Extremely low vapor‐pressure data as access to PC‐SAFT parameter estimation for ionic liquids and modeling of precursor solubility in ionic liquids

Precursor solubility is a crucial factor in industrial applications, dominating the outcome of reactions and purification steps. The outcome and success of thermodynamic modelling of this industrially important property with equations of states, such as Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT), vastly depends on the quality of the pure-component parameters. The pure-component parameters for low-volatile compounds such as ionic liquids (ILs) have been commonly estimated using mixture properties, e. g. the osmotic pressure of aqueous solutions. This leads to parameters that depend on the solvent, and transferability to other mixtures often causes poor modeling results. Mixture-independent experimental properties would be a more suitable basis for the parameter estimation offering a way to universal parameter sets. Model parameters for ILs are available in the literature [10.1016/j.fluid.2012.05.029], but they were estimated using pure-IL density data. The present work focuses on a step towards a more universal estimation strategy that includes new experimental vapor-pressure data of the pure IL. ILs exhibit an almost negligible vapor pressure in magnitude of usually 10−5 Pa even at elevated temperatures. In this work, such vapor-pressure data of a series of 1-ethyl-3-methyl-imidazolium-based [C2mim]-ILs with various IL-anions (e. g. tetrafluoroborate [BF4]−, hexafluorophosphate [PF6]−, bis(trifluoromethylsulfonyl)imide [NTf2]−) were experimentally determined and subsequently used for PC-SAFT parameter estimation. The so-determined parameters were used to predict experimental molecular precursor solubility in ILs and infinitely diluted activity coefficients of various solvents in ILs. The parameters were further compared to modeling results using classical parametrization methods (use of liquid-density data only for the molecular PC-SAFT and the ion-based electrolyte PC-SAFT). As a result, the modeled precursor solubilities using the new approach are much more precise than using the classical parametrization methods, and required binary parameters were found to be much smaller (if needed). In sum, including the pure-component vapor-pressure data of ILs opens the door towards parameter estimation that is not biased by mixture data. This procedure might be suitable also for polymers and for all kind of ionic species but needs extension to ion-specific parametrization in the long term

The melting properties of D-α-glucose, D-β-fructose, D-sucrose, D-α-galactose, and D-α-xylose and their solubility in water: a revision

Saccharides are still commonly isolated from biological feedstock by crystallization from aqueous solutions. Precise thermodynamic data on solubility are essential to optimize the downstream crystallization process. Solubility modeling, in turn, requires knowledge of melting properties. In the first part of this work, following our previous work on amino acids and peptides, D-α-glucose, D-β-fructose, D-sucrose, D-α-galactose, and D-α-xylose were investigated with Fast Scanning Calorimetry (FSC) in a wide scanning rate range (2000 K·s−1 to 10000 K·s−1). Using the experimental melting properties of saccharides from FSC allowed successfully modeling aqueous solubility for D-sucrose and D-α-galactose with the equation of state PC-SAFT. This provides cross-validation of the measurement methods to determine accurate experimental melting properties with FSC. Unexpectedly, the experimental FSC melting temperatures, extrapolated to zero scanning rates for thermal lag correction, were higher than results determined with DSC and available literature data. To clarify this inconsistency, FSC measurements towards low scanning rates from 10000 K·s−1 to 1 K·s−1 (D-α-glucose, D-β-fructose, D-sucrose) overlapping with the scanning rates of DSC and literature data were combined. At scanning rates below 1000 K·s−1, the melting properties followed a consistent non-linear trend, observed in both the FSC and the literature data. In order to understand the non-linear decrease of apparent melting temperatures with decreasing heating rate, the endothermic peaks were investigated in terms of isoconversional kinetics. The activation energies in the non-linear dependency region are in the range of 300<EA<600kJ∙mol−1. These values are higher than the enthalpy of sublimation for D-α-glucose, indicating that the non-linear behavior does not have a physical nature but attributes to chemical processes corresponding to the decomposition of molecular compounds within the crystal lattice before melting. The melting properties reported in the literature, commonly determined with conventional methods such as DSC, lead to inaccurate results due to the decomposition of these biomolecules at low heating rates. In addition, the FSC results at lower scanning rates coincide with results from DSC and literature in the overlapping scanning rate range, further validating the accuracy of FSC measurements to determine reliable melting properties of thermally labile biomolecules. The experimental FSC melting properties determined at higher scanning rates are considered as the correct equilibrium melting properties, which are not influenced by any chemical processes. The combination of FSC and PC-SAFT opens the door to model solubility of solid compounds that commonly decompose before melting

Hydrogen Bonding Between Ions of Like Charge in Ionic Liquids Characterized by NMR Deuteron Quadrupole Coupling Constants—Comparison with Salt Bridges and Molecular Systems

