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 enthalpy of formation of the praseodymium ion (3+) in an infinitely dilute aqueous solution

The enthalpy of reaction between praseodymium metal and 1.07 n HCl and the enthalpy of solution of praseodymium trichloride in 1.07 n HCl and water were measured in a swinging isoperibol calorimeter at 298.15 K. The results were used to calculate the enthalpy of formation of the praseodymium ion in the state of an infinitely dilute aqueous solution, Δ_f H°_298.15 Pr³⁺(sln, ∞H₂O) = ?687.8 ± 1.7 kJ/mol.     

Low-Temperature Heat Capacities of Terbium Molybdate Phosphates M 2 I Tb(MoO4)(PO4) (MI = Na or K)

The heat capacities of Na₂Tb(MoO₄)(PO₄) and K₂Tb(MoO₄)(PO₄) were measured by adiabatic calorimetry at low temperatures (6.34–333.74 and 7.20–341.17 K, respectively). Smoothed thermal-capacities values were used to calculate the entropy, enthalpy increments, and reduced Gibbs energy. The respective values at 298.15 K are as follows: for Na₂Tb(MoO₄)(PO₄), C _p ⁰ (298.15 K) = 240.1 ± 0.2 J/(K mol), ⁰ (298.15 K) = 307.4 ± 0.4 J/(K mol), H ⁰(298.15 K) ? H ⁰(0) = 44.95 ± 0.03 kJ/mol, and Φ⁰(298.15 K) = 156.6 ± 0.5 J/(K mol); and for K₂Tb(MoO₄)(PO₄): C _p ⁰ (298.15 K) = 245.1 ± 0.1 J/(K mol), S ⁰(298.15 K) = 322.9 ± 0.1 J/(K mol), H ⁰(298.15 K) ? H ⁰(0) = 46.58 ± 0.02 kJ/mol, and Φ⁰(298.15 K) = 166.6 ± 0.2 J/(K mol). The noncooperative magnetic component of the heat capacity was estimated.     

The thermodynamic characteristics of natural iron-lithium micas

A thermochemical study of natural lithium micas, iron-containing polylithionite and lepidolite, was performed on a high-temperature heat-flux Calvet microcalorimeter (Setaram, France). Melt solution calorimetry was used to measure the enthalpies of mineral formation from the elements Δ_f H°_el (298.15 K), ?5989.3 ± 9.6 and ?5981.3 ± 6.3 kJ/mol, respectively. The drop method was used to determine the enthalpy increments heating of the micas over the temperature interval 444–973 K. The equations for the temperature dependences of the heat capacities and enthalpies of Fe-polylithionite and Fe-lepidolite were obtained. The S° (298.15 K) and Δ_f G°_el (298.15 K) values were estimated. The thermodynamic functions of the micas were calculated over the temperature range 298.15–1000 K.     

Enthalpy of the formation of natural hydrous aluminum hydroxosulfate (aluminite)

A thermochemical study of natural aluminum hydroxosulfate Al₂[(OH)₄SO₄] · 7H₂O, aluminite (Nakhodka deposit, West Chukotka, Russia) is performed on a Tian-Calvet “Setaram” high-temperature heat-conducting microcalorimeter (France). The enthalpy of aluminite formation from simple compounds is obtained via the melt calorimetry of dissolution, Δ_f H ^○(298.15 K) = ?4986 ± 21 kJ/mol.     

Standard enthalpy of formation of La2CoO4(cr)

The enthalpies of reactions of La₂CoO₄(cr) and CoCl₂(cr) with hydrochloric acid were measured with an isothermal-jacket calorimeter. The results obtained and the available literature data were used to calculate the standard enthalpy of formation of La₂CoO₄(cr) at 298.15 K, Δ_f H ^o = ?2179 ± 7 kJ/mol.     

