Electronic properties of liquid hydrogen fluoride: A sequential quantum mechanical/Born-Oppenheimer molecular dynamics approach

The electronic properties of liquid hydrogen fluoride (HF) were investigated by carrying out sequential quantum mechanics/Born-Oppenheimer molecular dynamics. The structure of the liquid is in good agreement with recent experimental information. Emphasis was placed on the analysis of polarisation effects, dynamic polarisability and electronic excitations in liquid HF. Our results indicate an increase in liquid phase of the dipole moment (similar to 0.5 D) and isotropic polarisability (5%) relative to their gas-phase values. Our best estimate for the first vertical excitation energy in liquid HF indicates a blue-shift of 0.4 +/- 0.2 eV relative to that of the gas-phase monomer (10.4 eV). (C) 2010 Elsevier B.V. All rights reserved.

Catalytic liquid- and gas-phase oxidations for the synthesis of intermediates and specialty chemicals: some examples of industrial relevance

Nowadays, it is clear that the target of creating a sustainable future for the next generations requires to re-think the industrial application of chemistry. It is also evident that more sustainable chemical processes may be economically convenient, in comparison with the conventional ones, because fewer by-products means lower costs for raw materials, for separation and for disposal treatments; but also it implies an increase of productivity and, as a consequence, smaller reactors can be used. In addition, an indirect gain could derive from the better public image of the company, marketing sustainable products or processes. In this context, oxidation reactions play a major role, being the tool for the production of huge quantities of chemical intermediates and specialties. Potentially, the impact of these productions on the environment could have been much worse than it is, if a continuous efforts hadn’t been spent to improve the technologies employed. Substantial technological innovations have driven the development of new catalytic systems, the improvement of reactions and process technologies, contributing to move the chemical industry in the direction of a more sustainable and ecological approach. The roadmap for the application of these concepts includes new synthetic strategies, alternative reactants, catalysts heterogenisation and innovative reactor configurations and process design. Actually, in order to implement all these ideas into real projects, the development of more efficient reactions is one primary target. Yield, selectivity and space-time yield are the right metrics for evaluating the reaction efficiency. In the case of catalytic selective oxidation, the control of selectivity has always been the principal issue, because the formation of total oxidation products (carbon oxides) is thermodynamically more favoured than the formation of the desired, partially oxidized compound. As a matter of fact, only in few oxidation reactions a total, or close to total, conversion is achieved, and usually the selectivity is limited by the formation of by-products or co-products, that often implies unfavourable process economics; moreover, sometimes the cost of the oxidant further penalizes the process. During my PhD work, I have investigated four reactions that are emblematic of the new approaches used in the chemical industry. In the Part A of my thesis, a new process aimed at a more sustainable production of menadione (vitamin K3) is described. The “greener” approach includes the use of hydrogen peroxide in place of chromate (from a stoichiometric oxidation to a catalytic oxidation), also avoiding the production of dangerous waste. Moreover, I have studied the possibility of using an heterogeneous catalytic system, able to efficiently activate hydrogen peroxide. Indeed, the overall process would be carried out in two different steps: the first is the methylation of 1-naphthol with methanol to yield 2-methyl-1-naphthol, the second one is the oxidation of the latter compound to menadione. The catalyst for this latter step, the reaction object of my investigation, consists of Nb2O5-SiO2 prepared with the sol-gel technique. The catalytic tests were first carried out under conditions that simulate the in-situ generation of hydrogen peroxide, that means using a low concentration of the oxidant. Then, experiments were carried out using higher hydrogen peroxide concentration. The study of the reaction mechanism was fundamental to get indications about the best operative conditions, and improve the selectivity to menadione. In the Part B, I explored the direct oxidation of benzene to phenol with hydrogen peroxide. The industrial process for phenol is the oxidation of cumene with oxygen, that also co-produces acetone. This can be considered a case of how economics could drive the sustainability issue; in fact, the new process allowing to obtain directly phenol, besides avoiding the co-production of acetone (a burden for phenol, because the market requirements for the two products are quite different), might be economically convenient with respect to the conventional process, if a high selectivity to phenol were obtained. Titanium silicalite-1 (TS-1) is the catalyst chosen for this reaction. Comparing the reactivity results obtained with some TS-1 samples having different chemical-physical properties, and analyzing in detail the effect of the more important reaction parameters, we could formulate some hypothesis concerning the reaction network and mechanism. Part C of my thesis deals with the hydroxylation of phenol to hydroquinone and catechol. This reaction is already industrially applied but, for economical reason, an improvement of the selectivity to the para di-hydroxilated compound and a decrease of the selectivity to the ortho isomer would be desirable. Also in this case, the catalyst used was the TS-1. The aim of my research was to find out a method to control the selectivity ratio between the two isomers, and finally to make the industrial process more flexible, in order to adapt the process performance in function of fluctuations of the market requirements. The reaction was carried out in both a batch stirred reactor and in a re-circulating fixed-bed reactor. In the first system, the effect of various reaction parameters on catalytic behaviour was investigated: type of solvent or co-solvent, and particle size. With the second reactor type, I investigated the possibility to use a continuous system, and the catalyst shaped in extrudates (instead of powder), in order to avoid the catalyst filtration step. Finally, part D deals with the study of a new process for the valorisation of glycerol, by means of transformation into valuable chemicals. This molecule is nowadays produced in big amount, being a co-product in biodiesel synthesis; therefore, it is considered a raw material from renewable resources (a bio-platform molecule). Initially, we tested the oxidation of glycerol in the liquid-phase, with hydrogen peroxide and TS-1. However, results achieved were not satisfactory. Then we investigated the gas-phase transformation of glycerol into acrylic acid, with the intermediate formation of acrolein; the latter can be obtained by dehydration of glycerol, and then can be oxidized into acrylic acid. Actually, the oxidation step from acrolein to acrylic acid is already optimized at an industrial level; therefore, we decided to investigate in depth the first step of the process. I studied the reactivity of heterogeneous acid catalysts based on sulphated zirconia. Tests were carried out both in aerobic and anaerobic conditions, in order to investigate the effect of oxygen on the catalyst deactivation rate (one main problem usually met in glycerol dehydration). Finally, I studied the reactivity of bifunctional systems, made of Keggin-type polyoxometalates, either alone or supported over sulphated zirconia, in this way combining the acid functionality (necessary for the dehydrative step) with the redox one (necessary for the oxidative step). In conclusion, during my PhD work I investigated reactions that apply the “green chemistry” rules and strategies; in particular, I studied new greener approaches for the synthesis of chemicals (Part A and Part B), the optimisation of reaction parameters to make the oxidation process more flexible (Part C), and the use of a bioplatform molecule for the synthesis of a chemical intermediate (Part D).

