Mass transfer from copper melts by top-blowing of an argon-hydrogen plasma jet

The volatilization of lead, copper, tin, and zinc from copper melts using the technique of top-blowing with an argon-hydrogen plasma jet was experimentally investigated and theoretically evaluated. A plasma burner with 16 kW power was used in the experiments. The mole flow of the plasma gases was 0.017 mol/s (25 liters/min when T = 25°C and P_G = 1 bar). The temperature was 1830°C on the surface of the melt and between 1200 and 1500°C in the molten solution. When the zinc concentration is above 2 mole%, supersaturation of zinc occurs on the surface. In this range of concentrations the ratio of dilution of the concentration in relation to time is linear (zeroth-order reaction). When the concentration of zinc is below 2 mole%, the time dependence of volatilization can be described by an exponential law corresponding to a first-order reaction, because in this case the rate-determining step is the mass transport of zinc in the molten copper phase. From the change from zeroth-order to first-order reaction during the volatilization of zinc, the temperature on the surface of the melt can be estimated with a high degree of accuracy. On the other hand, the volatilization of tin and lead is determined by mass transfer in the gas phase, which leads to an exponential law for the whole range of concentrations. Reaction models were set up on the basis of the experimental data. The relationships thereby obtained permit one to evaluate in advance the yield of future industrial volatilization processes with top-blown plasma jets.Nomenclature A activity - A _e , m² effective mass-transport or mass-transfer area - k, mol/m² s^–1 mass-transfer coefficient - k _g , mol/m² s^–1 mass-transfer coefficient in the gas phase - k _s , mol/m² s^–1 mass-transfer coefficient in the melt phase - k, mol/m² s^–1 overall mass-transfer coefficient - K =P _i /x _i equilibrium coefficient (distribution coefficient) - K _T =P _i /a _i equilibrium coefficient - n _s , mol number of moles of the melt phase - n _G , mol number of moles of the gas phase - n _g , mol/s mole flow of the top-blown gas - n _i , mol/s mole flow of the extract i into the gas phase - P _i , N/ M² partial pressure of extract substance i in the gas phase - t, s time - T, °C or K temperature: T_s, in the melt; T , at the phase interface - x _i , mol/mol concentration in the melt - X _f ¹ , mol/mol concentration in the melt at the phase interface - w, s^–1 rate constant - y _i , mol/mol concentration in the gas phase - y _f ⁱ , mol/mol concentration in the gas phase at interface - z, m coordinate in the direction of mass transfer - activity coefficient - ^O Henry coefficient     

Separation of a binary gas mixture by pressure swing adsorption: Comparison of different PSA cycles

Gas separation of a binary gas mixture by various pressure swing adsorption (PSA) cycles was studied by a numerical simulation in order to provide a guidance in selecting PSA cycles. PSA cycles considered in this study are 3, 4-step cycles for production of only one component and a cycle with pressure equalization for production of a light component. 4 and 5-step cycles for simultaneous production of both components of a binary gas mixture are also considered. Separation of a CH₄/CO₂ gas mixture with zeolite 5A was chosen as a case study. Performances of cycles were examined and compared in view of purity, recovery and productivity. Their relative advantages were discussed. Inclusion of a purging step to a 3-step cycle for production of only one component improves a cycle performance. Further performance improvement of a cycle for production of a light component can be achieved by employing pressure equalization. Sircar's 4-step cycle with a recycle of effluent shows the best performance in view of purity and recovery among cycles for simultaneous production of both components.Nomenclature B Langmuir adsorption constant, bar^–1 - C concentration of sorbate in gas phase, mol/m³ - D defined by Eq. (7) - n amount of sorbate in solid phase, mol/kg - n _s monolayer amount adsorbed, mol/kg - P pressure, bar - R gas constant, J/mol K - T temperature, K - t time, s - U effluent gas velocity, m/s - z height of one cell, m - bulk density of a bed, kg/m³ - bed void fraction - A CH₄ - B CO₂ - H high pressure feed step - P purge step - R heavy-component rinse step - i cell number (i=1 toN)     

