Infrared matrix-isolation spectroscopy using pulsed deposition of p-H2

We employed pulsed deposition of p-H2 onto a cold target to form a matrix sample suitable for measurements of infrared absorption. Unlike the method of rapid vapor deposition at approximately 2.5 K, developed by Fajardo et al., this method can be performed at a temperature as high as 5.5 K, achievable with a closed-cycle refrigerator; pumping on liquid helium in a cryostat is eliminated. Compared with the enclosed-cell method developed by Oka, Shida, Momose, and co-workers, this method is more versatile in sample preparation, especially for samples at a greater concentration or with high reactivity. Two experiments were tested: the pulse-deposited sample of CH4/p-H2 yields an infrared absorption spectrum nearly identical to that recorded with rapid vapor deposition, and a sample of vinyl chloride (C2H3Cl) in solid p-H2 irradiated with laser emission at 193 nm yields C2H5, in contrast to formation of HCl, C2H2, and a complex of HClC2H2 observed upon photolysis of C2H3Cl in an Ar matrix. These experiments are also compared with those with n-H2 or Ne as the matrix host.     

Infrared spectra of monomeric thioformaldehyde in Ar,N2 and Xe matrices

Pyrolysis products of 1,3-dithietane were trapped in low-temperature matrices and their infrared spectra were recorded. The vibrational bands of monomeric H₂CS, which was not perturbed by other decomposition products, were identified in Ar, N₂ and Xe matrices. These results will be useful to evaluate the frequency shifts of H₂CS induced by the interaction with other molecules.     

Conformational study of monomeric 2,3-butanediols by matrix-isolation infrared spectroscopy and DFT calculations

The FT-IR spectra of two diastereomers of 2,3-butanediol, (R,S) and (S,S), isolated in low-temperature argon and xenon matrixes were studied, allowing the identification of two different conformers for each compound. These conformers were characterized by a +/-gauche arrangement around the O-C-C-O dihedral angle, thus enabling the establishment of a very weak intramolecular hydrogen bond of the O...H-O type. No other forms of these compounds were identified in matrixes, despite the fact that these four conformers had calculated relative energies from 0 to 5.1 kJ mol(-1) and were expected to be thermally populated from 50 to 6% in the gaseous phase of each compound. The nonobservation of additional conformers was explained in terms of low barriers to intramolecular rotation, resulting in the conformational relaxation of the compounds during deposition of the matrixes. The barriers to internal rotation of the OH groups were computed to be less than 4 kJ mol(-1) and are easily overcome in matrixes within the family of conformers with the same heavy atom backbone. The barriers for intramolecular rearrangement of the O-C-C-O dihedral angle in both diastereomers were calculated to range from 20 to 30 kJ mol(-1). Interconversions between the latter conformers were not observed in matrixes, even after annealing up to 65 K. Energy calculations, barriers, and calculated infrared spectra were carried out at the DFT(B3LYP)/6-311++G theory. Additional MP2/6-311++G calculations of energies and vibrational frequencies were performed on the most relevant conformers. Finally, independent estimations of the hydrogen-bond enthalpy in the studied molecules were also obtained based on theoretical structural data and from vibrational frequencies (using well-established empirical correlations). The obtained values for -DeltaH for both diastereomers of 2,3-butanediol amount to ca. 6-8 kJ mol(-1).     

Infrared spectra of the CF3I dimer: a concurrent application of matrix-isolation spectroscopy and cavity ring-down spectroscopy

We have observed infrared spectra of the CF(3)I dimer produced in a supersonic jet by matrix-isolation Fourier transform infrared spectroscopy and infrared cavity ring-down (IR-CRD) spectroscopy. In the matrix-isolation experiments, the dimer was isolated in an Ar matrix by the pulse-deposition method. The recorded spectral range covers the symmetric (nu(1)) and doubly degenerate (nu(4)) C-F stretching regions. From the concentration dependence of the matrix-isolation spectra we have assigned one dimer band for each fundamental region. It was not easy to identify the dimer band for the nu(4) band because of the multiplet feature of the monomeric nu(4) band caused by the site symmetry breaking. The spectra of (CF(3)I)(2) in the nu(4) band region were thus also measured in the gas phase by IR-CRD spectroscopy, where we detected two dimer bands. Comparing the observed band positions with the results of quantum chemical calculations, we have assigned the observed dimer bands to the head-to-head isomer. The structure of (CF(3)I)(2) and its photochemical implications are discussed, in comparison with methyl iodide dimer reported previously [Ito et al., Chem. Phys. Lett. 343, 185 (2001)].     

