DSC determination of the fusion and sublimation enthalpy of bis(2,4-pentanedionato)beryllium(II) and tris(2,4-pentanedionato)aluminium(III)

The sublimation enthalpy of bis(2,4-pentanedionato)beryllium(II) and of tris(2,4-pentanedionato)aluminium(III) has been determined by differential scanning calorimetry as 85.3 ± 3.5 kJ mole^?1 and 125.6 ± 3.2 kJ mole^?1, respectively. The corresponding fusion enthalpies are 15.67 ± 0.74 and 28.71 ± 1.34 kJ mole^?1, respectively.     

Thermodynamique de composes azotes. VII. Etude thermochimique du pyrazole et de l'imidazole

Enthalpies of sublimation for pyrazole and imidazole have been obtained by calorimetry at 298.15K. The ΔH⁰_sub (298.15 K) values for these two compounds are, respectively, 69.16 ± 0.32 and 74.50 ± 0.40 kJ mole^?1. From literature data obtained by combustion calorimetry for ΔH⁰_f (c, 298.15 K), the enthalpies of formation of these compounds in the gaseous state (pyrazole: 185.1 ± 2.3 kJ mole^?, imidazole: 133.0 ± 1.7 kJ mole^?1) have been derived. Several energy values related to the molecular structure of these two compounds (as resonance energy, enthalpy of isomerization, …) have been determined. The study of pyrazole has enabled us to contribute to the evaluation of some characteristics of the NN bond.     

Thermochemistry of hydrogen tungsten bronze phases HxWO3

The enthalpies of formation of two hydrogen tungsten bronze phases H_0.35WO₃ and H_0.18WO₃ have been determined by solution calorimetry. Values obtained for formation from H₂(g) and WO₃(s) at 298.15 K were H_0.35WO₃(s), ?9.6 ± 0.8 kJ mole^?1 and H_0.18WO₃(s), ?4.8 ± 0.6 kJ mole^?1. The stabilities of these phases towards decomposition, disproportionation and oxidation are discussed.     

Equilibrium sublimation and thermodynamic properties of SnS

Knudsen effusion studies of the sublimation of polycrystalline SnS, prepared by annealing and chemical vapor transport, have been performed employing vacuum micro-balance techniques in the temperature range 733–944 K and at pressures ranging from about 6 × 10^?3 to 11 Pa.The third-law heats of sublimation and second-law entropy of reaction SnS(s) = SnS(g) were determined to be ΔH⁰₂₉₈ = 220.4 ± 3.0 kJ mole^? and ΔS⁰₂₉₈ = 162.4 ± 4.5 J K^?1 mole^?1. From these data the standard heat of formation and absolute entropy of SnS(s) were calculated to be ?102.9 ± 4.0 kJ mole^?1 and 79.9 ± 6.0 J K^?1, respectively.     

Thermodynamic properties of benzoylferrocene and 1,1′-dibenzoylferrocene

The vapor pressures of benzoylferrocene and 1,1′-dibenzoylferrocene were measured by torsion-effusion technique. The following pressure-temperature equations were derived benzoylferrocene log P(kPa) = 10.75±0.22?(5314±82)/T 1,1′-dibenzoylferrocene log P(kPa) = 9.29±0.24?(4898±91 )/T Second-law treatment of the experimental data yielded the sublimation enthalpies for benzoylferrocene and 1,1′-dibenzoylferrocene: ΔH⁰_sub,298 = 116.3±6.0 kJ mole^?1 and ΔH⁰_sub,298 = 109.3±6.0 kJ mole^?1 respectively. Thermal functions of these compounds were also estimated.     

