Determination of enthalpy of ionization of water from 250 to 350° C

The enthalpy changes at zero ionic strength (H°) for the ionization of water (H₂O=H⁺+OH^–) were determined by flow calorimetry from the heats of mixing of aqueous NaOH and HCl solutions in the temperature range 250 to 350°C. Pitzer ion-interaction models developed by other workers were used to calculate enthalpies of dilution of aqueous NaOH, HCl, and NaCl solutions for the extrapolation of H values from the conditions of the experiment to infinite dilution. Equations are derived for thermodynamic quantities (log K, H°, S°, C _p ^° and V°) for the ionization of water using the H° values determined in this study from 250 to 350°C and literature log K and H° values from 0 to 225°C. Smoothed values of log K, H°, S°, C _p ^° , and V° are presented at rounded temperatures from 0 to 350°C and at the saturation pressure of water for each temperature. The equations in the present study provide a better representation of experimental thermodynamic data from 0 to 350°C than the Marshall-Franck equation.     

Densities and compressibilities of aqueous HCl and NaOH from 0 to 45°C. The effect of pressure on the ionization of water

The densities and sound speeds of aqueous HCl and NaOH solutions were measured from 0.1 to 1.0m and from 0 to 45°C. These data were combined with literature data and fitted to functions of molality and temperature. The apparent molal volumes V and compressibilities K of these solutions were fitted to functions of molality and temperature. The partial molal volumes and compressibilities of HCl and NaOH solutions were used to calculate the partial molal volume V and compressibility changes for the ionization of water. Combined with literature data these values of V adn were used to calculated the effect of pressure on the ionization constant of water K _w from 0 to 200°C. The effect of pressure on K _w calculated from partial molal quantities are in reasonable agreement with that determined directly from high pressure measurements taken from the literature up to 1000 bar. It is necessary to use the pressure dependence of K ⁰ to extend the calculated pressure dependence of K _w up to 6000 bar.     

Strain Energies of α-Alkylsubstituted Styrenes, 1,1-Di-phenyl-ethene,Tri-, and Tetra-phenyl-ethene

The standard (p° = 0.1 MPa) molar enthalpies of formation _fH°_m (1 or cr) at the temperature T = 298.15 K were determined by using combustion calorimetry for -ethyl-styrene (A), -iso-propyl-styrene (B), -tert-butyl-styrene (C), 1,1-di-phenyl-ethene (D), tri-phenyl-ethene (E), and tetra-phenyl-ethene (F). The standard molar enthalpies of vaporization _l ^g H°_m or sublimation _cr ^g H°_m of compounds A to F were obtained from the temperature variation of the vapor pressure measured in a flow system. Molar enthalpies of fusion _cr ^l H°_m of solid compounds were measured by d.s.c. Resulting values of _fH°_m (g) were obtained at the temperature T = 298.15 K and used to derive strain enthalpies of phenylalkenes. The interactions of the substituents are discussed in terms of deviations of _fH°_m (g)from the group additivity rules. These values provide a further improvement on the group-contribution methodology for estimation of the thermodynamic properties of organic compounds.     

Thermodynamics of protonation of amino acid carboxylate groups from 50 to 125°C

Flow calorimetry has been used to study the interaction of glycine, DL--alanine, DL-2-aminobutyric acid, -alanine, 4-aminobutyric acid, and 6-aminocaproic acid with protons in aqueous solutions from 323.15 K to 398.15 K and at 1.52 MPa. LogK, H°, S°, and C _p ^° for the protonation of the carboxylate groups of these amino acids have been obtained at each temperature studied. Equations are given expressing these values as functions of temperature. The protonation reactions are exothermic at lower temperatures and become endothermic as temperature increases. The logK, H°, and S° values are close together over the temperature range studied for the protonation of -amino acids, i.e., glycine, DL--alanine, and 2-aminobutyric acid. At each temperature, the magnitudes of these thermodynamic quantities increase as the number of methylene groups between the amino group and the carboxylate group increases. The C _p ^° value for the protonation of the carboxyl group is found to lie between those of an isocoulombic reaction and a charge reduction reaction. At 323.15 K, the protonation reactions of the carboxylate groups have larger C _p ^° values which approach those associated with charge reduction reactions. As the temperature increases, C _p ^° decreases and approaches those found for isocoulombic reactions. This result is explained by considering long-range and short-range solvent effects. The trend in H° and S° with temperature and with charge separation in the zwitterions is interpreted in terms of solvent-solute interactions and the electrostatic interaction of the two oppositely charged groups within the molecule.     

