Raman scattering study of toluene vibrational relaxation in benzene-toluene liquid system

The polarizes and depolarized profiles of the 520 cm^?1 Raman line of toluene in benzene solutions have been measured as a function of concentration. The vibrational correlation functions were obtained by Fourier inversion of Raman band contours. The concentration dependence of the experimental vibrational correlation time has been compared with that computed from the Fischer-Laubereau vibrational dephasing model modified for use in binary mixtures.     

Density and temperature effects on relative Raman intensities in liquid toluene

Raman spectra of toluene at pressures up to 4.1 kbar and temperatures up to 100°C, have been studied. The frequency and intensity changes of the symmetric (ν_6a) and antisymmetric (ν_6b) ring breathing vibrations have been related principally to changes in density. Increasing density at constant temperature increases I(ν_6b/ν6a) and increases the frequency of (ν_6a) but has little effect on the frequency of ν_6b. Increasing temperature at constant density decreases I(ν_6b/ν_6a) and increases the frequency of ν_6a but has little effect on the frequency of ν_6b. An explanation of the different intensity changes with density for these two bands is suggested in terms of the contrasting volume changes associated with the two modes.     

Polarized Raman spectra,thermodynamic functions and bidders to internal rotation of 2,3-dimethoxy toluene

Polarized Raman spectra of 2,3-dimethoxy toluene have been recorded in the region 50–4000 cm⁻¹ and IR spectra in the region 200–4000 cm⁻¹. All the 63 (40a′ + 23a″) normal modes of vibration have been assigned assuming a C_s point group. Consistent assignments for the internal modes of vibration of methyl (CH₃) and methoxy (OCH₃) groups have been proposed. In addition thermodynamic functions have been computed over the temperature range 100–1500 K on a MIGHTY II computer and barriers to internal rotations for the three methyl (CH₃) tops and the two methoxy (OCH₃) tops about their respective axes have been determined, using the assigned torsional frequencies and assumed structural parameter for the 2,3-dimethoxy toluene. The barrier heights have been found to be greater than 2.5 kcal mol⁻¹ for all five tops.     

The multiphoton ionization spectrum of toluene in a supersonic free jet: internal rotation of the methyl group

The S₁← S_o electronic transitions of toluene involving also some internal rotational levels were observed for the first time in the multiphoton ionization spectrum in a supersonic jet. A large population in several low-lying internal rotational levels and a strong coupling between electronic motion and the internal rotation are suggested.     

Direct Raman evidence for a weak continuous phase transition in liquid water

This paper presents the Raman depolarization ratio of degassed ultrapure water as a function of temperature, in the range 303.4-314.4 K (30.2-41.2 degrees C). The pressure of the sample was the vapor pressure of water at the measurement temperature. The data provide a direct indication of the existence of a phase transition in the liquid at 307.7 K, 5.8 kPa (34.6 degrees C, 0.057 atm). The minimum in the heat capacity, C(p)(), of water occurs at 34.5 degrees C, 1.0 atm (J. Res. Natl. Bur. Stand. 1939, 23, 197(1)). The minimum in C(p)() is shallow, and the transition is a weak-continuous phase transition. The pressure coefficient of the viscosity of water changes sign as pressure increases for temperatures below 35 degrees C (Nature 1965, 207, 620(2)). The viscosity minimum tracks the liquid phase transition in the P, T plane where it connects with the minimum in the freezing point of pure water in the same plane (Proc. Am. Acad. Arts Sci. 1911-12, 47, 441(3)). Previously we argued (J. Chem. Phys. 1998, 109, 7379(4)) that the minimum in the pressure coefficient of viscosity signaled the elimination of three-dimensional connectivity in liquid water. These observations coupled with recent measurements of the coordination shell of water near 300 K (Science 2004, 304, 995(5)) suggest that the structural component that changes during the phase transition is tetrahedrally coordinated water. At temperatures above the transition, there is no tetrahedrally coordinated water in the liquid and locally planar water structures dominate the liquid structure. Water is a structured liquid with distinct local structures that vary with temperature. Furthermore, liquid water has a liquid-liquid phase transition near the middle of the normal liquid range.     