Broadband RF current detector

The problems to be solved in this thesis were 1) development of a broadband RF preamplifier to be used with non-ferrous current probes so that the amplified signal exceeds the errors due to cable pickup, no detection is needed in this application, and 2) development of a self-contained device that amplifies and detects the output from a nonferrous current probe, providing a digital readout of the current. These instruments have been completed and are being tested for use by the National Institutes of Occupational Safety and Health (NIOSH). The self-contained current meter operates at frequencies up to 600 MHz, and detects currents as low as 8 mA . At these current magnitudes, the probe (pick-up coil) will output a voltage of 500μV (-53 dBm on 50Ω) which will have to be raised above 0 dBm. The final circuit uses a RF mixer as a variable attenuator in order to increase the dynamic range, two Monolithic Microwave Integrated Circuits (MMIC) for preamplification, a final broadband amplifier to raise the output compression point, a Schottky diode detector, a sample and hold circuit, and a liquid crystal digital panel meter.

The potential of solid phase microextraction (spme) for the recovery of explosives followed by gas and liquid chromatographic analysis

The potential of solid phase microextraction (SPME) in the analysis of explosives is demonstrated. A sensitive, rapid, solventless and inexpensive method for the analysis of explosives and explosive odors from solid and liquid samples has been optimized using SPME followed by HPLC and GC/ECD. SPME involves the extraction of the organic components in debris samples into sorbent-coated silica fibers, which can be transferred directly to the injector of a gas chromatograph. SPME/HPLC requires a special desorption apparatus to elute the extracted analyte onto the column at high pressure. Re suits for use of GC[ECD is presented and compared to the results gathered by using HPLC analysis. The relative effects of controllable variables including fiber chemistry, adsorption and desorption temperature, extraction time, and desorption time have been optimized for various high explosives.

