Temperature dependence of near-resonant vibration ↔ rotation energy transfer

V ? R,T deactivation of the ν₄ (243 cm^?1) level in BCl₃ by HCl has been measured over the range 220–340 K, with an infrared double resonance technique. The deactivation probabilities show an inverse temperature dependence below room temperature, indicating that long-range attractive forces are important in the resonant transfer process. The results are compared with the theory of Sharma and Brau.     

Thermal lens spectrometric determination of hexavalent chromium

The applicability of thermal lens spectrometry (TLS) for quantification and routine determination of hexavalent chromium was investigated by using a collinear dual beam thermal lens spectrometer. In aqueous solutions the LOD of 0.1 μg l⁻¹ was obtained for Cr(VI) by using 160 mW laser power. The performance of the technique was verified by the determination of hexavalent chromium in standard reference water samples (NIST SRM 1643a and NIST SRM 1643c) and comparing the results for Cr(VI) in CCA (Cr, Cu, As)-treated timber extracts to concentrations obtained by atomic absorption spectrometry (AAS). Good agreement between the TLS results and reported values for Cr(VI) in SRMs as well as AAS results for Cr(VI) in CCA-treated timbers confirmed that TLS is a reliable and accurate analytical technique applicable for the determination of Cr(VI) in aqueous solutions at concentration levels 0.5–100 μg l⁻¹.     

Studies on the extraction of chromium(VI) by ketones

A study of the extraction of chromium(VI) from aqueous media by ketones was made. Extraction of chromium was found to be most efficient from aqueous hydrochloric acid solutions. A mechanism for the extraction of chromium(VI) from aqueous hydrochloric acid solutions by methyl isobutyl ketone is proposed involving the formation of a receptor in the organic phase, the exchange of the chloride ion of the receptor for the anionic chromium(VI) species of the aqueous phase, and the solvation of the extracted chromium species. The differences in the abilities of various ketones to extract chromium(VI) from aqueous hydrochloric acid solutions, and the differences in the extraction of chromium (VI) from various aqueous acids by methyl isobutyl ketone are attributed to the differences in the formation of receptors.     

Interaction of polyvinylpyrrolidone and iodine

A nonsolvent preparation of the polyvinylpyrrolidone (PVP) complex provides new insight into the nature of the polymer-iodine interaction. The preparation is obtained by simply mixing PVP with crystalline iodine and is of interest because it provides a system in which no interfering ions are present and only one type of iodine is initially present. The iodine is shown to undergo hydrolysis with moisture in the polymer to give iodide and hypoiodite. The ionic forms of iodine appear to associate with the molecular iodine, resulting in the final stable PVP-iodine complex.     

Extremes of censored and uncensored lifetimes in survival data

Extremes - We consider a random censoring model for survival analysis, allowing the possibility that only a proportion of individuals in the population are susceptible to death or failure, and the...     

The anomalous Mössbauer fraction of ferritin and polysaccharide iron complex (PIC)

Mössbauer studies of the ubiquitous protein molecule ferritin and its synthetic biomimic polysaccharide iron complex (PIC) exhibit an anomaly in the Mössbauer spectrum wherein the recoil free fraction orf-factor has a sharp drop with respect to temperature as the temperature rises above 30 K for mammalian ferritin and 60 K for PIC. The anomaly coincides with the disappearance of hyperfine splitting, which is due to superparamagnetic relaxation above the blocking temperature. Different absorbers were used to experimentally investigate the effect of absorber thickness on the Mössbauer spectrum. The anomaly persists for thin absorbers. Also, spectra treated with FFT procedures to eliminate the thickness effect still exhibit this anomaly. Motion of the core with respect to the protein shell was also eliminated as a possible source for this phenomenon, by comparing the Debye temperature obtained from the temperature dependence of thef-factor and the isomer shift. A comparison of the magnetic anisotropy constants from magnetization studies with those obtained by relating the hyperfine fieldH of the Mössbauer spectra to the fluctuations of the magnetization imply that the ferritin and PIC molecules possess magnetic anisotropy energy which may not be strictly uniaxial. This, we believe, may be intimately connected with the mechanism causing thef-factor anomaly.This work was carried out in partial fulfilment of the requirements of the PhD degree at Tufts University.