The conductance of lithium-7 fluoride in dioxane-water mixtures at 25°C

Conductance data for lithium-7 fluoride in dioxane-water mixtures covering the range 78.35>D>36 in dielectric constant are presented. These data and other previous data on lithium-7 chloride and lithium-7 iodide were analyzed by the Fuoss 1980 conductance equation in order to find the limiting conductance _o, the pairing distance R and the conductometric association constant K. Setting K_a=K/V_M (where V_M is the molar volume of the solvent), the thermodynamic pairing constant and the corresponding change of the free energy g were calculated. Correlation among the values found for R and g=h–Ts and the properties characteristic of the ions and solvents are discussed.R. M. Fuoss died on 1^st December 1987 before this work was completed. A D'Aprano and F. Accascina dedicate this paper to him with respect and affection.     

Oxidation of [Co(en)2(SOCH2CO2)]+ by S2O82− and by IO4− in binary aqueous solvent mixtures at pressures up to 1.25 kbar

Second order rate constants and activation parameters H, S, and V have been measured for the oxidation of [Co(en)2(SOCH2CO2)]+ by S2O82– and by IO4– in highly aqueous H2O – t-BuOH mixtures. The changes in solvation on going from the initial to the transition state are discussed on the basis of the transfer functions Gto, Hto and Sto. Whereas Gt changes smoothly as the proportion of t-BuOH increases, the plots of Ht and TSt exhibit mirror behaviour and pass through extrema located around x2(t- BuOH)=0.038. Information on the role of solvation is complemented by the determination of activation volumes. These are discussed in terms of intrinsic and solvational contributions. It is proposed that changes in hydrophobic hydration are of principal importance in determining the response of H, S, and V to changes in solvent composition in H2O – t-BuOH mixtures.     

On the classification and coding of linear reaction mechanisms

Non-oriented kinetic graphs are classified and coded according to their topological properties.

---

.

---

---

Reported in part at The 5th All-Union Meeting on Homogeneous Catalysis, Alma-Ata, October 1979     

Catalytic oxidation of propylene to acrolein on a multicomponent oxide catalyst

Rate equations have been found and reaction schemes for oxidation of propylene to acrolein and acrylic acid have been suggested.

---

.

     

Mechanism of proton transfer from 2-nitrohexafluoropropane to amines

According to the analysis of NMR kinetic data, the proton transfer from the CH-acid 2-nitrohexafluoropropane to trioctylamine occurs in a hydrogen-bonded complex. The value of the k_H/k_D ratio (6) and the linearity of the ln k vs. T^–1 dependence indicate a classical mechanism of the process.

---

2- . . , . k_H/k_D 6 .

     

α,β-Butenolides

,-Dibromo--('-carbethoxyacetony)-^,-butenolide (I) reacts with amines in diethyl ether solution to give -bromo-amino--('-carbethoxyacetony)-^,-butenolides. Compounds n are converted to -bromo-amino--('-carbethoxyacetony)-^,-butenolides on reaction with amines. The corresponding arylhydrazones (VI and VII) are obtained by the reaction of I and II with p-nitro- and 2,4-dinitrophenylhydrazines. Compound I reacts with phenylhydrazine to give furopyridazine VIII.See [1] for communication IV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 867–871, July, 1972.     

Kinetics and mechanism of Os(VIII) catalyzed oxidation of dimethyl sulfoxide by vanadium(V)

The title reaction is first order each in vanadium(V) and Os(VIII) and fractional order with respect to DMSO. The rate is found to decrease with increasing concentrations of sulfuric, perchloric and acetic acid, whereas the rate increases with the increasing concentrations of sodium bisulfate and sodium perchlorate. Thermodynamic parameters like E_a, H, S and G were evaluated. A suitable mechanism consistent with the observed kinetics is proposed.     

Thermodynamic behavior of mixed benzodiazepines by a new liquid chromatographic method

Summary Using a rapid chemometric methodology to determine the separation factor, , at different temperatures, Gibbs Helmholtz parameters ( (H), (S), (G)) of two adjacent benodiazepines on a chromatogram were obtained from ln versus T^–1 plots. A temperature dependent reversal of the elution order was studied and the mobile phase composition and column temperature were optimized to obtain the best separation. A flow rate of 0.80 ml min^–1 with 52.6% methanol in the methanol-water mixture and a column temperature of 48°C gave the most efficient separation of ten benzodiazepines.     

