Enthalpy of formation of triphenylphosphine sulfide

The first measurements of the enthalpies of combustion, sublimation, and fusion of an organo-phosphorus sulfide, triphenylphosphine sulfide, are reported: _c H _m ^o (C₁₈H₁₅PS, cr)=–(10752.58 ±2.90), _sub H _m ^o (C₁₈H₁₅PS, 403 K)=(136.80±6.09), and _fus H _m ^o (C₁₈H₁₅PS, T_m=435.92 K) =(30.53±0.21) kJ·mol^–1. Correction of the phase change enthalpies toT=298.15K and p^o =0.1 MPa results in the standard phase change enthalpy values of _sub H _m ^o (298.15 K)=(142.8 ±6.8) and _fus H _m ^o (298.15 K)=(19.28±0.21) kj·mol^–1. Accordingly, the enthalpies of formation of solid, liquid, and gaseous triphenylphosphine sulfide are derived: _f H _m ^o (C₁₈H₁₅PS, cr) =(63.20±2.56), _fH _m ^o (C₁₈H₁₅PS, l)=(82.48±2.57), and _fH _m ^o (C₁₈H₁₅PS, g)=(206.0±7.3) kJ·mol^–1. From these ancillary data, the P=S double-bond enthalpy is 394 kJ-mol^–1 and in good agreement with earlier reaction calorimetry results. These phosphorus sulfide values are compared with those for the arsenic sulfides. Plausibility arguments are given for our results.     

Structural studies of cyclic ureas: 2. Enthalpy of formation of parabanic acid

Thermophysical and thermochemical studies have been carried out for crystalline parabanic acid. The thermophysical study was made by differential scanning calorimetry, DSC, over the temperature interval between T = (263 and 473) K. Two phase transitions were found: at T = (392.3 ± 1.6) K with the enthalpy of transition of (2.1 ± 0.4) kJ · mol⁻¹ and at T = (509.8 ± 1.5) K, when the compound was scanned to its fusion temperature. The standard (p = 0.1 MPa) molar enthalpy of formation, at T = 298.15 K, for crystalline parabanic acid was determined using static-bomb combustion calorimetry as −(590.2 ± 1.0) kJ · mol⁻¹. The standard molar enthalpy of sublimation, at T = 298.15 K, was derived from the variation of their vapour pressures, measured by the Knudsen-effusion method, with the temperature. These two thermochemical parameters yielded the standard molar enthalpy of formation in the gaseous phase, at T = 298.15 K, as −(470.8 ± 1.2) kJ · mol⁻¹.     

Standard molar enthalpies of formation of 2-, 3- and 4-cyanobenzoic acids

The standard (p = 0.1 MPa) molar enthalpies of formation of 2-, 3- and 4-cyanobenzoic acids were derived from their standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by static bomb combustion calorimetry. The Calvet high temperature vacuum sublimation technique was used to measure the enthalpies of sublimation of 2- and 3-cyanobenzoic acids. The standard molar enthalpies of formation of the three compounds, in the gaseous phase, at T = 298.15 K, have been derived from the corresponding standard molar enthalpies of formation in the condensed phase and standard molar enthalpies for phase transition. The results obtained are −(150.7 ± 2.0) kJ · mol⁻¹, −(153.6 ± 1.7) kJ · mol⁻¹ and −(157.1 ± 1.4) kJ · mol⁻¹ for 2-cyano, 3-cyano and 4-cyanobenzoic acids, respectively. Standard molar enthalpies of formation were also estimated by employing two different methodologies: one based on the Cox scheme and the other one based on several different computational approaches. The calculated values show a good agreement with the experimental values obtained in this work.     

Thermochemical studies for determination of the molar enthalpy of formation of aniline derivatives

The standard (p ^o=0.1 MPa) molar enthalpies of combustion atT=298.15 K were measured by static bomb combustion calorimetry for liquidN,N-diethylaniline,N,N-dimethyl-m-toluidine,N,N-dimethyl-p-toluidine, andN-ethyl-m-toluidine. Vaporization enthalpies forN,N-dimethyl-m-toluidine andN-ethyl-m-toluidine were determined by correlation gas chromatography. Derived standard molar values of _f H _m ^o (g) at 298.15 K forN,N-diethylaniline (62.1±7.6);N,N-dimethyl-m-toluidine (72.6±7.3),N,N-dimentyl-p-toluidine (68.9±7.4),N-ethyl-m-toluidine (30.5±3.8 kJ· mol^–1) were obtained.     

