Screening the origin and weathering of oil slicks by attenuated total reflectance mid-IR spectrometry

The combination of attenuated total reflectance-fourier transform mid-infrared spectrometry (ATR-FTMIR) and multivariate pattern recognition is presented as a fast and convenient methodology to ascertain the source product an oil slick comes from and to evaluate the extent of its weathering. Different types of hydrocarbons (including crude oils, several heavy distillates and the Prestige's heavy fuel oil) were spilled on metallic containers designed ad hoc and their fate monitored by ATR-FTMIR. Not only environmental conditions were considered for weathering but artificial IR- and UV-irradiation. Pattern-recognition studies revealed that the different hydrocarbons clustered at different locations on the score plots and that the samples corresponding to each oil became ordered according to the extent of their weathering. Among them, fuel oil samples coming from the recent disaster of the Prestige tanker off the Galician shoreline showed a distinctive behaviour. Comparison of natural-, IR- and UV-weathering of a crude oil showed that IR solar radiation can be important in oil-weathering, in addition to broadly-reported UV degradation.     

Kinetic analysis of thermogravimetric data,V

The statistical analysis of activation energy and of logZ values derived from thermogravimetric data for 134 decomposition reactions of bisdioximatocobalt(III) complexes shows the validity of a linear compensation law, i.e. both the effects of heating rate and of the nature of the ligand manifest themselves in the kinetic compensation effect. The parametera of the compensation law is sensitive to ligand effects and its value is influenced both by the nature of the coordinated dione-dioxime and by the nature of the outer sphere anion X, which replaces an ammonia molecule in the thermal decomposition reaction.

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Zusammenfassung Die statistische Analyse der aus den thermogravimetrischen Resultaten erhaltenen Aktivierungsenergiewerte und log Z-Werte von 134 Zersetzungsreaktionen der verschiedenen bisdioxamato Kobalt(III) Komplexen zeigte die Gültigkeit eines Gesetzes der linearen Kompensation, d.h. der Effekt der Heizungsgeschwindigkeit und der Natur des Liganden verursachten in erster Näherung den kinetischen Kompensationseffekt. Parametera des Kompensationsgesetzes (1) repräsentiert den Ligandeffekt. Sein Wert wird durch die Natur des koordinierten Dion-dioxims und des Anions X in der äußeren Sphäre beeinflußt, das ein Aminmolekül während der thermischen Zersetzungsreaktion ersetzt.

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Résumé L'analyse statistique des valeurs des énergies d'activation et de celles de logZ obtenues à partir des résultats thermogravimétriques de 134 réactions de décomposition des complexes différent de bisdioximato-cobalt(III) montre la validité d'une loi de compensation linéaire du type (1); ceci signifie que l'effet de la vitesse de chauffage et celui de la nature du ligand sont responsables en première approximation de l'effet de compensation cinétique. Le paramètrea de la loi de compensation est sensible aux effets du ligand et la nature de la bis-dioxime coordonnée ainsi que la nature de l'anion X dans la sphère externe remplaÇant une molécule d'aminé durant la réaction de décomposition thermique influencent sa valeur.

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logZ, 134 - (III), . a - X, .

     

Barreleneiridium(I) complexes. Crystal structures of [Ir(Me3TFB)(η6-C6H4Me2)]ClO4 and [Ir(TFB)(η5-PhNPh2)]BF4·CH2Cl2 (TFB = tetrafluorobenzobarrelene)

A new series of cationic areneiridium(I) complexes of formula [Ir(barrelene)(arene)]⁺ or [Ir(barrelene)(PhNRPh)]⁺ (R= Ph or H) have been synthesized from neutral iridium complexes of the type [IrY(barrelene)]_x (barrelene = Me₃TFB, Y = Cl or OMe (x = 2), Y = acac (x = 1); barrelene = TFB, Y = OMe (x = 2), Y = acac (x = 1)). The crystal structures of [Ir(Me₃TFB)(1,4-C₆H₄Me₂)]ClO₄ and [Ir(TFB)(PhNPh₂)]BF₄·CH₂Cl₂ have been determined by X-ray diffraction. They crystallize in the space groups Pbca and Pna2₁ respectively with lattice constants of 17.6947(11), 15.8072(10), 16.0019(11) Å and 9.8059(2), 20.8097(9), 14.3367(4) Å. Final R factors were 0.063 and 0.042 for the observed data. Both complexes show a staggered arrangement between the arene and the TFB moieties and deviation from planarity of the coordinated arene ligands. In the second complex the IrC and NC distances, the CNC angle, the type of arene puckering, and the spectroscopic data indicate a distortion of the coordinated arene towards a η⁵-coordinated iminocyclohexadienyl form.     

