Investigation of the Belousov-Zhabotinsky reaction by thermal lensing

The supramolecular interaction of rubidate (chemically 2,3-naphthalenedicarboxylic acid, 1,4-dihydroxy-diethyl ester) and beta-cyclodextrin (beta-CD) has been studied by spectrofluorimetry. The influence of temperature on the supramolecular system has also been investigated and the thermodynamic parameters were calculated. The results show that beta-CD reacts with rubidate to form a 1:1 host-guest complex with an apparent association constant of 566+/-23 l mol(-1). It was also demonstrated that the thermodynamics of beta-CD-rubidate complex displayed a compensatory enthalpy-entropy relationship. Based on the significant enhancement of the fluorescence intensity of rubidate produced through complex formation, a spectrofluorimetric method for the determination of rubidate in bulk aqueous solution in the presence of beta-CD was developed. The linear relationship between the fluorescence intensity and rubidate concentration was obtained in the range from 2.7x10(-2) to 3.0 mug ml(-1), with a correlation coefficient of 0.9988. The detection limit was 8.2 ng ml(-1) and the relative standard deviation was 1.6%. There was no interference from the excipients normally used in tablet formulations. The application of the present method to the determination of rubidate in tablets gave satisfactory results and was compared with the reference method.     

The two-photon spectrum of liquid pyridine by thermal lensing techniques

Thermal lensing is exploited to investigate the electronic properties of pyridine. The two-photon spectrum and polarization ratio of liquid pyridine has been measured from 2900 to 2000 Å. Absorptions corresponding to the two lowest ππ* states, of benzene parentage, and to the second excited nπ* state have been assigned. The latter, of A₂ symmetry, borrows two-photon intensity from A₁ states through vibronic coupling induced by a₂ vibrations. Calculations of allowed contributions to the two-photon cross sections for the lowest four excited levels support the assignment.     

Ultraviolet thermal lensing detection of amino acids

Thermal lensing (TL) permits ultra-sensitive measurements of optical absorption of analytes in very small liquid volumes. We report the construction and use of a TL detector based on pulsed ultraviolet (UV) laser excitation (266 nm). We applied this detector to quantitate amino acids using capillary electrophoresis (CE) as a means of separation. Sixteen individual amino acids are readily detected, but the signal has a complex dependence on intensity caused by the combination of (1) one-photon absorption; (2) two-photon absorption (TPA); and (3) photodestruction of amino acid molecules in the focus of the laser beam. An aqueous solution containing tyrosine, tryptophan, and cysteine is electrophoretically separated and the individual amino acids are detected by UV TL. The estimated limit of detection is 7 microM for tyrosine, 2.5 microM for tryptophan and 33 microM for cysterine, which translates into 0.35 fmol for tyrosine, 0.125 fmol for tryptophan, and 1.65 fmol for cysteine in the 140pL detection volume. It is found that two-photon absorption of water and the formation of color centers in the fused silica walls of the flowcell can contribute a significant, drifting background signal, but this interference can be minimized by selecting an appropriate focus condition and excitation-detection geometry. We suggest that as UV laser sources become available, UV TL may become a method of choice for measuring the concentrations of many analytes in different separation formats in which the volume is highly limited.     

The use of thermal analysis in the approximate determination of the cement content in concrete

Thermal analysis was first used to investigate the pattern of dissociation of hydrated ordinary Portland cement. Portlandite (Ca(OH)₂) decomposes at about 500°C. This was confirmed by kinetic calculations. Thermal analysis was then performed to establish the effect of varying the cement content on the percent mass loss associated with the decomposition of Ca(OH)₂ in cement mortar cured for 28 days. An increasing relation was obtained. Standard concrete cubes were then prepared with cement contents ranging from 200 to 450 kg m^-3. The loss in mass on heating, up to 750°C, of concrete samples cured for 28 days was then related to the cement content in concrete. The relation obtained was tested for concrete cubes of known cement content and found to be in better agreement than the results obtained by conventional chemical analysis. This method can be used for an approximate determination of the cement content in concrete. This revised version was published online in July 2006 with corrections to the Cover Date.     

The use of thermal analysis in determination of some urinary calculi of calcium oxalate

The human urinary calculi are mainly constituted by calcium oxalate, magnesium ammonium phosphate hexahydrate, and uric acid. The ions or molecules are easily characterized by wet chemical methods. The difficulties appear in the differentiation of the hydrates of calcium oxalate (monohydrate COM or Whewellite, and dihydrate COD or Weddelite). A high level of COD in the urinary stones leads, often, inflammation, sharp pain and blood in urine. In the worse cases, they must be extracted by surgical way. The identification of the main components of urinary calculi, the knowledge of the true number of water molecules bounded to the calcium oxalate, and the determination of each hydrate in the mixture, are the interests of this memory. The thermal analysis (simultaneous DTA-TG) was applied on thirty-three urinary calculi. The determination of the calcium oxalate hydrates was confirmed by calorimetry (DSC). This revised version was published online in July 2006 with corrections to the Cover Date.     