Thermochemistry of Amines: Experimental Standard Molar Enthalpies of Formation of N-Alkylated Piperidines

The standard molar enthalpies of formation _f H _m ^° (l) at the temperature T = 298.15 K were determined using combustion calorimetry for N-methylpiperidine (A), N-ethylpiperidine (B), N-propylpiperidine (C), N-butylpiperidine (D), N-cyclopentylpiperidine (E), N-cyclohexylpiperidine (F), and N-phenylpiperidine (G). The standard molar enthalpies of vaporization _l ^g H ^{m °} of these compounds were obtained from the temperature variation of the vapor pressure measured in a flow system. From these data the following standard molar enthalpies of formation in gaseous phase _f H _m ^° (g) were derived for: A –(61.39 ± 0.88); B –(88.1 ± 1.3); C –(105.81 ± 0.66); D –(126.2 ± 1.3); E ( –88.21 ± 0.75); F –(135.21 ± 0.94); G (70.3 ± 1.4) kJ · mol^–1. They are used to determine the strain enthalpies of the cyclic amines A–G. The N-alkylated piperidine rings have been found to be about strainless.     

Calorimetric study of phase transitions in the thiourea carbon tetrachloride inclusion compound

Heat capacities of the inclusion compound (thiourea)_3.00CCl₄ have been measured in the temperature range 15–300 K. A first-order phase transition was found at 41.3 K and a second-order transition at 67.17 K. The enthalpy and entropy of the transition are 149 J mol^–1 and 3.7 J K^–1 mol^–1 for the former, and 241 J mol^–1 and 3.9 J K^–1 mol^–1 for the latter. A divergent expression C = A{(T _c –T)/T _c} ^– was fitted to the excess heat capacity of the upper phase transition. The best-fit parameters wereA = 7.4 J K^–1 mol^–1,T _c = 67.166 K and = 0.31. Possible types of molecular disorder in the high temperature phase are discussed in relation to the transition entropy and the molecular and site symmetries of the guest molecule. The heat capacity of the lowest temperature phase was unusually large and may indicate the existence of very low frequency vibrational modes or labile configurational excitation of the guest molecule. Standard thermodynamic functions were calculated from the heat capacity data and are tabulated in the appendix.Contribution No. 11 from the Microcalorimetry Research Center.     

Low-temperature heat-capacity and standard molar enthalpy of formation of copper l-threonate hydrate Cu(C4H6O5)·0.5H2O(s)

The solid copper l-threonate hydrate, Cu(C₄H₆O₅)·0.5H₂O, was synthesized by the reaction of l-threonic acid with copper dihydrocarbonate and characterized by means of chemical and elemental analyses, IR and TG-DTG. Low-temperature heat-capacity of the title compound has been precisely measured with a small sample precise automated adiabatic calorimeter over the temperature range from 77 to 390 K. An obvious process of the dehydration occurred in the temperature range between 353 and 370 K. The peak temperature of the dehydration of the compound has been observed to be 369.304 ± 0.208 K by means of the heat-capacity measurements. The molar enthalpy, Δ_dH_m, of the dehydration of the resulting compound was of 16.490 ± 0.063 kJ mol⁻¹. The experimental molar heat capacities of the solid from 77 to 353 K and the solid from 370 to 390 K have been, respectively, fitted to tow polynomial equations with the reduced temperatures by least square method. The constant-volume energy of combustion of the compound, Δ_cU_m, has been determined as being −1616.15 ± 0.72 kJ mol⁻¹ by an RBC-II precision rotating-bomb combustion calorimeter at 298.15 K. The standard molar enthalpy of formation of the compound, , has been calculated to be −1114.76 ± 0.81 kJ mol⁻¹ from the combination of the data of standard molar enthalpy of combustion of the compound with other auxiliary thermodynamic quantities.     

Kinetic and EPR studies on radical polymerization. Radical polymerization of di-2[2-(2-methoxyethoxy)ethoxy]ethyl itaconate

The polymerization of di-2[2-(2-methoxyethoxy)ethoxy]ethyl itaconate (1) with dimethyl 2,2-azobisisobutyrate (2) was studied, in benzene, kinetically and spectroscopically with the electron paramagnetic resonance (EPR) method. The polymerization rate (R _p) at 50°C is given by the equation:R _p=k[2]^0.48 [1]^2.4. The overall activation energy of polymerization was calculated to be 34 kJ·mol^–1. From an EPR study, the polymerization system was found to involve EPR-observable propagating polymer radicals of 1 under the actual polymerization conditions. Using the polymer radical concentration, the rate constants of propagation (k _p) and termination (k _t) were determined. With increasing monomer concentration,k _p(1.54.3 L·mol^–1·s^–1 at 50°C) increases andk _t (1.0·10⁴4.2·10⁴ L·mol^–1·s^–1 at 50°C) decreases, which seems responsible for the high dependence ofR _p on the monomer concentration. The activation energies of propagation and termination were calculated to be 11 kJ·mol^–1 and 84 kJ·mol^–1, respectively. For the copolymerization of 1(M ₁) and styrene (M ₂) at 50°C in benzene the following copolymerization parameters were found:r ₁=0.2,r ₂=0.53, Q₁=0.57, ande ₁=+0.7.     

