Elimination de l'ion chrome hexavalent dans l'eau par les celluloses greffées

L'étude concerne le chrome (VI) et son élimination dans l'eau par les celluloses greffées (échangeuse d'anions) AE2 sous forme OH¯, Cl¯, S04=.La capacité d'échange correspond à 0,5-0,6 meq g-1 de cellulose. Les cinétiques d'échanges du Cr (VI) avec les ions CL¯ OH¯ et SO4 ont été déterminées en fonction du pH du milieu, de la température, de ta force ionique, de La quantité de détergents et des formes de celluloses AE2. Les résultats expérimentaux montrent que les formes de celluloses sont efficaces dans l'ordre OH¯ > Cl¯ > SO4= vis-à-vis du Cr (VI) et que l'échange décroît pour les ions étudiés dans l'ordre suivant : CrO4= > Cr207= > HCrO4¯.Ion exchange is used extensively for water and waste water treatment for the removal of a variety of ion species. It is known that at acidic pH nome anion-exchange resins can selectively remove and recover chromate from cooling water (SENGUPTA, 1986) where chromate is used as a corrosion inhibitor. This method is employed for plating waste treatment and to recover hexavalent chromium. The waste stream is first passed through a cation exchanger to remove metal ions such as iron, zinc, nickel and trivalent chromium. The hexavalent chromium passes through as CrO4=, and is subsequently removed in a anion exchanger.Hexavalent chromium may exist in the aqueous phase in different ionic forms with total chromate concentration and pH dictating which particular chromate species will predominate. The equilibrium reactions for different Cr (VI) species are :H2CrO4 ⇌ HCrO-4 + H+HCrO-4 ⇌ CrO-4- + H+Cr2O-7- + H2O ⇌ 2HCrO-4Cr2O-7- + H2O ⇌ 2CrO-4- + 2H+In the present study a description is given of the extraction of small quantities of Cr (VI) ion in water by modified cellulose (anionic form, (AE2) counterions OH¯, Cl¯, S04= ; 0,5-0,6 meq l-1 ion exchange capacity) which is represented by the following chemical formula : (CHATELIN, 1982 ; WATTIEZ, CHATELIN, 1981).Cell - O - CH2 - CH - O - CH2 - CH -                          |                         |                        CH2                    CH2                          |                         |                         N+    CL-             N+    CL-                       /  |  \                   /  |  \             CH3  CH3  CH3         CH3  CH3  CH3Kinetics of exchange and effects of pH, competiting ions, concentration, temperature, ionic strength, surfactants and types of cellulose (Cl¯, OH¯, SO4=) have been studied.Chromate only, chromate-pH, chromate-chloride, chromate-sulfate and chromate-surfactant kinetics (20 ± 1 °C) were determined for different anionic forms of modified cellulose. Kinetics data were generated by a batch equilibration technique where a weighed amount (5 g) of modified cellulose was shaken gently for 0.5-1 h with a fixed volume of solution (500 ml) containing Cr (VI) with successively H+, Cl¯, SO4=, a surfactant of known initial composition. A the end of the equilibration solution, the composition was determined again to calculate the Cr (VI) uptake. Equilibrium was achieved in 0.5 h, but 75 % of Cr (VI) was removed in 5 min.RESULTSSome specific aspects of the ion-exchange process for chromate recovery from industriel waste have been reported.It was observed that the more efficient types of cellulose for chromium removal where OH¯ > Cl¯ > SO4= respectively and that ion exchange decreased as followsCrO4= > Cr207= > HCrO4¯

Polycyclic Aromatic Hydrocarbons with armchair edges and the 12.7 {\mu}m band

In this Letter we report the results of density functional theory calculations on medium-sized neutral Polycyclic Aromatic Hydrocarbon (PAH) molecules with armchair edges. These PAH molecules possess strong C-H stretching and bending modes around 3 {\mu}m and in the fingerprint region (10-15 {\mu}m), and also strong ring deformation modes around 12.7 {\mu}m. Perusal of the entries in the NASA Ames PAHs Database shows that ring deformation modes of PAHs are common - although generally weak. We then propose that armchair PAHs with NC >65 are responsible for the 12.7 {\mu}m Aromatic Infrared Band in HII regions and discuss astrophysical implications in the context of the PAH life-cycle.Comment: Minor editin

Diffuse Interstellar Bands in z < 0.6 CaII Absorbers

The diffuse interstellar bands (DIBs) probably arise from complex organic molecules whose strength in local galaxies correlates with neutral hydrogen column density, N(HI), and dust reddening, E(B-V). Since CaII absorbers in quasar (QSO) spectra are posited to have high N(HI) and significant E(B-V), they represent promising sites for the detection of DIBs at cosmological distances. Here we present the results from the first search for DIBs in 9 CaII-selected absorbers at 0.07 < z_abs < 0.55. We detect the 5780Ang DIB in one line of sight at z_abs = 0.1556; this is only the second QSO absorber in which a DIB has been detected. Unlike the majority of local DIB sight-lines, both QSO absorbers with detected DIBs show weak 6284Ang absorption compared with the 5780Ang band. This may be indicative of different physical conditions in intermediate redshift QSO absorbers compared with local galaxies. Assuming that local relations between the 5780Ang DIB strength and N(HI) and E(B-V) apply in QSO absorbers, DIB detections and limits can be used to derive N(HI) and E(B-V). For the one absorber in this study with a detected DIB, we derive E(B-V) = 0.23mag and log[N(HI)] >= 20.9, consistent with previous conclusions that CaII systems have high HI column densities and significant reddening. For the remaining 8 CaII-selected absorbers with 5780Ang DIB non-detections, we derive E(B-V) upper limits of 0.1-0.3mag.Comment: 5 pages, 2 figures. Accepted to MNRAS Letter