Study of a hollow cathode arc discharge in the presence of chromium oxide

A hollow cathode arc discharge in hydrogen has been used for the purpose of chromium oxide reduction, the solid oxide being placed inside the anode. Mass transport from the oxide to the gas phase and excitation conditions in the plasma have been investigated. The results show that a substantial amount of oxide is transferred to the gas phase with subsequent reduction and deposition inside the cathode cavity, in the form of a pure metal. The residual part condenses on the discharge chamber wall as an amorphous substance, containing 50–60% of Cr metal, and on the anode surface under the form of a mixture of chromium oxide and metal crystals (10%). From spectroscopic investigations it follows that, inside the anode zone, total Cr concentration in the gas phase is of the order of 10¹⁴ cm^–3, the excitation temperature of the atoms and ions being 4500 and 5500 K, respectively, and the ionization temperature being about 6000 K.Notation I absolute spectral line intensity (W cm^–2 sr^–1) - emission coefficient (W cm^–3 sr^–1) - A relative absorption - absorption coefficient (cm^–1) - L plasma diameter (mm) - f _tk oscillator strength - _D full Doppler width (cm^–1) - S( ₀ L) Ladenburg-Levy function - wave number (cm^–1) - k _pl mass transport rate (mol cm^–2 s^–1) - k _th thermal reduction rate (mol cm^–2 s^–1) - u ion mobility (mm V^–1 s^–1 ) - E electric field strength (V mm^–1) - drift velocity (cm s^–1)     

Background elimination in three-dimensional spectroscopy using the intensian method

The method to eliminate background in the case of quantitative multidimensional spectroscopy, chromatography or any analytical 3-dimensional technique is shown. The 3-dimensional signal is required to be proportional to the concentration of determined substance and the additivity of signals should be obeyed. Eliminated background is assumed to be a low-order polynomial of two variables. The intensian method [1] is a generalization of the Beer-Lambert law, where a certain determinant called intensian replaces absorption and absorptivity. In practice there will be no need to use determinants, since usually they are replaced by expressions of few terms. Some details on the practical use of the method are given.Index of used symbols x, y UV, IR, GC, NMR or other scale. - A (x, y) intensity (absorption) of the 3-dimensional band of interest. - a (x, y) standard intensity (absorption) of the 3-dimensional band of interest. - B(x, y) intensity (absorption) of 3-dimensional background. - S(tx, y) intensity (absorption) of 3-dimensional multicomponent spectrum. - f (x, y) auxiliary function:f (x, y) =A (x, y), B(x, y), a(x, y), S(x, y). - (x _i, Yi) selected point,i positive integer number. - f(xi, yi) value off (x, y) in point (xi, yi). - S _i value ofS(x, y) in point (x _i, y_i). - b pathlength, measurement coefficient,c concentration. - , , , real numbers. - ij, _ij real coefficients of power expansions. - x ⁱy^j monomial of degree (i +j). - F(·) linear functional acting on 3-dimensional spectral functions. - J^3-dim(·) 3-dimensional intensian acting on 3-dimensional spectral functions. - J _n ^3-dim (·) 3-dimensionaln-points intensian. - d _i ith intensian coefficient, cofactor of expansion of J _n ^3-dim (f(x, y)) according to its first row (eq. (10)). - (.) absolute error. - r _i,, R random variables: eqs. (13) and (14). - G(.) (normal) distribution function. - z ordinate axis. - a - f , h abreviations for some arguments. - d _ijk,D _mnp abreviations defined in eq. (22).     

Contribution to the thermodynamics of emulsions

Summary In this paper there are derived equations for thermodynamically stable emulsions of phase II in phase I in the presence of surfactants.

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Zusammenfassung In dieser Arbeit werden Gleichungen für thermodynamisch stabile Emulsionen einer Phase II in Phase I in Gegenwart oberflächenaktiver Stoffe abgeleitet.