A calorimetric study of the thermodynamic properties of potassium molybdate

The low-temperature heat capacity of K₂MoO₄ was measured by adiabatic calorimetry. The smoothed heat capacity values, entropies, reduced Gibbs energies, and enthalpies were calculated over the temperature range 0–330 K. The standard thermodynamic functions determined at 298.15 K were C _p ^° (298.15 K) = 143.1 ± 0.2 J/(mol K), S°(298.15 K) = 199.3 ± 0.4 J/(mol K), H°(298.15 K)-H°(0) = 28.41 ± 0.03 kJ/mol, and Φ°(298.15 K) = 104.0 ± 0.4 J/(mol K). The thermal behavior of potassium molybdate at elevated temperatures was studied by differential scanning calorimetry. The parameters of polymorphic transitions and fusion of potassium molybdate were determined.     

Isopiestic Determination of the Osmotic and Activity Coefficients of Li2SO4(aq) at T=298.15 and 323.15 K, and Representation with an Extended Ion-Interaction (Pitzer) Model

Isopiestic vapor-pressure measurements were made for Li₂SO₄(aq) from 0.1069 to 2.8190 mol?kg^?1 at 298.15 K, and from 0.1148 to 2.7969 mol?kg^?1 at 323.15 K, with NaCl(aq) as the reference standard. Published thermodynamic data for this system were reviewed, recalculated for consistency, and critically assessed. The present results and the more reliable published results were used to evaluate the parameters of an extended version of Pitzer’s ion-interaction model with an ionic-strength dependent third-virial coefficient, as well as those of the standard Pitzer model, for the osmotic and activity coefficients at both temperatures. Published enthalpies of dilution at 298.15 K were also analyzed to yield the parameters of the ion-interaction models for the relative apparent molar enthalpies of dilution. The resulting models at 298.15 K are valid to the saturated solution molality of the thermodynamically stable phase Li₂SO₄?H₂O(cr). Solubilities of Li₂SO₄?H₂O(cr) at 298.15 K were assessed and the selected value of m(sat.)=3.13±0.04 mol?kg^?1 was used to evaluate the thermodynamic solubility product K _s(Li₂SO₄?H₂O, cr, 298.15 K) = (2.62±0.19) and a CODATA-compatible standard molar Gibbs energy of formation Δ_f G _m ^o (Li₂SO₄?H₂O, cr, 298.15 K) = ?(1564.6±0.5) kJ?mol^?1.     

The thermodynamic properties and thermal decomposition of octachlorotrisilane Si<Subscript>3</Subscript>Cl<Subscript>8</Subscript>

The standard enthalpies of formation of liquid and gaseous octachlorotrisilane were estimated, Δ_f H ^o (298.15, Si₃Cl₈, g) = ?1397(9) kJ/mol and Δ_f H ^o (298.15, Si₃Cl₈, l) = ?1447(9) kJ/mol. The decomposition of Si₃Cl₈ over the temperature range 400–1000 K was studied theoretically.     

The thermodynamic characteristics of vaporization of praseodymium triiodide

The vaporization of praseodymium triiodide was studied by high-temperature mass spectrometry. Monomeric (PrI₃) and dimeric (Pr₂I₆) molecules and the PrI ₄ ^? and Pr₂I ₇ ^? negative ions were recorded in saturated vapor over the temperature range 842–1048 K. The partial pressures of neutral vapor components were determined. The enthalpies of sublimation Δ_s H ^o(298.15 K) in the form of monomers (291 ± 10 kJ/mol) and dimers (400 ± 30 kJ/mol) were calculated by the second and third laws of thermodynamics. The equilibrium constants of ion-molecular reactions were measured and the enthalpies of the reactions determined. The enthalpies of formation Δ_f H ^o(298.15 K) of molecules and ions in the gas phase were calculated (?373 ± 11, ?929 ± 31, ?865 ± 25, and ?1433 ± 48 kJ/mol for PrI₃, Pr₂I₆, PrI ₄ ^? , and Pr₂I ₇ ^? , respectively).     

Calorimetric determination enthalpy of the formation of natural pyromorphite

A calorimetric study of natural pyromorphite Pb₅[PO₄]₃Cl was performed. Its enthalpy of formation was determined by melt solution calorimetry from elements Δ_f H _el^∘(298.15 K) = −4124 ± 20 kJ/mol. Value Δ_f G _el^o(298.15 K) = −3765 ± 20 kJ/mol was calculated.     

