Gibbs energies of formation of rare earth oxysulfides

The standard Gibbs energy change accompanying the conversion of rare earth oxides to oxysulfides by reaction of rare earth oxides with diatomic sulfur gas has been measured in the temperature range 870 to 1300 K using the solid state cell: Pt/Cu+Cu2S/R2O2S+R2O3‖(CaO)ZrO2‖Ni+NiO, Pt where R=La, Nd, Sm, Gd, Tb, and Dy. The partial pressure of diatomic sulfur over a mixture of rare earth oxide (R2O3) and oxysulfide (R2O2S) is fixed by the dissociation of Cu2S to Cu in a closed system. The buffer mixture of Cu+Cu2S is physically separated from the rare earth oxide and oxysulfide to avoid complications arising from interaction between them. The corresponding equilibrium oxygen partial pressure is measured with an oxide solid electrolyte cell. Gibbs energy change for the conversion of oxide to the corresponding oxysulfide increases monotonically with atomic number of the rare earth element. Second law enthalpy of formation also shows a similar trend. Based on this empirical trend Gibbs energies of formation of oxysulfides of Pr, Eu, Ho, and Er are estimated as a function of temperature.

Gibbs’ free energies of formation of Cu2Ln2O5 (Ln = Tb, Dy, Er, Yb) compounds

The standard Gibbs' free energies of formation of compounds of type Cu2L%05 (Ln = Tb,Dy,Er,Yb) were measured using the solid state cell in the temperature range of 970 to 1323 K For formation of Cu2L?O5 compounds from their binary component oxides according to the reaction 2 CUO (s) + L%03 (s) -, Cu,,L%05 (s),the Gibbs' free energy changes can be represented by the following equations:AGO = 13 080 - 13.70 'I" (+80) J mol-' (Ln = Tb)AGq = 11 480 - 13.51 T (260) J mol-I (Ln = Dy)AGO = 10 750 - 13.99 T (260) J mol-I (Ln = Er)AGO = 9 920 - 13.90 T (260) J mol-' (Ln = Yb) Since formation of the compounds is endothermic, the compounds become thermodynamically unstable with respect to their component oxides below 955 K for Cu2Tb205, 850 K for Cu2Dy205, 768 K for Cu2Er205 and 714 K for Cu2Yb2OS When the oxygen partial pressure over Cu2L%05 is lowered, they decompose according to the scheme, 2 CU,L%O, (s) -r 2 L%03 (s) +2 cu20 (s) + 02(g)The equilibrium chemical potentials of oxygen corresponding to the dissociation reactions are computed from the emf data and auxiliary information on Cu20 and CuO. The computed decomposition temperatures at an oxygen partial pressure of 5.0 x ld Pa are compared with those obtained directly from combined thermogravimetric (TGA) and differential thermal analyses (DTA).The free energy, enthalpy and entropy of formation of Cu2Ln205 compounds show systematic variation with the ionic radius of the trivalent lanthanide ion. The trends obtained in this study are compared with information available in the literature. The staZbility of Cu2Ln205 compounds increases with the decrease in ionic radii of the ~ n ion~. +

A combined XPS-UPS-EELS study of nitrogen adsorbed on clean and barium-promoted iron surfaces: The nature of the precursor to dissociation

For N2 on a clean Fe surface, the adsorbed precursor in a parallel orientation becomes predominant around 110 K, while at lower temperatures it coexists with a weakly adsorbed species. On a Ba-promoted Fe surface, however, N2 is present exclusively in the precursor state in the temperature range 80–150 K following moderate exposure. Besides exhibiting a low N-N stretching frequency of 1530 cm−1, the precursor shows a clear separation between the 5σ and 1π levels in the UPS; the precursor dissociates to give a nitridic species around 160 K.