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Notation A interfacial area between phase I and phase II - interfacial tension between phase I and phase II - ⁰ interfacial tension without presence of a surfactant - n _i number of moles = amount of componenti - C ₃ concentration of the surfactant = component 3 in phase I in mol/cm³ With 1 figure and 2 tables     

Tantalum(v) oxoalkoxides. Synthesis and structure

Anodic oxidation of tantalum in isopropyl alcohol or prolonged reflux of an alcohol solution of Ta(OPrⁱ)₅ afford crystalline oxoisopropoxide Ta₂O(OPrⁱ)₈ · PrⁱOH (1). In its molecule, two octahedra about Ta atoms are linkedvia the shared edge [(OPrⁱ)O]. Compound1 is the first example of oxoalkoxide containing such a small number of metal atoms. Unlike the known polynuclear molecules M _n O _m (OR) _p , oxoalkoxide1 is stable in solutions; on transition to the gas phase, this compound is desolvated to form a very stable molecule Ta₂O(OPrⁱ)₈ (apparently, consisting of two octahedra with a shared edge). According to the data of mass spectrometry, analogous molecules exist in the gas phase over Ta(OAlk)₅ (Alk = Me, Et, Prⁱ, or Bu¹¹). When compound1 is heated invacuo (10^–2–10^–3 Torr), Ta(OPrⁱ)₅ is sublimated. Crystals of Ta₇O₉(OPrⁱ)₁₇ (2) were formed upon prolonged storage of solutions of1 in PrⁱOH. Heptanuclear molecule2 consists of two [Ta₄] tetrahedra with a shared vertex. These tetrahedra are additionally linked togethervia one ₃-oxo and two ₂-OPrⁱ groups. Complex2 is a representative of heptameric oxoalkoxides of a new structural type.Deceased in I995.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 125–131, January, 1996.     

Pulverized coal plasma gasification

A number of experiments on the plasma-vapor gasification of brown coals of three types have been carried out using an experimental plant with an electric-arc reactor of the combined type. On the basis of the material and heat balances, process parameters have been obtained: the degree of carbon gasification (_c), the level of sulfur conversion into the gas phase (_s), the synthesis gas concentration (CO+Hz) in the gaseous products, and the specific power consumption for the gasification process. The degree of gasification was 90.5-95.0%, the concentration of the synthesis gas amounted to 84.7–85.7%, and the level of sulfur conversion into the gas phase was 94.3–96.7%. Numerical study of the process of plasma gasification of coals was carried out using a mathematical model of motion, heating, and gasification of polydisperse coal particles in an electric-arc reactor of the combined type with an internal heat source (arc). The initial conditions for a conjugate system of nonlinear differential equations of the gas dynamics and kinetics of a pulverized coal stream interacting with the electric arc and oxidizer (water vapor) agree with the initial conditions of the experiments. The computation results satisfactorily correlate with the experimental data. The mathematical model can be used for the determination of reagent residence time and geometrical dimensions of the plasma reactor for the gasification of coals.Nomenclature c _i volume concentration of components (kmol m^–3) - x longitudinal coordinate (m) - f _i source members, determined by variation of the ith component due to chemical reactions in unit volume in unit time (kmol m^–3s^–1) - velocity (m s^–1) - M _s ash mass in one particle (kg) - C _D particle drag coefficient - 3.14 - r _s particle radius (m) - d particle diameter (m) - density (kg m^–3) - C _p heat capacity of components (J mol^t– K^–1) - Q _j thermal effect of reaction (J kmol^–1) - E_j activation energy of reaction - N _l volume concentration of particles of thelth fraction (m^–3) - T temperature (K) - emissivity factor of coal particles - 5.67 × 10^–8, blackbody emissivity coefficient (W m^–2 K^–4) - P pressure (Pa) - S reactor cross section (m²) - D reactor diameter (m) - V reactor volume (m³) - L _R reactor length (m) - F _W friction force on the wall (N) - f _g friction coefficient - residence time (s) - Nu Nusselt number - Re Reynolds number - Pr Prandtl number - thermal conductivity of gas (J m^– s^–1 K^–1) - R 8.3 × 10³, universal gas constant (J kmol K^–1) - µ _i molecular mass of component (kg kmol^–1) - dynamic viscosity coefficient of gas (kg m^–1 s^–1) - thermal efficiency of plasma reactor - q_arc specific heat flow from arc (W m^–3) - P ₁ heat supplied in vapor at T = 405 K (W) - P ₂ heat loss to wall (W) - P ₃ heat loss in the gas and slag separator chamber (W) - P ₄ heat loss in the synthesis gas oxidation chamber (W) - P ₅ heat loss in the slag catcher (W) - P ₆ heat carried away in the off-gas (W) - P heat input of arc (W) - P _arc electric power of arc (W) - Q_sp specific power consumption (kw Hr kg^–1) - d _w specific heat flow to wall (W m^–2) - _c degree of carbon gasification (%) - _s level of sulfur conversion into gas phase (%)     