We present deuteron quadrupole coupling constants (DQCC) for hydroxyl-functionalized ionic liquids (ILs) in the crystalline or glassy states characterizing two types of hydrogen bonding: The regular Coulomb-enhanced hydrogen bonds between cation and anion (c–a), and the unusual hydrogen bonds between cation and cation (c–c), which are present despite repulsive Coulomb forces. We measure these sensitive probes of hydrogen bonding by means of solid-state NMR spectroscopy. The DQCCs of (c–a) ion pairs and (c–c) H-bonds are compared to those of salt bridges in supramolecular complexes and those present in molecular liquids. At low temperatures, the (c–c) species successfully compete with the (c–a) ion pairs and dominate the cluster populations. Equilibrium constants obtained from molecular-dynamics (MD) simulations show van't Hoff behavior with small transition enthalpies between the differently H-bonded species. We show that cationic-cluster formation prevents these ILs from crystallizing. With cooling, the (c–c) hydrogen bonds persist, resulting in supercooling and glass formation. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA

New experimental melting properties as access for predicting amino-acid solubility

The properties of melting are required for the prediction of solubility of solid compounds. Unfortunately, direct determination of the enthalpy of fusion and melting temperature by using conventional DSC or adiabatic calorimetry is often not possible for biological compounds due to decomposition during the measurement. To overcome this, fast scanning calorimetry (FSC) with scanning rates up to 2 × 104 K s−1 was used in this work to measure the melting parameters for L-alanine and glycine. The enthalpy of fusion and melting temperature (extrapolated to zero heating rate) were ΔfusH = (22 ± 5) kJ mol−1 and Tfus = (608 ± 9) K for L-alanine, and ΔfusH = (21 ± 4) kJ mol−1 and Tfus = (569 ± 7) K for glycine. These melting properties were used in the modeling framework PC-SAFT to predict amino-acid solubility in water. The pure-component PC-SAFT parameters and one binary parameter were taken from literature, in which these parameters were fitted to solubility-independent thermodynamic properties such as osmotic coefficients or mixture densities. It was shown that this allowed accurately predicting amino-acid solubility in water over a broad temperature range. The combined methodology of PC-SAFT and FSC proposed in this work opens the door for predicting solubility of molecules that decompose before melting