Nucleosome core protein: Asymmetric dissociation of the octamer

The octameric nucleosomal core-histone complex, (H2A)2-(H2B)2-(H3)2-(H4)2, isolated from rat liver, undergoes dissociation during gel exclusion chromatography as a result of dilution occurring in the columns. The elution pattern at pH 7.0 and 4°C showed a sharp leading peak containing all four histones but predominantly H3 and H4, and a trailing peak containing equal amounts of histones H2A and H2B. As column length was increased the area under the leading peak decreased and that under the trailing peak increased. In addition the relative positions of the two peaks varied with column length. From an analysis of the data on increase in elution volume of the leading peak in relation to column length an apparent molecular weight of 86 000 was calculated for the undissociated molecule. Its apparent molecular weight, histone composition and pattern of further dissociation in relation to column length suggest that this species is the hexamer, (H2A-H2B)-(H3)2-(H4)2. At pH 7.0 and 4°C the dissociation of the core complex appears to be as follows: (H2A)2-(H2B)2-(H3)2-(H4)2 → (H2A-H2B) + (H2A-H2B)-(H3)2-(H4)2 → 2(H2A-H2B) + (H3)2-(H4)2 This dissociation was accelerated by an increase in temperature or decrease in pH and was accompanied by marked conformational changes as judged by circular dichroism measurements.

Charge-resonance energies in dimer cations of aromatics

t is shown that the charge-resonance contribution to binding of the radical dimer cations of aromatic hydrocarbon decreases as the size of the hydrocarbon molecule increases.

Thiol-Disulfide Interchange Mediated Reversible Dendritic Megamer Formation and Dissociation

We report the formation of dynamic, reversible cross-linked dendritic megamers and their dissociation to monomeric dendrimers, through a thiol-disulfide interchange reaction. For this study, poly(alkyl aryl ether) dendrimers up to three-generations presenting thiol functionalities, were prepared. The series from zero to three generations of dendrimers were installed with 3, 6, 12, and 24 thiol functionalities at their peripheries. Upon synthesis, cross-linking of the dendrimer was accomplished through disulfide bond formation. The cross-linking of dendrimers was monitored through optical density changes at 420 nm. Dense cross-linking led to visible precipitation of dendritic megamers and the morphologies of the megamers were characterized by transmission electron microscopy. The disulfide cross-links between megamer monomers could be dissociated readily upon reduction of disulfide bond by dithiothreitol reagent. Preliminary studies show that dendritic megamers encapsulate C-60 and the efficiency of encapsulation increased with increasing generation of dendritic megamer.

A Simple Method of Obtaining the Band Strengths in the Electronic Spectra of Diatomic Molecules

Relative band strengths of diatomic molecules for which the product of Franck-Condon factor and r-centroid is approximately equal to 1 for (0,0) band can be determined by a simple method which will be in good agreement with the smoothed array of experimental values.

Gibbs Energy of Formation of MnO: Measurement and Assessment

Based on the measurements of Alcock and Zador, Grundy et al. estimated an uncertainty of the order of +/- 5 kJ mol(-1) for the standard Gibbs energy of formation of MnO in a recent assessment. Since the evaluation of thermodynamic data for the higher oxides Mn3O4, Mn2O3, and MnO2 depends on values for MnO, a redetermination of its Gibbs energy of formation was undertaken in the temperature range from 875 to 1300 K using a solid-state electrochemical cell incorporating yttria-doped thoria (YDT) as the solid electrolyte and Fe + Fe1-delta O as the reference electrode. The cell can be presented as Pt, Mn + MnO/YDT/Fe + Fe1+delta O, Pt Since the metals Fe and Mn undergo phase transitions in the temperature range of measurement, the reversible emf of the cell is represented by the three linear segments. Combining the emf with the oxygen potential for the reference electrode, the standard Gibbs energy of formation of MnO from alpha-Mn and gaseous diatomic oxygen in the temperature range from 875 to 980 K is obtained as: Delta G(f)(o)/Jmol(-1)(+/- 250) = -385624 + 73.071T From 980 to 1300 K the Gibbs energy of formation of MnO from beta-Mn and oxygen gas is given by: Delta G(f)(o)/Jmol(-1)(+/- 250) = -387850 + 75.36T The new data are in excellent agreement with the earlier measurements of Alcock and Zador. Grundy et al. incorrectly analyzed the data of Alcock and Zador showing relatively large difference (+/- 5 kJ mol(-1)) in Gibbs energies of MnO from their two cells with Fe + Fe1-delta O and Ni + NiO as reference electrodes. Thermodynamic data for MnO is reassessed in the light of the new measurements. A table of refined thermodynamic data for MnO from 298.15 to 2000 K is presented.