Fractional factorial design study of a pressure swing adsorption-solvent vapor recovery process

A two-level fractional factorial study was performed by computer simulation on the periodic state process performance of a pressure swing adsorption-solvent vapor recovery process (PSA-SVR). The goal was to investigate factor (parameter) interaction effects on the process performance, i.e., interaction effects that cannot be ascertained from the conventional one-at-a-time approach. Effects of seven factors, i.e., the purge to feed ratio, pressure level, pressure ratio, heat transfer coefficient, feed concentration, feed volumetric flow rate and bed length to diameter ratio, on the process performance were investigated. The results were judged in terms of the light product purity, heavy product enrichment (and relative enrichment) and recovery, and bed capacity factor. Only the purge to feed ratio, pressure ratio, and feed concentration had significant effects on the benzene vapor enrichment (and relative enrichment); and no two-factor and higher interactions were observed. The light product purity was affected by all seven factors; and the relative importance of the effect of each factor depended on the levels of the other factors, i.e., significant two-factor interaction effects existed. Two-factor interaction effects also existed on the benzene vapor recovery, although the effects of all seven factors and their interactions were relatively small. The bed capacity factor was affected mainly by the purge to feed ratio, the heat transfer coefficient and the feed concentration; two factor and higher order interaction effects were insignificant. Overall, this study demonstrated the utility of fractional factorial design for revealing factor interactions and their effects on the performance of a PSA-SVR process.Nomenclature BCF bed capacity factor, % - b, b ₀ isotherm parameters, m³/(mol K^0.5) - C _pg gas phase heat capacity, kJ/(kg K) - C _ps solid phase heat capacity, kJ/(kg K) - E enrichment - E _I ideal enrichment - E _R relative enrichment - H heat transfer coefficient, kJ/m² s K) - H heat of adsorption, kJ/mol - k number of factors, or mass transfer coefficient, l/s - l number of levels - L bed length, m - LD bed length to diameter ratio - PF purge to feed ratio - P _H adsorption high pressure, kPa - P _L desorption pressure, kPA - PL pressure level, represented byP _I - PR pressure ratio - q amount adsorbed, mol/kg - q ^xx equilibrium amount adsorbed, mol/kg - q ^xx _j equilibrium amount adsorbed at the feed conditions, mol/kg - r _b bed radius, m - R solvent vapor recovery, % or gas constant, m³ (mole K) - T temperature, K - T ₀ ambient temperature, K - t time, s - u interstitial velocity, m/s - VF volumetric feed flow rate, m³ STP/s - YF feed mole fraction - Y _p light product mole fraction - z axial coordinate, m Greek Symbols _g gas phase density, kg/m³ - _s solid phase density, kg/m³ - bed void fraction     

Kinetics of the competitive chlorinations of some perfluoroalkyl iodides determination of the bond dissociation energies D(CD3-I), D,(C2F5-I), and D,(i,-C3F7-I)

The reactions (R = CF₃, C₂F₅, and i,-C₃F₇) have been studied competitively in the gas phase over the range of 27–231°C. The following Arrhenius parameters were obtained:

Theory-enforced Re-investigation of the Origin of the Large Metal–Carbon Bond Strength in PdCH2I+ and its reactions with unsaturated hydrocarbons

State-of-the-art ab initio studies demonstrate that the reaction Pd⁺ + CH₃I → PdCH₂I⁺ + H^. is endothermic by ca. 20 kcal/mol, which translates into a bond dissociation energy (BDE) of ca. 83 kcal/mol for the Pd⁺? CH₂I bond. This figure is in agreement with an experimental bracket of 68 kcal/mol < BDE(Pd⁺? CH₂I) < 92 kcal/mol. Based on these findings, the previously studied Pd⁺/CH₃I system was re-investigated, and double-resonance experiments demonstrate that the formation of PdCH₂I⁺ occurs stepwise via PdCH as a reactive intermediate. Further, ion/molecule reactions of PdCH₂I⁺ with unsaturated hydrocarbons are studied, which reveal the formation of carbon–carbon bonds in the gas phase.     

