Complexes of divalent ions in mixed solvent media. III. Outer-sphere interactions in amine + diluent solutions

The standard enthalpies and (in part) free energies and entropies of transfer from amine (L) to amine + diluent (D) mixtures have been determined for MX₂L₂ complexes at 25°C using chloroform, 1,1,2,2,-tetrachloroethane (TCE), benzene, chlorobenzene, and ethyl acetate as diluents (M=Co and Zn; X=Cl and Br; L = pyridine, -picoline, and -picoline). Thermodynamic functions of transfer indicate specific outer-sphere interactions of the complexes with amine and protic diluents (chloroform and TCE) and reveal solvent-solvent interactions of amine + protic diluent mixtures. The effects of the nature of X, L, and M of the MX₂L₂ complexes on their interaction with the components of the mixed solvent are discussed.Deceased.     

Empirical equations of state for adsorption layer: Alkylthiopolyoxyethylene glycols

Surface tension isotherms ofn-alkylthiopolyoxyerhylene glycols:n-C _x H_2x+1S(CH₂CH₂O) _y H, wherex=5 to 8,y=3 or 4, were approximated with orthogonal polynomials to get good quality values of surface pressure (II) and molar area of the adsorbed layer (). The modified Volmer (*(–₀)=Z*R*T) van der Waals and virial equations of state were used to correlate and in terms of real two-dimensional gas. The combination of Volmer and van der Waals equations of state made it possible to determine the interaction energy, , which was prescribed to cohesion of hydrophobic chains in the adsorption layer. The value of for the amphiphiles in question was in the range 0.97–1.91R*T and the average contribution per methylene group was ca. 0.21R*T.The Lennard-Jones potentials calculated from second virial coefficient were of the same range as , but no clear relation was found between their values and number of structure elements of the alkylthiopolyoxyethlene glycols.Presented during 7th International Conference: Surface and Colloid Science, July 7–13, 1991, Compiegne, France     

Kinetics of triphenylphosphite ozonide consumption in reaction with triphenylphosphite

Kinetic regularities of triphenylphosphite ozonide reaction with triphenylphosphite have been studied at T=–75°C to –40°C. The rate of ozonide consumption is estimated as W=k₁[(C₆H₅O)₃P·O₃]+k₂[(C₆H₅O)₃P·O₃][(C₆H₅O)₃P], where k₁=(2.03±0.39)×10^–5s^–1(–50°C), 1gk₂=(3.82±0.33)–(6.61±0.32)/gq dm³/mol s and =2.303RT kcal/mol.

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–75°C –40°C . : W=k₁[(C₆H₅O)₃P·O₃]+k₂[(C₆H₅O)₃P·O₃][(C₆H₅O)₃P], k₁=(2,03±0,39)·10^–5–1(–50°C); 1g k₂=(3,82±0,33)–(6,61±0,32)/ /·, =2,303·RT /

     

Etude thermoanalytique de conditions de formation du gallate de sodium,II

Résumé L'étude par TG, ATD, analyse chimique et IR du système Na₂O₂/Ga₂O₃ a montré qu'au début du chauffage, sous l'action de la soude, il se formait de l'hydroxogallate qui se transformait en gallate vers 130–150C. Entre 287 et 350, Na₂O₂ et NaOH attaquent conjointement Ga₂O₃. NaGaO₂ obtenu possède des groupements GaO₄. La sensibilité de l'ATD permet de différencier les domaines de réactivité maximale des deux composés sodiques. Audelà de 350, une nouvelle réaction de Na₂O₂ produit principalement du gallate à groupements GaO₆. L'attaque de Ga₂O₃ au cours de ces différentes phases dépend essentiellement de sa variété cristalline.

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Thermogravimetric, differential thermoanalytical and infrared spectroscopic studies of the system Na₂O₂/Ga₂O₃ have shown that in the reaction with sodium hydroxide hydroxogallate is formed, which transforms to gallate in the range of 130 to 150. Between 287 and 350 Na₂O₂ and NaOH attack Ga₂O₃ together, and the NaGaO₂ obtained contains GaO₄ groups. The DTA method permitted to distinguish the ranges of maximum reactivity of the two sodium compounds. Above 350 gallate containing GaO₆ groups is mainly formed in a new reaction of Na₂O₂. The attack of Ga₂O₃ in the course of the different steps depends mainly on its crystal structure.

