Kirk H. Michaelian

A reinvestigation of the Raman spectrum of water

The Raman spectrum of liquid water has been reinvestigated using a technique which automatically records the depolarization ratio along with the polarized Raman spectrum. The exceptionally accurate depolarization ratios thus obtained, as well as the isotropic and the anisotropic spectra of water, indicate that the libration region extends to higher frequencies than previously thought and that a new polarized band originating from restricted translation occurs near 290 cm−1. The translational spectrum is in good agreement with that calculated by Weres and Rice.

Silica-coated super paramagnetic iron oxide nanoparticles (SPION) as biocompatible contrast agent in biomedical photoacoustics

In this study, we report for the first time the use of silica-coated superparamagnetic iron oxide nanoparticles (SPION) as contrast agents in biomedical photoacoustic imaging. Using frequency-domain photoacoustic correlation (the photoacoustic radar), we investigated the effects of nanoparticle size, concentration and biological media (e.g. serum, sheep blood) on the photoacoustic response in turbid media. Maximum detection depth and the minimum measurable SPION concentration were determined experimentally. The nanoparticle-induced optical contrast ex vivo in dense muscular tissues (avian pectus and murine quadricept) was evaluated and the strong potential of silica-coated SPION as a possible photoacoustic contrast agents was demonstrated.

Comparison of Laboratory Methodologies to Evaluate Corrosion Inhibitors for Oil and Gas Pipelines

Abstract Experiments were carried out using a loop in three fields (gassy-oil, oily-gas, and oil-transmission pipes) under 17 operating conditions, using six inhibitors (three continuous and three ...

Nonpolar nitrous oxide dimer: Observation of combination bands of (14N2O)2 and (15N2O)2 involving the torsion and antigeared bending modes

Spectra of the nonpolar nitrous oxide dimer in the region of the N(2)O ν(1) fundamental band were observed in a supersonic slit-jet apparatus. The expansion gas was probed using radiation from a quantum cascade or a tunable diode laser, with both lasers employed in a rapid-scan signal averaging mode. Four bands were observed and analyzed: new combination bands involving the intermolecular conrotation of the monomers (A(g) antigeared bend) for ((14)N(2)O)(2) and ((15)N(2)O)(2), the previously reported torsional combination band for ((14)N(2)O)(2) with improved signal-to-noise ratio, and the same torsional combination band for ((15)N(2)O)(2). The resulting frequencies for the intermolecular antigeared mode are 96.0926(1) and 95.4912(1) cm(-1) for ((14)N(2)O)(2) and ((15)N(2)O)(2), respectively. This is the third of the four intermolecular frequencies which has now been measured experimentally, the others being the out-of-plane torsion and the geared bend modes. Our experimental results are in good agreement with two recent high level ab initio theoretical calculations.

Arrhenius behavior of hydrocarbon fuel photochemical reaction rates by thermal lens spectroscopy

The temperature dependence of thermo-optical and photochemical reaction properties of hydrocarbon fuels is investigated using thermal lens spectroscopy. We consider the time dependence of the absorption coefficient due to the photoinduced chemical reaction (PCR) and species diffusion to evaluate nonequilibrium characteristics of the samples. The measured temperature dependences of the reaction rates are found to follow the Arrhenius correlation. Experimental results for thermophysical properties of the samples and an analysis of the connection between PCR properties and the chemistry of the samples are also presented.

Soret effect and photochemical reaction in liquids with laser-induced local heating

We report a theoretical model and experimental results for laser-induced local heating in liquids, and propose a method to detect and quantify the contributions of photochemical and Soret effects in several different situations. The time-dependent thermal and mass diffusion equations in the presence and absence of laser excitation are solved. The two effects can produce similar transients for the laser-on refractive index gradient, but very different laser-off behavior. The Soret effect, also called thermal diffusion, and photochemical reaction contributions in photochemically reacting aqueous Cr(VI)-diphenylcarbazide, Eosin Y, and Eosin Y-doped micellar solutions, are decoupled in this work. The extensive use of lasers in various optical techniques suggests that the results may have significance extending from physical-chemical to biological applications.

Thermal-lens study of photochemical reaction kinetics.

