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.     

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.     

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.     

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.     

Steric and electronic contributions to barriers of internal rotation in 1,8-dibenzoylnaphthalenes

Restricted rotation about the naphthalenylcarbonyl bonds in the title compounds resulted in mixtures of cis and trans rotamers, the equilibrium and the rotational barriers depending on the substituents. For 2,7-dimethyl-1,8-di-(p-toluoyl)-naphthalene (1) ΔH° = 3.66 ± 0.14 kJ mol^?1, ΔS° = 1.67 ± 0.63 J mol^?1 K^?1, ΔH^≠_ct = 55.5 ± 1.3 kJ mol^?1, ΔH^≠_ct = 51.9 ± 1.3 kJ mol^?1, ΔS^≠_ct = ?41.3±4.1 J mol^?1 K^?1 and ΔS^≠_ct = ?42.9±4.1 J mol^?1 K^?1. The rotation about the phenylcarbonyl bond requires ΔH^≠ = ?56.9±4.4 kJ mol^?1 and ΔS^≠ = ?20.5±15.3 J mol^?1 K^?1 for the cis rotamer, and ΔH^≠ = 43.5Δ0.4 kJ mol^?1 and ΔS^≠ =± ?22.4Δ1.3 J mol^?1 K^?1 for the trans rotamer. The role of electronic factors is likely to be virtually the same for both these rotamers but steric interaction between the two phenyl rings occurs in the cis rotamer only. Hence, the difference of the activation enthalpies obtained for the cis and trans rotamers, ΔΔH^?1 = 13.4 kJ mol^?1, provides a basis for the estimation of the role of steric factors in this rotation. For the tetracarboxylic acid 2 and its tetramethyl ester 3 the equilibrium is even more shifted towards the trans form because of enhanced steric and electrostatic interactions between the substituents in the cis form. The barriers for the rotation around the phenylcarbonyl bond and the cis-trans isomerization are lowered; an explanation for this result is presented.     

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.     

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.     

Synthesis,structure and fluxional behaviour of isomeric bis(trimethylstannyl)dihydropentalenes

Interaction of dihydropentalene (IV) with trimethylstannyldiethylamide in molar ratios of 1:1 or 1:2 leads to mono- or bis-organotin derivatives of IV, respectively. X-ray analysis of trans(E)-bis(trimethylstannyl)dihydropentalene (Va) has been carried out, R = 3.4%. Molecules of Va are centrosyommetric. The parmeters of monoclinic cell: a 8.680(1), b 7.322(1), c 13.073(2) Å, β 97.74(1)°, space group P2₁/c, Z = 2. Geometrical parameters of Va have been determined and their values are discussed in comparison with the same parameters for η¹-cyclopentadienyl compounds of elements. Chemical shifts ¹³C, ¹H and ¹¹⁹Sn and coupling constants ¹³C-¹¹⁹Sn and ¹¹⁷Sn-¹¹⁹Sn of bis- and tris-organotin derivatives of IV have been determined. Rapid intramolecular suprafacial metallotropic rearrangement, proceeding as a [1,5]-sigmatropic shift of SnMe₃ group, has been found in Va and cis-(Z)-bis(trimethylstannyl)dihydropentalene (Vb). Activation parameters have been evaluated by the analysis of temperature dependence of ¹³C NMR spectra within the framework of degenerate two-site exchange in the isomers Va and Vb, E_A: 42.2±0.9 and 31.2±0.6 kJ · mole⁻¹; ΔH^≠₂₉₈: 39.8±0.9 and 27.7±0.6 kJ · mole⁻¹; ΔS^≠₂₉₈: −6.2±4.0 and −87.0±3.1 J · mole⁻¹ · K⁻¹ and ΔG^≠₂₉₈: 41.6±1.5 and 54.6±1.1. kJ δ mole⁻¹, respectively.     

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.     

The fluorobasicities of ReF7 and IF7 as measured by the enthalpy change ΔH°(EF7(g) → EF6+(g) + F−(g))

Iridium hexafluoride oxidizes ReF₆ (via an ReF₆⁺ salt) and at room temperatures IrF₆, ReF₆, ReF₇ and (IrF₅)₄ are each present in the equilibrium mixture. From these and related findings: ΔH°(ReF₆ → ReF₆⁺ + e^?) 1092 ± 27 kj mole^?1(261 ± 6 kcal mole^?1), and thermodynamic data are selected to yield ΔH°(ReF_7(g) → ReF₆⁺_(g) + F^?_(g))=893 ± 33 kj mole^?1(213 ± 8 kcal mole^?1). From observations on the stability of IF₆⁺BF₄^? and the lattice enthalpy evaluation for the salt, ΔH°(IF_7(g) → IF₆⁺_(g) + F^?_(g))= 870 ± 24 kj mole^?1(208 ± 6 kcal mole^?1).     