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Zusammenfassung Thermogravimetrische, differentialthermoanalytische und infrarotspektroskopische Untersuchungen des Systems Na₂O₂/Ga₂O₃ zeigten, daß bei Einwirkung von Natriumhydroxyd Hydroxogallat gebildet wurde, das zwischen 130–150 in Gallat überging. Zwischen 287 und 350 greifen Na₂O₂ und NaOH gemeinsam das Ga₂O₃ an, das erhaltene NaGaO₂ enthält GaO₄ Gruppen. Durch DTA gelang es die Gebiete der maximalen Reaktivität der zwei Natriumverbindungen zu differenzieren. über 350 entsteht durch eine neue Reaktion von Na₂O₂ hauptsächlich Gallat mit GaO₆ Gruppen. Der Aufschluß von Ga₂O₃ hängt während dieser verschiedenen Phasen im wesentlichen von seiner kristallinen Beschaffenheit ab.

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Na₂O₂/Ga₂O₃ , , , 130–150. 287 350 Na₂O₂, NaOH, Ga₂O₃ NaGaO₂ G₄-. . Na₂O₂ 350, , G₆-. G₂₃ .

     

Discrimination of active sites for ethylene homologation and ethylene metathesis on molybdena silica catalyst

Active sites for ethylene homologation (3C₂H₄2C₃H₆) and ethylene metathesis (C₂H₄–¹²C₂+C₂H₄–¹³C₂2C₂H₄–¹³C₁) were discriminated by adding platinum to a reduced molybdena silica catalyst, and the former was presumed to be composed of several molybdenum species, while the latter was presumed to be composed of one molybdenum species.

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(3C₂H₄2C₃H₆) (C₂H₄–¹²C₂+C₂H₄–¹³C₂2C₂H₄–¹³C₁) . , , .

     

Coadsorption of ethylene and oxygen on an iridium surface

It is established that the hydrocarbon coverage (0<1) formed at T<400 K on the Ir surface is oxidized upon oxygen exposures to CO and H₂O by an adsorption mechanism. Complete oxidation to CO₂ and H₂O is achieved at T350 K after C₂H₄ exposures of the oxygen coverage.

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, (<1), T<400 K Ir, CO H₂O . CO₂ H₂O T350 K C₂H₄ .

     

Molecular isotope exchange of14CO in surface carbonyl complexes of rhodium

Molecular isotope exchange of CO with¹⁴CO for Rh₆(CO)₁₆/Sn(II)–SiO₂, Rh₆(CO)₁₆/Al₂O₃, Rh(I)(CO)₂/Al₂O₃, Rh₄(CO)₁₂/Al₂O₃ carbonyl complexes of rhodium has been studied. Estimates of the activation energies and a mechanism of the CO exchange are suggested.

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, (Rh₆(CO)₁₆/Sn(II)–SiO₂, Rh₆(CO)₁₆/Al₂O₃, Rh^I(CO)₂/Al₂O₃, Rh₄(CO)₁₂/Al₂O₃), ¹⁴CO. CO .

     

Equilibres solide ⇄ liquide ⇆ vapeur du systeme binaire CoCl2-H2O

Résumé Les équilibres solide liquide vapeur du système binaire CoCl₂-H₂O sont étudiés dans le domaine de température 120–720. La pression de la solution saturée est mesurée entre 1 et 60 atm. et le diagramme de phases est établi.Deux composés intermédiaires: CoCl₂ · 2H₂O et CoCl₂ · H₂O sont observés; ils subissent une décomposition péritectique à 206 et 335.Un tri et un tétrahydrate n'ont pas été obtenus malgré une étude systématique faisant intervenir des mesures d'analyse thermique, de thermogravimétrie et d'ébulliométrie.L'enthalpie et l'entropie de fusion du chlorure de cobalt sont évaluées à partir de la pente de la courbe de liquidus.Les valeurs calculées de l'enthalpie de déshydration de CoCl₂ · 2H₂O et CoCl₂ · H₂O entre 1 et 60 bars sont respectivement de 17 et 16 Kcal. mole^–1.