Reaktive E = C(p-p)π-Systeme. XLII [1]. Neue Koordinationsverbindungen des 2-(Diisopropylamino)-1-phosphaethins: [{η4-(iPr2NCP)2}Ni{η2-(iPr2NCP)}], [(Ph3P)2Pt{η2-(iPr2NCP)}] und [Co2(CO)6{η2-η2-(iPr2NCP)}]

Reactive E = C(pp)π-Systems. XLII [1]. Novel Coordination Compounds of 2-(Diisopropylamino)-1-phosphaethyne: [{η⁴-(iPr₂NCP)₂}Ni{η²-(iPr₂NCP)}], [(Ph₃P)₂Pt{η²-(iPr₂NCP)}], and [Co₂(CO)₆{η²-μ²-(iPr₂NCP)}] 2-(Diisopropylamino)-phosphaethyne iPr₂N? C?P ( 2 ) reacts with the Ni(0)-complexes [Ni(1,5-cyclooctadiene)₂] and [Ni(CO)₃(1-azabicyclo[2.2.2]octane)], respectively, to give the novel complex [{η⁴-(iPr₂NCP)₂}Ni{η²-(iPr₂NCP)}] ( 5 ), with the 1,3-diphosphacyclobutadiene derivative and 2 (side-on) as π-ligands. The molecular structure of 5 determined by X-ray diffraction on single crystals proves the spin systems and rotational barriers deduced from NMR-data (¹H, ¹³C-, ³¹P). The PC distances of the four-membered ring of 1.817(2) and 1.818(2) Å – as expected – are considerably longer than the PC bond of the η²-coordinated phosphaalkyne 2 [1.671(2) Å]. – In the reactions of 2 with [(Ph₃P)₂Pt(C₂H₄)] or [Co₂(CO)₈] the ligand properties of 2 resemble those of alkynes affording the complexes [(Ph₃P)₂Pt{η²-(iPr₂NCP)}] ( 7 ) with side-on coordinated 2 and [Co₂(CO)₆{η²-μ²-(iPr₂NCP)}] with 2 acting as a 4e donor bridge in quantitative yield. In attempts to prepare copper(I) complexes of the aminophosphaalkyne 2 by reaction with CuCl or CuI the only isolable product formed in reasonable amounts under the influence of air and moisture is the 1 λ³, 3 λ⁵-diphosphetene (iPr₂N) ( 10 ) (isolated yield: ca. 20%). The crystal structure analysis of 10 indicates a strong structural relationship to the diamino-2-phosphaallyl cation [Me(iPr₂N)]⁺ ( 12 ), the 1,3-diphosphacyclobutadiene ligand (iPr₂NCP)₂ in the binuclear complex [{η¹, μ²-(iPr₂NCP)₂}Ni₂(CO)₆] ( 3a ) as well as to the heterocycles (dme)₂LiOE₂′ (E′ = S, 11a ; E′ = Se, 11b ) prepared by Becker et al. [11b, 35].     

Synthesis and characterization of β-diketonato- and phenoxoderivatives of mono(dizirconium-ennea-isopropoxy)copper(II)

Summary -Diketonato- and phenoxo-derivatives of mono(dizirconium-ennea-isopropoxy) copper(II), [Cu{Zr₂(OPr-i)₉}-(RCOCHCOR)] and [Cu{Zr₂(OPr-i)₉}(-OAr)], have been prepared by the interaction of K(RCOCHCOR) or KOAr (1 mol) [R = R = Me (1a); R = R = CF₃ (1b); R = Me, R = CF₃ (1c); OAr = 2,6-Me₂C₆H₃O (2a), 3,5-Me₂C₆H₃O (2b), p-ClC₆H₄O (2c)] with [Cu{Zr₂-(OPr-i) ₉}(-Cl)] (1 mol) in PhH. Alcohol interchanges of the derivative [Cu{Zr₂(OPr-i)₉}(-Cl)] have also been studied. These new compounds have been characterized by elemental analyses, i.r., electronic and e.s.r. spectra, and magnetic susceptibility measurements. The studies indicate a distorted octahedral geometry around Cu^II.     