Reaction of methylmagnesium iodide with steroid keto oxides

Summary The reaction of the 3-acetate of the 20-ketal of 16,17-oxido-⁵-pregnenol-3-one-20 with methylmagnesium iodide and subsequent hydrolysis of the reaction product yielded 16-methyl-⁵-pregnenediol-3 –17-one –20. 18-Nor-17-methyl-17-iso-^5.11-pregnadienediol-3,16-one-20 was formed as a by-product.     

Free energies of adsorption of amino acids, short linear peptides and 2,5-piperazinediones on silica from water as estimated from high-performance liquid-chromatographic retention data

Equilibrium constants (K) and free energies (— G) of adsorption of amino acids, short linear peptides and cyclic dipeptides (2,5-piperazinediones) on silica from neutral aqueous solutions were calculated from the retention values measured by means of high-performance liquid chromatography on a silica gel column. For most amino acids and linear peptides — G values were negative and K < 1, thus showing very weak adsorption. 2,5-Piperazinediones exhibited higher adsorbability (for most of them, — G > 0 and K > 1) as compared to related dipeptides. Influence of the structure of a-substituent on the adsorbability is analyzed. A linear dependence of — G on the number of aliphatic carbon atoms in a sorbate molecule was found for the series of aliphatic bifunctional amino acids, related dipeptides and 2,5-piperazinediones, as well as for the group from glycine to triglycyl glycine.     

Gibbs Energy and Entropy of Mixing in the NaNO2-KNO3 System

The activity and activity coefficients of the components of the NaNO₂-KNO₃ system, determined from the experimental data on the saturated vapor pressure at 798, 823, and 848 K, are used to calculate the relative and excess partial molar Gibbs energies (G _i and G _i ^{e x c}), entropies (S _i and S _i ^{e x c}), and integral relative and excess thermodynamic functions (G, G ^{e x c}, S, and S ^{e x c}) of the system.     

Temperature effect on the composition and activity of iron(III) stearate based organometallic catalysts in hydrogenation reactions

The observed temperature dependence of the composition of FeSt₃–AlEt₃ catalytic system indicates that with increasing temperature the maximum catalytic activity and the content of the associated polynuclear complex change in parallel. This complex probably plays a decisive role in catalytic processes.

---

FeSt₃–AlEt₃ . . , .

     

Study of solid-phase reaction between CsNO3 AND V2O5 in the molar ratio 6:5

Using DTA, DTG and TG methods, the solid-phase reaction between CsNO₃ and V₂O₅ in the molar ratio 65 has been studied in oxygen and air streams in the temperature range 20–550°. The reaction proceeds stepwise and CsV₃O₈ has been identified as an intermediate. A mixture of CsVO₃ and Cs₂V₄O₁₁ is formed as final product of the reaction at 520°. The composition of this mixture does not change up to 1000°.

---

Zusammenfassung Unter Anwendung der Methoden DTA, DTG und TG wurde die Festphasenreaktion von CsNO₃ und V₂O₃ im Molverhältnis von 65 im Sauerstoff- und Luftstrom im Temperaturbereich von 20 bis 550° untersucht. Die Reaktion verläuft stufenweise und CsV₃O₃ wurde als Zwischenprodukt identifiziert. Als Endprodukt der Reaktion bei 520° bildete sich ein Gemisch von CsVO₃ und Cs₃V₃O₁₁. Die Zusammensetzung dieses Gemisches ändert sich bis 1000° nicht.

---

Resumé On a étudié par ATD, TGD et TG, la réaction en phase solide entre CsNO₃ et V₂O₅ avec le rapport molaire de 65, dans un courant d'oxygène et d'air, dans l'intervalle de températures compris entre 20 et 550°. La réaction s'effectue par étapes et on a identifié CsV₃O₃ comme produit intermédiaire. Lors de la réaction à 520°, un mélange de CsVO₃ et Cs₂V₄O₃ se forme comme produit final. La composition de ce mélange ne varie pas jusqu'à 1000°.

---

, , CsNO₃ V₂O₅ 6 5 20–550°. CsV₃O₈. 520° CsVO₃ Cs₂V₄O₁₁, 1000°.