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Solid liquid vapor equilibria of the binary system CoCl₂-H₂O are investigated in the temperature range 120–720. The pressure of saturated solutions is measured between 1 and 60 atm, and the phase-diagram is established.Two intermediate compounds, CoCl₂ · 2H₂O and CoCl₂ · H₂O, are observed; they undergo peritectic decomposition at 206 and 335.Tri- and tetrahydrate have not been detected in spite of systematic research involving thermal analysis, thermogravimetry and ebulliometry.The enthalpy and entropy of fusion of cobalt chloride are calculated from the slope of the liquidus curve.The calculated enthalpy of dehydration values of CoCl₂ · 2H₂O and CoCl₂ · H₂O between 1 and 60 atm are 17 and 16 Kcal · mole^–1, respectively.

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Zusammenfassung Die Gleichgewichte Festkörper Flüssigkeit Dampf des binären Systems CoCl₂-H₂O wurden im Temperaturbereich von 120 bis 720C untersucht. Der Druck der gesättigten Lösung wurde zwischen 1 und 60 Atm. gemessen und das Phasendiagramm aufgenommen.Zwei Intermediärverbindungen: CoCl₂ · 2H₂O und CoCl₂ · H₂O wurden beobachtet; diese zersetzen sich bei 206 und 335 peritektisch.Ein Tri- und ein Tetrahydrat wurden trotz systematischer Untersuchungen mittels thermoanalytischer, thermogravimetrischer und ebulliometrischer Messung nicht gefunden.Die Enthalpie und Entropie der Kobaltchloridschmelze wurden aus der Steigung der Liquiduskurve ermittelt.Die errechneten Werte der Dehydratierungsenthalpie betrugen für CoCl₂ · 2H ₂ O und CoCl₂ · H₂O zwischen 1 und 60 bar 17 bzw. 16 Kcal₂ mol^–1.

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l₂-₂ 120–720. 1 60 . . CoCl₂. 2₂ l₂ · ₂, 206 335. , , , . . l₂. 2₂ l₂. ₂ 1 60 ., , 17 16 . ^–1.

     

Spin crossover studies in tris(N,N′-dialkyldithiocarbamato)iron(III) complexes

A series of fifteen complexes of the type [Fe(RRNCS₂)₃] with symmetric (R=R=n- C₆H₁₃, n-C₈H₁₇, CH₂–CH=;CH₂, C₆H₅, C₆H₁₁ and C₆H₅CH₂), unsymmetric (R = CH₃; R = n-C₄H₉, C₆H₁₁, C₆H₅ and R = C₂H₅; R = n-C₄H₉, C₆H₁₁, C₆H₅ and i-C₃H₇) and ring substituents (RNR=pyrrolidyl and piperidyl) have been synthesized and their magnetic moments and Mössbauer spectra recorded from room temperature (RT) to liquid nitrogen temperature (LNT). Room temperature Mössbauer spectra of all the complexes exhibit an asymmetric doublet, which could be resolved into two doublets, each corresponding to low and high spin states in equilibrium. The crystal structure of tris(N, N-diallyldithiocarbamato)iron(III) shows it to be monoclinic with trigonally distorted octahedral geometry and space group C2/c. Fe–S stretching vibrations in the far i.r. region also show equilibria, HS LS. Depending on the nature of the alkyl group substituent, variable temperature magnetic moment and Mössbauer spectral studies, all the complexes may be divided into three groups; high spin complexes exhibiting spin-crossover (⁶A_1g ²T_2g), high spin complexes exhibiting spin transition (⁶A_1g ⁴T_1g) and intermediate spin complexes showing spin transition (⁴A_1g ²T_2g). On the basis of areas of the two doublets corresponding to high and low spin states, their percent contributions were calculated. Furthermore, magnetic moments of the equilibrium mixture calculated on the basis of respective areas compare well with the experimentally determined _eff values. E_Q values for both high and low spin states show linear decrease with increasing temperature.     

