Multiply charged ions in the mass spectra of aromatics

The prominence of multiply charged molecular and fragment ions upon electron-impact in the mass spectrometer is proposed as an experimental, empirical indication of aromatic character. The effects of electron withdrawing and donating substituents on the production of multiply charged ions are considered and appearance potentials are noted for several species.     

Dissociation quotients of succinic acid in aqueous sodium chloride media to 225°C

The first and second molal dissociation quotients of succinic acid were measured potentiometrically with a hydrogen-electrode, concentration cell. These measurements were carried out from 0 to 225°C over 25° intervals at five ionic strengths ranging from 0.1 to 5.0 molal (NaCl). The dissociation quotients from this and two other studies were combined and treated with empirical equations to yield the following thermodynamic quantities for the first acid dissociation equilibrium at 25°C: log K_1a=–4.210±0.003; H _1a ⁰ =2.9±0.2 kJ-mol^–1; S _1a ⁰ =–71±1 J-mol^–1-K^–1; and C _p1a ⁰ =–98±3 J-mol^–1-K^–1; and for the second acid dissociation equilibrium at 25°C: log K_2a=–5.638±0.001; H _2a ⁰ = –0.5±0.1 kJ-mol^–1; S _2a ⁰ =–109.7±0.4 J-mol^–1-K^–1; and C _p2a ⁰ = –215±8 J-mol^–1-K^–1.     

PM3-SM3: A general parameterization for including aqueous solvation effects in the PM3 molecular orbital model

Our recently proposed scheme for including aqueous solvation free energies in parameterized NDDO SCF models is extended to the Parameterized Model 3 semiempirical Hamiltonian. The solvation model takes accurate account of the hydrophobic effect for hydrocarbons, as well as electric polarization of the solvent, the free energy of cavitation, and dispersion interactions. Eight heteroatoms are included (along with H and C), and the new model is parameterized accurately for the water molecule itself, which allows meaningful treatments of specifically hydrogen bonded water molecules. The unphysical partial charges on nitrogen atoms predicted by the Parameterized Model 3 Hamiltonian limit the accuracy of the predicted solvation energies for some compounds containing nitrogen, but the model may be very useful for other systems, especially those for which PM3 is preferred over AM1 for the solute properties of the particular system under study. © 1992 by John Wiley & Sons, Inc.     

Ternary mutual diffusion coefficients of ZnCl2−KCl−H2O at 25°C by Rayleigh interferometry

Mutual diffusion coefficients and densities were measured for aqueous ZnCl₂–KCl mixtures at 25° by using free-diffusion Rayleigh interferometry and pycnometry, respectively. The ZnCl₂ concentrations were fixed at 1.5 mol-dm^–3, whereas those of KCl were 0.5, 1.25, 2.0, or 4.0 mol-dm^–3. This corresponds to a half charged zinc-chlorine storage battery at various suporting electrolyte concentrations. The main-term coefficient of ZnCl₂ only varies by 10% with KCl concentration, whereas that of KCl varies by about 22%. The ZnCl₂ cross-term coefficient remains small and positive; in contrast the KCl cross-term coefficient goes through a maximum and is negative at high and low KCl concentrations. At KCl concentrations of 0.5 and 4.0 mol-dm^–3, solutions with the KCl c0 are statically and dynamically (diffusively) unstable at the top and bottom of the boundary. Evaluation of the parameters of the non-linear least-squares solution to the diffusion equation is difficult for the 1.25 mol-dm^–3 KCl case, since this system has nearly equal eigenvalues in its diffusion coefficient matrix.     

Geometry and force constant determination from correlated wave functions for polyatomic molecules: Ground states of H2O and CH2

Ab initio calculations including electron correlation are reported for the water and methylene molecules as a function of geometry. A large contracted gaussian basis set is used and the multiconfiguration wave functions, optimized by the iterative natural orbital procedure, include 277 and 617 configurations for H₂O and CH₂ respectively. The method of selecting configurations, yielding first-order wave functions, is discussed in some detail. For H₂O, the SCF geometry is r=0,942 Å, =105,8°, the correlated result is r=0,968 Å, =103,2°, and the experimental r=0,957 Å, =104,5°. The water stretching force constants, in millidynes/Å, are 8,72 (SCF), 8,75 (CI), and 8,4 (experiment). Bending force constants are 0,88 (SCF), 0,83 (CI), and 0,76 (experiment). For methylene the SCF geometry is r=1,072 Å, =129,5°, while the result from first-order wave functions is r=1,088 Å, =134°. The predicted CH₂ force constants are 6,16 (SCF) and 6,13 (CI) for stretching and 0,44 (SCF) and 0,33 (CI) for bending.