Raman spectral changes of alcoholic zinc chloride solutions from liquid state to glassy state

Raman spectral changes associated with vitrification were measured for ZnCl₂·4OROH solutions (ROH=methanol, ethanol and 1-propanol). Solvated ZnCl₂ is the only major Zn-species in these solutions at room temperature while the dominant Zn-species stabilized in the glassy alcoholic solutions are ZnCl ₃ ^– , ZnCl ₄ ^2– and [Zn(MeOH)₆]²⁺ for the methanol solution, ZnCl₂ and ZnCl ₃ ^– for the ethanol solution and ZnCl₂ for the 1-propanol solution. Together with Raman data for aqueous ZnCl₂ solutions, the differences in the dominant Zn-species in the glassy alcoholic solutions are discussed in terms of the dielectric constants of solvents (water and alcohols).     

Radioluminescence quenching of toluene scintillators by methyl methacrylate

It was established that singlet electronic excited state of toluene is quenched by MMA /but is not quenched by PMMA/. The value of quenching rate constant k_g=0.6×10⁹ l.mol^–1.s^–1 indicates that the quenching is a diffusion controlled process. It is assumed that the excitation energy of toluene sensitizes the polymerization process of MMA. The increase of radioluminescence intensity and quantum yield of excitation energy transfer is the result of diminishing the quantity of MMA in the solution during polymerization time.     

Transport of toluene/methyl ethyl ketone mixtures in polyisobutylene

In this study, the diffusion behavior of methyl ethyl ketone (MEK)/toluene mixtures, with MEK molar fractions (x₁) in the liquid source lower than 0.2, in polyisobutylene (PIB) was investigated with vapor‐sorption Fourier transform infrared attenuated total reflectance (FTIR‐ATR) spectroscopy. FTIR‐ATR Fickian diffusion models for both binary and ternary systems were used to determine diffusion coefficients. Obtained diffusion coefficients for MEK from the binary diffusion model did not agree with those determined previously for the diffusion of MEK/toluene mixtures, with x₁ > 0.2, in PIB. When the ternary diffusion model was used, the main‐term and cross‐term diffusion coefficients of MEK were comparable. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 908–914, 2001     

Raman study of ratational diffusion in methyl iodide

The usefulness of Raman and NMR spin relaxation spectroscopic methods in probing the details of molecular motions in liquids is demonstrated in a study of methyl iodide. Analysis of the lineshape of the ν₃ Raman band of methyl iodide as a function of temperature yields values of the perpendicular component D_⊥ of the diffusion tensor D_i and an activation energy of reorientation perpendicular to the C₃ axis of the molecule of 2.1 kcal/mole. Coupling the Raman data with ²D NMR spin relaxation data yields values of D_| and an activation energy for reorientation about the C₃ axis of 0.4 kcal/mole indicating quasi-free rotation for this motion. Thus the reorientational motions of methyl iodide are shown to be highly anisotropic in the liquid state.     

On the atmospheric oxidation of liquid toluene

This communication presents preliminary computational results on the interaction between triplet (3Sigma) and singlet (1Sigma, 1Delta) oxygen molecules with toluene. All three oxygen species form very weak complexes with toluene and all also appear capable of abstracting a benzylic hydrogen atom to form the HO2 radical. Reaction with singlet molecular oxygen does not convincingly explain the formation of benzylhydroperoxide from toluene residues stored over a long time in brown glass bottles, and it is speculated that this may be a surface-catalysed photochemical reaction. The possible involvement of singlet oxygen molecules in the spontaneous ignition of tyre rubber and of soft coal is discussed briefly and the need for new experimental studies is stressed.     

Reaction of toluene with ozone in the liquid phase

Reaction of toluene with ozone in acetic anhydride was studied. The dependence of the direction, selectivity, and extent of oxidation on the reaction temperature, solvent nature, and catalyst composition was examined.     