Reactions of the iso-butyl radical during 1,1′-azoisobutane pyrolysis

Quantitative analysis of the products formed in 1,1′-azoisobutane pyrolyses in the temperature range of 553°–602°K has shown that the major reactions of the iso-butyl radical are Analysis of initial rate data gave log₁₀k₄/(k_c)^1/2(cm^?3/2.mol ^1/2.sec^?1/2) = 7.54±0.44 ? (136.5 + 4.8) kJ/mol/2.303RT, the Arrhenius parameters obtained being in good agreement with thermodynamic data for reaction (4). Measured values of k_a/(k_c)^1/2 where k_a is the rate constant of the reaction iC₄H₉ + AIB → iC₄H₁₀ +. AIB were consistent with published parameters determined by photolysis of 1,1′-azoisobutane. Combination of photolysis and pyrolysis data gave log₁₀ k_a/(k_c)^1/2(cm^3/2.mol^?1/22.sec^?1/2) = 3.68 ± 0.15 ? (27.2 ± 1.2) kJ/mol/2.303RT. The crosscombination ratio for methyl and iso-butyl radicals has been found to be 0.25, indicating that the geometric mean rule does not hold for methyl and iso-butyl radicals.     

Modification of the Pitzer model to calculate the mean activity coefficients of electrolytes in a water-alcohol mixed solvent solution

The approach tested in this work consists in adapting the Pitzer model, initially designed for aqueous solutions of electrolytes, to the case of solutions with a mixed solvent, without systematically readjusting the coefficients. This modified model was applied successfully to the calculation of the mean activity coefficients of NaBr in the mixed solvent H₂O+MeOH, H₂O+EtOH and compared with the experimental values obtained from electrode potential measurements.General D dielectric constant - G ^ex excess Gibbs energy - I ionic strength - k Boltzman's constant - m _i molality - N _o Avogadro's number - n _w number of kilograms of water - R gas constant - T temperature (K) - T _c critical temperature - T _cm critical temperature of mixed solvent - x _i molar fraction - z _i ionic charge - electronic charge - osmotic coefficient - ± mean activity coefficient of electrolyte - number of moles of ions given by one mole of electrolyte - _M number of moles of cations given by one mole of electrolyte - _X number of moles of anions given by one mole of electrolyte - _W density of water Debye- Hückel Model A Debye-Hückel parameter - a distance of closest approach of ions in solution - B Debye-Hückel parameter Pitzer Model b numerical parameter of model - numerical parameter of model - ₁, ₂ numerical parameters of model, used in the case of 2:2 electrolyte - _MX ⁽⁰⁾ numerical parameter of electrolyte MX - _MX ⁽¹⁾ numerical parameter of electrolyte MX - _MX ⁽²⁾ numerical parameter of 2:2 electrolyte MX - C _MX numerical parameter of electrolyte MX - binary interaction parameter - ternary interaction parameter     

Interfacial properties of mixtures of lecithin with a block copolymer surfactant at the water/air and water/oil interfaces

Surface pressure-area isotherms have been determined for both a pure lecithin (L, -dipalmitoyl phosphatidyl choline) and an impure lecithin (soya bean lecithin) at the water/air and water/oil interfaces. Equations of state have been applied and an equation of Gaines was found to be particularly successful in describing the isotherms. Mixed monolayers with an ABA nonionic block copolymer surfactant (A is poly(12-hydroxystearic) acid and B is poly(ethylene oxide)) were also investigated. The additivity rule was obeyed only at high surface pressures; inefficient packing was observed at low surface pressures. The polymer may promote a horizontal headgroup orientation in the lecithin, which gives rise to this effect. The presence of electrolyte up to very high concentrations in the aqueous phase (8.75 mol dm^–3 NH₄NO₃) was shown to expand the lecithin monolayer.Glossary of symbols W/A Water-air interface - W/O Water-oil interface - E/A Electrolyte-air interface - L-C Liquid-condensed - A _c Area per molecule obtained by conventional extrapolation of the -A isotherm at close-packing - A _e Experimentally determined area per molecule - A _t Theoretically predicted area per molecule - A _v Area per molecule obtained by vertical extrapolation of the -A isotherm at close-packing - A ₀ Head group area term - f _i Activity coefficient of water in surface region - i Constant - x _i Mol fraction of componenti - Z Compressibility factor=A/kT - Interfacial tension - Surface pressure - _i Partial molar area of component i     

