The second part of this compendium concludes with a collection of phase change enthalpies of organic molecules inclusive of C11–C192 reported over the period 1880–2015. Also included are phase change enthalpies including fusion, vaporization, and sublimation enthalpies for organometallic, ionic liquids, and a few inorganic compounds. Paper I of this compendium, published separately, includes organic compounds from C1 to C10 and describes a group additivity method for evaluating solid, liquid, and gas phase heat capacities as well as temperature adjustments of phase changes. Paper II of this compendium also includes an updated version of a group additivity method for evaluating total phase change entropies which together with the fusion temperature can be useful in estimating total phase change enthalpies. Other uses include application in identifying potential substances that either form liquid or plastic crystals or exhibit additional phase changes such as undetected solid–solid transitions or behave ani...

/pdf/phase-transition-enthalpy-measurements-of-organic-and-4j1idcstf9.pdf

Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds and Ionic Liquids. Sublimation, Vaporization, and Fusion Enthalpies from 1880 to 2015. Part 2. C11–C192

The glycerophosphodiester-degrading enzyme GpdQ from Enterobacter aerogenes is a promising bioremediator owing to its ability to degrade some organophosphate pesticides and diester products originating from the hydrolysis of nerve agents such as VX. Here, the cadmium derivative of GpdQ was prepared by reconstituting the apoenzyme. Catalytic measurements with (Cd2+)2-GpdQ and the phosphodiester substrate bis(4-nitrophenyl)phosphate yield k
 cat = 15 s−1. The pK
 a of 9.4, determined from the pH dependence of the catalytic activity, implicates a hydroxide ligand as the catalytic nucleophile. Also prepared was the cadmium-containing biomimetic [Cd2((HP)2B)(OAc)2(OH2)](PF6) (where (HP)2B is [2,6-bis([(2-pyridylmethyl)(2-hydroxyethyl)amino]methyl)-4-methylphenol]), which mimics the asymmetry of the metal ion coordination in the active site of GpdQ. The phosphoesterase-like activity of [Cd2((HP)2B)(OAc)2(OH2)](PF6) was studied using the substrate bis(2,4-dinitrophenyl)phosphate, yielding a kinetically relevant pK
 a of 8.9, with k
 cat = 0.004 s−1. In summary, the model is both an adequate structural and a reasonable functional mimic of GpdQ.

Cadmium(II) complexes of the glycerophosphodiester-degrading enzyme GpdQ and a biomimetic N,O ligand.

A universally applicable method for the prediction of the isobaric heat capacities of the liquid and solid phase of molecules at 298.15 K is presented, derived from their “true” volume. The molecules’ “true” volume in A3 is calculated on the basis of their geometry-optimized structure and the Van-der-Waals radii of their constituting atoms by means of a fast numerical algorithm. Good linear correlations of the “true” volume of a large number of compounds encompassing all classes and sizes with their experimental liquid and solid heat capacities over a large range have been found, although noticeably distorted by intermolecular hydrogen-bond effects. To account for these effects, the total amount of 1303 compounds with known experimental liquid heat capacities has been subdivided into three subsets consisting of 1102 hydroxy-group-free compounds, 164 monoalcohols/monoacids, and 36 polyalcohols/polyacids. The standard deviations for Cp(liq,298) were 20.7 J/mol/K for the OH-free compunds, 22.91 J/mol/K for the monoalcohols/monoacids and 16.03 J/mol/K for the polyols/polyacids. Analogously, 797 compounds with known solid heat capacities have been separated into a subset of 555 OH-free compounds, 123 monoalcohols/monoacids and 119 polyols/polyacids. The standard deviations for Cp(sol,298) were calculated to 23.14 J/mol/K for the first, 21.62 J/mol/K for the second, and 19.75 J/mol/K for the last subset. A discussion of structural and intermolecular effects influencing the heat capacities as well as of some special classes, in particular hydrocarbons, ionic liquids, siloxanes and metallocenes, has been given. In addition, the present method has successfully been extended to enable the prediction of the temperature dependence of the solid and liquid heat capacities in the range between 250 and 350 K.

Calculation of the Isobaric Heat Capacities of the Liquid and Solid Phase of Organic Compounds at and around 298.15 K Based on Their “True” Molecular Volume

A new linear trinuclear MnIII-MnII-MnIII complex 1 has been synthesized and characterized by elemental, spectral, X-ray and magnetic analysis. X-ray diffraction studies show that the central MnII ion is located at a crystallographic inversion center and is triply bridged to the terminal MnIII ions through one methoxide, one syn-syn carboxylate and one hydroxyl oxygen bridges with the short MnIII…MnII distance that is 3.047 A. The intermolecular C-H…O, C-H…π and ring-metal interactions are observed in the hydrogen-bonded assembly of 1. Magnetic studies reveal that the mixed-valence complex 1 has S = 3/2 ground state with antiferromagnetic exchange interactions between MnII and MnIII ions.