Thermodynamics of redox reactions involving nicotinamide adenine dinucleotide

Literature data on the thermodynamics of redox nicotinamide adenine dinucleotide (NAD) dependent reactions have been analyzed. It has been established that for the redox reaction of NAD

where all substances except H₂ are in the aqueous buffer with the ionization enthalpy equal to zero, the most reliable thermodynamic parameters should be considered as: ΔH(298.15 K; pH 7)=?27.4±1.7 kJ mole^?1; ΔG (298.15K; pH 7)=±17.8 kJ mole^?1. From the above thermodynamic parameters of the reaction ΔH, ΔG and ΔS for reactions of NAD with natural substrates, synthetic mediators and some inorganic compounds have been calculated.     

The gas-phase rotamers of 1,1,2,2-tetrafluoroethane - force field,vibrational amplitudes and geometry - a joint electron-diffraction and spectroscopic study

The gas-phase conformational mixture of the anti and gauche rotamers of 1,1,2,2-tetrafluoroethane has been subjected to an electron-diffraction study at 253 K. Effective least-squares refinement of the geometry and relative proportions of the conformers was achieved with vibrational amplitudes for both conformers fixed at values calculated from spectroscopic data. In order to calculate the amplitudes, a force field was deduced which reproduced the observed wave numbers for both conformers; the assignment of the modes proposed in the literature was modified slightly. At 253 K, the rotamer composition was found to be 84% anti : 16%gauche, which corresponds to an energy difference of 1170 cal mol^?1; the geometrical parameters (r_a values) and e.s.d. are C-C = 1.518 ± 0.005 Å, C-H = 1.098 ± 0.006 Å, C-F = 1.350 ± 0.002 Å. ∠CCF = 108.2 ± 0.3°, ∠FCF = 107.3 ± 0-3°, ∠ CCH = 110.3 ± 1.0δ, and the torsion angleτ _hcch in the gauche form is 78 ± 2°.     

Temperature dependence of the reaction rate constants for O(3P) atoms with C2H4, C3H6 and NO(M = N2O), determined by a modulation technique

Rate constants for the reaction of O(³P) atoms with C₃H₄, C₃H₆ and NO(M = N₂O) have been measured over the temperature range 300–392°K using a modulation-phase shift technique. The Arrhenius expressions obtained are:C₂H₄, k₂ = 3.37 × 10⁹ exp[?(1270 ± 200)/RT]liter mole^?1 sec^?1,C₃H₆, k₂ = 2.08 × 10⁹ exp[?(0 ± 300)/RT]liter mole^?1 sec^?1,NO(M = N₂O), k₁ = 9.6 × 10⁹ exp[(900 ± 200/RT]liter² mole^?2 sec^?1.These temperature dependencies of k₂ are in good agreement with recent flash photolysis-resonance flourescence measurements, although lower than previous literature values.     

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.     

Picosecond photochemistry of Cr(CO)6: Solvation and dynamics of the primary intermediate

Picosecond absorption spectroscopy has been used to examine the primary photoproduct of Cr(CO)₆ in both neat and mixtures of THF and cyclohexane. The primary intermediate observed is shown to be the solvated pentacarbonyl in which one solvent molecule occupies the coordination site created by the photoelimination of CO. The rate of exchange of cyclohexane from (cyclohexane)Cr(CO)₅ by THF to form (THF)Cr(CO)₅ was found to be bimolecular, k = (4 ± 1) × 10⁷ mole^?1 s^?1, with an enthalpy and entropy of activation of 1 ± 1 kcal/mole and ?20 ± 4 eu, respectively.     

Thermal [1,5] sigmatropic rearrangements in (σ-7-cycloheptatrienyl)triphenyltin and (σ-5-cyclohepta-1,3-dienyl)triphenyltin: A 1H and 13C NMR reinvestigation

It has been confirmed by ¹H and ¹³C NMR spectroscopies that Sn(σ-C₇H₇)Ph₃ undergoes either 1,4- or 1,5-shifts of the SnPh₃ moiety around the cycloheptatrienyl ring with ΔH³ = 13.8 ± 0.4 kcal mol^?1, ΔS3 = ?5.6 ± 1.2 cal mol^?1 deg^?1, and ΔG³₃₀₀ = 15.44 ± 0.14 kcal mol^?1. Similarly, (σ-5-cyclohepta-1,3-dienyl)triphenyltin undergoes 1,5-shifts with ΔH³ = 12.4 ± 0.6 kcal mol^?1, ΔS³ = ?11.2 ± 1.8 cal mol^?1 deg^?1, and ΔG³₃₀₀ = 15.76 ± 0.13 kcal mol^?1. It is therefore probable that Sn(σ-5-C₅H₅)R₃ and Sn(σ-3-indenyl)R₃ do not undergo 1,2-shifts as previously suggested but really undergo 1,5-shifts.     