Analysis of99Tc atmospheric samples

The analysis of⁹⁹Tc was carried out in filter, peat and rainwater samples. A solvent extraction technique was used to separate Tc from them, where tributylphosphate was the extracting agent. Radiochemical yield was obtained by using^99mTc as an internal tracer. A typical value of 60% was found for it. However, problems encountered in its determination are discussed in the text. Additionally, rainwater samples were analyzed for¹³⁷Cs. This was adsorbed in ammonium phosphomolibdate. Radiochemical yield was obtained by using¹³⁴Cs as an internal tracer.Work partially supported under Contract CAICYT No. 2849/83.     

Kinetics and mechanism of substitution reactions of complexes,XX

Thermal decomposition of 21 complexes of the type [Co(DH)₂(amine)₂]NCS has been studied under the conditions of thermogravimetric analysis, by using different heating rates. From the thermogravimetric curves apparent kinetic parameters of the pyrolysis reaction have been derived by means of the modified Doyle method. Apparent reaction order increases and apparent activation energy decreases with increasing heating rate. Thus, the obtained kinetic parameters do not characterize the purely chemical reaction, but the complex heterogeneous process as a whole. The explanation of the observed effect is discussed. Results are compared with those obtained with other analogous complexes.

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Zusammenfassung Die thermische Zersetzung von 21 Komplexen des Typs [Co(DH)₂(Amin)₂]NCS wurde thermogravimetrisch bei verschiedenen Aufheizungsgeschwindigkeiten untersucht. Aus den TG-Kurven wurden die scheinbaren kinetischen Parameter der Reaktion mit Hilfe der Doyleschen Methode ermittelt. Bei zunehmender Aufheizungsgeschwindigkeit wächst die scheinbare Reaktionsordnung während die scheinbare Aktivierungsenergie abnimmt. Die erhaltenen chemischen Parameter kennzeichnen nicht die eigentliche chemische Reaktion, sondern den ganzen komplexen heterogenen Vorgang. Die beobachteten Effekte wurden diskutiert und die Ergebnisse verglichen mit Resultaten von Untersuchungen anderer analoger Komplexe.

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Résumé On a étudié par thermogravimétrie, avec différentes vitesses d'échauffement, la décomposition thermique de 21 complexes du type [Co(DH)₂(amine)₂SCN. On a calculé suivant la méthode deDoyle les paramètres cinétiques apparents déduits des courbes d'ATG. L'ordre apparent de la réaction augmente si la vitesse d'échauffement croît, alors que l'énergie d'activation apparente décroît. Les paramètres cinétiques obtenus ne caractérisent que le processus hétérogène complexe et non la réaction chimique proprement dite. Les effets observés ont été discutés et comparés avec les résultats obtenus avec d'autres complexes analogues.

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21 [(D)₂()₂]NS , . . . , , . . , .

     

Passive method for the determination of the equilibrium factor between 222Rn gas and its short period progeny

This work describes a method which was developed to determine the concentration of ²²²Rn gas and the equilibrium factor F between the concentration of the gas and its progeny by means of a single device that uses two Makrofol passive track detectors. The device is completely passive and time integrated. Conditions make it very appropriate to be used in any atmospheres in which human activity takes place, such as houses, schools, works and underground mines. A series of measurements of ²²²Rn gas concentration and equilibrium factor F were made in different cities of the Argentine Republic and the corresponding levels of doses were estimated.     

Thermal behaviour of thallium(I) fatty acid salts,II

The electrical conductivity (EC) changes of thallium(I) salts of fatty acids, which possess liquid crystalline phases, were investigated as a function of temperature. It was found that sharp EC jumps are associated with the phase transitions. The EC of the liquid crystalline phases depended not only on the temperature, the molecular weight and the geometry of the measuring cell, but also very sensitively on the heat treatment conditions which affect the relative magnitude of the EC in the mesophases.Study of these dependences revealed a memory effect. An explanation is given for this phenomenon.

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Zusammenfassung Die Änderungen der elektrischen Leitfähigkeit (EC) von Fettsäure-Thalium(I)-Salzen mit flüssig-kristallinen Phasen wurden als Funktion der Temperatur untersucht. Es wurde festgestellt, daß den Phasenübergängen scharfe EC-Sprünge entsprechen. Die EC der flüssig-kristallinen Phase hängt nicht nur von der Temperatur, dem Molekulargewicht und der Geometrie der Meßzelle ab, sondern auch — in sehr empfindlicher Weise — Phasen bestimmen.Die Untersuchung dieser Zusammenhänge führte zur Beobachtung eines »Memorieeffektes« Eine Erklärung dieser Erscheinung wird gegeben.