Standard enthalpy of formation of LaCoO3(cr)

An isothermal-jacket calorimeter was used to measure the enthalpies of the reactions of LaCoO₃(cr), LaCl₃(cr), and CoCl₂(cr) with a 2m hydrochloric acid solution. Based on these values and the published data, the standard enthalpy of formation of LaCoO₃(cr) at 298.15 K was calculated (Δ_f H ⁰ = ?1232 ± 6 kJ/mol).     

Thermodynamique de substances azotees. IX. Etude thermochimique de la benzamide. Comparaison des grandeurs energetiques liees a la structure de quelques amides et thioamides

The enthalpy of sublimation of benzamide was obtained by calorimetry in the range 323<T (K)<350. From values of ΔH_sub(T)=f(T), it was possible to determine ΔH⁰_sub (298.15 K)=101.7±1.0 kJ mole^?1. Using previous data on ΔH⁰_f (c, 298.15 K) obtained by combustion calorimetry, the value of ΔH⁰_f (g, 298.15 K)=?100.9±1.2 kJ mole^?1 was calculated. With the use of energetical values concerning thioacetamide, thiobenzamide and thiourea, on the one hand, and acetamide, benzamide and urea, on the other, a comparative study was made.     

Low-temperature heat capacity and high-temperature thermal behavior of sodium lutetium molybdate phosphate Na<Subscript>2</Subscript>Lu(MoO<Subscript>4</Subscript>)(PO<Subscript>4</Subscript>)

The low-temperature heat capacity of Na₂Lu (MoO₄)(PO₄) was measured by adiabatic calorimetry in the range of 7.47–345.74 K. The experimental data were used to calculate the thermodynamic functions of Na₂Lu (MoO₄)(PO₄). At 298.15 K, the following values were obtained: C _p ⁰ (298.15 K) = 237.7 ± 0.1 J/(K mol), S ⁰(298.15 K) = 278.1 ± 0.8 J/(K mol), H ⁰(298.15 K) ? H ⁰ (0 K) = 42330 ± 20 J/mol, and Φ⁰(298.15 K) = 136.1 ± 0. 3 J/(K mol). A heat capacity anomaly was found in the range of 10-67 K with a maximum at T _tr = 39.18 K. The entropy and enthalpy of transition are ΔS = 12.39 ± 0.75 J/(K mol) and ΔH = 403 ± 16 J/mol. The thermal investigation of sodium lutetium molybdate phosphate in the high-temperature range (623–1223 K) was performed using differential scanning calorimetry. It was found that during melting in the range of 1030–1200 K, Na₂Lu(MoO₄)(PO₄) degrades to simpler compounds; the degradation scenario is verified by X-ray powder diffraction.     

Determination of constant‐volume combustion energy for the complexes of zinc nitrate with three amino acids

Five solid complexes of zinc with L‐α‐methionine, L‐α‐phenylalanine and L‐α‐histidine were prepared. The constant‐volume combustion energies of the complexes, ΔE_c (coordination), were determined by a precise rotating bomb calorimeter at 298.15 K. They were ‐ 2969.03 ± 0.34, ‐2929.46 ± 1.59, ‐9597.13 ± 6.12, ‐4378.98 ± 3.27 and ‐14047 ± 6.75 kJ/mol, respectively. Their standard enthalpies of combustion, ΔH^θ_m,c(coordination, s, 298.15 K), and standard enthalpies of formation, ΔH^θ_m,f (coordination, s, 298.15 K), were calculated. They were ‐2959.73 ± 0.34, ‐2923.88 ± 1.59, ‐9649.18 ± 6.12, ‐4373.40 ± 3.27, ‐14048.53 ± 6.75 kj/mol and ‐1180.94 ± 0.92, ‐1401.26 ± 1.77, ‐2501.69 ± 6.50, ‐1381.47 ± 3.49, ‐1950.19 ± 7.65 kJ/mol, respectively.     