Analysis of the normal modes of molecules with D3h symmetry: Infrared spectra of monomeric s-triazine and cyanuric acid

Normal modes of s-triazine and cyanuric acid were calculated at the DFT(B3LYP)/6-311++G(d,p) level. These modes were analyzed in terms of potential energy distribution (PED), computed using a specially designed set of symmetry coordinates. The normal-mode analysis was described in detail and the PED matrix definition used in the calculations was provided. Particular attention has been devoted to the degenerate vibrations. The experimental infrared spectra of s-triazine and cyanuric acid isolated in low-temperature Ar matrices have been recorded and interpreted by comparison with the theoretically predicted normal modes. In the spectrum of matrix-isolated s-triazine, the IR bands originating from ¹³C and ¹⁵N isotopologues with one of the ring atoms substituted by a rare isotope were detected. These bands were identified thanks to the excellent agreement between the experimentally observed and theoretically predicted isotope shifts.     

Infrared spectra of some polybasic acid triphenyltin IV derivatives

Triphenyltin IV polybasic acid derivatives have been synthesized, and structures suggested on the basis of their IR spectra. Tetrahedral oxoanions behave as polydentate ligands giving infinite type structures. The cleavage of these infinite type structures occurs when the derivatives react with strong Lewis bases giving discrete structure adducts. A particular type of coordination of the selenite (tetradentate) has been established.     

Infrared spectra of heptafluorobutyric acid and some of its esters

Infrared spectra obtained for seven alkyl esters of heptafluorobutyric acid show that 18 vibrations of the CF₃CF₂CF₂CO₂ group have characteristic frequencies in these esters, with most having average deviations of only about 1 cm^?1. The relative intensities of the bands are also quite constant. The infrared spectrum obtained for heptafluorobutyric acid indicates that the acid is completely associated in the neat liquid.     

Infrared absorption spectra of pyridine N-oxide and benzoic acid complexes

The infrared absorption spectra in the 4000–1600cm⁻¹ region of some benzoic acid pyridine N-oxide derivative complexes are described.     

Transesterification of oxalic acid esters

Conclusions Transesterification of some lower oxalate esters with alcohols in the presence of acidic or basic catalysts gave the corresponding higher esters in good yield.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1102–1105, May, 1968.     

Decomposition of oxalic acid with nitric acid

Oxalic acid or oxalate is widely used as a precipitant and a detergent in the field of nuclear energy. The present work aimed at developing a method of decomposing oxalic acid with HNO₃ in the presence of Mn²⁺ ion. The use of Mn²⁺ ion as low as 10^?3 mol/l facilitated the complete decomposition of oxalic acid, and the acidity of the resulting solution became as low as 0.1 eq/1 under the optimum conditions. The decomposition of oxalic acid is a first order reaction and proceeds at temperatures above 80°C; the activation energy of the reaction is 18.6 kcal/mol. This decomposition method is applicable to the dissolution of an oxalate precipitate.     

Infrared flame spectra

Summary This paper presents a summary of recent work on the emission spectra of hydrocarbon flames in the region from 1 to 5.5 microns. The temperature of flames as determined by intensities of the infrared rotational and vibrational bands is found to be about 2600° K. Further temperature measurements on the incandescent particles in an oxyacetylene flame have been made and it was found that the values determined agree with those obtained from the spectral measurements.

---

Zusammenfassung Eine Übersicht neuerer Arbeiten über Emissionsspektren von Kohlenwasserstoff-Flammen im Gebiet von 1 bis 5,5 Mikron wird gegeben. Die Messung der Intensität der infraroten Rotations- und Vibrationsbanden ergab eine Flammentemperatur von etwa 2600° K. Weitere Temperaturmessungen wurden an unverbrannten Teilchen in einer Acetylen-Sauerstoff-Flamme vorgenommen. Die dabei erhaltenen Werte stimmen mit den spektrometrischen Messungen überein.

---

Résumé On présente dans cette communication un résumé des travaux récents sur le spectre d'émission des flammes dans la région spectrale de 1 à 5,5 microns. La température des flammes est déterminée à partir des intensités des bandes infra-rouges de vibration et de rotation; elle est environ 2600° K. On a fait d'autres mesures de température de particules incandescentes dans une flamme oxy-acétylénique; les valeurs trouvées sont en bon accord avec celles qu'on déduit de mesures spectrales.

     

Infrared and far-infrared spectra of solid oxamic acid,deutero-oxamic acid and their salts

The i.r. and far-i.r. room temperature spectra of oxamic acid, deutero-oxamic acid, sodium oxamate, sodium deutero-oxamate, potassium-, barium-, and copper(II) oxamates, and potassium bis(oxamato)cuprate(II) are reported. The group vibrations of oxamic acid, sodium oxamate, and potassium bis(oxamato)cuprate(II) are assigned and discussed. A normal coordinate analysis of oxamic acid and oxamide is presented and a discussion of the similarities is given. The spectral evidence indicates that oxamic acid does not exist as the zwitterion in the solid state.     