Relativistic perturbation theory of molecular structure

Summary The recently developed relativistic double perturbation theory is extended to handle relativistic changes of molecular structure more easily. This is achieved by simple coordinate scalings. Accurate higher order mixed perturbation energies for H ₂ ⁺ are calculated. The relativistic changes of bond energy,DE, of bond length,R _e , and especially of force constant,k, and of anharmonicity,a, are large, up to 100%·(Z/c)². The dominant contributions tok anda are due to the indirect change of the nonrelativistick anda connected with the relativistic change of bond length. Accordingly the relativistic changes obey Badger's and Gordy's rules (–RDEk).Dedicated to Prof. Klaus Ruedenberg in appreciation of his fundamental contributions to both formal theory and physical explanations in quantum chemistry     

The Influence of Dimerization of Water-Soluble Metalloporphyrins as Photosensitizers on the Efficiency of Generation of Singlet Oxygen

Quantum yields () for the generation of singlet oxygen sensitized by Pd(II) complexes of water-soluble porphyrins: meso-tetrakis(4-N-methylpyridyl)porphine [PdTMPyP]⁴⁺ ( = 0.9), meso-tetrakis(4-N,N,N-trimethylaminophenyl)porphine [PdTTMAPP]⁴⁺ ( = 0.8), meso-tetrakis(4-carboxyphenyl)porphine [PdTCPP]^4– ( = 0.7), and meso-tetrakis(4-sulfonatophenyl)porphine [PdTSPP]^4– ( = 0.5) were determined using a chemical method. It was found that the dimerization and aggregation of metalloporphyrins greatly influence the value. The quantum yields evaluated for the formation of singlet oxygen sensitized by metalloporphyrin monomeric and dimeric forms are _{, M} 0.9 and _{, D} 0.2, respectively, and do not depend on the porphyrin nature.     

A Spectroscopic Study of Charge Transfer Complexes of Tetraphenylporphyrin

Summary. The fluorescence quenching and complexation behaviour of tetraphenylporphyrin (TPP) with some organic acceptors such as chloranilic acid (CHL), 5,5-dithiobis-2-nitrobenzoic acid (DTNB), or 3,4-dinitrobenzoic acid (DNB) and tetravalent metal ions such as Th⁴⁺ and Zr⁴⁺ have been studied in methanol. The second-order fluorescence quenching rate constant (k_q), the association constant (K), the molar absorption coefficient (), and the thermodynamic parameters of the complexation process (G°, H°, and S°) have been evaluated using different organic solvents.     

Charge control of the complex formation of phenol with unsaturated compounds containing organoelement substituents from group IV

The frequency shifts (v (OH)) of phenol and the resonance components (v_r) of these shifts in the IR spectra of forty H-complexes of phenol with furan derivatives containing organic, organosilicon, organogermanium, and organotin substituents are studied. The values of v and v_R are linearly related to quantum chemical parameters of the variation of the effective charges of the furan ring atoms affected by - and -interactions with organic substituents. The effect of the conjugation between an organoelement substituent and the furan ring on the effective charges is estimated. The resonance parameters (_R) of organoelement substituents in derivatives of benzene, thiophene, and furan and the reasons for the non-versatility of _R are considered.For report 7, see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 289–295, February, 1995.This work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-18372).     