Removal of Zn(II) Ions from Aqueous Solution Using BPHA‐Impregnated Polyurethane Foam

Zn(II) ions sorption onto N‐Benzoyl‐N‐Phenylhydroxylamine (BPHA) impregnated polyurethane foam (PUF) has been studied extensively using radiotracer and batch techniques. Maximum sorption (～98%) of Zn(II) ions (8.9 × 10^?6 M) onto sorbent surface is achieved from a buffer of pH 8 solution in 30 minutes using 7.5 mg/mL of BPHA‐impregnated polyurethane foam at 283 K. The sorption data follow Langmuir, Freundlich and Dubinin‐Radushkevich (D‐R) isotherms. The Langmuir constants Q = 18.01 ± 0.38 μ mole g^?1 and b = (5.39 ± 0.98) × 10³ L mole^?1 have been computed. Freundlich constants 1/n = 0.29 ± 0.01 and C_m = 111.22 ± 12.3 μ mole g^?1 have been estimated. Sorption capacity 31.42 ± 1.62 μ mole g^?1, β = ?0.00269 ± 0.00012 kJ² mole^?2 and energy 13.34 ± 0.03 kJ mole^?1 have been evaluated using D‐R isotherm. The variation of sorption with temperature yields ΔH = ?77.7 ± 2.8 k J mole^?1, ΔS = ?237.7 ± 9.3 J mole^?1 K^?1 and ΔG = ?661.8 ± 117.5 k J mol^?1 at 298 K reflecting the exothermic and spontaneous nature of sorption. Cations like Fe(III), Ce(III), Al(III), Pb(II) and Hg(II) and anions, i.e., oxalate, EDTA and tartrate, reduce the sorption significantly, while iodide and thiocyanate enhanced the sorption of Zn(II) ions onto BPHA‐impregnated polyurethane foam.     

Kinetics of the dissociation and cis-trans isomerization of o,o'-azodioxytoluene (dimeric o-nitrosotoluene)

The dimer-monomer reactions were investigated for the system cis and transo,o'-azodioxytoluene-o-nitrosotoluene in acetonitrile solvent. For the reaction cis dimer-monomer the following thermodynamic and activation parameters have been derived: ΔH°=58.5±2.5 kJ mole^?1, ΔS°=206.2±3.8 J mole^?1 K^?1, ΔH^≠=63.6±3.3 kJ mole^?1, ΔS^≠=6.3±0.3 J mole^?1 K^?1. The corresponding values for the reaction trans dimer-monomer are: ΔH°=45.6±2.1 kJ mole^?1, ΔS°=162.7±7.1 J mole^?1 K^?1, ΔH^≠=80.8±2.9 kj mole^?1, ΔS^≠=-13.4±0.8 mole^?1 K^?1. There is no evidence of a direct cis-trans isomerization (i.e. a reaction not proceeding via the monomer). NMR and various perturbation techniques monitoring the visible absorption of the monomer were employed.     

Mass spectrometric evidence for the very high stability f gaseous ThIr and ThPt and method of calculating dissociation energies of diatomic intermetallic compounds with multiple bonds

The dissociation energes, D⁰₀, of the molecules ThIr and ThPt have been measured by high temperature Knudsen cell mass spectrometry as 136.4=10 and 130.7=10 kcal mole^?1 or 570.7±41.8 and 546.6±41.8 kJ mole^?1, respectively.A method is proposed for the calculation of dissociation energies of gaseous intermetallic compounds with multiple bonds.     

Thermochemistry of polyhalides. II. Caesium and rubidium dibromoiodides

Using a solution-reaction calorimeter the standard enthalpies of formation of crystalline caesium and rubidium dibromoiodides have been determined as ?445.5±4.1 and ?428.3±4.2 kJ mol^?1, respectively. Thermodynamic parameters, including lattice energies, are calculated and the thermal stability of polyhalides discussed. Thermometric titrations have been used to investigate the mechanism of reaction of caesium dibromoiodide with aqueous silver nitrate.     