Study of the tracking performance of a liquid Argon detector based on a novel optical imaging concept

The Deep Underground Neutrino Experiment (DUNE) is a long-baseline accelerator experiment designed to make a significant contribution to the study of neutrino oscillations with unprecedented sensitivity. The main goal of DUNE is the determination of the neutrino mass ordering and the leptonic CP violation phase, key parameters of the three-neutrino flavor mixing that have yet to be determined. An important component of the DUNE Near Detector complex is the System for on-Axis Neutrino Detection (SAND) apparatus, which will include GRAIN (GRanular Argon for Interactions of Neutrinos), a novel liquid Argon detector aimed at imaging neutrino interactions using only scintillation light. For this purpose, an innovative optical readout system based on Coded Aperture Masks is investigated. This dissertation aims to demonstrate the feasibility of reconstructing particle tracks and the topology of CCQE (Charged Current Quasi Elastic) neutrino events in GRAIN with such a technique. To this end, the development and implementation of a reconstruction algorithm based on Maximum Likelihood Expectation Maximization was carried out to directly obtain a three-dimensional distribution proportional to the energy deposited by charged particles crossing the LAr volume. This study includes the evaluation of the design of several camera configurations and the simulation of a multi-camera optical system in GRAIN.

Combining Monte Carlo simulation and density-functional theory to describe the spectral changes of Na(2) in liquid helium

Spectral changes of Na(2) in liquid helium were studied using the sequential Monte Carlo-quantum mechanics method. Configurations composed by Na(2) surrounded by explicit helium atoms sampled from the Monte Carlo simulation were submitted to time-dependent density-functional theory calculations of the electronic absorption spectrum using different functionals. Attention is given to both line shift and line broadening. The Perdew, Burke, and Ernzerhof (PBE1PBE, also known as PBE0) functional, with the PBE1PBE/6-311++G(2d,2p) basis set, gives the spectral shift, compared to gas phase, of 500 cm(-1) for the allowed X (1)Sigma(+)(g) -> B (1)Pi(u) transition, in very good agreement with the experimental value (700 cm(-1)). For comparison, cluster calculations were also performed and the first X (1)Sigma(+)(g) -> A (1)Sigma(+)(u) transition was also considered.

Polaron liquid-gas crossover at the orthorhombic-rhombohedral transition of manganites

High-resolution synchrotron x-ray powder diffraction in La(0.7)Ca(0.3)MnO(3) shows in detail a first-order structural phase transition from orthorhombic (space-group Pnma) to rhombohedral (space-group R (3) over barc) crystal structures near T(S)=710 K. Magnetic susceptibility measurements show that the rhombohedral phase strictly obeys the Curie-Weiss law as opposed to the orthorhombic phase. A concomitant change in the electrical resistivity behavior, consistent with an alteration from nonadiabatic to adiabatic small polaron hopping regimes, was also observed at T(S). The simultaneous change in transport and magnetic properties are identified as a transition from a correlated polaron liquid for TT(S), driven by the change in the crystal symmetry.

Part I : Comparing derivatization methods for amino acids – one and two-step procedures using gas chromatography – flame ion detector (GC-FID) Part II: Story of an icon from its execution until its conservation

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Conservação e Restauro

Development of new membranes based on ionic liquid materials for gas separation

In the field of energy, natural gas is an essential bridge to a clean, low carbon, renewable energy era. However, natural gas processing and transportation regulation require the removal of contaminant compounds such as carbon dioxide (CO2). Regarding clean air, the increasing atmospheric concentrations of greenhouse gases, specifically CO2, is of particular concern. Therefore, new costeffective, high performance technologies for carbon capture have been researched and the design of materials with the ability to efficiently separate CO2 from other gases is of vital importance.(...)