Degree of equivalence between writing and speech using German as an example

Związek między pismem a mową był przedmiotem badań językoznawców od kilku stuleci i właściwie do dnia dzisiejszego nie osiągnięto w tej kwestii ogólnego porozumienia. Istnieje wiele różnych poglądów na temat pisma: od takich, które traktują pismo jako system odrębny od mowy, po takie, które nie przypisują pismu żadnej roli.Owo pytanie, mimo teoretycznie wzbogacających korzyści, nie ma jednak większego znaczenia, gdy chodzi o pismo jako artefakt życia człowieka. Bez wątpienia można je rozpatrywać jako przedmiot badań naukowych.Analiza przeprowadzona w niniejszej pracy ma na celu zachęcenie do nowego sposobu badania pisma, opartego na metodach ilościowych. Badania tego rodzaju mają wnieść pewną jasność w odpowiedzi na pytanie, jaki stopień równoważności można uznać za wzorcowy, tak aby przyszłe reformy ortograficzne mogły oprzeć na nim swoje wytyczne.W niniejszej pracy wysunięto na pierwszy plan obliczenie idealnego typu dla wybranego języka, na tle którego można zobrazować i następnie wyjaśnić wszelkie odstępstwa od niego. W związku z tym pod uwagę brana jest jedynie wymowa poszczególnych słów i dźwięków, na którą nic nie ma wpływu. Jak wynika z prezentacji teoretycznych podstaw pracy, żadna ze skrajności – ani alfabet fonetyczny, ani odwrotny – nie może być praktycznym rozwiązaniem dla ortografii. Pisownia fonetyczna wprowadziłaby zbyt dużą zmienność kontekstową, co byłoby niepożądane z praktycznego i pragmatycznego punktu widzenia. Wynika to m. in. asymilacji i procesów ekwiwalentnych (którym podlegają również niemieckie fonemy), które mogą wpływać na pisownię w obrębie tego samego morfemu. Opanowanie i korzystanie z takiego pisma byłoby czasochłonne i wymagałoby wysiłku zarówno ze strony czytelnika, jak i piszącego.Przeciwną skrajność można uznać za nierealistyczną nawet w ramach eksperymentu myślowego, ponieważ każda litera nie może odpowiadać każdemu dźwiękowi.W związku z tym rozwiązaniem musi być jakiś kompromis między tymi dwoma ekstremami. Aby dowiedzieć się, gdzie dokładnie leży granica tolerancji, należy oprzeć się na dokładnych danych liczbowych. Celem niniejszego opracowania jest przedstawienie analizy ilościowej odnośnego obszaru językoznawstwa. Intencją niniejszej analizy jest również rozpoczęcie szeregu badań na ten temat w celu stworzenia bazy wiedzy, która pozwoli naszkicować jasny obraz dla przyszłych reform ortograficznych.The relationship between writing and speech has been puzzling linguists for several centuries, and to date no kind of agreement has been reached on this question. There is a wide range of views of writing: from that which regards writing as a system separate from speech to that which assigns no great role to writing at all.This question, however, despite its theoretically enriching benefits, is of little importance when it comes to writing as a fact of human life. It can undoubtedly be taken into consideration.The analysis undertaken in this bachelor’s thesis is intended to encourage a new way of researching scripture based on quantitative methods. Ideally, similar research should answer the question of what degree of equivalence can be considered exemplary so that future orthographic reforms base their guidelines on it.In the present work, it is a matter of calculating an ideal type for the selected language, in the background of which any deviations from it can be illustrated and subsequently explained. Accordingly, only the pure pronunciation of individual words and sounds is taken into account, which is not influenced by anything. As is already evident in the presentation of the theoretical basis of the work, no extreme – neither a phonetic alphabet nor the reverse – could be a practical solution for orthography. Phonemic spelling would introduce too much contextual variance, which would be undesirable from a practical and pragmatic point of view. This results from the effect of assimilation and equivalent processes (to which German phonemes are also subject), which could then influence spelling within the same morpheme. Acquiring and using such writing would be time-consuming and effort-intensive for both the reader and the writer.The opposite extreme can even be determined to be unrealistic in the context of a mental experiment because each letter cannot correspond to each sound.Accordingly, the solution must be some kind of compromise between the two extremes. To find out exactly where the tolerance border lies, one must rely on the exact numbers. The aim of this work is to deepen the corresponding field of linguistics in a quantitative manner. It is also the intention of this analysis to introduce a series of contributions on the subject in order to create a knowledge base that provides a clear view for future orthographic reforms.Das Verhältnis zwischen der Schrift und der Rede stand seit einiger Jahrhunderte im Interesse von Sprachwissenschaftlern, und bis heute wurde eigentlich keine Art Einverständnis in dieser Frage erreicht. Es gibt eine breite Palette von Ansichten von Schrift: von der Einstellung, die die Schrift als ein von der Sprache separates System betrachtet, bis zu solcher, die der Schrift überhaupt keine große Rolle zuweist.Diese Fragestellung, trotz ihres theoretisch bereichernden Nutzens, ist aber von kleiner Bedeutung, wenn es sich um die Schrift als Tatsache menschlichen Lebens handelt. Die kann bei einer wissenschaftlichen Erörterung zweifellos in Betracht gezogen werden.Die in der vorliegenden Bachelorarbeit durchgeführte Analyse soll zum neuen, auf quantitativen Methoden basierenden Forschungsweg der Schrift ermutigen. Idealerweise sollten ähnliche Untersuchungen die Frage beantworten, welchen Äquivalenzgrad für mustergültig gehalten werden kann, damit die zukünftigen orthografischen Reformen ihre Richtlinien darauf basieren können.Ferner handelt es sich um die Berechnung eines Idealtyps für die ausgewählte konkrete Sprache, in wessen Hintergrund eventuelle Abweichungen davon veranschaulicht und danach erklärbar sind. Demensprechend wird bloß die reine Aussprache einzelner Wörter und Laute in Rücksicht genommen, die von nichts beeinflusst wird. Wie es sich schon beim Darstellen der theoretischen Vorlagen der Arbeit herausstellte, kann kein Extremum – weder ein phonetisches Alphabet noch das Umgekehrte, als eine praktische Lösung für die Orthographie sein. Die phonemische Schreibung würde nämlich zu viel kontextabhängige Varianz einführen, die aus praktischer und pragmatischer Sicht ungewollt wäre. Dies resultiert u. a. aus der Auswirkung der Assimilation und gleichwertiger Prozesse (denen auch die deutschen Laute unterliegen), das dann auf die Schreibung innerhalb derselben Morpheme den Einfluss haben könnten. Aneignen und Verwenden solcher Schrift wäre sowohl für den Leser als auch für den Schreibenden zeit- und kraftsaufwendig.Das umgekehrte Extremum lässt sich sogar im Rahmen eines mentalen Experiments als unrealistisch beurteilen, weil jeder Buchstabe jedem Laut keinesfalls entsprechen kann.Dementsprechend muss die Lösung eine Art Kompromiss zwischen den beiden Grenzwerten sein. Um genau herauszufinden, wo die Toleranzgrenze liegt, muss man sich auf die genauen Zahlen stützen. Diese Arbeit verfolgt das Ziel, den entsprechenden Bereich der Sprachwissenschaft quantitativ zu vertiefen. Auch wird mit der unternommenen Analyse beabsichtigt, eine Reihe der (wissenschaftlichen) Beiträge zum Thema einzuleiten, um eine den Klarblick auf die Rechtsschreibungsreformierung gebende Wissensbank herzustellen