Exploring the interaction energies for the binding of hydroxydiphenyl ethers to enoyl-acyl carrier protein reductases

It is now well established that the potent anti-microbial compound, triclosan, interrupts the type II fatty acid synthesis by inhibiting the enzyme enoyl-ACP reductase in a number of organisms. Existence of a high degree of similarity between the recently discovered enoyl-ACP reductase from R falciparum and B. napus enzyme permitted building of a satisfactory model for the former enzyme that explained some of the key aspects of the enzyme such as its specificity for binding to the cofactor and the inhibitor. We now report the interaction energies between triclosan and other hydroxydiphenyl ethers with the enzymes from B. napus, E. coli and R falciparum. Examination of the triclosan-enzyme interactions revealed that subtle differences exist in the ligand binding sites of the enzymes from different sources i.e., B. napus, E. coli and P falciparum. A comparison of their binding propensities thus determined should aid in the design of effective inhibitors for the respective enzymes.

Thermodynamic and kinetic studies on the mechanism of binding of methylumbelliferyl glycosides to jacalin

The binding of Artocarpus integrifolia lectin (jacalin) to 4-methylumbelliferyl (Meumb)-glycosides, Gal alpha Meumb, Gal beta Meumb, GalNAc alpha Meumb, GalNAc beta-Meumb, and Gal beta 3GalNAc beta Meumb was examined by extrinsic fluorescence quenching titration and stopped flow spectrofluorimetry. The binding was characterized by 100% quenching of fluorescence of Meumb-glycosides. Their association constants range from 2.0 x 10(4) to 1.58 x 10(6) M-1 at 15 degrees C. Entropic contribution is the major stabilizing force for avid binding of Meumb-glycosides indicating the existence of a hydrophobic site that is complementary to their methylumbelliferyl group. The second order association rate constants for interaction of these sugars with lectin at 15 degrees C vary from 8.8 x 10(5) to 3.24 x 10(6) M-1 S-1, at pH 7.2. The first order dissociation rate constants range from 2.30 to 43.0 S-1 at 15 degrees C. Despite the differences in their association rate constants, the overall values of association constants for these saccharides are determined by their dissociation rate constants. The second order rate constant for the association of Meumb-glycosides follows a pattern consistent with the magnitude of the activation energies involved therin. Activation parameters for association of all ligands illustrate that the origin of the barrier between binding of jacalin to Meumb-glycosides is entropic, and the enthalpic contribution is small. A correlation between these parameters and the structure of the ligands on the association rates underscores the importance of steric factors in determining protein saccharide recognitions.

On the stacking fault energies of some close-packed hexagonal metals

It is now realised (1,2,3) that a knowledge of stacking fault energy is fundamental for an understanding of the mechanical behaviour of metals. There are several processes in which the imperfect dislocations have to recombine locally to form an unextended dislocation . For intersection of two dislocations it is, for example, necessary to form 'constrictions'. Cross slip of extended dislocations also involves constriction. The onset of stage llI work hardening in a crystal with close-packed structure is attributed to cross slip and hence is controlled by the stacking fault energy (SPE). Methods of estimation of SFE are based on either the direct observation of stacking faults in an electron microscope or their effects on the deformation processes.

Compressibilities of some electrolyte solutions in relation to their stepwise dissociation

The compressibilities of some electrolytic solutions at low concentrations have been determined by employing Carstensen's phase-comparison pulse method for measuring the ultrasonic velocity differences and by simultaneously measuring their densities with a Weld-type pyknometer. The apparent molal compressibilities φ(χ̄2) of NaHSO4, KHSO 4, NaP2PO4 and Na-HPO4 have been plotted against the square root of the molarities c. The observations are explained in terms of incomplete dissociation.