Influence of valence and concentration of electrolytes on the ζ-potential of polyacrylic lattices

The -potential of copolymer particles of acrylic amide, acrylic acid, acrylic butyl ester, and styrene were measured in different electrolyte solutions. In an isotonic solution of sodium chloride, they vary with the content of acrylic acid between –36 mV and –49 mV. In the presence of 21-electrolytes, the -potential could be correlated with the logarithm of the electrolyte concentration. The 21-electrolytes predominantly determine the -potential of the particles not only in the solutions of these electrolytes, but also in mixed electrolyte solutions. In the presence of human serum, the electrophoretic mobility increases with increasing acrylic acid content of the polymer.     

On the electrophoretic mobility and zeta potential of montmorillonite in non-aqueous media

Experimental results on the electrophoretic velocity and mobility of Ca-montmorillonite in 2-propanol are reported. The variation of the electrophoretic velocity with the externally applied electric field and the particle size range, at constant volume fraction and temperature, is considered. Given the difficulties for determining the types and concentrations of ions present in these liquid media, two methods are discussed for the estimation of the double layer thickness and hence the product, necessary for the determination of the zeta potential () of the interface. Although both methods of calculation yield different values of, the results for the zeta potential are very similar in the regions of and characteristic of our systems. The application to the experimental data of three theoretical relations between electrophoretic mobility and zeta potential is also discussed.     

Effect of the Surface Conductance on Electrokinetic Potential Measured in Nonaqueous Media

The effect of the surface conductance on the -potential of dispersed particles determined from their electrophoretic mobility in nonaqueous electrolyte solutions was considered. The conductivity of dilute quartz suspensions and the electrophoretic mobility of quartz particles in NaBr solutions in butanol-1 and dimethyl sulfoxide as well as in LiBr solutions in acetone at the salt concentration C= 10^–5–10^–2M were determined by conductometry and microelectrophoresis. The dependences of surface conductivity and -potential on the electrolyte content were calculated by formulas of the Wagner and Henry theories. It was shown that, in the region of dilute solutions, (log C) curves thus obtained significantly differ from corresponding functions calculated by the Smoluchowski equation. At the same time, these dependences agreed closely with the (log C) dependences determined for the same systems by the streaming potential method with allowances for experimental values of the surface conductivity. Using aluminum oxide suspensions in NaBr and HBr ethanol solutions as examples, it was shown that, to obtain correct values of the -potential from electrophoretic mobility of porous particles impregnated with a solution, it is necessary to allow for the bulk conductance of the particles.     

Oxidative coupling of thiophene catalyzed by Pd(II)

The yield and isomer composition of bithiophene in the oxidative coupling of thiophene catalyzed by Pd(II) in the presence of Fe(III) salts have been studied. The reaction mechanism is discussed.

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, Pd(II) Fe(III). .

     

Transformations of cyclohexanol on a platinum-alumina catalyst: Effect of poisons

Vapor-phase dehydrogenation/dehydration of cyclohexanol has been investigated over a bifunctional platinum-alumina catalyst. The products of the reactions are cyclohexane, cyclohexene, benzene, cyclohexanone and phenol. Studies using the poisons CO, H₂S and NH₃ have been made in order to elucidate the nature of the sites responsible for the formation of the various products.

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/ џ . , , , . CO, H₂S NH₃ , .

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Part of the Ph. D. thesis of S. Sivasanker     

Dispersity of (Ru+Pd)/SiO2 catalysts and their properties in CO hydrogenation and ethane hydrogenolysis

The decreased activity of bimetallic catalysts obtained by the interaction of Ru₃(CO)₁₂ with Pd/SiO₂ in the synthesis of hydrocarbons from CO and H₂ and in ethane hydrogenolysis compared with Ru/SiO₂ is due to the dilution, of ruthenium by less active palladium atoms.

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, Ru₃(CO)₁₂ Pd/SiO₂, CO Ru/SiO₂ .

     

Conductance of Cs+ ion in water: Molecular dynamics simulation

The continuum theory of Hubbard-Onsager predicts for the friction coefficients the following behavior: >0 and /P<0. In contrast to Hubbard-Onsager theory, experimental observations on Cs⁺ ion in water show that at low temperatures <0 and /P>0. To explain the observed behavior of Nakahara et al. proposed the passage through cavities (PTC) mechanism. We performed a molecular dynamics computer simulation to determine if the PTC mechanism is responsible for the observed behavior of . No passage through cavities was observed. Molecular dynamics computer simulations were performed on Cs⁺ ion in water at temperature of 268 K and densities of 1.00 and 1.083 g-cm^–3. Our results indicate that the observed behavior of for Cs⁺ ion is related to the difference in the reorientation times of water molecules in the solvation shell and in the bulk.     