Tendencje w motywacji urbanonimii w Bobrujsku w czasie II wojny światowej

Nazwy ulic i placów jako nośniki kultury i forma wyrazu językowego obrazu świata stanowią elementy w przestrzeni miejskiej, które nierzadko łatwo mogą posłużyć jako elementy wyrażające paradygmat kulturowy, program aktualnej polityki oraz propagandy. Z tego względu ulice często mogą ulegać sztucznej renominacji, tak aby mieściły się w ramach przyjętej linii politycznej. Zmiana hodonimów w Bobrujsku (Białoruś) podczas II. wojny światowej oraz sformułowanie schematów tego procesu przy jednoczesnym wskazaniu jego tendencji stanowi cel analizy przedwojennych nazw ulic oraz ich konfrontacji z nazwami niemieckimi utrwalonymi w dokumentach dyktatury narodowo-socjalistycznej z lat 40-tych XX w. Badanie stanowi kontynuację analiz podobnych zjawisk na terenie okupowanej Polski i pozwala ocenić, czy i w jakim stopniu przebywający tam Niemcy przejmowali białorusko-radziecki językowy obraz świata, charakterystyczny dla konkretnego kręgu językowego i kulturowego.Street and square names are carriers of culture and the expression form of the linguistic picture of the world. They make up elements in the city, which can easily serve as elements expressing cultural paradigm, political agenda as well as propaganda. From that perspective the city streets and squares are likely to be artificially renamed in order to make them go along with the current policy. The street and square renaming in Bobruisk (Belarus) during World War II as well as the patterns of the process with its tendencies make up the objective of the prewar and wartime urbanonym comparative analysis. The research is a continuation of the work on similar processes on the area of occupied Poland and allows evaluating, whether and to what extent the then occupying Germans adopted Soviet-Belorussian linguistic picture of the world which is characteristic for a specific linguistic and cultural area. The motivation to take up a theme with World War II in the background was the 75. anniversary of the end of this military conflict in Europe. This work seeks to drive more attention to the subject of Belarusian urbanonimics and urbanonimics as a whole.Названия улиц и площадей являются носителями культуры и формой выражения лингвистической картины мира. Они относятся к элементам городского пространства, которые легко могут отражать культурную парадигму, политическую повестку и пропаганду. Ввиду этого названия городских улиц и площадей подвержены искусственному переименованию с целью согласования их с актуальной политической линией. Переименование названий улиц и площадей в Бобруйске во время Второй мировой войны вместе с описанием основных шаблонов этого процесса в сравнении с довоенными названиями городских объектовобразовывают цель нижеизложенного анализа.Данная статья продолжает исследованиeаналогичных процессов на территории оккупированной Польши и позволяет оценить, перенимали ли немецкоязычные захватчики советско-белорусскую языковую картину мира. В качестве мотивации для проведения исследования на фоне Второй мировой войны послужила семьдесят пятая годовщина окончания этого военного конфликта в Европе. Данной работой хотелось бы привлечь внимание к предмету белорусской урбанонимии и урбанонимии в целом

Thermodynamics of Biodiesel: Combustion Experiments in the Standard Conditions and Adjusting of Calorific Values for the Practically Relevant Range (273 to 373) K and (1 to 200) bar

Calorific values of rapeseed methyl ester (RME) and soybean methyl ester (SME) biodiesel blends have been determined by using of the high-precision combustion calorimeter. Temperature and pressure dependences of the calorific values in the range (273 to 373) K and (1 to 200) bar have been derived for the RME and SME biodiesel blends B100. Practical equations for calculating of the thermal correction for calorific values taking into account the composition, temperature, and pressure have been proposed

Molecular Liquids versus Ionic Liquids: The Interplay between Inter-Molecular and Intra-Molecular Hydrogen Bonding as Seen by Vaporisation Thermodynamics

In this study, we determined the enthalpies of vaporisation for a suitable set of molecular and ionic liquids using modern techniques for vapour pressure measurements, such as the quartz crystal microbalance, thermogravimetric analysis (TGA), and gas chromatographic methods. This enabled us to measure reasonable vapour pressures, avoiding the problem of the decomposition of the ionic liquids at high temperatures. The enthalpies of vaporisation could be further analysed by applying the well-known “group contribution” methods for molecular liquids and the “centerpiece” method for ionic liquids. This combined approach allowed for the dissection of the enthalpies of vaporisation into different types of molecular interaction, including hydrogen bonding and the dispersion interaction in the liquid phase, without knowing the existing species in both the liquid and gas phases