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Zusammenfassung Es wird über ab intito-Rechnungen mit Berücksichtigung der Elektronenkorrelation berichtet, die an Wasser- und Methylenmolekülen als Funktion der Geometrie durchgeführt worden sind. Dazu benutzt man einen großen kontrahierten Gauß-Basissatz. Die Multikonfigurationswellenfunktionen, die unter Benutzung von natürlichen Orbitalen nach der iterativen Prozedur optimiert werden, enthalten für H₂O 277 Konfigurationen und für CH₂ 617. Die Auswahlmethode, die zu Wellenfunktionen 1. Ordnung führt, wird diskutiert. Im Falle des Wassers erhält man die SCF-Geometrie zu r=0,942 Å, =105,8°, das korrelierte Resultat ist: r=0,968 Å, =103,2° und das experimentelle r=0,957 Å, =104,5°. Für Wasser ergeben sich die Valenzkraftkonstanten (in Millidyn Å^–1) 8,72 (SCF), 8,75 (CI) und 8,4 (Experiment). Die Deformationskonstanten sind 0,88 (SCF), 0,83 (CI) und 0,76 (Experiment). Im Falle des Methylens ist die SCF-Geometrie r=1,072 Å, =129,5°, während man mit Wellenfunktionen 1. Ordnung r=1,088 Å und =134° erhält. Die CH₂-Kraftkonstanten werden für die Valenzschwingung zu 6,16 (SCF) und 6,13 (CI) bzw. für die Deformationsschwingung zu 0,44 (SCF) und 0,33 (CI) vorausgesagt.

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Work performed under the auspices of the U.S. Atomic Energy Commision.

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Supported by the grants from the Research Corporation and the University of California Committee on Research.     

The infrared,Raman and mass spectra of F3C-CC-CC-CF3

The IR spectra of the vapor, liquid and solid phases of hexafluorohexa-2-diyne, F₃C-CC-CC-CF₃, were measured. The liquid phase Raman spectrum with polarizations was measured. These vibrational spectra fit D_3d selection rules, establishing that the molecule has a linear carbon skeleton. The IR spectra indicate that the -CF₃ groups rotate freely in the vapor phase, but that conformers exist in the condensed phases. The electron impact mass spectrum was measured and the molecular ion produced the strongest peak.     

Regiochemistry of nucleophilic displacements in chloroquinones

Nucleophilic displacement of halide from 2-halo 1,4-quinones occurs at the $\text{ipso}$ carbon or at the carbon vicinal to it depending on the nature of the nucleophile and the solvent.     

Simultaneous determination of trace concentrations of saturated and α,β-unsaturated carbonyl compounds in organic systems

A method for the simultaneous determination of trace concentrations of saturated and α,β-unsaturated carbonyl compounds in complex systems is presented. Carbonyl as the alkaline 2,4-dinitrophenylhydrazone is determined spectrophotometrically at 2 selected wavelengths of 480 and 426 nm. The apparent total carbonyl concentration is obtained from prepared calibration curves at the selected wavelengths based on known concentrations of n-heptaldehyde. From the observed relative response of known concentrations of n-heptaldehyde and 2-ethyl-2-hexenal, the true concentration for saturated and α,β-unsaturated carbonyl is obtained by a simple calculation. The method has been used extensively for alcohol systems ranging up to tetracontanol but is equally useful for hydrocarbons, aromatic oxygenates and hydrocarbons, petroleum distillates and kerosenes, organic acids and esters, and some ethers.     

Improved Yields in the Synthesis of Alkyl Glycosides

Recent syntheses of alkyl glycosides have involved a rnodification of the Koenigs-Knorr reaction in which a sugar peracetate is first brominated and finally reacted with the desired alcohol in the presence of silver ion as a catalyst. In 1980 Rosevear et a1.² reported a simplified synthesis of alkyl glycosides in which the acetobromosugar was not isolated, but was reacted with the alcohol and the deacetylated final product was purified using column chromatography on Dowex 1. While yield s obtained for alkyl glucosides by this procedure were as high as 60%, those for alkyl maltosides were only 25%. More recently Landauer et a1.3 have reported yields of 55 to 68% in the preparation of alkyl malto-sides. However, their procedure involves t h e isolation and purification of the acetobromosugar intermediate and reported yields are calculated on the basis of this intermediate.