Four novel classes of heterobimetallic isopropoxides of chromium(III)

Four novel classes of hydrocarbon-soluble isopropoxometallates of chromium(III): [Cr{²-Zr(OPr ⁱ )₅}₃], [Cr- {²-M₂(OPr ⁱ )₉}₃] [M = Zr^IV, Sn^IV], [Cr{²-M(OPr ⁱ ) _x Cl}₃] (M = Al, x = 3; M = Nb, x = 5), and [Cr{⁴-Zr₂-(OPr ⁱ )₈Cl}Cl₂]/[Cr{³-Zr₂(OPr ⁱ )₈Cl}{²-Zr₂(OPr ⁱ )₈Cl}Cl] [ ⁿ represents the number of connectivity sites (n = 2, 3, 4) involved in binding Cr^III] have been prepared for the first time and characterized by the elemental analyses, spectroscopic (i.r., electronic) and magnetic susceptibility studies as well as molecular weight measurements. The [Cr{²-Ga(OPr ⁱ )₄}₃] derivative has also been prepared and its magnetic and electronic properties compared with the above four novel types of Cr^III complexes.     

The reaction of 2,5-dimethylpyrrole with O2(a1Δg) in the gas phase

The chemical reaction of 2,5-dimethylpyrrole (C₆H₉N) with O₂(¹Δ_g) was studied in the gas phase in an isothermal flow reactor at room temperature and low pressures. The C₆H₉N concentration profiles were studied under pseudo-first order conditions [C₆H₉N]_° ? [O₂(¹Δ_g)] with mass-spectrometric detection of C₆H₉N. O₂(¹Δ_g) was produced either in a microwave discharge or in a chemical reaction. The value for the rate constant: was measured. The rate constant is compared to the value obtained for the quenching process. The primary product C₆H₉NO₂ was detected by mass spectrometry and the reaction mechanism is proposed. The possibility of using this reaction as a gas phase titration reaction for O₂(¹Δ_g) is discussed.     

Heterotri- and -tetrametallic alkoxides of chromium(III) containing aluminium(III), gallium(III) and niobium(V)

CrCl₃ · 3THF reacts with two equivalents of potassium alkoxometallates K{M(OPr ⁱ ) _x } [M = Al(A), Ga(B), x = 4; M = Nb(C), x = 6] to give heterobimetallic chloride isopropoxides [Cr{M(OPr ⁱ ) _x }₂Cl(THF)] [M = Al(A – 1), Ga(B – 1), and Nb(C – 1)], in which the replacement of the chloride with an appropriate alkoxometallate (tetraisopropoxoaluminate, tetraisopropoxogallate, or hexaisopropoxoniobate) results in the formation of novel heterotrimetallic derivatives. The 'single pot synthesis of an heterotetrametallic isopropoxide [Cr{Nb(OPr ⁱ )₆}{Al(OPr ⁱ )₄}{Ga(OPr ⁱ )₄}] (7) has been carried out by the sequential addition of (A), (B), and (C) to a benzene suspension of CrCl₃ · 3THF. Alcoholysis of [Cr{Al(OPr ⁱ )₄}₂{Nb(OPr ⁱ )₆}] (1) and [Cr{Al(OPr ⁱ )₄}₂{Ga(OPr ⁱ )₄}] (5) with t-BuOH has also been studied and the derivatives characterized by elemental analyses, molecular weight determinations, spectroscopic [Electronic, i.r., ²⁷Al-n.m.r.] and magnetic susceptibility studies.     

Very-low-pressure pyrolysis (VLPP) of group IV (A) tetramethyls: Neopentane and tetramethyltin

The decomposition of neopentane was studied using the very-low-pressure pyrolysis (VLPP) technique at temperatures from 1000 to 1260 K. The derived Arrhenius parameters are consistent with δH_f⁰(t-butyl) = 8.4 kcal/mol. Using the above A factor, data on the decomposition of tetramethyltin yield DH⁰(Sn(CH₃)₃ - CH₃) = 69 ± 2 kcal/mol.