XPS, UPS and TDS studies of CO adsorption on platinum

XPS, UPS and TDS studies of the adsorption of carbon monoxide on partially recrystallized platinum foil at 300 K indicate that the adsorption is of nondissociative character and there are two CO_ads states.

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300 K. , . CO.

     

Thermal desorption of atmospheric organic pollutants enriched on charcoal

A technique of thermal vacuum desorption of charcoal, used in passive dosimeters to enrich organic pollutants of toxicological importance, is described. It combines the advantages of the classic procedure of using highly active charcoal followed by solvent desorption and the environmental one-step procedure of analyzing the whole thermally desorbed sample. For pollutants such as trichloroethylene, tetrachloroethylene, ether, benzene and ethanol, the recovery and reproducibility are satisfactory. The unexpected decomposition of halothane and ethylacetate at higher temperatures is caused by the catalytic activity of the charcoal, but this can be tolerated under constant operating conditions.

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Zusammenfassung Eine Methode zum Anreichem toxikologisch bedeutender organischer Luftverunreinigungen durch thermische Vakuumdesorption von Aktivkohle nach dem Einsatz in passiven Dosimetern wird beschrieben. Die Methode kombiniert die Vorteile der klassischen Prozedur unter Verwendung hochaktiver Kohle mit nachfolgender Desorption durch Lösungsmittel einerseits mit denen der Umwelt-Analyse der gesamten desorbierten Probe in einem Schritt andererseits. Für Luftverunreinigungen wie Trichlorethylen, Tetrachlorethylen, Ether, Benzen und Ethanol werden ausreichende Wiedergewinnung und Reproduzierbarkeit ermittelt. Die unerwartete Zersetzung von Halothan und Ethylacetat bei höheren Temperaturen wird auf die katalytische Wirkung der Aktivkohle zurückgeführt. Sie kann unter konstanten Versuchsbedingungen jedoch toleriert werden.

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, . . , - , , . .

     

Difference method of evaluation of dynamic integral thermogravimetric curves in decomposition of polypropylene

A new differential method of evaluating integral thermogravimetric records of the formation of volatile products during the degradation of polypropylene in air is presented. The method, applied to 0–100% conversion of the polymer to volatile products, may distinguish the initial presence of low molecular compounds in the polymer, as well as changes in the mechanism of degradation of the material.

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Zusammenfassung Es wird eine neue differentielle Methode zur Auswertung der die Bildung von flüchtigen Produkten während der Zersetzung von Polypropylen in Luft widerspiegelnden integralen thermogravimetrischen Kurven dargelegt. Mit der im Bereich 0–100% Konversion von Polymer zu flüchtigen Produkten anwendbaren Methode können sowohl die Anwesenheit niedermolekularer Verbindungen im Polymer als auch Veränderungen im Abbaumechanismus des Materials erkannt werden.

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, . , 0–100%- , , .

     

Thermal analysis in studies of photochemical transformations in PVC

The effects of photochemical processes in PVC in response to UV irradiation at 253.7 nm on its thermal stability were investigated. It was found that small differences in the efficiency of the photochemical processes taking place in the PVC can be recorded in the thermal measurements, and that photodehydrochlorination lowers the temperature of thermal dehydrochlorination, while photooxidation and crosslinking increase the temperature of complete decomposition of this polymer.

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Zusammenfassung Der Einfluß der durch UV-Bestrahlung bei 253,7 nm hervorgerufenen fotochemischen Prozesse auf die thermische Stabilität von PVC wurde untersucht. Mittels der thermischen Untersuchungen wurde gefunden, daß im Ergebnis der im PVC stattfindenden fotochemischen Prozesse kleine Unterschiede bestehen. Fotodehydrochlorierung vermindert die Temperatur für die thermische Dehydrochlorierung, während Fotooxidation und Vernetzung die Temperatur für die vollständige Zersetzung dieses Polymers erhöhen.

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() , 253,7 . , , , . , , .