Dielectric study of side-group rotation of methyl methacrylate in copolymers

The dielectric absorption due to the side-group rotation of the methyl methacrylate (MMA) unit in MMA-styrene and MMA-p-chlorostyrene (pCS) copolymers was measured. The relaxation time for MMA-pCS copolymers with low MMA contents could be interpreted quantitatively in terms of the Kramers rate-constant theory at the low-friction limit. On the other hand, the frictional effect on the relaxation time could not be ignored for any copolymers except for the MMA-pCS copolymers with low MMA contents. The relaxation time for pure poly(methyl methacrylate) could be interpreted by the Kramers theory at the high-friction limit.     

Effect of methyl rotation on the electronic spectrum of the methyl peroxy radical

Recent experiments have prompted a theoretical investigation of the effect of methyl rotation on the A-X electronic spectrum of the CH3O2 and CD3O2 radicals. Quantum chemistry calculations have mapped the potential for the methyl rotation. Using these results, we calculate the torsional eigenvalues for both the A and X states and simulate the A-X spectrum. We find that the simulation captures the salient features of the spectrum. These features include torsional sequence structure, whose band contours change dramatically as the lower level nears the barrier, as well as atypical torsional transitions occurring from levels near the top and above the barrier. "Experimental" barrier heights are deduced for both the X and A states of methyl peroxy by modestly scaling the calculated potential to best reproduce the observed spectra.     

Surface-enhanced Raman spectral measurements of 5-fluorouracil in saliva

The ability of surface-enhanced Raman spectroscopy (SERS) to measure 5-fluorouracil (5-FU) in saliva is presented. The approach is based on the capacity of Raman spectroscopy to provide a unique spectral signature for virtually every chemical, and the ability of SERS to provide microg/mL sensitivity. A simple sampling method, that employed 1-mm glass capillaries filled with silver-doped sol-gels, was developed to isolate 5-FU from potential interfering chemical components of saliva and simultaneously provide SERSactivity. The method involved treating a 1 mL saliva sample with 1 mL of acetic acid, drawing 10 microL of sample into a SERS-active capillary by syringe, and then measuring the SER spectrum. Quality SER spectra were obtained for samples containing as little as 2 microg of 5-FU in 1 mL saliva. The entire process, the acid pretreatment, extraction and spectral measurement, took less than 5 minutes. The SERS of 5-fluorouridine and 5-fluoro-2'-deoxyuridine, two major metabolites of 5-FU, were also measured and shown to have unique spectral peaks. These measurements suggest that disposable SERS-active capillaries could be used to measure 5-FU and metabolite concentrations in chemotherapy patient saliva, thereby providing metabolic data that would allow regulating dosage. Tentative vibrational mode assignments for 5-FU and its metabolites are also given.     

Raman resonance effect in liquid water

Raman spectroscopy is a technique preferably used for studies of water structure because the proportions of intensities of main OH stretching modes are thought to reflect well a network of "intermonomer" hydrogen bonds as well as its disturbance by the presence of some solutes. The work presented herein demonstrates how the intensity ratio of two main components (around 3200 and 3400 cm (-1)) depends on the excitation wavelength in the visible range. Polarized Raman spectra indicate that the component at ca. 3200 cm (-1) is in resonance with light from the red range, which is in agreement with the presence of vibrational overtones in UV-vis absorption spectrum of water. These results are the first report on the occurrence of the Raman resonance effect in liquid water.     

Raman bandshape analysis in liquid fluorine

A bandshape study of the Raman diffusion by liquid fluorine over the temperature range 75–100°K is presented. A discussion of the molecular reorientation process is developed.     

Electronic spectral detection in liquid chromatography

The use of absorbance and fluorescence spectrometers as liquid chromatography detectors is described. These detectors offer sensitive detection that can also identify the peaks in a chromatogram. Many examples, mainly from the separation of polycyclic aromatic hydrocarbons, are given that show the selectivity and usefulness of these detectors.