The use of thermal techniques in the determination of the phase diagram of lanthanide salt based polymer electrolytes

Differential thermal analysis, optical microscopy and ionic conductivity studies have been carried out on polymer electrolyte films prepared by deposition of solutions of neodymium trifluoromethanesulphonate and poly(ethylene oxide). A wide range of electrolyte concentrations were examined and a partial pseudo-equilibrium phase diagram of the system was determined. From the results obtained it is evident that the presence of relatively high concentrations of ionic guest species in the polymer host results in an inhibition of the growth of crystalline material (polymer spherulites or a polymer—salt coordination complex).     

The studies of the reaction of bismuth(III) with iodide at nanogram level by thermal lensing

By the example of the analytical system based on the reaction of bismuth with iodide, it is shown that thermal lens spectrometry can be used for studying changes in analytical reactions at the nanogram level of reactants. The stability constants of bismuth(III) iodides at the concentration level are found. The solubility constants of iodides of metals interfering with bismuth determination are estimated. It is shown that the due regard to the new conditions could enhance the sensitivity and selectivity of determination.     

A thermal lensing study of a photolysis of di-t-butyl peroxide

A photolysis of di-t-butyl peroxide (BOOB) was studied by using a thermal lensing technique. This technique is found to be applicable to the determination Of the rate Constants of the decay of t-butoxy radical (BO ) and the hydrogen abstraction reaction.     

The use of furfural thiosemicarbazone for the gravimetric determination of palladium

The use of furfural thiosemicarbazone as a gravimetric reagent for palladium is described. The optimum analytical conditions for precipitation of the palladium complex and the effect of possible interferences have been investigated.     

The determination of thermal junction potential difference

A novel method has been designed and exploited to determine the thermal junction potential difference(TJPD) between two acids or alkalies of the same composition but with different temperature. The absolute value of measured TJPD between two strong acids(or alkalies) maintained at different temperatures increases with increasing of the temperature difference between the two electrolytes over the range from 0 to 40 °C. In strong acids, the hot end always has the lower potential while in strong alkalies, the cold end has the lower potential. This is because the ions of fast diffusion rate contribute most to the TJPD. Our results demonstrate the importance of the correction for TJPD in deriving the kinetic parameters when studying the temperature effect on reaction kinetics.     

The use of radionuclides for the determination of adsoroption isotherms of volatile chlorides

It is demonstrated that gas-solid chromatography is a useful method for the investigation of the adsorption, properties of inorganic compounds at temperatures up to 1100 K. The use of radioisotopes enables the application of this method to extreme small concentrations and surface areas. Adsorption entropies and enthalpies for various chlorides on a quartz glass surface are presented, as well as several other adsorption data of inorganic chlorides. The possibility to use data obtained by this method for the optimization of separations is shown.     

The use of copper solid amalgam electrodes for determination of the pesticide thiram

The complexes formed between copper and thiram and between mercury and thiram have been electrochemically (voltammetrically) investigated in the present work. Their structure was confirmed using electrospray ionization mass spectrometry. Due to formation of the complex between copper (from copper solid amalgam electrode) and thiram, the concentration of this pesticide can be determined. The voltammetric behavior of thiram was investigated at polished (p-CuSAE) and mercury meniscus modified (m-CuSAE) copper solid amalgam electrodes (inner diameter 1.5 mm) by differential pulse voltammetry (DPV) and by direct current voltammetry (DCV). Optimum conditions for DPV determination of thiram were found in Britton–Robinson buffer. The reaction mechanism was investigated using DCV and elimination voltammetry with linear scan. DPV with optimized parameters was applied for determination of thiram in analyzed solutions. The limits of detection were calculated as 16 nmol?L^?1 (t _acc?=?100 s) for m-CuSAE and 23 nmol?L^?1 (t _acc?=?60 s) for p-CuSAE. The proposed method was successfully applied for thiram determination in real sample solutions.     