     

Electrokinetic study on concentrated suspensions using colloid vibration potential measurements

-potentials of a silica suspension and three types of polystyrene latex suspensions with different surface charge groups were measured, as a function of the particle concentration () in the suspension over a wide range, using the colloid vibration potential (CVP) technique. The concentration dependence of the-potential in silica suspension is explained well by Levine et al.s [1] cell model theory, verifying the applicability of the cell model to the CVP in silica suspension. However, the-potential of latex suspensions ordinarily decreases as the particle concentration increases, even after being corrected by the term of (1-). This tendency is especially noticeable in the systems that have particles with high surface charge densities. Furthermore, the conductivity measurements of these suspensions reveal that the conductivity of these systems, especially in their highly charged state, increases as the particle concentration is increased; opposite in tendency to silica suspensions. These new findings can be explained as follows: on the highly charged surface of a latex particle, a polyelectrolyte-like (hairy) layer is present, which overlaps at some point. This permits interparticle surface conduction and results in the abnormal behavior of CVP in these systems.     

Demulsification rate and zeta potential of O/W emulsions

Dilute oil-in-water (O/W) emulsions have been used to study the correlation between demulsification rate and-potential as a function of surfactant concentration. The demulsification rate of octane and isooctane emulsions stabilized by sodium dodecyl sulfate (SDS) or cetyldimethylbenzylammonium chloride (CDBACl) are evaluated by counting the particle number. Flocculation is considered the main factor of instability. The-potential of the droplets is also calculated from microelectrophoretic measurements by a new demountable microelectrophoretic apparatus. The stability of the emulsions is attributed mainly to electrostatic repulsion. Small differences between straight and branched-chain hydrocarbons are observed.     

Electrokinetic Properties of the Methylated Surface of Quartz Capillaries

The surface charge and electrokinetic potential of quartz capillaries with hydrophobized (methylated) surface are measured. It is shown that, during the flow of an electrolyte solution through the capillary, the potential lowers with time due to formation of gas bubbles on the surface screening the surface charge. In a certain period of time, drastic jump of the potential to its initial value is observed, which is interpreted as a detachment of bubbles by the flowing solution. The formation of bubbles is provoked by the roughness of the methylated surface with asperities of up to 20 nm in height. The profiles of the methylated surface were obtained by the atomic force microscopy. An addition of a nonionic surfactant hydrophilizing the hydrophobic surface to the electrolyte solution lowers the -potential, which could be caused by the suppression of the slip effect. Estimations made on the basis of an earlier developed theory lead to the values of slip coefficient that are close to those measured for micron-sized hydrophobic capillaries.     

Reactivity of hydrogen adsorbed on platinum black towards ethylene

TPD studies of the reactivity of hydrogen adsorbed on dispersed Pt-black towards ethylene at –90, 30 and 200°C indicate that molecular forms of hydrogen with E_des from 3 to 16 kcal/mol are reactive species.

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Pt- –90, 30, 200°C . , . 3 16 /.

     

Comportement thermique des benzènesulfonates de lithium,sodium et potassium

Résumé Le comportement thermique des benzènesulfonates de lithium, sodium et potassium a été étudié par TG et ATD à l'air et sous atmosphère d'azote.Dans la zone de stabilité des sels anhydres, nous avons mis en évidence des transformations réversibles (changements de phase cristalline) dont certaines ont fait l'objet de mesures calorimétriques.L'étude des résidus solides de la décomposition a montré une proportion importante de sulfates dans les produits obtenus dans l'air, alors que sous azote, il s'agissait surtout de sulfures. Les sulfites ne se présentent qu'en très faible quantité dans les deux cas.

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The thermal behaviour of benzènesulphonates of lithium, sodium and potassium has been investigated by TG and DTA in air and in an atmosphere of nitrogen.We have shown in the stability interval of the anhydrous salts reversible transformations (phase transitions), some of which were quantitatively studied by calorimetry.The radiocristallographic study of the solid residues has shown an important proportion of sulphates in the residues in air and of sulphides in an inert atmosphere. The sulphites were found in very small quantity in both cases.