Thermodynamics of solid solution formation in NiOMgO and NiOZnO

High-temperature calorimetric measurements of the enthalpies of solution in molten 2PbO · B₂O₃ of (Ni_xMg_1?x)O and (Ni_xZn_1?x)O permit the calculation of the enthalpy of the zincite to rocksalt transformation in ZnO, and the enthalpies of mixing, relative to rocksalt standard states, in the two solid solution series. The enthalpy of the zincite to rocksalt transformation is 24,488 ± 3,592 J mole^?1 with a corresponding positive entropy change of 0.48 ± 3.3 J K^?1 mole^?1. The small positive entropy change for the transformation necessitates a very flat and perhaps negative $\text{dP}\text{dT}$ slope for the phase boundary. Both solid solutions, when referred to rocksalt standard states, show negative enthalpies of mixing. For (Ni_xMg_1?x)O the negative enthalpies of mixing are fitted by a subregular model, where ΔH_mix = X_AX_B(BX_A + AX_B), with A = ?21,971 ± 4,953 J mole^?1 and B = ?5103 ± 1151 J mole^?1. The associated negative excess entropies of mixing, calculated from the heats of mixing and previously measured activity-composition relations, are similarly modeled with A = ?10.7 J K^?1 mole^?1 and B = + 1.1 J K^?1 mole^?1. Negative enthalpies of mixing in (Ni_xZn_1?x)O conform to a regular solution model with W = ?13520 ± 5581 J mole^?1. The negative enthalpies of mixing are interpreted in terms of a tendency toward ordering in the solid solutions, the proposed ordering scheme finding support in spectroscopic, structural, and magnetic data. These tendencies toward order are used to explain observed phase relations and thermodynamic properties in some other systems containing a transition metal cation and another ion of similar size, namely carbonates, hydrated sulfates and the systems CuOMO (M = Mg, Co, Ni).     

Etude catorimetrique de la decomposition thermique des sels de tetraflouroammonium (NF4)2NiF6 et NF4SbF6

The study of the thermal decomposition of the tetrafluoroammonium salts (NF₄)₂NiF₆ and NF₄SbF₆ by differential scanning calorimetry also gave enthalpies of decomposition for (NF₄)₂NiF₆ and NF₄SbF₆ of 134.7 ± 13.0 kJ mol^?1 and 245.6 ± 28.9 kJ mol^?1 respectively. The corresponding standard enthalpies of formation are found to be ?1033 and ?1649 kJ mol^?1 respectively.     

Vapour pressures and sublimation enthalpies of thymine and cytosine

The vapour pressures of cytosine and thymine were measured using the torsion-effusion technique. The sublimation processes of cytosine and thymine were investigated over the temperature ranges 480–553 K and 420–503 K, respectively. The following pressure—temperature equations were derived by least-squares treatment of the vapour pressure data

The standard sublimation enthalpies were obtained by second-and third-law treatment of the experimental data and the values ΔH⁰₂₉₈ = 167 ± 10 kJ mole^?1 and ΔH⁰₂₉₈ = 138 ± 10 kJ mole^?1 were derived for cytosine and thymine, respectively. IR and Raman spectra were recorded in the gas phase in order to evaluate the thermodynamic functions of gaseous cytosine and thymine.     

Vapor pressure measurements of ferrocene,mono- and 1,1′-di-acetyl ferrocene

By using different techniques the vapor pressure of ferrocene, mono-acetyl ferrocene and 1,1′-di-acetyl ferrocene was measured. The following pressure—temperature equations were derived ferrocene log P(kPa)= 9.78 ± 0.14 ? (3805 ± 46)/T mono-acetyl ferrocene log P(kPa) = 14.83 ± 0.14 ? (5916 ± 48)/T 1,1′-di-acetyl ferrocene log P(kPa) = 8.82 ± 0.11 ? (4289 ± 44)/T By second- and third-law treatment of the vapor data the ΔH⁰_sub,298 = 74.0 ± 2.0 kJ mole^?1 for the sublimation process of ferrocene was calculated and compared with the literature data. For the sublimation enthalpy of mono- and 1,1′-di-acetyl ferrocene the values ΔH⁰_sub,298 = 115.6 ± 2.5 kJ mole^?1 and ΔH⁰_sub,298 = 91.9 ± 2.5 kJ mole^?1 were derived by second-law treatment. Thermal functions of these compounds were also estimated.     

High temperature Knudsen cell mass spectrometric determination of the heats of atomization of AlAu2 and Al2Au

The atomization energies, ΔH⁰_at,0 of the molecules, AlAu₂ and Al₂ and Al₂Au have been determined as 121 ± 6 and 110 ± 5 kcal mole^?1 or 506.3 ± 25.1 and 460.2 ± 20.9 kJ mole^?1, respectively.Theses atomization energies are discussed in terms of bond strengths and the Pauling model of a polar bond. Available information suggests that AlAu₂ has the structure AuAlAu, but that Al₂Au has the structure AlAlAu. For both molecules divalent gold is shown to be unlikely.     

