Heat of formation of lanthanum-lead alloys

In the La? Pb system the heats of formation were measured, using a differential direct isoperibol calorimeter, and checking composition and state of the samples by chemical, metallographic and X-ray analyses. For the various compounds the _H (for the reaction among solid phases at 300 K) correspond to the following values (Kcal/g · at.): La₅Pb₃ = ?17.2₅ ± 0.5, La₄Pb₃ = ?16.7 ± 0.5, La₅Pb₄ = ?16.5 ± 0.5, La₃Pb₄ = ?15.3 ± 0.5, LaPb₂ = ?14.4 ± 0.5, LaPb₃ = ?13.7 ± 0.5. The results obtained are briefly discussed and compared with those calculated using the method suggested by MIEDEMA .     

Heat of formation of PraseodymiumBismuth alloys

In the PrBi system the heats of formation were measured using a direct isoperibol calorimeter. The composition and equilibrium state of the samples have been checked by chemical, metallographic and X-ray analyses. The following values were found for the two known compounds (reaction in the solid state, 300 K):

The results obtained, compared with those already achieved in other REBi systems, are briefly discussed.     

Pattern formation during electrodeposition of alloys

The increase in the content of the alloying element in electrodeposited alloys reflects in the changes of their phase composition, when the saturation limit of the lattice of the basic metal is reached. At higher percentages, the excess amount of the alloying element forms one or more new, richer in this element phases. The coatings become multi-phase, heterogeneous and their physical–mechanical properties change. Sometimes an ordered distribution of the different phases of the heterogeneous alloy coating could be observed. Examples of self-organization phenomena during electrodeposition of different alloy systems, such as Ag-Sb, Ag-Bi, Ag-In, Ag-Sn, Ag-Cd, Cu-Sb and In-Co, resulting in pattern formation and formation of spatio-temporal structures on the surface of the obtained coatings are presented and compared. Instabilities resulting in potential or current oscillations are registered in most of the investigated systems. The phase composition of the alloy coatings and especially of the observed pattern is determined and some similarities in the structure of the phases forming the pattern are registered. The pattern formation is registered on the cathode not only in cyanide silver alloys electrolytes, but also during deposition of other alloy systems in acidic electrolytes like Cu-Sb and In-Co. The effect of the natural convection in non-agitated electrolytes on the pattern formation is discussed. The possibility of formation of periodic structured coatings without applying external electrical pulses which could result in appropriate modification of some properties of the electrodeposited alloys is demonstrated. The hypothesis that similar pattern formation could be observed in agitated electrolytes at different hydrodynamic and electrolysis conditions, when the same percentage or the same phase composition of the alloy is reached was examined for Ag-Cd, In-Co and Ag-Sb alloys in jet-plating experiments.     

Enthalpies of formation of solid cobalt-tellurium alloys

The enthalpies of formation of solid Co?Te alloys were determined at room temperature with an isoperibol solution calorimeter of the submarine type. Co?Te alloys and mechanical mixtures of the pure components were dissolved in separate experiments in a saturated hydrochloric acid (8.000n)—bromine mixture and the enthalpies of formation obtained by difference. For the NiAs-type β-phase ΔH _f ^o(N_Te)=(4.079–15.017N _Te) kcal·g-atom^?1 and for the marcasitetype γ-phase ΔH _f ^o(N _Te)=(3.787–14.400N _Te) kcal·g-atom^?1. Combining these results with data from the literature integral thermodynamic properties of solid Co—Te alloys were calculated at room temperature and at 600°C.     

Anodic oxide formation on aluminium-terbium alloys

Aluminium terbium alloys were prepared by simultaneous thermal evaporation resulting in a thin film library covering a 5 to 25 at.% Tb compositional spread. Synchrotron x-ray diffraction (XRD) proves all of the alloys to be amorphous. Scanning electron microscopy (SEM) measurements reveal the structural changes upon increase in Tb content with the formation of small, Tb-rich segregations right before a drastic change in morphology around 25 at.% Tb. Anodic oxides were formed systematically in cyclic voltammograms using scanning droplet cell microscopy. Coulometric analysis revealed a linear thickness over formation potential behaviour with film formation factors ranging from 1.2 nm V^?1 (5 at.% Tb) to 1.6 nm V^?1 (25 % Tb). Electrochemical impedance spectroscopy was performed for each incremental oxidation step resulting in a linear relation between inverse capacity and formation potential with dielectric constants ranging from 8 (5 at.% Tb) to 16 (25 at.% Tb).     

Heat of formation of Benzophenone Oxide

The heat of formation of benzophenone oxide, Ph₂CO₂, was measured using photoacoustic calorimetry. The enthalpy of the reaction Ph₂CN₂ + O₂ → Ph₂CO₂ + N₂ was found to be ?48.0 ±0.8 kcal mol^?1 and ΔH_f(Ph₂CN₂) was determined by measuring the reaction enthalpy for Ph₂CN₂ + EtOH → Ph₂CHOEt + N₂ (?53.6 ±1.0 kcal mol^?1). Taking ΔH_f(PhCHOEt) = ?10.6 kcal mol^?1 led to ΔH_f(Ph₂CN₂) = 99.2 ± 1.5 kcal mol^?1 and hence to ΔH_f(Ph₂CO₂) = 51.1 ± 2.0 kcal mol^?1. The results imply that the self-reaction of benzophenone oxide i.e., 2Ph₂CO₂ → 2Ph₂CO + O₂ is exothermic by ?76.0 ±4.0 kcal mol^?1.     