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Zusammenfassung Das thermische Verhalten der Benzolsulfonate von Lithium, Natrium und Kalium wurde durch TG und DTA in Luft und in Stickstoff untersucht.Im Stabilitätsbereich der wasserfreien Salze wurden reversible Umwandlungen (Phasenübergänge) nachgewiesen, von denen einige quantitativ durch Kalorimetrie untersucht wurden.Das radiokristallographische Studium der festen Rückstände zeigte, daß in Luft ein bedeutender Anteil der Rückstände aus Sulfaten und in inerter Atmosphäre aus Sulfiden besteht. Sulfite wurden in beiden Fällen in sehr geringen Mengen gefunden.

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, . , , ( ), . , , - . .

     

Zur Wechselwirkung von Polyanionen mit Pigmenten II. Untersuchungen an Hämatit,Quarz und graphitiertem Ruß

Zusammenfassung Durch Messungen der Adsorption, des elektrokine-tischen Potentials und der Immersionswärmen wurde die Wechselwirkung zwischen drei Pigmenten (Hä-matit, Quarz, graphitierter Ruß) und einige Poly-anionen (Natriumtriphosphat, 1-Hydroxyäthan-1,1-diphosphonat, Phosphonoacetat, -Phosphonopropio-nat und Mellitsäure) untersucht. Dabei zeigte sich, daß die Pigmentoberflächen mit den Anionen sehr unterschiedlich reagieren.An Hämatit werden die Polyanionen über einen sehr weiten pH-Bereich stark adsorbiert, wobei eine deutliche Zunahme des pH-Wertes beobachtet wird. Da gleichzeitig die (bei pH > 4) bereits negative Partikelladung stark erhöht wird, beruht die Wechselwirkung sehr wahrscheinlich auf einer Chemisorption der Polyanionen an der Hämatitoberfläche. Mit steigenden pH-Werten nimmt die Adsorptionsdichte stark ab, bei Hydroxyäthandiphosphonat durchläuft sie ein Minimum bei etwa pH 9. Das -Potential ist deutlich geringer pH-abhängig als die Adsorption. Es durchläuft ein breites Maximum (ca. pH 8), bei Hydroxyäthandiphosphonat nimmt es jedoch mit steigendem pH zu. Aus der Messung der Immersionswärmen folgt, daß die Wechselwirkung zwischen Hämatit und den Polyanionen annähernd ohne Enthalpieänderung verläuft und folglich wesentlich durch die Entropie kontrolliert werden muß.Die Adsorption der Polyanionen an Quarz ist sehr gering und erfolgt nur unterhalb des IEP (pH 1,3). Das zeigen sowohl direkte Adsorptionsbestimmungen als auch die Messungen des -Potentials, denenzufolge die Gegenwart der Polyanionen bei pH > 2 keinen Einfluß auf die Höhe des -Potentials der Quarzteilchen hat.Davon verschieden sind die Verhältnisse der Wechselwirkung bei graphitiertem Ruß. Hier erfolgt auch bei positiver Partikelladung keine Adsorption der untersuchten phosphorhaltigen Polyanionen. Dagegen wird Mellitsäure unter diesen Bedingungen stark adsorbiert und verschiebt den IEP von etwa pH 6,3 auf pH 5,3. Substituiert man in Hydroxyäthandiphosphonsäure die Methyl- durch eine Phenylgruppe, so wird auch diese Verbindung an graphitiertem Ruß adsorbiert. Bei der Adsorption von aromatischen Verbindungen an graphitiertem Ruß ist daher eine Wechselwirkung zwischen den -Elek-ktronensystemen von Adsorbens und Adsorbat anzunehmen.

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Summary The interaction between three solids (hematite, silica and graphitized carbon) with some polyanions (sodiumtripolyphosphate, ethane-I,I-diphosphonate, phosphonoacetate, -phosphonopropionate and mellitic acid) in aqueous solution was studied by measuring adsorption, electrokinetic potential and heat of immersion. It was observed that there are great differences in the interaction of the three solids investigated.Polyanions adsorb strongly at the hematite solution interface over a very wide range of pH, whereby a significant increase of pH is observed. In addition, since the particles are already negatively charged at pH > 4 it is concluded that chemisorption is involved. With increasing pH adsorption decreases. In the case of hydroxyethane-1,1-diphosphonate adsorption passes a minimum at pH 9. -potential is significantly less dependent on pH and passes a broad maximum at pH8. In case of hydroxyethane-1,1-diphosphonate -potential increases with pH monotonously. It follows from measurement of heats of immersion that the enthalpy of interaction is approximately zero. Consequently, the process is mainly governed by entropy change.Adsorption of polyanions on silica is very small and occurs at pH < IEP (= pH 1,3) only, as could be shown by measuring adsorption and -potential. At pH > 2 the presence of polyanions does not affect the -potential of the quartz particles.Quite different is the interaction between graphitized carbon particles and various polyanions. No adsorption has been observed of phosphorous containing polyanions even on positively charged particles. Mellitic acid adsorbs strongly under these conditions whereby IEP is shifted from pH 6,3 to 5,3, approximately. If the methyl group of hydroxyethane-1,1-diphosphonate is substituted by a phenyl this compound adsorbs at the carbon interface. It is likely to assume that the -electrons of the ring systems of adsorbent and adsorbate are involved in the adsorption of aromatic compounds.