Thermal decomposition kinetics of bisthiourea cadmuim(II) tetrathiocyanato diammine chromate(III)

Cadmium thiourea reinickate undergoes two-stage thermal decomposition on heating. The DTG peak temperatures are 291 and 469°C and the corresponding DTA temperatures are 255 and 490°C. The kinetic parameters for the first stage decomposition are E* ≈ 120kJ mole^?1; Z ≈ 1.2 × 10⁸ cm³ mole^?1 sec^?1 and ΔS* ≈ ?95 J mole^?1 K^?1. For the second stage, E* ≈ 133 kJ mole^?1; Z ≈ 6.1 × 10⁵ cm^?1 mole^?1 sec^?1 and ΔS* ≈ ?142 J mole^?1 K^?1.     

A re-evaluation of the enthalpy of sublimation of some metal acetylacetonate complexes

Sublimation enthalpies for Al(III), Fe(III) and Zn(II) acetylacetonates derived using isoteniscopic, sublimation bulb and spoon gauge techniques are reported. Selected sublimation enthalpies are Al(C₅H₇O₂)₃, 118.6 ± 7.8; Fe(C₅H₇O₂, 113.6 ± 3.8; and Zn(C₅H₇O₂)₂, 117 ± 3 kJ mole^?1, respectively.     

Thermal decomposition of zinc and cadmium zirconyl oxalates

The enthalpy of formation at 298.15 K of the polymer Al₁₃O₄(OH)₂₈(H₂O)³⁺₈ and an amorphous aluminium trihydroxide gel was studied using an original differential calorimetric method, already developed for adsorption experiments, and aluminium-27 NMR spectroscopy data. ΔH_f “Al₁₃” (298.15 K) = ? 602 ± 60.2 kJ mole^?1 and ΔH_f Al(OH)₃ (298.15 K) = ? 51 ± 5 kJ mole^?1. Using theoretical values of ΔG_R “Al₁₃” and ΔG_R Al(OH)₃, we calculated ΔG_f “Al₁₃” (298.15 K) = ? 13282 kJ mole^?1; ΔS_f “Al₁₃” (298.15 K) = + 42.2 kJ mole^?1; ΔG_f Al(OH)₃ (298.15 K) = ? 782.5 kJ mole^?1; and ΔS_f Al(OH)₃ (298.15 K) = + 2.4 kJ mole^?1.     

The solution thermochemistry of antimony pentafluoride and some fluoroantimonates

From hydrolysis and solution measurements the enthalpies of formation of SbF₅(?), LiSbF₆(s), NaSbF₆(s), KSbF₆(s), CsSbF₆(s), AgSbF₆(s), and SbF₆^?aq. are estimated to be ?1324 ± 12, ?2062 ± 5, ?2060 ± 6, ?2080 ± 3, ?2082 ± 15, ?1653 ± 3, and ?1789 ± 4 kJ mol^?1 respectively. Less precise estimates of the enthalpies of formation of O₂SbF₆ and of CsSb₃F₁₆ are also given. From the results the fluoride ion affinity of SbF₅, the single ion hydration enthalpy of SbF₆^? (g), and the charge distribution within the SbF₆^? ion have been calculated.     

Etudes calorimetriques en milieu solvant organique. V. Enthalpies de dissolution de l'alanate de sodium,NaAlH4, dans le tetrahydrofuranne

The enthalpies of dissolution of sodium tetrahydridoaluminate NaAlH₄ in THF have been determined for different concentrations. The enthalpies of dissolution and dilution are exothermic from 1 to 7 · 10^?3 M. The enthalpy of dissolution at infinite dilution has been calculated: ΔH^∝_diss = ?6.38 kcal mole^?1.     

The acetyl radical studied by flash photolysis and kinetic spectroscopy

The acetyl radical absorption spectrum is a broad band with maximum decadic extinction coefficient of (1.0 ± 0.1) × 10⁴ ? mole^?1 cm^?1 at 215 nm and an oscillator strength of 0.23 ± 0.03. Absolute rate constants were estimated as 4.5 × 10¹⁰ ? mole^?1 s^?1 for the mutual interaction of acetyl radicals, and as 7.5 × 10¹⁰ ? mole^?1 s^?1 for the cross interaction of acetyl and methyl radicals.