A DSC Study of Hydrated Sugar Alcohols. Isomalt

A DSC study has been carried out on isomalt, a commercial sugar alcohol derived from sucrose and widely used as a sweetener in the food industry. Isomalt is a mixture of two isomers:α-D-glucopyranosyl–1-6-mannitol (GPM) and α-D-glucopyranosyl–1-6-sorbitol (GPS). Release of the water of crystallisation (around 100°C)and melting (around 150°C) have been phenomenologically characterised using different scanning rates and heat treatments. The effect of dehydration/re-hydration on the melting has been investigated. The isomalt glass transition, at about 60°C, was studied on samples cooled after melting. The dynamic aspect of structural relaxation of isomalt has been quantified by its fragility parameter. Glassy state stability has been evaluated by performing ageing experiments at sub-T _g temperatures. During ageing, apart from the expected enthalpy relaxation effects, isomalt showed a peculiar behaviour, due to its isomeric composition. These preliminary and phenomenological results have been interpreted in terms of isomer structure and of carbohydrate-water interactions in the mixture. This revised version was published online in July 2006 with corrections to the Cover Date.     

Infrared method for the rapid detection of dealkylation products in the adducts of metal salts with neutral organophosphoryl esters

Ohne Zusammenfassung

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Plastic — unsuitable packing material for samples used for carbon determination

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An den Untersuchungen waren beteiligt: E. Lassner, Metallwerk Plansee AG., Reutte/Tirol; H. Rothmann und K. Bencker, Gesellschaft für Elektrometallurgie m.b.H., Zentrale Forschung, Nürnberg und F. Wagner, Süddeutsche Kalk-Stickstoff-Werke AG., Karbidwerk Hart.     

Thermal properties of isomalt: A diastereomer mixture

Isomalt, a commercial sugar alcohol widely used as a sweetener, is approximately a 1:1 mixture of two diastereomers, -D-glucopyranosyl-1-6-mannitol (GPM) and -D-glucopyranosyl-1-6-sorbitol (GPS). A calorimetric investigation has been carried out on mixtures of isomalt with GPS, in the (molar) composition range 0.45<x_GPS<1, for both crystalline and amorphous states.The GPS-rich portion of the solid-liquid GPM/GPS phase diagram was established and discussed in light of the existing literature. New evidence was given for the non-ideality of GPM/GPS mixtures, by indicating excess interactions in the melt and/or in the solid state. The commonly accepted hypothesis of a simple GPM/GPS eutectic forming isomalt was refuted in favour of more complicated mixture behaviour with possible formation of a complex.Glass transition and physical ageing of isomalt and GPS were re-visited, with peculiar attention given to the measurement conditions. Standard thermal histories were adapted to each sample and the fictive temperature was used for the characterisation of the structural glass states. A linear increase of the fictive temperature was found upon passing from pure GPS to x_GPS=0.45. GPS showed a slightly higher enthalpy relaxation rate than isomalt.This revised version was published online in November 2005 with corrections to the Cover Date.     

Thermochemistry of complex salts of transition metal perchlorates with tetrazole ligands

The combined use of combustion and solution calorimetry was proposed as a method for determining the standard enthalpy of formation of the complex salts of transition metals, viz., cobalt(II), nickel(II), and zinc, with the organic ligand (5-aminotetrazol-1-yl)acethydrazide. The enthalpies of solution in water and in a 0.1 M solution of hydrochloric acid were measured for the complex salts and ligand. The enthalpy of combustion of the ligand was determined by the combustion calorimetry method, and its standard enthalpy of formation was calculated. The thermochemical cycle was developed for determining the standard enthalpy of formation of the complex salts. The reliable values of the enthalpies of formation of the salts in the standard states were obtained, and the enthalpies of formation of the earlier unknown complex ions were determined.     

二水醋酸镉与邻氨基苯甲酸的分步固相反应的热化学研究

用溶解量热法,以一定比例的盐酸(0.2mol·L     

Study on hydration enthalpy of N-methylacetamide in water

In order to determine the hydration enthalpy of N-methylacetamide (NMA), the enthalpy change for mixing NMA with liquid water was measured calorimetrically. NMA molecules can self-associate both in the liquid state and in aqueous solutions. The population distribution of the self-associated polymeric species in liquid NMA was evaluated by using the results of ab initio MO calculations for the monomer, dimers, and trimers of trans-NMA, while that in aqueous NMA was obtained by NMR spectroscopy. The relationship between these distributions and the mixing enthalpy was formulated on the basis of the similar energy cycle as Born-Haber type, the schematic diagram of energy cycle is given, and the hydration enthalpy of the NMA monomer was determined accurately. The enthalpy thus obtained was found to be in good agreement with that calculated by ab initio MO theory.     