We consider the time dependence of the absorption coefficient due to the photoinduced chemical reaction (PCR) and species diffusion to calculate the temperature rise in the thermal-lens (TL) effect. The TL signal at the detector plane is also calculated. This theoretical approach removes the restriction that the PCR time constant is much greater than the characteristic TL time constant, which was assumed in a previously published model. Hydrocarbon fuel and aqueous Cr(VI) samples are investigated, and quantitative experimental results for the thermal, optical, and PCR properties are obtained. While similar results were obtained for the Cr(VI) solution using the previous and present models, the relative difference between the PCR time constants extracted from the same experimental data for a hydrocarbon fuel sample is found to be more than 220%. This demonstrates the significant difference of the two models.

Comparison of Techniques for Monitoring Corrosion Inhibitors in Oil and Gas Pipelines

Abstract Addition of corrosion inhibitors is one of the common methods to control both general and pitting corrosion of oil and gas pipelines. Development of an integrity management program to control internal corrosion of such pipelines depends on our ability to monitor the efficiency of the inhibitor performance. Monitoring in an oil and gas pipeline is a complex process due to the multitude of conditions that exist in such an environment. In this paper, the reliability of weight loss, linear polarization resistance (LPR), electrochemical impedance spectroscopy (EIS), electrochemical noise (EN), and externally mounted hydrogen probes for monitoring inhibitor performance in oil and gas pipelines is investigated.

Study of the interaction between caesium bromide and kaolinite by differential thermal analysis

The reaction occurring during the wet grinding of kaolinite with CsBr was studied by simultaneous Differential Thermal Analysis -Thermogravimetry (DTA-TG), supplemented by infrared spectroscopy of isothermally treated CsBr disks. The DTA and TG curves were compared with those of untreated kaolinite and of kaolinite mixed or air ground with different alkali halides. A new endothermic DTA peak at 75–115°, accompanied by weight loss, is due to the desorption of surface and interparticle water located mainly at the “interface” between the mineral and the salt. A second endothermic peak at about 500° represents the simultaneous dehydroxylation of the clay and thermal hydrolysis of CsBr. The presence of a separate CsBr phase was identified from two endothermic peaks which characterize melting and boiling of the salt; only mixtures with more than 140 mmol CsBr per 100 g kaolinite show the presence of this phase. All of the CsBr below this concentration occurs in the CsBrHOH-kaolinite intercalation complex. This degree of saturation is smaller than that obtained previously for CsCl.ZusammenfassungMittels simultaner DTA-TG wurde die sich während des Naßmahlens von Kaolinit mit CsBr stattfindende Reaktion untersucht, ergänzt durch IR-spektroskopische Untersuchungen von isotherm wärmebehandelten CsBr-Plättchen. Die DTA und TG Kurven wurden mit denen von unbehandeltem Kaolinit und von Kaolinit, vermischt oder an Luft gemahlen mit verschiedenen Alkalihalogeniden. Ein neuer endothermer DTA-Peak bei 75–115°C., begleitet von einem Gewichtsverlust, wird der Desorption von Oberflächen- oder interpartikelgebundenem Wasser zugeschrieben, das hauptsächlich an den Übergangsflächen Mineral/Salz lokalisiert ist. Ein zweiter endothermer Peak bei 500°C steht für die gleichzeitige Dehydroxylierung der Tonerde und die thermische Hydrolyse von CsBr. Aus zwei für Schmelzen und Sieden des Salzes charakteristischen endothermen Peaks konnte auf eine separate CsBr-Phase geschlossen werden; nur Gemische mit mehr als 141 mmol CsBr pro 100 g Kaolinit zeigen die Gegenwart einer solchen Phase. Unterhalb dieser Konzentrationsgrenze ist alles CsBr in CsBr-HOH-Kaolinit Durchdringungskomplexen vorhanden. Dieser Sättigungsgrad ist niedriger als der für CsCl.

Mid-infrared photoacoustic spectroscopy of solids using an external-cavity quantum-cascade laser

We describe the use of a pulsed external-cavity quantum-cascade laser (EC-QCL) for the acquisition of mid-IR photoacoustic (PA) spectra of solids. The EC-QCL employed in this work operates from 990 to 1075 cm(-1) (9.30-10.10 microm). A gas-microphone PA cell was used as the detector, and the signal was demodulated using a lock-in amplifier. PA EC-QCL spectra of solids display bands significantly narrower than those in corresponding PA Fourier transform infrared spectra.