Thermochemistry of Alcohols: Experimental Standard Molar Enthalpies of Formation and Strain of Some Alkyl and Phenyl Congested Alcohols

The standard molar enthalpies of formation _f H _m ^° (cr) at the temperature T = 298.15 K were determined using combustion calorimetry for di-tert-butyl-methanol (A), di-tert-butyl-iso-propyl-methanol (B), and di-phenyl-methyl-methanol (C). The standard molar enthalpies of sublimation _cr ⁸ H _m ^° of these compounds and of di-phenyl-methanol (D) were obtained from the temperature variation of the vapor pressure measured in a flow system. Molar enthalpies of fusion _cr ¹ H _m ^° of the compounds A–D and of tri-phenyl-methanol (E) were measured by differential scanning calorimeter (DSC). From these data and data available from the literature, the following standard molar enthalpies of formation in gaseous phase _f H _m ^° (g) for A, (–397.0 ± 1.2); B, (–418.1 ± 2.3); C, (–34.2 ± 1.3); and D, (0.9 ± 2.1) kJ · mol^–1 were derived, which correspond to strain enthalpies (H _S) of 46.1, 114.7, 8.1, and 5.0 kJ · mol^–1, respectively.     

Kinetics and thermodynamic aspect of the adsorption of Fe(III) on HTTA-imbedded polyurethane foam

The batch kinetics of Fe(III) adsorption on HTTA-loaded polyurethane (PU) foam have been investigated. The rate of controlling the adsorption is found to be intraparticle diffusion. The reaction rate of adsorption and desorption was also evaluated and found to increase and decrease with temperature, respectively. This indicates an endothermic adsorption behavior of Fe(III) on HTTA loaded PU foam. The activation energy of adsorption (80±10 kJ·mol^–1) and of desorption (–45±±2 kJ· mol^–1) indicates the chemical adsorption rather than physical adsorption. The isosteric heat of adsorption (H _ads) was found to be –82.7±5.05 kJ·mol^–1. This shows the formation of new chemical bonds among Fe(III)-HTTA-PU foam. The thermodynamic parameters of G, H and S, and equilibrium constantK _c have been calculated. These functions further support that the process of adsorption of Fe(III) on HTTA-loaded PU foam is endothermic and chemisorption, stabilized through thermodynamic functions.     

On the reliability of equilibrium data of the charge-transfer complex between 2,3-dichloro-1,4-naphthoquinone and hexamethylbenzene

In view ofHammond's warning⁶ about the Conspiracy of errors, found in the case of low values of equilibrium constants of charge-transfer complexes a case is made out for redetermining the values for the system hexamethylbenzene—2,3-dichloro-1,4-naphthoquinone. Uncertainties in the parameters were estimated using theLiptay ⁸ matrix procedure. The solvent used was dichloromethane. The following data were obtained at 25°C: vC T = 22,220 cm^–1;E _A=0.99 eV;K =2599±57 l²·cm^–1·mol^–2. _max= 1020 ± 148 cm^–1··1;K=2.55±0.37 l·mol^–1; –H=2.7±0.3 kcal·mol^–1.With 1 Figure     

The kinetics of the oxidation-reduction reaction between uranium(VI) and titanium(III) in HCl solution

The oxidation-reduction reaction between U(VI) and Ti(III) in HCl solution was studied spectrophotometrically. The reaction is second-order at all concentrations of reactants, HCl, ferrous chloride and mannitol used in this work. In 5M HCl the rate constantk increases with increasing Ti(III) concentration, whereas it decreases with increasing U(VI) concentration, with increasing HCl concentration from 1.00M to 7.17M and increases thereafter from 7.17M to 11.79M. The addition of mannitol causes a consistent decrease in the rate of reaction, whereas ferrous chloride has no effect. The activation energy for this oxidation-reduction reaction was 47.90±0.11 kJ·mol^–1. The values of H , G and S were 45.40±0.11 kJ·mol^–1, 72.50±0.17 kJ·mol^–1 and –91.10±0.22J·k^–1·mol^–1, respectively. The mode of reaction is discussed in the light of kinetic results.     