Thermodynamic quantities for the interaction of Cl− with Mg2+, Ca2+ and H+ in aqueous solution from 250 to 325°C

The aqueous reactions, Mg²⁺+Cl^–=MgCl⁺, Ca²⁺+Cl^–=CaCl⁺, and H⁺ +Cl^–=HCl(aq), were studied as a function of ionic strength at 250, 275, 300, and 325°C using a flow calorimetric technique. The logK, H, S and C_p values were determined from the fits of the calculated and experimental heast. The data were reduced assuming a known functionality of the activity coefficient. Hence, the logK, H, S and C_p values determined in this study are dependent on the activity coefficient model used. These thermodynamic values were compared with literature results. The logK values for the formation of MgCl⁺ agree reasonably well with those reported in the literature. The logK values for CaCl⁺ formation agree reasonably well with those reported in the literature at 300 and 325°C. At lower temperatures, the agreement is poorer. The logK values for the formation of HCl(aq) are generally lower than those reported in the literature. The logK, H, S and C_p values for all three ion association reactions are positive and increase with temperature over the temperature range studied. These values are the first determined calorimetrically for the formation of MgCl⁺ and CaCl⁺ in the temperature range 275–325°C.Presented at the Second International Symposium on Chemistry in High Temperature Water, Provo, UT, August 1991.     

Marked differences between acetonitrile/water and methanol/water mobile phase systems on the thermodynamic behavior of benzodiazepines in reversed phase liquid chromatography

Summary Two different methods were used to determine the separation factor at different temperatures and the Gibbs-Helmholtz parameters ((H), (S)) of two adjacent benzodiazepines on a chromatogram were obtained from plots of ln versus 1/T. We first studied each factor (fraction of water in the ACN/water mixture and column temperatureT), which controls the retention mechanism, and then we examined the simultaneous variation of all these factors. The changes in (H) and (S) in relation to a volume fraction of water in an ACN/water mixture were examined. In the ACN/water system, (H) was fairly constant in the acetonitrile region of 0.52 and appears to be a roughly linear function of for 0.52. In this system (S) is approximately a parabolic function of with an optimum at 0.52. The retention mechanism of ten benzodiazepines was found to be significantly different in the methanol/water and ACN/water mixtures. The separation optimization of these ten benzodiazepines was then considered. A fraction of water of 0.43 in the ACN/water mixture and a column temperature of 44°C gave the most efficient separation conditions in the ACN/water mixture.     

Thermodynamic quantities for the interaction of H+ and Na+ with C2H3O 2 − and Cl− in aqueous solution from 275 to 320°C

The aqueous reactions, {ie865-1}were studied as a function of ionic strength at 275, 300, and 320°C using a flow calorimetric technique. Log K, H and S values were determined from the fits of the calculated and experimental heats while Cp values were calculated from the variation of H values with temperature. The log K and H values for the first two reactions agree well with literature values at these temperatures. No previous results have been reported for the third reaction. The use of equations containing identical numbers of positive and identical numbers of negative charges on both sides of the equal sign (isocoulombic reaction principle) was applied to the log K values determined in this study. The resulting plots of log K for the isocoulombic reactions vs. I/T were approximately linear, which demonstrates that the Cp values for these reactions are approximately zero.Deceased 5 September 1987     

Numerische Auswertung von Enzymanalysen

Zusammenfassung Für eine numerische Auswertung von Enzymanalysen erscheint es zunächst naheliegend, in die Meßpunkte eine Ausgleichsgerade einzupassen und deren Steigung als Schätzwert für die gesuchte Anfangsgeschwindigkeit E/t ₀ zu nehmen. Die Steigung der Ausgleichsgeraden liefert aber die mittlere Reaktionsgeschwindigkeit über die gesamte Meßzeit und unterschätzt E/t ₀ immer dann, wenn die Reaktion gegen Ende der Meßzeit etwas langsamer läuft. Bei automatischen Geräten muß das Auswerteverfahren auch in solchen Fällen E/t ₀ richtig schätzen. In der vorliegenden Arbeit wird eine einfache Möglichkeit, die zu diesem Ziel führt, diskutiert, nämlich die Schätzung von E/t ₀ mit einer Ausgleichsparabel, die dem Reaktionsverlauf folgen kann.

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Numerical evaluation of enzyme analyses

To calculate enzyme concentrations numerically, it seems obvious to fit a straight line into the data points and take the slope as an estimate for the starting velocity E/t ₀. This slope, however, is proportional to the average reaction rate over the total measurement interval and always underestimates E/t ₀ when the reaction is slowing down towards the end. Automatic analyzers must correctly estimate E/t ₀ even in such cases. As discussed in this article, this can be achieved by fitting a second order parabola, that can follow the reaction, into the data points.