40 K Neon liquid energy storage unit

Cryocoolers have been progressively replacing the use of the stored cryogens in cryogenic chains used for detector cooling, thanks to their higher and higher reliability. However, the mechanical vibrations, the electromagnetic interferences and the temperature fluctuations inherent to their functioning could reduce the sensor’s sensitivity. In order to minimize this problem, compact thermal energy storage units (ESU) are studied, devices able to store thermal energy without significant temperature increase. These devices can be used as a temporary cold source making it possible to turn the cryocooler OFF providing a proper environment for the sensor. A heat switch is responsible for the thermal decoupling of the ESU from the cryocooler’s temperature that increases when turned OFF. In this work, several prototypes working around 40 K were designed, built and characterized. They consist in a low temperature cell that contains the liquid neon connected to an expansion volume at room temperature for gas storage during the liquid evaporation phase. To turn this system insensitive to the gravity direction, the liquid is retained in the low temperature cell by capillary effect in a porous material. Thanks to pressure regulation of the liquid neon bath, 900 J were stored at 40K. The higher latent heat of the liquid and the inexistence of triple point transitions at 40 K turn the pressure control during the evaporation a versatile and compact alternative to an ESU working at the triple point transitions. A quite compact second prototype ESU directly connected to the cryocooler cold finger was tested as a temperature stabilizer. This device was able to stabilize the cryocooler temperature ((≈ 40K ±1 K) despite sudden heat bursts corresponding to twice the cooling power of the cryocooler. This thesis describes the construction of these devices as well as the tests performed. It is also shown that the thermal model developed to predict the thermal behaviour of these devices, implemented as a software,describes quite well the experimental results. Solutions to improve these devices are also proposed.

40 K neon liquid energy storage unit

Cryocoolers have been progressively replacing the use of the stored cryogens in cryogenic chains used for detector cooling, thanks to their higher and higher reliability. However, the mechanical vibrations, the electromagnetic interferences and the temperature fluctuations inherent to their functioning could reduce the sensor’s sensitivity. In order to minimize this problem, compact thermal energy storage units (ESU) are studied, devices able to store thermal energy without significant temperature increase. These devices can be used as a temporary cold source making it possible to turn the cryocooler OFF providing a proper environment for the sensor. A heat switch is responsible for the thermal decoupling of the ESU from the cryocooler’s temperature that increases when turned OFF. In this work, several prototypes working around 40 K were designed, built and characterized. They consist in a low temperature cell that contains the liquid neon connected to an expansion volume at room temperature for gas storage during the liquid evaporation phase. To turn this system insensitive to the gravity direction, the liquid is retained in the low temperature cell by capillary effect in a porous material. Thanks to pressure regulation of the liquid neon bath, 900 J were stored at 40K. The higher latent heat of the liquid and the inexistence of triple point transitions at 40 K turn the pressure control during the evaporation a versatile and compact alternative to an ESU working at the triple point transitions. A quite compact second prototype ESU directly connected to the cryocooler cold finger was tested as a temperature stabilizer. This device was able to stabilize the cryocooler temperature ((≈ 40K ±1 K) despite sudden heat bursts corresponding to twice the cooling power of the cryocooler. This thesis describes the construction of these devices as well as the tests performed. It is also shown that the thermal model developed to predict the thermal behaviour of these devices,implemented as a software, describes quite well the experimental results. Solutions to improve these devices are also proposed.

Liquid chromatography-tandem mass spectrometry (LC/APCI-MS/MS) methods for the quantification of captan and folpet phthalimide metabolites in human plasma and urine.