The enthalpy of formation of the praseodymium ion (3+) in an infinitely dilute aqueous solution

The enthalpy of reaction between praseodymium metal and 1.07 n HCl and the enthalpy of solution of praseodymium trichloride in 1.07 n HCl and water were measured in a swinging isoperibol calorimeter at 298.15 K. The results were used to calculate the enthalpy of formation of the praseodymium ion in the state of an infinitely dilute aqueous solution, Δ_f H°_298.15 Pr³⁺(sln, ∞H₂O) = ?687.8 ± 1.7 kJ/mol.     

Eine neue Methode zur volumetrischen Bestimmung von Phosphit und Hypophosphit nebeneinander

Zusammenfassung Zur Bestimmung von phosphoriger und von unterphosphoriger Säure in Bädern zur stromlosen Herstellung von Metallüberzügen werden zwei neue Methoden beschrieben.Unterphosphorige Säure wird mit Silberperchlorat oxydiert und der Überschuß an Silberionen mit Natriumchlorid zurücktitriert. Die Summe von phosphoriger Säure und unterphosphoriger Säure wird bromatometrisch in 0,11 N salzsaurer Lösung bestimmt. Zur Erfassung der phosphorigen Säure eignet sich das von Norkus, Lunjackas u. Carankute beschriebene jodometrische Verfahren.

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Summary Two new methods are described for the determination of phosphorous and hypophosphorous acid in bath solutions for the production of metal coatings without current. Hypophosphorous acid is oxidized with silver perchlorate and the excess of silver ions is back-titrated with sodium chloride. The sum of phosphorous and hypophosphorous acid is determined bromatometrically in 0.11 N hydrochloric acid solution. Phosphorous acid can be determined by the iodometric procedure according to Norkus, Lunjackas and Carankute.

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1 Diplomarbeit, Bergakademie Freiberg 1967.     

Thermochemistry of myricetin flavonoid

The enthalpies of myricetin dissolution are measured by means of calorimetry with mol dilutions of flavonoid: 96 mol % ethanol equal to 1: 9000, 1: 18000, and 1: 36000. The standard enthalpies of dissolution for the biologically active substance in an infinitely diluted (standard) solution of 96% ethanol are calculated from the experimental data. Physicochemical means of approximation are used to estimate the values of the standard enthalpy of combustion, and the enthalpy of melting is calculated for the investigated flavonoid. Finally, the compound’s standard enthalpy of formation is calculated using the Hess cycle.     

Automated clean-up procedure for the analysis of sugars and acids in food

Summary In the gas-chromatographic analysis of sugars and acids in foodstuffs, isolation and purification of the two types of components is time-consuming and laborious. An automated clean-up procedure, based on ion-exchange, has therefore been developed. A liquid food sample is successively percolated over a cation and anion and a cation exchanger. Sugars and acids are collected under the second and third column, respectively. A time programmer operates a set of pumps and a pneumatic valve system enabling simultaneous regeneration of columns not being eluted. Hence, handling of samples is continuous; each clean-up cycle takes 50 min.

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Automatisiertes Abtrennungsverfahren für die Analyse von Zuckern und Säuren in Nahrungsmitteln

Zusammenfassung Eine flüssige Nahrungsmittelprobe wird nacheinander über einen Kationen-, einen Anionen- und einen Kationenaustauscher perkoliert. Die Zucker und die Säuren werden abgetrennt und im Eluat der zweiten bzw. dritten Austauschersäule gefunden. Ein Steuergerät schaltet auf Zeitbasis eine Gruppe von Pumpen und ein System mit pneumatischen Hähnen derart, daß in einem Cyclus (50 min) die Substanzen eluiert und die Säulen regeneriert werden. Anschließend werden die Proben verarbeitet. Einige Ergebnisse verschiedener Nahrungsmittel werden angeführt.

On leave from Lisbon University, Portugal.     