Theoretical and matrix-isolation experimental study of the infrared spectra of 5-azauracil and 6-azauracil

The infrared absorption spectra of 5-azauracil and 6-azauracil isolated in low-temperature Ar and N₂ matrices are reported. Within the limits of accuracy of spectroscopic measurements, both compounds appear to exist, in Ar and N₂ matrices, exclusively in dioxo tautomeric forms. An assignment of the observed infrared absorption bands is proposed based on the comparison of experimental frequencies and intensities with those calculated theoretically at ab initio Hartree-Fock level with 6-31G** basis set. Infrared spectra predicted at this level of theory reproduce the experimental spectra sufficiently accurately to enable a reliable assignment. Basis set dependency (6-31G**, 3–21G) of the theoretical result was also accounted for and it turned out that for accurate prediction of frequencies and intensities the use of basis set augmented with polarization functions is of crucial importance.     

Uranium leaching using citric acid and oxalic acid

Journal of Radioanalytical and Nuclear Chemistry - Citric acid and oxalic acid, the main metabolites of fungi, have different leaching effects on uranium ore. Herein, uranium leaching from a...     

Infrared and Raman spectra of N-acetyl-l-amino acid methylamides with aromatic side groups

Infrared and Raman spectra of N-acetyl-l-phenylalanine methylamide, N-acetyl-l-tyrosine methylamide and N-acetyl-l-tryptophan methylamide, as model compounds of aromatic amino acid residues in proteins, were measured in the solid state and in methanol solutions. Vibrational assignments of the spectra were made by utilizing the deuteration effect and by comparison with the spectra of related compounds which include toluene, p-cresol and 3-methylindole. The amide I, III and IV bands were strong in Raman scattering, but other characteristic amide bands were ill-defined. In the Raman spectra of methanol solutions, only the bands due to the aromatic side group vibrations were markedly observed, but those due to the peptide backbone vibrations were very weak, suggesting the coexistence of various molecular conformations in solution.     

草酸电还原制取乙醛酸的研究

研究了由草酸电解还原制备乙醛酸时，温度、草酸纯度、电解时间、电极状态和电解产物对电流效率和产率的影响。实验发现，除温度和原料纯度是重要的影响因素外，电极表面的有机物吸附和电解产物－乙醛酸的浓度具有更大的影响。     

Cation-exchange in oxalic acid-nitric acid media

Summary The adsorption behaviour of 16 elements on the strongly acidic cation-exchange resin AG 50W, X-8 has been examined in mixed oxalic-nitric acid media. The distribution coefficients are presented as a function of nitric acid concentration (0.13.0 M) in 0.05 M oxalic acid solution. There are marked differences in adsorbability between terand quadrivalent metal and bivalent metal groups. The system can be applied to the multielement analysis of manganese nodules for iron, zinc, copper, cobalt, manganese and nickel, coupled with chromatographic elution of bivalent metals with mineral acid-organic solvent mixtures. The versatility of the system is also demonstrated by the analysis of a biological standard reference material, pepperbush, of NIES for the same six elements. The results are in good agreement with the certified values (NIES: National Institute for Environmental Studies, Japan Environment Agency).

---

Kationenaustausch in Oxalsäure-Salpetersäure-LösungAnalytische Anwendung zur Bestimmung von sechs Spurenelementen in Manganknollen und Pflanzenmaterial

Zusammenfassung Das Adsorptionsverhalten von 16 Elementen an dem stark sauren Kationenaustauscher AG 50W, X-8 wurde in Oxalsäure-Salpetersäure-Gemischen untersucht. Die Verteilungskoeffizienten werden angegeben als Funktion der Salpetersäurekonzentration (0,13,0 M) in 0,05 M Oxalsäure. Die Adsorbierbarkeit der drei- und viersowie zweiwertigen Metallionen weist deutliche Unterschiede auf. Das Verfahren kann zur Multielementanalyse von Manganknollen auf Fe, Zn, Cu, Co, Mn und Ni angewendet werden. Die Elution der zweiwertigen Metallionen erfolgt mit Gemischen von Mineralsäuren und organischen Lösungsmitteln. Die Vielseitigkeit der Methode wird durch die Analyse eines biologischen Referenzmaterials (Pepperbush, NIES) demonstriert. Die Ergebnisse stimmten mit den zertifizierten Werten gut überein.