Heats of formation of gadolinium—bismuth alloys

The heats of formation of Gd—Bi alloys were measured using a direct isoperibol calorimeter. The composition and equilibrium state of the samples were checked by metallographic and X-ray analyses.The following values were found for the different compounds [ΔH form, reaction in the solid state, 300 K, kcal (g-atom)^?1 ± 0.5]: Gd_5+xBi₃, ?20.0 ± 0.7; Gd₅Bi₃, ?20.9; Gd₄Bi₃, ?22.0; GdBi, ?23.1.The results obtained were compared with those already achieved for other rare earth bismuthides.     

Heat of activation during gel formation

Summary The activation energies have been determined during the gel formation obtained by metathetical processes. They are found to vary widely depending upon the charge and size of the particles. It is said that due to the residual electric charge on the colloidal particles the value ofP is effected leading to an increase or decrease in the rate of gel formation, whilst the heat of activation is associated with the size of the colloidal units undergoing gelation.

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Zusammenfassung Die Aktivierungsenergie bei der Gel-Bildung für metathetische Prozesse wurden bestimmt. Es wurde gefunden, daß sie in weitem Maße von der Ladung und Größe der Teilchen abhängt. Gemäß der restlichen elektrischen Ladung an den Kolloid-Partikeln wird der Wert vonP, dem vorexponentiellen Faktor, beeinflußt, was zu einer Zunahme oder Abnahme der Geschwindigkeit der Gel-Bildung führt. Die Aktivierungswärme dagegen hängt mit der Größe der Kolloideinheiten zusammen, die gelieren.

     

Electrochemical formation and phase control of Mg-Li alloys

The electrochemical formation of Mg-Li alloys was investigated in a molten LiCl-KCl(58-42 mol%)eutectic melt at 723 K. The cyclic voltammogram for a Mo electrode showed that the electroreduction of Li~ proceeds in a single step and the deposition potential of Li metal was -2.40 V(vs.Ag/AgCl).For Mg electrode,the electroreduction of Li~ takes place at less cathodic potential than that at the Mo electrode which was caused by the formation of Mg-Li alloys.Phase of the deposited Mg-Li alloys could be controlled by the electrolysis potential,and the samples were characterized by X-ray diffraction and scanning electron microscopy. The results showed thatα-Mg andβ-Li phases were obtained at -2.35 and -2.55 V,respectively.     

Enthalpies of formation of solid nickel-gallium and nickel-germanium alloys

Tin solution calorimetry has been used to measure the enthalpies of formation of the solid phases of the nickel-gallium system at 300 K and of the nickel-germanium system at 330 K. Values are reported for the two nickel-rich binary solid solutions and for the intermediate phases Ni₃Ga, Ni₂Ga, Ni₃Ga₂, NiGa, Ni₂Ga₃, Ni₃Ga₇, Ni₃Ge, Ni₂Ge and NiGe. These and previously determined enthalpies of formation of related palladium alloy compounds are compared and factors affecting the bonding mechanisms are discussed; a dependence of intercomponent transfer upon electron concentration and electronegativity differences is suggested by a re-examination of the intermediate phase data.     

Enthalpies of formation of gaseous Zintl-molecules over sodium-tellurium alloys

The vapor over sodium-tellurium alloys was investigated using Knudsen effusion mass spectrometry. The stoichiometries of the molecules in the gas phase are compared with the stoichiometries of those appearing in liquid ammonia. Enthalpies of formation for the gaseous molecules are obtained using van't Hoff plots and third law evaluations.     

Thermodynamics of hydrogen solution and hydride formation in Pd-Mn alloys. 2. Ordered alloys

There are marked differences in H(2) solubilities between ordered and disordered Pd-Mn alloys with the largest difference found between the L1(2) and the disordered form of the Pd(3)Mn alloy. The thermodynamics of H(2) solution have been determined for the L1(2) form, the long-period superstructure (lps), and the disordered forms of the Pd(0.80)Mn(0.20) and Pd(0.75)Mn(0.25)(Pd(3)Mn) alloys. Relative partial molar enthalpies and entropies were determined mainly by reaction calorimetry over the range of H contents accessible from p(H)()2 approximately 10 Pa to approximately 0.3 MPa (303 K). The enthalpies for absorption of H(2) are more exothermic over most of the range of H contents for the L1(2) forms of the Pd(3)Mn and Pd(0.80)Mn(0.20) alloys than for their other forms. The reaction enthalpies are constant across a relatively wide range of H contents for the L1(2) form of the Pd(0.80)Mn(0.20) and Pd(3)Mn alloys indicating that there are two-phase coexistence regions (303 K). The H-H attractive interaction, which leads to hydride formation, is much greater for the L1(2) than for the other forms of the Pd(3)Mn alloy and for Pd itself. It has been found that the H-H interaction always decreases in magnitude and, accompanying this, the THS (terminal hydrogen solubility) always increases by alloying Pd.(1) The L1(2) ordered Pd(3)Mn alloy is an exception to this, and therefore, the generalization about THS must be restricted to disordered face centered cubic (fcc) Pd alloys.     