Spin density distributions in radical anions of heterocyclic amine N-oxides

The unrestricted Hartree-Fock (UHF) method of Snyder and Amos is used to calculate, in the -electron approximation, the spin density distributions in radical anions of heterocyclic amine N-oxides. The computed spin densities are observed to be in good agreement with the experimental values. The computed spin density distribution of the radical anion of pyridine N-oxide is consistent with the greater susceptibility of pyridine N-oxide relative to pyridine to electrophilic nitration. Also, the calculations are consistent with the lower basicity of the N-oxides relative to the parent bases.     

Reaction of ammonium sulphate with aluminium oxide

The reaction between ammonium sulphate with aluminium oxide was studied. It was confirmed by X-ray diffraction and chemical analysis that three intermediate reaction products, (NH₄)₃Al(SO₄)₃, NH₄Al(SO₄)₂ and Al₂(SO₄)₃, are formed. The thermal decompositions of these three compounds were carried out. It has been shown that the same rate law is valid for them. The activation energies for (NH₄)₃Al(SO₄)₃, NH₄Al(SO₄)₂ and Al₂(SO₄)₃ are 95.9, 177.9 and 291.0 kj/mol, respectively.

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Zusammenfassung Die Reaktion von Ammoniumsulfat mit Aluminiumoxid wurde untersucht. Durch Röntgendiffraktion und chemische Analyse wurde bestätigt, daß drei Zwischenprodukte (NH₄)₃Al(SO₄)₃, NH₄Al(SO₄)₂ und Al₂(SO₄)₃ gebildet werden. Die thermische Zersetzung der drei Verbindungen wurde durchgeführt. Es wurde gezeigt, daß für alle drei dasselbe Geschwindigkeitsgesetz Gültigkeit hat. Die Aktivierungsenergien für (NH₄)₃Al(SO₄)₃, NH₄Al(SO₄)₂ und Al₂(SO₄)₃ sind 95.9, 177.9 und 291.0 kJ/Mol.

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. - : (NH₄)₃Al(SO₄)₃, NH₄Al(SO₄)₂ Al₂(SO₄)₃. , , . (NH₄)₃Al(SO₄)₃, NH₄Al(SO₄)₂ Al₂(SO₄)₃, , 95.9; 177.9 291.0 . ^–1.

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The authors are grateful to Dr. H. Osada and Mr. H. Nakamura, Department of Environmental Engineering, Kyushu Institute of Technology, for their helpful discussions.     

Sintering of supported palladium

Sintering results of Pd supported on carbon black at 723–973 K, in water vapor, in H₂ and under high vacuum are reported. They are compared with sintering data of Pd on other supports. The observed sequences are: SiO₂C>sepioliteAl₂O₃>AlPO₄ and H₂O>high vacuum>H₂.

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Pd 723–973 , , H₂ . Pd . : SiO₂Al₂O₃>AlPO₄ H₂O> >H₂.

     

Catalysts for selective hydrogenation of conjugated dienes into olefins in the presence of PdCl2 complexes

Complexes of PdCl₂ with amines or pyridine reduced by (iso-Bu)₂ AlH are shown to be catalytically active in the selective hydrogenation of conjugated dienes into olefins in aromatic media. The promoting effect of H₂O and O₂ has been established.

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PdCl₂ , (-Bu)₂ AlH, . H₂O O₂.

     

Decomposition of hydrotrioxides catalyzed by carboxylic acids

Carboxylic acids (HCOOH, CH₃COOH, CH₂ClCOOH, CCl₃COOH, CF₃COOH and C₄H₉COOH) are shown to increase the firstorder effective rate constant of chemiluminescence quenching (k_q) in the decomposition of hydroxides Me₂C(OH)OOOH and Me₂CHOC(OOOH)Me₂. With decreasing pK_a of an acid, its catalytic effect on k_q grows.

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, HCOOH, CH₃COOH, CH₂ClCOOH, CCl₃COOH, CF₃COOH, C₄H₉COOH () Me₂C(OH)OOOH Me₂CHOC(OOOH)Me₂. .

     

An IR study of the Ziegler system Co(acad)3/Mg(n-butyl)2 in THF

Applying IR spectroscopy for studying the Ziegler system Co(acac)₃/Mg(Bu)₂ (Bu=n-butyl) in tetrahydrofuran, it could be shown that the following reactions take place: reduction of cobalt (III), exchange of the acetylacetonate groups and their interaction with Mg(Bu)₂.