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Mit 13 Abbildungen und 8 Tabellen     

Study of α- and β-relaxation processes in supercooled sucrose liquids

The relaxation map of highly concentrated sucrose water mixtures was built using mechanical and impedance spectroscopies. Data of - and -relaxation processes obtained with both techniques complete calorimetric and rheological measurements. The temperature evolutions of the relaxations were extrapolated using the measured data and the equations commonly used to describe the relaxations: Arrhenius and WLF behaviours for respectively the - and -relaxations. The temperature/frequency domain when and processes merge for 99% sucrose solution is discussed with respect to scenery proposed in the literature.This revised version was published online in November 2005 with corrections to the Cover Date.     

The measurement of heats of mixing of polymer alloys by a heat of solution method

Direct measurement of the heat of mixing (interaction) of polymers is not feasible due to their high viscosity. The indirect approach described here is a heat of solution method, in which a Hess's Law cycle is used to determine the heat of mixing from the individual heats of solution of the alloy and its constituent polymers in a common solvent. The main limitation of this approach lies in obtaining adequate precision on the experimentally determined heats of solution, as these are large compared to the calculated heat of mixing.With this method the heat of mixing of a 75/25 (%by wt) poly(dimethyl) phenylene oxide/polystyrene alloy has been determined by Setaram C-80 microcalorimeter as 4.9 + 0.2 Jg^–1. The precision of the method shows an improvement compared with published data.

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Zusammenfassung Die direkte Messung der Mischungswärme (Wechselwirkungswärme) von Polymeren ist wegen ihrer hohen Viskosität nicht möglich. Die hier beschriebene indirekte Vorgehensweise beruht auf der Lösungswärme, wobei ein Hess'scher Kreisprozess verwendet wird, um aus den einzelnen Lösungswärmen der Mischung und der sie aufbauenden individuellen Komponenten im gleichen Lösungsmittel die Mischungswärme zu bestimmen. Die entscheidende methodische Grenze ist die notwendige Genauigkeit bei der Bestimmung der Lösungswärmen, da diese gross gegenüber der berechneten Mischurigswärme sind.Mit dieser Methode wurden die Mischungswärme einer Mischung aus 75% Poly(dimethylphenylenoxid) und 25% Polystyren in einem Mikrokalorimeter Setaram C 80 zu 4.9 +- 0.2 J g^–1 bestimmt. Verglichen mit veröffentlichten Daten ist die Methode genauer.

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() - . , , - . , . -80 — 75 25 %, 4,9 ± 0,2 ·^–1. .

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The permission of the British Petroleum Company plc to publish this paper is gratefully acknowledged. The authors would like to thank Professor Karasz for useful discussions.     

A thermal analysis study of lanthanide adipate hydrates

The multi-step dehydration and decomposition of trivalent lanthanide adipate hydrates has been investigated by TG, DTG and DTA, together with infrared study of these compounds and the corresponding intermediate decomposition products. X-ray diffraction data for adipate complexes of general stoichiometry Ln₂(C₆H₈O₄)₃· 10H₂O, where Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu are also reported.

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Zusammenfassung Die in mehreren Schritten verlaufende Dehydratisierung und Zersetzung von Adipat-Hydraten der dreiwertigen Lanthanide wurden mittels TG, DTG und DTA untersucht. Diese Verbindungen und bei deren Zersetzung auftretende Zwischenprodukte wurden auch infrarotspektroskopisch charakterisiert. Röntgendiffraktometrische Daten sind für Adipatkomplexe der allgemeinen StöchiometrieLn₂(C₆H₈O₄)₃·10H₂O (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb und Lu) angegeben.

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, , Ln₂(C₆H₈O₄)₃·10₂. . .