     

Mixed ligand derivatives of Th(IV)-EDTA,-CDTA or-DTPA chelate with glycollic and malic acids

The interaction of 11 Th(IV)-EDTA,-CDTA or-DTPA chelate with glycollic and malic acids has been investigated potentiometrically and the formation of 111 mixed ligand chelates inferred from the potentiometric curves. The hydrolysis and dimerization constants of the binary chelates and the equilibrium constants of the ternary derivatives have been evaluated at 30±1° and 35±1°C and also the thermodynamic functions, viz. F ⁰, H and S.With 3 Figures     

A study of solid-state thermal decomposition characteristics of some metallo-organic compounds

The solid-state dehydration of the hydrated Ca(II), Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) salts of pyridine-2-carboxylic acid (picolinic acid) and subsequent decarboxylation of the corresponding anhydrous salts have been studied by simultaneous TG, DTA and DTG. The sequences of thermal stability of the hydrated and the anhydrous compounds have been established from analysis of the TG, DTA and DTG traces for dehydration of the hydrated salts and for decarboxylation of the anhydrous compounds. Thermal parameters such as activation energy, enthalpy change and order of reaction for the different stages of each process have been computed by standard methods. An attempt has been made to account for the observed trend in the thermal stability of the anhydrous salts towards decarboxylation. A mechanism of thermal decraboxylation of calcium picolinate has been proposed.

---

Zusammenfassung Die Dehydratisierung der hydratisierten Ca(II)-, Mn(II)-, Co(II)-, Ni(II)-, Cu(II)- und Zn(II)-Salze der Pyridin-2-carboxylsäure (Picolinsäure) in fester Phase und die nachfolgende Decarboxylierung der entsprechenden wasserfreien Salze wurden mittels simultaner TG, DTA und DTG untersucht. Aus den thermoanalytischen Kurven wurde die der thermischen Stabilität entsprechende Reihenfolge der hydratisierten und wasserfreien Verbindungen ermittelt. Thermische Parameter wie Aktivierungsenergie, Enthalpieänderung und Reaktionsordnung wurden für die einzelnen Schritte jedes Prozesses nach Standardmethoden berechnet. Es wurde ein Versuch unternommen, den Trend in der thermischen Stabilität der wasserfreien Salze gegenüber Decarboxylierung zu erklären. Ein Mechanismus der thermischen Decarboxylierung von Calciumpicolinat wird vorgeschlagen.

---

, , , , , , . . , . . .

     

Examination of the flow behaviour of HEC and hmHEC solutions using structure–property relationships and rheo-optical methods

The effect of solely intermolecular interactions due to hydrophobic alkyl substituents on the flow behaviour of hmHEC solutions was determined via comparison of the structure–property relationships of hmHECs and HECs based on the overlap parameter c[]. For this purpose the ₀–[]–c relationship for HEC was determined to be ₀=8.91·10^–4+8.91·10^–4·c[]+1.07·10^–3(c[])²+1.83·10^–7(c[])^5.56. In addition the structure–property relationship for the longest relaxation time via the –[]–c relationship ·c^1+1/a=2.65·10^–8(c[])²+4.25·10^–8(c[])³+5.44·10^–12(c[])^5.27 has been determined. Although the hmHECs had a higher zero shear viscosity than HECs of comparable overlap parameters at a range of 1<c[]<13, the flow curves could be described via the same –[]–c relationship in that range, indicating a timescale of the intermolecular interactions below the longest relaxation time.The behaviour of the supramolecular structures in solution with an applied shear field was characterized by rheo-optical analysis of the shear thickening behaviour which occurs with addition of surfactant. Contrary to expectations, a slope >1 of the flow birefringence n as a function of shear rate could be observed in double logarithmic plotting. The degree of orientation of the flow birefringence primarily decreases with increasing shear rate, but increases later on at a characteristic shear rate. These two exceptional phenomena can be explained by a pronounced anisotropy of the polymer coils caused by the dilatant flow.This assumption is backed up by the occurrence of a maximum in the dichroism curves which is caused by a finite stability of the aggregated structures in solution. On a molecular basis, these observations agree with the theoretically predicted (Witten and Cohen) transition from intra- to intermolecular polymer micelles. The detected aggregates correspond with the polymer chains that are aligned in one micelle.Abbreviations a Exponent of the Mark–Houwink relationship - c_[]* Critical concentration (determined by intrinsic viscosity) - c_LS* Critical concentration (determined by light scattering) - HASE Hydrophobically modified alkali-swellable emulsions - HEUR Hydrophobically modified ethoxylated urethanes - hmHEC Hydrophobically modified hydroxyethylcellulose - HEC Hydroxyethylcellulose - HPMC Hydroxypropylmethylcellulose - M Molecular mass - MS Molar degree of substitution - n Slope of the flow curve - SEC Size exclusion chromatography - R_G Radius of gyration - Viscosity - ₀ Zero-shear viscosity - _sp Specific viscosity - Longest relaxation time - n Birefringence - n_i Intrinsic birefringence - n_f Form birefringence - n Dichroism - Orientation of the birefringence - ̇ Shear rate     

Synthesis of furan analogs of 1, 3, 5-triphenylpyrazoline derivatives

Furan analogs of chalcones are condensed with phenylhydrazine to give a number of ²-pyrazolines hitherto not described in the literature. It is shown that in , -unsaturated ketones, a nitro-group in the nucleus and remote from the carbonyl group makes cyclization to the corresponding ²-pyrazolines more difficult than does one adjacent to the carbonyl.     