Linear trinuclear mixed valance MnIII-MnII-MnIII complex: Synthesis, crystal structure and characterization

This paper reports that low-temperature heat capacities of 4-(2-aminoethyl)-phenol (C8H11NO) are measured by a precision automated adiabatic calorimeter over the temperature range from 78 to 400 K. A polynomial equation of heat capacities as a function of the temperature was fitted by the least square method. Based on the fitted polynomial, the smoothed heat capacities and thermodynamic functions of the compound relative to the standard reference temperature 298.15 K were calculated and tabulated at the interval of 5 K. The energy equivalent, epsilon(calor), of the oxygen-bomb combustion calorimeter has been determined from 0.68 g of NIST 39i benzoic acid to be epsilon(calor)=(14674.69 +/- 17.49)J.K-1. The constant-volume energy of combustion of the compound at T=298.15 K was measured by a precision oxygen-bomb combustion calorimeter to be Delta U-c=-(32374.25 +/- 12.93)J.g(-1). The standard molar enthalpy of combustion for the compound was calculated to be Delta H-c(m)circle minus = -(4445.47 +/- 1.77) kJ . mol(-1) according to the definition of enthalpy of combustion and other thermodynamic principles. Finally, the standard molar enthalpy of formation of the compound was derived to be Delta H-f(m)circle minus(C8H11 NO,s) = -(274.68 +/- 2.06) kJ . mol(-1), in accordance with Hess law.

Low-temperature heat capacities and standard molar enthalpy of formation of 4-(2-aminoethyl)-phenol (C8H11NO)

This paper reports that low-temperature heat capacities of N-methylnorephedrine C11H17NO(s) have been measured by a precision automated adiabatic calorimeter over the temperature range from T = 78 K to T = 400K. A solid to liquid phase transition of the compound was found in the heat capacity curve in the temperature range of T = 342–364 K. The peak temperature, molar enthalpy and entropy of fusion of the substance were determined. The experimental values of the molar heat capacities in the temperature regions of T = 78–342 K and T = 364–400 K were fitted to two polynomial equations of heat capacities with the reduced temperatures by least squares method. The smoothed molar heat capacities and thermodynamic functions of N-methylnorephedrine C11H17NO(s) relative to the standard reference temperature 298.15 K were calculated based on the fitted polynomials and tabulated with an interval of 5 K. The constant-volume energy of combustion of the compound at T = 298.15K was measured by means of an isoperibol precision oxygen-bomb combustion calorimeter. The standard molar enthalpy of combustion of the sample was calculated. The standard molar enthalpy of formation of the compound was determined from the combustion enthalpy and other auxiliary thermodynamic data through a Hess thermochemical cycle.

Low-temperature heat capacities and standard molar enthalpy of formation of N-methylnorephedrine C11H17NO(s)

A new bicadmium (II) complexe with hydroxyisopropyl pendants was synthesized by [2+2] Schiff base condensation of 1‐[bis(3‐aminopropyl)amino]‐2‐propanol with sodium 2,6‐diformyl‐4‐Cl‐phenolate in the presence of Cd2+. Crystals of complex 1 were monoclinic, space group P21/c with a=15.136(6), b=17.713(7), c=17.609(7) A and β=92.560(7)°. Cd(1) atom lies in an N3O3 coordination environment and possesses a distorted octahedral geometry. Cd(2) atom was hepta‐coordinated with the coordination surrounding of monocapped‐octahedral geometry. The toxicity of the complex was evaluated by testing antimicrobial activity against bacterial strands, such as Candida albicans, Staphylococcus aureus, Bacillus pumilus, Klebsiella pneumoniae and Escherichia coli.

Study on the Structure and Toxicity of a New Bicadmium(II) Complex with Macrocyclic Hexaaza Bearing Hydroxyisopropyl Pendants

Construction of lanthanide complexes based on 3,4-dichlorobenzoic acid and 5,5′-dimethyl-2,2′-bipyridine: Supramolecular structures, thermodynamic properties and luminescent behaviors

A new mixed‐valence trinuclear manganese(III/II/III) complex was synthesized by ethanolamine and paeonol in the presence of Mn(acetato)2·4H2O. The crystal of the complex was characterized by X‐ray diffraction, IR, UV spectroscopy, molar conductivity and elemental analyses. The structurally characterized mixed‐valence complex has strictly 180° MnIII‐ MnII‐ MnIII angle as required by crystallographic inversion symmetry. The Mn(1) … Mn(2)#1 separation is 3.0500(8) A. Antimicrobial activity study found that the complex was active against Salmonella species, Staphylococcus aureus, Bacillus pumilus and Eschierichia coli.

Synthesis, Structure and Properties of a Linear Trinuclear Manganese(III/II/III) Complex

In the title compound, C22H20N2O4, the mol­ecule is centrosymmetric. The mol­ecules are linked by one C—H⋯O and one C—H⋯π inter­action into an [001] chain of R22(30) rings and an [010] chain of R22(22) rings.

Wang Da-Qi

Papers

Low-temperature heat capacities and standard molar enthalpy of formation of N-methylnorephedrine C11H17NO(s)

Study on the Structure and Toxicity of a New Bicadmium(II) Complex with Macrocyclic Hexaaza Bearing Hydroxyisopropyl Pendants

Construction of lanthanide complexes based on 3,4-dichlorobenzoic acid and 5,5′-dimethyl-2,2′-bipyridine: Supramolecular structures, thermodynamic properties and luminescent behaviors

Synthesis, Structure and Properties of a Linear Trinuclear Manganese(III/II/III) Complex

N,N′-Bis[(3,4-methylenedioxyphenyl)methylene]phenylene-1,4-diamine