étude thermodynamique de certains médicaments

Two compounds of sulphamide type:p-amino-benzene sulphonamide (I) and 3,4-dimethylisoxazol 5-sulphanylamide (II) were studied by combustion calorimetry and by differential scanning calorimetry (DSC).The enthalpies in solid state at 298,15 K of combustion, _c H _m ^o (I)=-2788,5±1,6 kJ mol^–1, _c H _m ^o (II)=-5036±3,8 kJ mol^–1 and of formation, _f H _m ^o (I)=-458,3±1,6 kJ mol^–1, _fH _m ^o (II)=-180,1±3,8 kJ mol^–1 were determined.The thermal effects concerning the melting and phase transition of this compounds were also measured.

     

Structural studies of cyclic ureas: 3. Enthalpy of formation of barbital

A thermochemical and thermophysical study has been carried out for crystalline barbital [5,5′-diethylbarbituric acid]. The thermochemical study was made by static bomb combustion calorimetry, from which the standard () molar enthalpy of formation of the crystalline barbital, at T = 298.15 K, was derived as −(753.0 ± 1.8) kJ · mol⁻¹. The thermophysical study was made by differential scanning calorimetry over the temperature interval (265 to 470) K. A solid–solid phase transition was found at T = 413.3 K. The vapour pressures of the crystalline barbital were measured at several temperatures between T = (355 and 377) K, by the Knudsen mass-loss effusion technique, from which the standard molar enthalpy of sublimation, at T = 298.15 K was derived as (117.3 ± 0.6) kJ · mol⁻¹. The combination of the experimental results yielded the standard molar enthalpy of formation of barbital in the gaseous phase, at T = 298.15 K, as −(635.8 ± 1.9) kJ · mol⁻¹. This value is compared and discussed with our theoretical calculations by several methods (Gaussian-n theories G2 and G3, complete basis set CBS-QB3, density functional B3P86 and B3LYP) by means of atomization and isodesmic reaction schemes.     

Thermochemical study of two anhydrous polymorphs of caffeine

The mean values of the standard massic energy of combustion of caffeine in phase I (or alpha) and in phase II (or beta) measured by static-bomb combustion calorimetry in oxygen, at T = 298.15 K, are Δ_cu^° (C₈H₁₀O₂N₄, I) = −(21823.27 ± 0.68) J · g⁻¹ and Δ_cu^° (C₈H₁₀O₂N₄, II) = −(21799.96 ± 1.08) J · g⁻¹, respectively.The standard (p^° = 0.1 MPa) molar enthalpy of formation in condensed phase for each form was derived from the corresponding standard molar enthalpies of combustion as, and .The difference between the standard enthalpy of formation of the two polymorphs in condensed phase was also evaluated by using reaction-solution calorimetry. The obtained result, 2.04 ± 0.25 kJ · mol⁻¹, is in agreement, within the uncertainty, with the difference between the molar enthalpies of formation obtained from combustion experiments (4.5 ± 3.2) kJ · mol⁻¹, which can be considered as an internal test for consistency of the results.A value for the standard enthalpy of formation of caffeine in the gaseous state was proposed: , estimated from the values of the standard enthalpies of formation of both crystalline forms obtained in this work, and the data on standard enthalpies of sublimation collected from the literature.     

Thermal decomposition of silver cyano complex and characterization its decomposition products by ETA,DSC, DTA and TG

It was found by DTA and TG that [Phenyl₂I][Ag(CN)₂] in the solid state is chemically stable on heating in argon up to 160°C. During heating to higher temperatures it decomposes, forming volatile products such as [Phenyl]I, [Phenyl]NC and (CN)₂ [1]. After heating the sample to 500°C metallic silver resulted. The volatile and intermediate solid products were analysed by IR-spectroscopy.It was found by means of DTA and ETA that an isophase reversible transition takes place when the sample is heated and cooled, not higher than 100°C. At heating higher than 100°C the sample melts (melting pointT _m=135°C). The enthalpy melting was determined by means of DSC (H=–28 kJ·mol^–1).By means of ETA the disorder degree of the final decomposition product was estimated. The value of the activation energy of radon diffusion in the temperature range 720°–500°C equals 32.6 kJ·mol^–1.Dedicated to Prof. I. N. Bekman Moscow State University at the occasion of his 50th birthday     

Pulse radiolysis investigations on the reactions of primary radiolytic species of water with atropine