Linear titration plots for the potentiometric titration of partially neutralized weak acids and bases

Summary A linear titration plot method has been derived for the determination of partially neutralized weak acids or weak bases from pH-titration data. A FORTRAN program calculates the total concentration of acid or base in solution as well as the fraction remaining to be neutralized. The program also detects the presence of strong acid with a weak acid or a strong base with a weak base. The weak acid or base may be polyfunctional with overlapping dissociation steps. Activity coefficients are calculated iteratively.

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Lineare Titrationskurven für die potentiometrische Titration von teilweise neutralisierten schwachen Säuren und Basen

Zusammenfassung Lineare Titrationskurven werden für potentiometrische Titrationen von schwachen Säuren und Basen, die bereits teilweise neutralisiert sind, abgeleitet. Eine Fortran-Prozedur berechnet sowohl die Gesamtkonzentration der Säure oder Base als auch den Neutralisationsgrad. Das Rechenprogramm erfaßt auch die Anwesenheit einer starken Säure zusammen mit einer schwachen Säure oder einer starken Base zusammen mit einer schwachen Base. Die schwache Säure oder Base darf mehrere überlappende Dissoziationsstufen aufweisen. Aktivitätskoeffizienten werden mittels eines Iterationsverfahrens berechnet.

     

Bestimmung des tats?chlichen S?urechloridgehalts von Benzoylchlorid und Palmitoylchlorid

Zusammenfassung Zur Bestimmung des Säurechloridgehalts von Benzoyl- und Palmitoylchlorid wird ein Verfahren beschrieben, bei dem die zu untersuchende Probe in Gegenwart von eisessigsaurer Quecksilber(II)-acetatlösung mit einer Lösung von Morpholin in Tetrachlorkohlenstoff umgesetzt wird. Das Säurechlorid reagiert mit dem Morpholin unter Säureamidbildung. Der Überschuß der Morpholinbase wird mit HClO₄ in Gegenwart von Tropäolin 00 als Indicator zurücktitriert. Parallel wird eine Blindprobe durchgeführt. Säurechloride mit kürzeren Kohlenstoffketten lassen sich mit dieser Methode nicht bestimmen.     

Thermochemical properties of dinitramidic acid salts

Enthalpies of formation and solution of hydrazinium, guanidinium, aminoguanidinium, and triaminoguanidinium salts of nitric and dinitramidic (HN(NO₂)₂, DN) acids were determined by combustion and solution calorimetry methods. Enthalpies of formation of respective cations in infinitely dilute aqueous solution were calculated using the enthalpy of formation of the nitrate ion. The enthalpy of formation of the DN acid anion was determined based on the enthalpy of formation and solution of the acid salts. The weight-average enthalpy of formation of the DN acid anion equal to 8.40±0.13 kcal mol⁻¹ was obtained. The enthalpy of solution of ammonium dinitramide (ADN) was measured (8.71±0.01 kcal mol⁻¹). From these data, the enthalpy of formation of ADN was calculated (−32.14±0.14 kcal mol⁻¹). The energy of combustion of ADN was measured by the calorimetry method, and the enthalpy of formation of ADN was calculated for a sample with purity above 99.9% (−32.20±0.19 kcal mol⁻¹). The weight-average enthalpy of formation of ADN equal to −32.16±0.11 kcal mol⁻¹ is recommended for use. Enthalpies of formation of sodium, potassium, and cesium salts of DN acid were determined.     

Standard enthalpy of formation of lanthanum oxybritholites

Lanthanum-bearing silicate-oxyapatites or britholites, Ca_10–xLax(PO₄)_6–x(SiO₄)_xO with 1≤x≤6, have been synthesized by solid state reaction at high temperature. They were characterized by X-ray diffraction and IR spectroscopy. Using two microcalorimeters, the heat of solution of these compounds have been measured at 298 K in a solution of nitric and hydrofluoric acid. A strained least squares method was applied to the experimental results to obtain the solution enthalpies at infinite dilution, and the mixing enthalpy in two steps. In the first step the mixing enthalpy obtained is referenced to the britholite monosubstituted and to the oxysilicate. The mixing enthalpy referenced to the oxyapatite and to the oxysilicate is then extrapolated. In order to determine the enthalpies of formation of all the terms of the solution, thermochemical cycles were proposed and complementary experiments were performed. The results obtained show a decrease of the enthalpy of formation with the amount of Si and La introduced in the lattice. This was explained by the difference in the bond energies of (Ca–O, P–O) and (La–O, Si–O).     