Thermodynamic properties of aluminum monooxycarbide Al2OC

It was shown that the published data on the thermodynamic properties of aluminum monooxycarbide Al₂OC (ed) are not consistent with the phase diagram of the Al₂O₃-Al₄C₃ system. A thermodynamic modeling of the equilibrium state of the Al₂O₃-Al₄C₃ system made it possible to obtain new estimates of the standard entropy and enthalpy of formation of aluminum monooxycarbide: S°(298.15 K, cd. Al₂OC) = 45.3 J/(K mol) and Δ_f H°(298.15 K, cd, Al₂OC) = ?625.6 kJ/mol.     

Calorimetric determination of the enthalpy of formation of partheite,a calcium zeolite

A thermochemical study of partheite of composition (Ca_1.96Mg_0.04Na_0.01K_0.01) · [(Al_4.04Fe _0.01 ³⁺ )Si_3.95O_14.97(OH)_2.03] · 4.2H₂O, a natural calcium zeolite extracted from gabbro pegmatites of the Denezhkin Kamen’ deposit (North Ural, Russia), was performed. The enthalpies of formation of partheite from the constituent oxides, (Δ_f H°_ox(298.15 K) = ?359 ± 21), and elements, (Δ_f H°_el(298.15 K) = ?10108 ± 21), were determined by means of high-temperature in-melt-dissolution calorimetry. On the basis of the experimental data obtained, the enthalpy of formation of partheite of theoretical composition Ca₂[Al₄Si₄O₁₅(OH)₂] · 4H₂O from the elements was evaluated, ?10052 ± 21 kJ/mol.     

The enthalpies of formation of bis-(benzene)molybdenum and of bis-(toluene)tungsten

Microcalorimetric measurements at 520–523 K of the heats of thermal decomposition and of iodination of bis-(benzene)molybdenum and of bis-(toluene)tungsten have led to the values (kJ mol^?): ΔH^o_f[Mo(η-C₆H₆)₂, c] = (235.3 ± 8) and ΔH^o_f[W(η⁶-C₇H₈)₂, c] = (242.2 ± 8) for the standard enthalpies of formation at 25°C. The corresponding ΔH^o_f(g) values, using available and estimated enthalpies of sublimation, are (329.9 ± 11) and 352.2 ± 11) respectively, from which the metalligand mean bond-dissociation enthalpies, $\text{D}$(Mo—benzene) = (247.0 ± 6) and $\text{D}$(W—toluene) = (304.0 ± 6) kJ mol^?1, are derived.     

Low-temperature heat capacity of sodium erbium molybdophosphate Na<Subscript>2</Subscript>Er(MoO<Subscript>4</Subscript>)(PO<Subscript>4</Subscript>)

Adiabatic calorimetry is used to measure the low-temperature heat capacity of Na₂Er(MoO₄)(PO₄)from 6.41 to 347.87 K. Experimental data are used to calculate the thermodynamic functions of Na₂Er(MoO₄)(PO₄), which at 298.15 K are as follows: C _p ⁰ (298.15 K) = 243,3 ± 0.4 J/(K mol), S ⁰(298.15 K) = 312.8 ± 0.8 J/(K mol), H ⁰(298.15 K) ? H ⁰(0 K) = 45280 ± 90 J/mol, and Φ⁰(298.15 K) = 136.1 ± 0.3 J/(K mol). A diffuse heat-capacity anomaly associated with splitting of the Stark levels (Schottky anomaly) is discovered in the low-temperature region.     

Thermochemical properties of free radicals from G3MP2B3 calculations

For a set of 32 selected free radicals, energy minimum structures, harmonic vibrational wave numbers ω_e, principal moments of inertia I_A, I_B, and I_C, heat capacities C°_p(T), entropies S°(T), thermal energy contents H°(T) ? H°(0), and standard enthalpies of formation Δ_fH°(T) were calculated at the G3MP2B3 level of theory in the temperature range 200–3000 K. In this article, thermodynamic functions at T = 298.15 K are presented and compared with recent experimental values. The mean absolute deviation between calculated and experimental Δ_fH°(298.15) values resulted in 3.91 kJ mol^?1, which is close to the average experimental uncertainty of ± 3.55 kJ mol^?1. The influence of hindered rotation on thermodynamic functions is studied for isopropyl and tert‐butyl radicals. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 550–560, 2002