The use of thermal analysis methods for authentication and conservation state determination of historical and/or cultural objects manufactured from leather

Leather products have been useful materials since the dawn of human history. Many leathers objects are valuable treasures due to the history they represent, and their preservation challenges museum custodians and private collectors alike. In this article, the applications of thermal analysis methods (Micro Hot Table (MHT), thermogravimetry/derivative thermogravimetry (TG/DTG), dynamic scanning calorimetry (DSC), differential thermal analysis (DTA), and dynamic mechanical analysis (DMA)) for the characterization of the recently manufactured and old leathers are presented. These methods can be used for the assessment of deterioration degree of leathers, and, therefore, the data obtained by these techniques could be useful for achievement of the suitable preservation procedures as well as the effects of conservation treatments. In addition, it was pointed out that these methods are suitable for qualitative distinction between the recently manufactured leathers and heritage items.     

The use of emanation thermal analysis for the investigation of radioactive waste fixation processes

The process of incorporation of radioactive wastes into a suitable matrix to form a stable product for long term disposal has been studied. The changes, occuring during the thermal treatment with glassy materials, i.e. drying, transformation processes, sintering, melting, etc. have been followed using emanation (radon) thermal analysis. This method was found useful in solving the problems of process development.     

The use of thermal analysis methods for conservation state determination of historical and/or cultural objects manufactured from lime tree wood

The TG, DTG and DSC methods were used for investigation of the thermo-oxidative degradation in static air atmosphere and oxygen flow of some sorts of lime tree wood (recent lime tree woods with different preparations, old lime tree woods extracted from some Romanian historical and/or cultural objects). At the progressive heating in the mentioned atmospheres, all the investigated materials exhibit three successive processes, associated with dehydration and two complex thermo-oxidative processes. Each analyzed material has a characteristic thermogram (TG, DTG and/or DSC curve) that can be considered a material “fingerprint”. It was pointed out that the following non-isothermal parameters can be used for distinction between a new and old lime tree wood: mass loss in the first process of thermo-oxidation, ratio between the mass losses in the first and the second processes of thermo-oxidation, the maximum rate of the first process of thermo-oxidation. Consequently, the certification of a patrimonial object manufactured from lime tree wood could be performed by applying the thermal analysis methods.     

The use of thermal analysis to predict the thermal life of organic electrical insulating materials

Three different thermoanalytical methods are introduced as significant time-saving techniques in conventional life tests of some organic electrical insulating materials. DTA in cyclically alternated atmospheres of nitrogen and oxygen according to Randino and Andreotti, and TG analysis methods at different heating rates according to Flynn and Wall and to Broido were applied to two electrical insulations based on aromatic poly-imide and epoxy resin. The activation energies obtained are compared with those derived from the slopes of the life-lines produced via conventional life tests. The assumptions necessary for applying the thermal analyses in these cases are discussed.

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Zusammenfassung Drei verschiedene thermoanalytische Methoden werden als wesentlich zeitsparende Techniken bei der üblichen Prüfung der Lebensdauer einiger organischer elektrischer Isoliermaterialien beschrieben. DTA in zyklisch wechselnden Atmosphären von Stickstoff und Sauerstoff nach Randino und Andreotti und Methoden der TG-Analyse bei verschiedenen Aufheizgeschwindigkeiten nach Flynn und Wall und Broido wurden bei zwei elektrischen Isolierstoffen auf aromatischer Polyimid und Epoxyd-Harz Basis eingesetzt. Die erhaltenen Aktivierungsenergien werden mit den aus der Neigung der an Hand konventioneller Lebensdauertests erhaltenen Lebenslinien verglichen. Die nötigen Voraussetzungen zur Anwendung der Thermoanalyse in diesen Fällen werden erörtert.

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Résumé On présente trois méthodes thermoanalytiques différentes qui permettent de réaliser un gain de temps important lors de l'examen conventionnel de la durée de vie de quelques isolants électriques organiques. L'analyse termique différentielle en atmosphères cycliquement alternées d'azote et d'oxygène, suivant Randino et Andreotti, et la thermogravimétrie avec différentes vitesses de chauffage, suivant Flynn et Wall et Broido, ont été appliquées à deux isolants électriques à base de polyimide aromatique et de résine époxy. Les énergies d'activation obtenues sont comparées à celles déduites de la pente des lignes de vie, obtenues par des examens conventionnels de durée de vie. Les approximations nécessaires pour appliquer l'analyse thermique à ces différents cas sont discutées.

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Two-photon absorption of liquid pyridine: a study using thermal lensing and cars spectroscopy.

The two-photon spectrum of liquid pyridine has been obtained by thermal lensing and CARS bandshape analysis. Four transitions have been detected between 315 and 200 nm. The maximum occurring at 244 nm has been assigned to the two-photon allowed n>π* transition of A₂ symmetry.