室温固相反应制备纳米四水磷酸锌的热化学研究

Nanocrystalline zinc phosphate tetrahydrate was synthesized by solid-state reaction at ambient temperature using Na3PO4·12H2O and ZnSO4·7H2O as regents. The enthalpy of reaction and the standard enthalpy of formation of zinc phosphate tetrahydrate were studied by microcalorimeter. According to Hess s law, a new thermochemical cycle was designed. The dissolution enthalpies of reactant (△H1) and product (△H2) were performed by a RD496 microcalorimeter at 298.15 K using aqueous solution of hydrochloric acid (4mol/L) as a calorimetric solvent. Ultraviolet spectrum, conductivity and refractive index were measured respectively. The results show as follows: △H1=(-47.180±0.084) kJ/mol, △H2=(-7.617±0.096 )kJ/mol. The ultraviolet spectra of the above solution are the same. Conductivity values after 500 times diluted are 2180 and 2181μs/cm respectively. Refractive indexes are 1.3679 and 1.3678 respectively. The standard enthalpy value of the reaction was calculated: △rHm=-39.530 kJ/mol. The standard enthalpy of formation for zinc phosphate tetrahydrate are recommended -4354.004 kJ/mol.     

Crystal Structure and Thermochemical Properties of 2-Pyrazine Carboxylate Lithium Monohydrate [Li(pyza)(H2O)]n(s)(pyza=2-Pyrazine Carboxylate)

A 2-pyrazine carboxylate lithium monohydrate [Li(pyza)(H₂O)]_n was synthesized in a mixed solution of redistilled water and anhydrous ethanol. X-Ray crystallography was applied to characterizing its crystal structure. Low temperature molar heat capacities were measured in a temperature range of from 78 K to 400 K with a precision automatic adiabatic calorimeter. Two polynomial equations of experimental molar heat capacity as a function of temperature were obtained by the least-squares method. The smoothed molar heat capacities and thermodynamic functions of the compound were calculated based on the fitted polynomial equations. In accordance with Hess's law, a reasonable thermochemical cycle was designed based on the preparation reaction of the target compound. The standard molar enthalpies of dissolution for the reactants and products of the designed thermochemical reaction were measured by an isoperibol solution-reaction calorimeter, and the enthalpy change of the reaction was obtained, i.e.,Δ_rH_m^θ=-(30.084±0.329) kJ/mol. The standard molar enthalpy of the formation of the target compound was determined as Δ_fH^θ_{m{[Li(pyza)(h2o)]n(s)}}=-(260.844±1.178) kJ/mol based on the enthalpy change of the reaction and standard molar enthalpies of the formation of other reactants and products. In addition, UV-Vis spectroscopy and the data of the refractive indexes were used to confirm whether the designed Hess thermochemical cycle was reasonable and reliable.     

Thermochemistry of complex salts of transition metal perchlorates with tetrazole ligands

Standard enthalpies of formation of transition metal (cobalt, nickel, and zinc) complex salts with an organic ligand 5-aminotetrazol-2-ylacetohydrazide (ATH-2) were obtained by combustion and solution calorimetry. The enthalpy of combustion of the ligand was determined using combustion calorimetry and the standard enthalpy of formation of the ligand was calculated. For calculations by reaction calorimetry, a thermochemical cycle was developed that allows determination of the standard enthalpy of formation of complex salts. The enthalpies of solution of the ligand and transition metal complex salts in water and in 0.1 M hydrochloric acid were determined. The data obtained allow calculations of the enthalpies of salts formation and the enthalpies of three new complex ions. The enthalpies of position isomerization in different compounds were analyzed.     

Milligram level determination of mercury(II) and bismuth (III): p-mercaptoacetamidophenetidine as a gravimetric reagent

Summary The gravimetric estimation of mercury(II) and bismuth(III) has been carried out on a mg scale usingp-mercaptoacetamidophenetidine as the precipitant. The reagent has the required aqueous solubility and is superior to the commonly used analytical reagents of the mercaptan family. The complexes of the reagent with mercury(II) and bismuth(III) are obtained in pure state, definite in composition and stable in hot acid media.

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Zusammenfassung Die gravimetrische Bestimmung von Hg(II) und Bi(III) mit p-Mercaptoacetamidophenetidin als Fällungsmittel wurde ausgearbeitet. Dieses Reagens ist den üblicherweise verwendeten Merkaptanen überlegen. Die KomplexVerbindungen mit Hg und Bi erhält man rein und in definierter Zusammensetzung. Sie sind gegenüber heißer Säure beständig.