Sequence structure emission in The Red Rectangle Bands

We report high resolution (R~37,000) integral field spectroscopy of the central region (r<14arcsec) of the Red Rectangle nebula surrounding HD44179. The observations focus on the 5800A emission feature, the bluest of the yellow/red emission bands in the Red Rectangle. We propose that the emission feature, widely believed to be a molecular emission band, is not a molecular rotation contour, but a vibrational contour caused by overlapping sequence bands from a molecule with an extended chromophore. We model the feature as arising in a Polycyclic Aromatic Hydrocarbon (PAH) with 45-100 carbon atoms.Comment: 13 pages, 9 figures, accepted for publication in ApJ. A version of the paper with full resolution figures is available at: http://www.aao.gov.au/local/www/rgs/Sequence-Structure

Detection of diffuse interstellar bands in M31

We investigate the diffuse interstellar band (DIB) spectrum in the interstellar medium of M31. The DEIMOS spectrograph of the W. M. Keck observatory was used to make optical spectroscopic observations of two supergiant stars, MAG 63885 and MAG 70817, in the vicinity of the OB78 association in M31 where the metallicity is approximately equal to solar. The 5780, 5797, 6203, 6283 and 6613 DIBs are detected in both sightlines at velocities matching the M31 interstellar Na I absorption. The spectra are classified and interstellar reddenings are derived for both stars. Diffuse interstellar band (DIB) equivalent widths and radial velocities are presented. The spectrum of DIBs observed in M31 towards MAG 63885 is found to be similar to that observed in the Milky Way. Towards MAG 70817 the DIB equivalent widths per unit reddening are about three times the Galactic average. Compared to observations elsewhere in the Universe, relative to reddening the M31 ISM in the vicinity of OB78 is apparently a highly favourable environment for the formation of DIB carriers

Detection of C5N- and vibrationally excited C6H in IRC +10216

We report the detection in the envelope of the C-rich star IRC +10216 of four series of lines with harmonically related frequencies: B1389, B1390, B1394 and B1401. The four series must arise from linear molecules with mass and size close to those of C6H and C5N. Three of the series have half-integer rotational quantum numbers; we assign them to the 2Delta and 2Sigma vibronic states of C6H in its lowest (v_11) bending mode. The fourth series, B1389, has integer J with no evidence of fine or hyperfine structure; it has a rotational constant of 1388.860(2) MHz and a centrifugal distortion constant of 33(1) Hz; it is almost certainly the C5N- anion.Comment: Accepted for publication in ApJ Letter

Centrosymmetric molecules as possible carriers of diffuse interstellar bands

In this paper, we present new data with interstellar C2 (Phillips bands A-X), from observations made with the Ultraviolet-Visual Echelle Spectrograph of the European Southern Observatory. We have determined the interstellar column densities and excitation temperatures of C2 for nine Galactic lines. For seven of these, C2 has never been observed before, so in this case the still small sample of interstellar clouds (26 lines of sight), where a detailed analysis of C2 excitation has been made, has increased significantly. This paper is a continuation of previous works where interstellar molecules (C2 and diffuse interstellar bands) have been analysed. Because the sample of interstellar clouds with C2 has increased, we can show that the width and shape of the profiles of some diffuse interstellar bands (6196 and 5797 A) apparently depend on the gas kinetic and rotational temperatures of C2; the profiles are broader because of the higher values of the gas kinetic and rotational temperatures of C2. There are also diffuse interstellar bands (4964 and 5850 A) for which this effect does not exist.Comment: 8 pages, 4 figures, accepted to MNRAS 201

The CH2CN- molecule: Carrier of the lambda8037 diffuse interstellar band?

The hypothesis that the cyanomethyl anion CH2CN- is responsible for the relatively narrow diffuse interstellar band (DIB) at 8037.8 +- 0.15 Angstroms is examined with reference to new observational data. The 0_0^0 absorption band arising from the ^1B_1 - X ^1A' transition from the electronic ground state to the first dipole-bound state of the anion is calculated for a rotational temperature of 2.7 K using literature spectroscopic parameters and results in a rotational contour with a peak wavelength of 8037.78 Angstroms. By comparison with diffuse band and atomic line absorption spectra of eight heavily-reddened Galactic sightlines, CH2CN- is found to be a plausible carrier of the lambda8037 diffuse interstellar band provided the rotational contour is Doppler-broadened with a b parameter between 16 and 33 km/s that depends on the specific sightline. Convolution of the calculated CH2CN- transitions with the optical depth profile of interstellar Ti II results in a good match with the profile of the narrow lambda8037 DIB observed towards HD 183143, HD 168112 and Cyg OB2 8a. The rotational level populations may be influenced by nuclear spin statistics, resulting in the appearance of additional transitions from K_a = 1 of ortho CH2CN- near 8025 and 8050 Angstroms that are not seen in currently available interstellar spectra. For CH2CN- to be the carrier of the lambda8037 diffuse interstellar band, either a) there must be mechanisms that convert CH2CN- from the ortho to the para form, or b) the chemistry that forms CH2CN- must result in a population of K_a'' levels approaching a Boltzmann distribution near 3 K