On pulse radiolysis of N₂O saturated aqueous solutions of atropine, an optical absorption band (_max at 320 nm,e=2.81·10³ dm³·mol^–1·cm^–1) was observed, which is assigned to the product of reaction of OH radicals with the solute. This absorption decayed following second order kinetics with a rate constant of 4.5·10⁸ dm³·mol^–1·s^–1. The rate constant for the reaction of OH radicals with atropine as estimated by following the build-up kinetics is 2.7·10⁹ dm³·mol^–1·s^–1. The H atoms also reacted with this compound to produce a transient absorption band behaving similarly to the one observed in the case of reaction with OH radicals. The transient species formed in both cases is assigned to a radical derived by H atom abstraction by H/OH radicals from the parent compound. This radical was unreactive towards 2-mercaptoethanol. e _aq ^– was found to react with atropine forming a transient band with _max at 310 nm (=3.55·10³ dm³·mol^–1). Its decay was also second order with a rate constant of 1.64·10⁹ dm³·mol^–1·s^–1. The bimolecular rate constant for the reaction of e _aq ^– with atropine as estimated from the decay of e _aq ^– absorption at 720 nm is 3.9·10⁹ dm³·mol^–1·s^–1. Specific one-electron oxidizing and reducing agents (such as Cl ₂ ^– , Tl²⁺, SO ₄ ^– and (CH₃)₂COH, CO ₂ ^– , respectively) failed to oxidize or reduce this compound in aqoues solutions. The radical anion of atropine formed by its reaction with e _aq ^– was found to reduce thionine and methyl viologen with bimolecular rate constant of 3.8·10⁹ and 3.2·10⁹ dm³·mol^–1·s^–1, respectively.     

Molecular structure,conformational mobility,vibrational spectra,and thermochemistry of peroxyacetic acid: an ab initio and density functional study

The structure of the peroxyacetic acid (PAA) molecule and its conformational mobility under rotation about the peroxide bond was studied by ab initio and density functional methods. The free rotation is hindered by the trans-barrier of height 22.3 kJ mol^–1. The equilibrium molecular structure of AcOOH (C _s symmetry) is a result of intramolecular hydrogen bond. The high energy of hydrogen bonding (46 kJ mol^–1 according to natural bonding orbital analysis) hampers formation of intermolecular associates of AcOOH in the gas and liquid phases. The standard enthalpies of formation for AcOOH (–353.2 kJ mol^–1) and products of radical decomposition of the peroxide — AcO^· (–190.2 kJ mol^–1) and AcOO^· (–153.4 kJ mol^–1) — were determined by the G2 and G2(MP2) composite methods. The O—H and O—O bonds in the PAA molecule (bond energies are 417.8 and 202.3 kJ mol^–1, respectively) are much stronger than in alkyl hydroperoxide molecules. This provides an explanation for substantial contribution of non-radical channels of the decomposition of peroxyacetic acid. The electron density distribution and gas-phase acidity of PAA were determined. The transition states of the ethylene and cyclohexene epoxidation reactions were located (E _a = 71.7 and 50.9 kJ mol^–1 respectively).     

Activation energy of Se2Ge0.2Sb0.8 chalcogenide glass by differential scanning calorimetry

Results of differential scanning calorimetry (DSC) at different heating rates on Se₂Ge_0.2Sb_0.8 chalcogenide glass are reported and discussed. As the heating rate () changed, also the glass transition temperature (T _g) and onset temperature of crystallization (T _c) changed. As the value of the transition activation energyE _t changed, the crystallization fraction (), heat flow (_q and the crystallization peak temperature (T _p) also changed. The value of the effective activation energy of crystallizationE _c was calculated by means of six different methods. The Se₂Ge_0.2Sb_0.8 chalcogenide glass has two crystallization mechanisms, a one-dimensional and an other surface crystallization growth. The average value ofE _t for Se₂Ge_0.2Sb_0.8 is equal to 194.95±3.9 kJ·mol^–1 and the average value ofE _c is equal to 164±3.3 kJ·mol^–1.     

Optical and gamma irradiation studies of morin in ethanol

Spectral studies of morin in aqueous ethanol and other alcohols have been carried out as a function of its concentration and that of ethanol, and the pH of aqueous buffer. The effect of gamma radiations on morin solution in ethanol was also studied as a function of dose in the range of 0.15–2.28 kGy and of morin concentration (10^–5–10^–4 mole·dm^–3). Morin concentration in ethanol solution showed a linear response for G values to a dose of 1.83 kGy. Molar absorption coefficients () for morin in ethanol have been estimated to be _260nm=2.28·10⁴ dm³·mol^–1·cm^–1 and _291nm=8.22·10³ dm³·mol^–1·cm^–1 for unirradiated and _{291 nm}=1.75·10⁴ dm³·mol^–1·cm^–1 for irradiated solutions to a dose of 1.83 kGy.