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Résumé On a étudié les variations de la conductibilité électrique (EC) des sels de thallium(I) des acides gras possédant des phases cristallines liquides, en fonction de la température. On a établi que les variations brusques d'EC correspondent aux transitions de phases. L'EC des phases cristallines liquides dépend non seulement de la température, de la masse molaire et de la géométrie de la cellule de mesure, mais aussi, et d'une manière très sensible, des conditions du traitement thermique qui affectent l'amplitude relative de l'EC dans les mésophases.Un «effet de mémoire» a été observé lors de l'étude de ces phénomènes, dont on donne une explication.

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(I) , , . , . - , , , . « ». .

     

Thermal behaviour or thallium(I) fatty acid salts,I

We have studied the thermal behaviours of the fatty acid (C₁-C₉, C₁₂, C₁₄, C₁₆ and C₁₈) thallium(I) salts.Investigating the dependence of the thermal decomposition reactions on the experimental conditions, we established that they decompose differently depending on the atmosphere, and on the shape and material of the sample holders.We also determined the heat-stable temperature ranges of the compounds in which they can be investigated without any thermal decomposition.The temperatures and enthalpy changes of the polymorphic and phase changes were measured and the corresponding entropy changes were calculated.

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Zusammenfassung Das thermische Verhalten der Thallium(I)-Salze der Fettsäuren mit C₁ bis C₉, C₁₂, C₁₄ und C₁₈ wurden untersucht. Die Temperaturen und Enthalpien der einzelnen polymorphen und Phasenänderungen, sowie die thermische Stabilität der Verbindungen wurden bestimmt. Es wurde festgestellt, daß die zu Ketonen und Gemischt-Ketonen führende thermische Zersetzung in der Schmelzphase von Destillationsprozessen begleitet wird, welche von der Molekülstruktur und von zahlreichen Versuchsbedingungen abhängig sind.

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Résumé Etude du comportement thermique des sels de thallium(I) d'acides gras (de C₁ à C₉, C₁₂, C₁₄ et C₁₈). L'étude de la décomposition thermique en fonction des conditions expérimentales a permis d'établir que les sels étudiés se décomposent différemment suivant l'atmosphère utilisée, ainsi que suivant la forme et la nature des supports échantillons. Détermination des domaines de température où ces composés restent thermiquement stables. Mesure des températures et des variations d'enthalpie des transitions de phase et des transitions polymorphiques et calcul des variations d'entropie correspondantes.

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(I) C₁-C₉, C₁₂, C₁₄, C₁₆, C₁₈. , . , , , .

     

Kinetic analysis of thermogravimetric data

Four many curves methods, viz. calculation techniques based on Eqs (30), (31), (34) and (36), respectively, for deriving kinetic parameters from several TG curves recorded with different heating rates are tested on two sets of theoretical TG curves. The maximum reaction rate temperature and conversion, as well as the approximate formulae used for their calculation are discussed. Some aspects of the kinetic compensation effect are analysed. The final conclusion is that the use of the many curves methods is not reasonable.     

Terbium-sensitized luminescence determination of levofloxacin in tablets and human urine and serum

A selective and sensitive luminescence method for the determination of levofloxacin is described. The method is based in the luminescence signal from a terbium(III)-levofloxacin complex, in a micellar solution of sodium dodecyl sulfate (SDS), using a chemical deoxygenation agent (Na2SO3). The method allows the determination of 8-600 ng mL-1 of levofloxacin in 10 mM SDS solution containing 0.04 M acetic acid-sodium acetate buffer (pH 6) and 7.5 mM Na2SO3 with lambda exc = 292 nm and lambda em = 546 nm. The luminescence method was applied to the determination of the levofloxacin in a Spanish commercialized pharmaceutical formulation Tavanic (Hoechst Marion Roussel). Good concordance was found between the nominal and experimental values (500 and 488 mg, respectively), with a relative standard deviation (RSD) of 0.6%. The proposed method was shown to be 100-fold more sensitive than the spectrophotometric method, and nearly 2-fold more sensitive than the fluorescence method. The method was also applied to levofloxacin determination in human serum (by external calibration method) and urine (by standard additions method), spiked at levels found after drug administration at normal clinical doses. Average recoveries found were 90.1 (RSD 1%) and 102 (RSD 1.9%), respectively.