 2-indanone, and 1,3-indandione were derived from the standard molar enthalpies of combustion, in oxygen, at T = 298.15 K, measured by static bomb combustion calorimetry. The standard molar enthalpies of sublimation for 1-indanone and 2-indanone, at T = 298.15 K, were measured both by correlation-gas chromatography and by Calvet microcalorimetry leading to a mean value for each compound. For 1,3-indandione, the standard molar enthalpy of sublimation was derived from the vapor pressure dependence on temperature. The following enthalpies of formation in gas phase, at T = 298.15 K, were then derived: 1-indanone, -64.0 +/- 3.8 kJ mol(-1); 2-indanone, -56.6 +/- 4.8 kJ mol(-1); 1,3-indandione, -165.0 +/- 2.6 kJ mol(-1). The vaporization and fusion enthalpies of the indanones studied are also reported. In addition, theoretical calculations using the density functional theory with the B3LYP and MPW1B95 energy functionals and the 6-311G** and cc-pVTZ basis sets have been performed for these molecules and the corresponding one-ring species to obtain the most stable geometries and to access their energetic stabilities.

Energetics of the N-O bonds in 2-hydroxyphenazine-di-N-oxide.

The standard enthalpy of formation and the enthalpy of sublimation of crystalline 2-hydroxyphenazine-di-N-oxide, at T = 298.15 K, were determined from isoperibol static bomb combustion calorimetry and from Knudsen effusion experiments, as -76.7 +/- 4.2 kJ.mol(-1) and 197 +/- 5 kJ.mol(-1), respectively. The sum of these two quantities gives the standard enthalpy of formation in the gas-phase for this compound, delta(f)H(m)degrees(g) = 120 +/- 6 kJ.mol(-1). This value was combined with the gas-phase standard enthalpy of formation for 2-hydroxyphenazine retrieved from a group estimative method yielding the mean (N-O) bond dissociation enthalpy, in the gas-phase, for 2-hydroxyphenazine-di-N-oxide. The result obtained with this strategy is (DH(m)degrees (N - O)) = 263 +/- 4 kJ.mol(-1), which is in excellent agreement with the B3LYP/6-311+G(2d,2p)//B3LYP/6-31G(d) computed value, 265 kJ.mol(-1).

Thermodynamic study of sesamol, piperonyl alcohol, piperonylic acid and homopiperonylic acid: a combined experimental and theoretical investigation.

The standard (p(o)= 0.1 MPa) molar energies of combustion in oxygen, at T= 298.15 K, of four 1,3-benzodioxole derivatives (sesamol, piperonyl alcohol, piperonylic acid and homopiperonylic acid) were measured by static bomb calorimetry. The values of the standard molar enthalpies of sublimation, at T= 298.15 K, were derived from vapour pressure-temperature measurements using the Knudsen effusion technique. Combining these results the standard molar enthalpies of formation of the compounds, in the gas phase, at T= 298.15 K, have been calculated: sesamol (-325.7 +/- 1.9) kJ mol(-1); piperonyl alcohol (-329.0 +/- 2.0) kJ mol(-1); piperonylic acid (-528.9 +/- 2.6) kJ mol(-1) and homopiperonylic acid (-544.5 +/- 2.9) kJ mol(-1). The most stable geometries of all the compounds were obtained using the density functional theory with the B3LYP functional and two basis sets: 6-31G** and 6-311G**. The nonplanarity of the molecules was analyzed in terms of the anomeric effect, which is believed to arise from the interaction between a nonbonded oxygen p orbital and the empty orbital sigma*(CO) involving the other oxygen atom. Calculations were performed to obtain estimates of the enthalpies of formation of all the benzodioxoles using appropriate isodesmic reactions. There is a perfect agreement between theoretical and experimental results.