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Co(acac)₃/Mg(Bu)₂ (Bu=-) - , (III), Mg(Bu)₂.

     

Relative enthalpies and related thermodynamic functions of some organic compounds by drop calorimetry

The values of thermodynamic functions of the following eight organic compounds under non-reacting conditions within the temperature range 298.15 – 550 K are given: N,N dimethylformamide, CHO · N(CH₃)₂; 4-nitro-1-chlorobenzene, Cl · C₆H₄ · NO₂; sodiump-nitrophenoxide, NO₂ · C₆H₄ · ONa; 1-methyl-2-pyrrolidone, 4,4-dinitrodiphenyl ether, (NO₂ · C₆H₄)₂O; 4,4-diaminodiphenyl ether, (NH₂ · C₆H₄)₂O; bis-(4-aminophenyl)methane, (NH₂ · C₆H₄)₂CH₂; bis(4-maleic acidimidphenyl)methane, The relative enthalpy was obtained from calorimetric data by drop calorimetry. The heat capacity and relative entropy are functions derived from the foregoing. The equations of the temperature variation of the relative enthalphy were obtained by computer processing of the calorimetric data by the least squares method. The parameters of solid-liquid transitions were determined from the discontinuity of the temperature variation of the relative enthalpy.

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Zusamenfassung Die Werte der thermodynamischen Funktionen folgender 8 organischer Verbindungen werden unter nicht-reagierenden Bedingungen im Temperaturbereich von 298.15 bis 550 K angegeben: Dimethylformamid, CHO · N(CH₃)₂;p-Nitrochlorbenzol, Cl · C₆H₄NO₂; Natrium-p-Nitrophenoxid, NO₂ · C₆H₄ONa; N-Methylpyrrolidon, 4-4-Dinitrodiphenyläther, (NO₂ · C₆H₄)₂O; 4-4-Diaminodiphenyläther, (NH₂C₆H₄)₂O; 4-- 4-Diaminodiphenylmethan, (NH₂ · C₆H₄)₂CH₂; 4-4-bis-Maleinimid-Diphenylmethan, Die relative Enthalpie wird aus kalorimetrischen Daten der Temperaturgefällekalorimetrie erhalten. Die Wärmekapazität und die relative Entropie sind Funktionen der erwähnten Werte. Die Gleichungen der Temperaturänderung der relativen Enthalpie wurden mittels Computerverarbeitung der kalorimetrischen Daten, mit der Methode der kleinsten Quadrate erhalten. Die Parameter der fest-flüssig Übergänge wurden an Hand der Diskontinuität der Temperaturänderung der relativen Enthalpie bestimmt.

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Résumé On donne les valeurs des fonctions thermodynamiques des 8 composés organiques suivants, en conditions non réactionnelles, dans l'intervalle de températures 298.15–550 K: diméthylformamide CHO · N(CH₃)₂,p-nitrochlorobenzène Cl · C₆H₄ · NO₂,p-nitrophé noxysodium NO₂ · C₆H₄ · ONa, N-méthylpyrrolidone dinitrodiphényl-4,4 éther (NO₂ · C₆H₄)₂O, diaminodiphényl-4,4 méthane (NH₂ ·H ₄CH₂, 4-4 bis maléinimide diphénylméthane L'enthalpie relative a été obtenue à partir de données calorimétriques fournies par un calorimètre à chute. La chaleur spécifique et l'entropie relative sont des fonction dérivées de la précédente. Les équations donnant la variation de l'enthalpie relative en fonction de la température sont obtenues par traitement des données calorimétriques sur ordinateur par la méthode des moindres carrés. Les paramètres des transitions solide-liquide ont été déterminés à partir de la discontinuité de la variation de l'enthalpie relative avec la température.

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, 298,15–550 , : — · N(CH₃)₂;- — l · ₆₄ · NO₂.- -NO₂·₆₄·ONa; N-—₃·N··₂·₂₂; 4,4- — (NO₂·₆₄)₂; 4,4- — (NH₂·₆₄)₂; 4,4- — (NH₂·₆₄)₂₂; 4,4-- —(₆₄.N. . :. )₂₂. . , . . - .