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.     

Sigmatropic [1,3]-boron shift (permanent allylic rearrangement) in 3-allyl-3-borabicyclo[3.3.1]nonanes

2D ¹H-¹H EXSY NMR spectroscopy show that the free energy of activation ΔG ^≠ in six 3-allyl-3-borabicyclo[3.3.1]nonane derivatives is significantly higher (72–86 kJ mol^?1) than that in typical allylboranes (48–66 kJ mol^?1). For the first member of the series, viz., 3-allyl-3-borabicyclo[3.3.1]nonane, the activation parameters of the permanent allylic rearrangement were also determined (ΔH ^≠ = 82.7±3.4 kJ mol^?1, ΔS ^≠ = ?11.8±10.3 J mol^?1 K^?1, E _A = 85.5±3.4 kJ mol^?1, lnA = 29.2±1.2).     

Spectra and structure of small ring compounds: Part XXXVIII. Cyclobutanol

The Raman spectrum of gaseous cyclobutanol has been recorded and the far infrared spectrum of the gas has been obtained at a resolution of 0.5 cm^?1. At least six Q-branches arising from the low frequency ring-puckering motion have been observed and assigned on the basis of a potential of the form V(X) = (6.32 ± 0.21) × 10⁵X⁴?(4.18 ± 0.04) × 10⁴X²+ (8.81 ± 1.20) × 10³X³ with a reduced mass of 170 amu. An energy difference between the equatorial and axial forms was found to be 50–150 cm^?1 with the equatorial being more stable and a barrier of 700–900 cm^?1 was found for the interconversion. Three O-H stretching modes were observed in the Raman spectrum. It is concluded that the O-H moiety has both the gauche and trans conformations present in the equatorial form but only the gauche conformer is present in the axial form of the ring. Three O-H torsional modes were observed at 244 (trans conformer), 226.5 and 181.5 cm^?1 (gauche conformer) for the equatorial form and one O-H torsion at 237.5 cm^?1 (gauche conformer) for the axial form. The potential function governing the O-H torsional motion for the equatorial form was found to be V₁ = 280 ± 7 cm^?1 (800 cal mole^?1) and V₃ = 425 ± 3 cm^? (121.5 cal mole^?1) with the trans conformer being more stable than the gauche by approximately 206 cm^?1 (589 cal mole^?). The barriers to trans-gauche and gauche-gauche interconversion have essentially the same values, 500 cm^?1 (1430 cal mole^?1).     

Molecular structure and conformation of 2,3-dichloro-1-propene as determined by gas-phase electron diffraction

The molecular structure and conformation of 2,3-dichloro-1-propene have been determined by gas-phase electron diffraction at nozzle temperatures of 24, 90 and 273°C. The molecules exist as a mixture of two conformers with the chlorine atoms anti (torsion angle ∠φ = 0°) or gauche (∠φ = 109°) to each other and with the anti form the more stable. The composition (mole fraction) of the vapor with uncertainties estimated at 2σ was found to be 0.55 (0.08), 0.49 (0.08) and 0.41 (0.10) at 24, 90 and 273°, respectively. These values correspond to an energy difference with estimated standard deviation ΔE° = E°_g-E°_a = 0.7 ± 0.3 kcal mol^?1 and an entropy difference ΔS° = S°_g-S°_a = 0.6 ± 0.9 cal mol^?1 K^?1. Some of the diffraction results, together with spectroscopic observations, permit the evaluation of an approximate torsional potential function of the form 2V = V₁ (1 - cos φ) + V₂ (1 - cos 2φ) + V₃ (1 - cos 3φ); the results are V₁ = 4.4 ± 0.5, V₂ = ?2.9 ± 0.5 and V₃ = 4.8 ± 0.2, all in kcal mol^?1. The results at 24°C for the distance (r_a) and angle (∠_α) parameters, with estimated uncertainties of 2σ, are: r(C_sp²-H) = 1.098(0.020)Å, r(C_sp³-H) = 1.103(0.020)Å, r(CC) = 1.334(0.009)Å, r(C-C) = 1.504(0.013)Å, r(C_sp²-Cl) = 1.752(0.021)Å, r(C_sp³-Cl) = 1.776(0.020)Å, ∠C-CC = 127.6(1.1)°, ∠C_sp³-C_sp²-Cl = 110.2(1.0), ∠C_sp²-C_sp³-Cl = 113.1(1.2)°, ∠H-C_sp³-H = 109.5° (assumed), ∠CC-H = 120.0° (assumed) and ∠φ = 108.9(3.4)°.