     

Enthalpy of solution of carbohydrates using a modified differential scanning calorimeter

A differential scanning calorimeter (DSC) was modified for the determination of enthalpies of solution. The measurements were performed on aqueous solutions of the deoxy- and fluoro-deoxy derivatives of D-glucopyranose (Glu) where the OH group on the C1, C2, C3, and C6 is replaced by H (1HGlu, 2HGlu, 3HGlu, and 6HGlu) and by F (1FGlu, 2FGlu, 3FGlu, and 6FGlu), 4-deoxy 4-fluoro--D-glucopyranoside (4FGlu), 1-methoxy--D-glucopyranoside (MeOGlu), 1-phenoxy--D-glucopyranoside (PheOGlu), D-mannopyranose (Man), and 3-methoxy--D-glucopyranoside (3MeOGlu), at 15.1, 25.0, 35.0, and 45.1°C. The enthalpies of solution _sH⁰(T) ranged from 1.00±0.25 kJ-mol^–1 for 6HGlu at 15.1°C to 20.4±1.4 for PhOGlu at 45.1°C and were in good agreement with literature values for Man, Glu, MeOGlu, and 3MeOGlu at 25.0 and 35.0°C and for MeOMan and 2HGlu at 35.0°C. _sH⁰(T) for the derivatives were then extrapolated up to the melting temperature T_m and compared with their enthalpies of fusion, _fH also determined from DSC measurements. If the agreement between _sH⁰(T_m) and _fH was within the 95% confidence level, then it was concluded that intermolecular interactions between the carbohydrate molecules in the liquid phase were the same as between the carbohydrate and water molecules in the solution phase. This agreement was observed for aqueous solutions of Man, Glu, MeOGlu, 3HGlu, 3FGlu, and 6FGlu.     

Electrical conductance of aqueous solutions of KCl solutions at pressures up to 2000 atm

Electrical conductance measurements are reported for aqueous KCl solutions at 25°C as a function of concentration up to 0.02 M and pressure up to 2000 atm. The data from 103 runs were analyzed with the Fuoss-Hsia-Fernandez-Prini (FHFP) equation. The standard error of fit varies from 0.018 at 1 atm to 0.12 at 2000 atm. The increase of with pressure arises from increasing nonrandomness in the distribution of errors about the FHFP equation, suggesting that modifications in the theory are necessary. Departures from the Walden product for KCl as a function of pressure are compared with MgSO₄ and CaSO₄ in aqueous solutions.     

Thermodynamic behavior of mixed benzodiazepines by a new liquid chromatographic method

Summary Using a rapid chemometric methodology to determine the separation factor, , at different temperatures, Gibbs Helmholtz parameters ( (H), (S), (G)) of two adjacent benodiazepines on a chromatogram were obtained from ln versus T^–1 plots. A temperature dependent reversal of the elution order was studied and the mobile phase composition and column temperature were optimized to obtain the best separation. A flow rate of 0.80 ml min^–1 with 52.6% methanol in the methanol-water mixture and a column temperature of 48°C gave the most efficient separation of ten benzodiazepines.     

Experimental Evaluation of ΔS°rxn, ΔH°rxn, and ΔG°rxn Using Voltaic Cells: A First-Year College Chemistry Laboratory

Six voltaic cells have been evaluated for their suitability in the determination of thermodynamic parameters. The cells were prepared with all species present at conditions that approximate standard-state conditions and cell potentials were measured as a function of temperature. From these measurements graphs of voltage versus temperature were prepared. From these graphs it was possible to determine the standard heats of reaction (II_rxn), standard change in entropy or disorder (S°_rxn), and the Gibbs free energy (G°_rxn) for the spontaneous oxidation-reduction reactions. The standard cell potential (E°_cell values were also calculated. Two cells with opposite temperature dependence of the cell potential were found to produce good agreement with the literature values of G°_rxn, H°_rxn, S°^rxn and E°_cell. Criteria for identifying additional cells that may be suitable for potentiometric studies of thermodynamic parameters are also included.     