     

Interaction between nitrous oxide and ruthenium catalysts

TPD data indicate that N₂O is desorbed from Ru and -Al₂O₃ without decomposition in one step and from Ru/Al₂O₃ in two steps with simultaneous decomposition to nitrogen and oxygen.

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, N₂O Ru -Al₂O₃ , Ru/Al₂O₃— .

     

Thermal and some other properties of the complexes crystallizing from the system Ni(II)-en-[Ni(CN)4]2−-H2O

Seven complex compounds exhibiting the compositions Ni(en)₃Ni(CN)₄·H₂O (I), Ni(en)₃Ni(CN)₄ (II),-Ni(en)₂Ni(CN)₄ (III), Ni(en)Ni(CN)₄·2H₂O (IV), Ni(en)Ni(CN)₄ (V), Ni(en)₂Ni(CN)₄ · 2.5H₂O (VI) and-Ni(en)₂Ni(CN)₄ (VII) were prepared from the system Ni-en-[Ni(CN)₄]^2–-H₂O. These compounds were examined by the methods of infrared spectroscopy, X-ray powder diffractometry, UV-VIS reflectance spectroscopy, and also by the measurement of magnetic moments. The thermal stability, the stoichiometry of thermal decomposition and the mutual transformations were investigated with a derivatograph. The reactions proceeding according to the following schemes were observed if the system was heated to appropriate temperature: (I)(II)(III)(V)(IV) and (VI)(VII)(III)(V)(IV) Process (VII)(III) represents isomerization. The reversibility of the process (V)(IV) is due to the high hygroscopicity of the anhydrous complex. The changes in structure in the course of the individual processes are discussed.

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Zusammenfassung Aus einem System Ni-en-[Ni(CN)₄]^2–-H₂O wurden sieben Komplexe der Formeln Ni(en)₃Ni(CN)₄·H₂O (I), Ni(en)₃Ni(CN)₄ (II),-Ni(en)₂Ni(CN)₄ (III), Ni(en)Ni(CN)₄·2H₂O (IV), Ni(en)Ni(CN)₄ (V), Ni(en)₂Ni(CN)₄ · 2.5H₂O (VI) und-Ni(en)₂Ni(CN)₄ (VII) hergestellt. Diese Verbindungen wurden mittels IR-Spektroskopie, Röntgenpulverdiffraktometrie, UV-Reflexionsspektroskopie und durch Messungen des magnetischen Momentes untersucht. Die Wärmestabilität, die Stöchiometrie des thermischen Zerfalles und die gegenseitigen Umwandlungen wurden mittels eines Derivatographen untersucht. Wird das System auf geeignete Temperaturen erhitzt, kann der Reaktionsverlauf durch folgendes Schema dargestellt werden: (I)(II)(III)(V)(IV) und (VI)(VII)(III)(V)(IV).Der Prozeß (VII)(III) verkörpert eine Isomerisierung. Die Umkehrbarkeit von Prozeß (V)(IV) ist auf die ausgeprägten Hygroskopieeigenschaften des wasserfreien Komplexes zurückzuführen. Es werden die im Ablaufe der einzelnen Prozesse vorgehenden Strukturveränderungen besprochen.

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Ni- -[No(N)]² -₂ Ni(en)₃Ni(CN)₄ · ₂ (I), Ni(en)₃Ni(CN)₄ (II),-Ni(en)₂Ni(CN)₄ (III), Ni(en)Ni(CN)₄-2H₂O (IV), Ni(en)Ni(CN)₄ (V), Ni(en)₂Ni(CN)₄ · 2,5H₂O (VI) -Ni(en)₂Ni(CN)₄ (VII). , , - , . , . (I)(II)(III)(V)(IV) (VI)(VII)(III)(V)(IV). (VII)(III) . (V)(IV) . .

     

IR-spectroscopic studies of strength and concentration of acid centers on V2O5/Al2O3 catalysts

The strength of protonic sites and the concentration of acid centers in V₂O₅/Al₂O₃ catalysts have been estimated according to pyridine and ammonium adsorption.

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V₂O₅/Al₂O₃.