Effect of the activation conditions on the catalytic properties of Pt/Al2O3 catalysts

The effect of the activation conditions of Pt/Al₂O₃ catalysts has been investigated in the hydrogenation of benzene and in the hydrogenolysis of ethane. Whatever the conditions of calcination or reduction, specific activities of all catalysts for benzene hydrogenation remain constant. On the other hand, for identical dispersities, the cacination in a wet argon flow increases the specific activity of platinum for hydrogenolysis of ethane, pointing out the role of wet pretreatment on defect building or on the faceting of supported metallic catalysts.

---

Pt/Al₂O₃ . , . , , . .

     

Effects of alkyl chain length on surface and micellar properties of octaethyleneglycol-n alkyl ethers

Summary Surface and micellar properties of a homologous series of Octaethylene glycol-n-alkyl ethers (C _n E₈;n = 9 to 15) have been studied in aqueous solutions by the surface tension measurements. The effects of the alkyl chain length comprising even and carbon numbers have been examined in order to evaluate the surface free energy G _A-W and the standard free energy G _m for the micellization obtained from their surface tension data. The areas per molecule and the equilibrium surface tension values at the CMC decreased with an increasing carbon number and they showed zigzag curves by the difference in even and odd carbon numbers.These findings may be attributed to the differences in the molecular orientation between the molecules with even carbon number and ones with odd carbon number on the air-water interface at CMC. G _A-W values decreased linearly with an increasing alkyl chain length but did not show a zigzag line by the differences in even and odd carbon numbers. This suggests that the molecular orientation is not influenced by the difference between their even and odd carbon numbers in the alkyl chain on the surface of the very diluted solution, and their molecules form some stable adsorbed films with an increase of the alkyl chain length. A division of G _A-W into the contribution made both by the hydrophilic group G _A-W (-W) and by the hydrophobic group G _A-W (-CH₂-) was attempted as follows; G _A-W (-CH₂-) = – 0.80 kcal/mol and G _a-W (-W) = + 0.15 kcal/mol.The free energy changes G _m of micellization were discussed on the basis of the CMC data obtained from the surface tension measurements by treating the formation of micelles as analogous to phase separation, and the contribution from the each moieties in the molecule were calculated as follows; G _m (-CH₂-) = – 0.68 kcal/mol and G _m (-W) = + 1.54 kcal/mol. The difference between G _A-W and G _m is discussed using their data.     

Use of thermal analysis in the synthesis of vinylidenediphosphonic acid

Simultaneous TG-DTA was applied to establish the optimum conditions for the synthesis of vinylidenediphosphonates via the intramolecular dehydration of 1-hydroxyethylidenediphosphonate salts (Li, Na, K, Rb, NH₄, Ca and Ba). The tested salts underwent water elimination at different temperatures. Consequently, they are of different values for the synthesis of vinylidenedi phosphonates. The dibarium salt proved to be the best for this purpose, whereas the tetrammonium salt can not be used because of its uncontrolled thermal decomposition. The kinetic parameters do not reveal any influence of the metal cation on the intramolecular dehydration process.

---

Zusammenfassung Simultane TG-DTA wurde eingesetzt, um die optimalen Bedingungen für die Synthese der Vinidylidendiphosphonate durch intramolekulare Wasserabspaltung aus den 1-Hydroxiethylidendiphosphaten des Li, Na, K, Rb, NH₄, Ca und Ba zu ermitteln. Aus den untersuchten Salzen wurde das Wasser bei verschiedenen Temperaturen abgespalten, sie sind daher unterschiedlich brauchbar zur Synthese der Vinylidenphosphonate. Das Bariumsalz erwies sich am geeignetsten, während das Tetra-ammoniumsalz wegen seiner unkontrollierten thermischen Zersetzung ungeeignet ist. Die kinetischen Parameter der intramolekularen Wasserabspaltung zeigen keinen Einfluss des vorhandenen Metallkations.

---

1- 1- , , , , , . . , . , , , , . , .