Captan and folpet are fungicides largely used in agriculture. They have similar chemical structures, except that folpet has an aromatic ring unlike captan. Their half-lives in blood are very short, given that they are readily broken down to tetrahydrophthalimide (THPI) and phthalimide (PI), respectively. Few authors measured these biomarkers in plasma or urine, and analysis was conducted either by gas chromatography coupled to mass spectrometry or liquid chromatography with UV detection. The objective of this study was thus to develop simple, sensitive and specific liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry (LC/APCI-MS/MS) methods to quantify both THPI and PI in human plasma and urine. Briefly, deuterated THPI was added as an internal standard and purification was performed by solid-phase extraction followed by LC/APCI-MS/MS analysis in negative ion mode for both compounds. Validation of the methods was conducted using spiked blank plasma and urine samples at concentrations ranging from 1 to 250 μg/L and 1 to 50 μg/L, respectively, along with samples of volunteers and workers exposed to captan or folpet. The methods showed a good linearity (R (2) > 0.99), recovery (on average 90% for THPI and 75% for PI), intra- and inter-day precision (RSD, <15%) and accuracy (<20%), and stability. The limit of detection was 0.58 μg/L in urine and 1.47 μg/L in plasma for THPI and 1.14 and 2.17 μg/L, respectively, for PI. The described methods proved to be accurate and suitable to determine the toxicokinetics of both metabolites in human plasma and urine.

Indirect hydrogen analysis by gas chromatography coupled to mass spectrometry (GC-MS).

Gas chromatography (GC) is an analytical tool very useful to investigate the composition of gaseous mixtures. The different gases are separated by specific columns but, if hydrogen (H2 ) is present in the sample, its detection can be performed by a thermal conductivity detector or a helium ionization detector. Indeed, coupled to GC, no other detector can perform this detection except the expensive atomic emission detector. Based on the detection and analysis of H2 isotopes by low-pressure chemical ionization mass spectrometry (MS), a new method for H2 detection by GC coupled to MS with an electron ionization ion source and a quadrupole analyser is presented. The presence of H2 in a gaseous mixture could easily be put in evidence by the monitoring of the molecular ion of the protonated carrier gas. Copyright © 2013 John Wiley & Sons, Ltd.

Rapid high-performance liquid chromatographic determination with fluorescence detection of furosemide in human body fluids and its confirmation by gas chromatography-mass spectrometry.

Furosemide (FD: Lasix) is a loop diuretic which strongly increases both urine flow and electrolyte urinary excretion. Healthy volunteers were administered 40 mg orally (dissolved in water) and concentrations of FD were determined in serum and urine for up to 6 h for eight subjects, who absorbed water at a rate of 400 ml/h. Quantification was performed by HPLC with fluorescence detection (excitation at 233 nm, emission at 389 nm) with a limit of detection of 5 ng/ml for a 300-microliters sample. The elution of FD was completed within 4 min using a gradient of acetonitrile concentration rising from 30 to 50% in 0.08 M phosphoric acid. The delay to the peak serum concentration ranged from 60 to 120 min. FD was still easily measurable in the sera from all subjects 6 h after administration. In urine, the excretion rates reached their maximum between 1 and 3 h. The total amount of FD excreted in the urine averaged 11.2 mg (range 7.6-14.0 mg), with a mean urine volume of 3024 ml (range 2620-3596 ml). Moreover, the urine density was lower than 1.010 (recommended as an upper limit in doping analysis to screen diuretics) only for 2 h. An additional volunteer was administered 40 mg of FD and his urine was collected over a longer period. FD was still detectable 48 h after intake. Gas chromatography-mass spectrometry with different types of ionization was used to confirm the occurrence of FD after permethylation of the extract. Negative-ion chemical ionization, with ammonia as reactant gas, was found to be the most sensitive method of detection.

Response-to-comments about: "Is it really the method for carbon dioxide determination in human postmortem cardiac gas samples using Headspace-Gas Chromatography-Mass Spectrometry valid?" from T. Saffaj and B. Ihssane

Saffaj et al. recently criticized our method of monitoring carbon dioxide in human postmortem cardiac gas samples using Headspace-Gas Chromatography-Mass Spectrometry. According to the authors, their demonstration, based on the latest SFSTP guidelines (established after 2007 [1,2]) fitted for the validation of drug monitoring bioanalytical methods, has put in evidence potential errors. However, our validation approach was built using SFSTP guidelines established before 2007 [3-6]. We justify the use of these guidelines because of the post-mortem context of the study (and not clinical) and the gaseous state of the sample (and not solid or liquid). Using these guidelines, our validation remains correct.