The conductance of lithium-7 fluoride in dioxane-water mixtures at 25°C

Conductance data for lithium-7 fluoride in dioxane-water mixtures covering the range 78.35>D>36 in dielectric constant are presented. These data and other previous data on lithium-7 chloride and lithium-7 iodide were analyzed by the Fuoss 1980 conductance equation in order to find the limiting conductance _o, the pairing distance R and the conductometric association constant K. Setting K_a=K/V_M (where V_M is the molar volume of the solvent), the thermodynamic pairing constant and the corresponding change of the free energy g were calculated. Correlation among the values found for R and g=h–Ts and the properties characteristic of the ions and solvents are discussed.R. M. Fuoss died on 1^st December 1987 before this work was completed. A D'Aprano and F. Accascina dedicate this paper to him with respect and affection.     

Enthalpies of formation of amidyl free radicals

The enthalpies of formation (#x0394;H°_f) of twenty-one amidyl radical (R) belonging to the formamidyl homological series were calculated using the published values of R—H bond dissociation energies. Among them, the H°_f values of nine radicals were first calculated and those of eight radicals were refined. Most of the H°_f values of corresponding starting molecules RH (H°_f(RH)) were obtained using the macroincrementing schemes. Based on the group additivity scheme, the structure—enthalpy of formation relationships for the radicals considered were examined, the H°_f(R) values were analyzed, and their reliability was confirmed. Parameters for calculating the H°_f values of radicals belonging to this homologous series were suggested.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1574–1577, August, 2004.     

Thermodynamics of protonation of AMP,ADP, and ATP from 50 to 125°C

The interaction of adenosine 5-monophosphate (AMP), adenosine 5-diphosphate (ADP), and adenosine 5-triphosphate (ATP) ions with protons in aqueous solution has been studied calorimetrically from 50 to 125°C and 1.52 MPa. At each temperature, the reaction of acidic AMP with tetramethylammonium hydroxide was combined with the heat of ionization for water to obtain the enthalpy of protonation of AMP, while the reactions of HCl with deprotonated tetramethylammonium salts of ADP and ATP were used to obtain the enthalpies of protonation of ADP and ATP. Equilibrium constant K, enthalpy change H^o, entropy change S^o, and heat capacity change C _p ^o values were calculated for the stepwise protonation reactions as a function of temperature. The reactions involving the first protonation of AMP, ADP, and ATP and the third protonation of ADP and ATP were endothermic over the temperature range studied, while that involving the second protonation is exothermic for AMP and ADP, but is exothermic below 100°C and endothermic at 125°C in the case of ATP. Consequently, log K values for the first and third protonation reactions (phosphate groups) increase while those for the second protonation reaction (N₁-adenine) decrease in the cases of AMP and ADP and go through a minimum in the case of ATP as temperature increases. The H^o values for all protonation reactions increase with temperature. The magnitude and the trend for the H^o, S^o, and C _p ^o values with temperature are discussed in terms of solvent-solute interactions. The magnitude of the C _p ^o values for the second protonation is consistent with little interaction between the phosphate ion and the protonated N₁ site of the adenine moiety in AMP, but indicates moderate interaction between these groups in ADP, and strong interaction in ATP.     

Charge control of phenol complexation with unsaturated compounds containing organosilicon substituents. Thiophene derivatives

The frequency shifts of the O-H stretching modes and the resonance components _R of these shifts in the IR spectra of H-complexes of phenol with thiophene derivatives having organic and organosilicon substituents have been analyzed. Relationship of and _R parameters to values calculated by nonempirical methods that characterize the electronic effect of organic substituents on the effective charges of the thiophene ring atoms has been established. It has been shown that in the complexation of phenol (hard acid) with thiophene derivatives charge control prevails over frontier orbital control. The changes in the effective charges of the thiophene ring atoms due to the effect of organosilicon substituents have been calculated.For the previous publication of this series see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2163–2168, December, 1994.This work was supported by the Russian Foundation for Basic Research, Project No. 93-03-18725.