Heat capacity contributions to the formation of inclusion complexes

An analysis scheme for the formation of the inclusion complexes in water is presented. It is exemplified for the case where the host is alpha-cyclodextrin and the guest is a linear alcohol (1-propanol to 1-octanol) or the isomers of 1-pentanol. Eight transfer isobaric heat capacities, DeltatCp, involving different initial and final states are evaluated at infinite dilution of the guest using both data determined in this work and from the literature. Apart from the usual definition for the inclusion heat capacity change, three inclusion transfers are used. The sign of each DeltatCp indicates if the transfer is an order-formation or an order-destruction process. From the DeltatCp data, the main contributions to the heat capacity of cyclodextrin complexation, namely, those due to dehydration of the hydrophobic section of the guest molecule, H-bond formation, formation of hydrophobic interactions, and release of water molecules from the cyclodextrin cavity, are estimated. The relative weight of each of these contributions to the DeltatCp values is discussed, providing a better characterization of the molecular recognition process involved in the inclusion phenomena.     

The conditions of formation and stability of quasi-crystalline phases in aluminum-manganese alloys

The conditions of formation, stability, and thermodynamic properties of the icosahedral and decagonal quasi-crystalline phases in the Al-Mn system were studied experimentally. The thermodynamic properties of equilibrium crystalline Al-Mn compositions over the composition and temperature ranges 0–26 at % Mn and 628–1193 K, respectively, and of melts over wide temperature and composition ranges (1043–1670 K and 0–50.1 at % Mn) were determined. Measurements were made by the integral variant of the effusion method under the conditions of an ultrahigh oilless vacuum and Knudsen mass spectrometry. An original technique based on the initiation and study of equilibria in reactions of the alloys with special admixtures of sodium or magnesium fluorides with the formation of volatile products was used to extend the interval of measurements to low temperatures. Complete, reliable, and consistent data on the thermodynamic properties of icosahedral and decagonal quasi-crystalline and crystalline phases based on aluminum and Al-Mn melts were obtained for the first time. Al-Mn melts were shown to contain associates of three types, AlMn, Al₂Mn, and Al₅Mn. The contributions of covalent interactions to the Gibbs energy and enthalpy of mixing was found to be by far predominant. The thermodynamic properties of alloys of the same chemical composition in the quasi-crystalline and equilibrium crystalline states were compared. The decagonal phase was found to be more stable than icosahedral quasi-crystals. The difference of the Gibbs energies of quasi-crystals of the two types and crystalline compositions increased as the temperature lowered. Arguments in favor of the entropy nature of the stabilization of quasi-crystals were obtained. These phases, like metallic glasses, are only an intermediate state between liquids and crystals and cannot be ground stable alloy states. The conditions of obtaining quasi-crystalline phases from melts were found to be controlled by the appearance of a substantial fraction of icosahedral short-range order in liquids in the region of compositions where associates of a certain kind (Al₅Mn) were formed in substantial amounts, x(Al₅Mn) ≥ 0.11.     

Heat treatment of rapidly solidified Fe−Cr−Zr−B alloys

The crystallization behaviour of amorphous melt spun Fe_82?x?yCr₁₈Zr_xB_y (x=0–8, y=10–20) ribbons have been investigated using differential scanning calorimetry. The crystallization temperature and crystallization behaviour change with varzing Zr and B content. The microstructural development during annealing of amorphous Fe₆₄Cr₁₈Zr₈B₁₀ has been investigated by a combination of transmission electron microscopy and energy dispersive X-ray microanalysis. Isothermal annealing for 2 h at temperatures in the range 600–1000°C produces a variety of different microstructures depending on the annealing temperature. At 600°C, the amorphous alloy partially crystallizes to a form a microstructure consisting of 9 nm sized bee ferrite grains embedded in an amorphous matrix. At temperatures in the range 700–900°C, the alloy microstructure transforms into a mixture of bee ferrite, faulted fcc MB₁₂ boride particles and tetragonal M₃B boride particles. At 1000°C, the faulted fcc MB₁₂ boride particles are replaced by orthorhombic M₄B boride particles.     

Thermodynamics of hydrogen solution and hydride formation in Pd-Mn alloys. 1. Disordered alloys and a correlation effect

The thermodynamics of H(2) solution and hydride formation/decomposition have been determined by reaction calorimetry (303 K) for disordered face centered cubic (fcc) Pd-Mn alloys. This alloy system belongs to the expanded lattice category which predicts that and DeltaH(plat) for H(2) absorption should be more exothermic than those for Pd; the experimental results are that the former is more exothermic, at least at the higher Mn contents, but the latter is not. There is a regular decrease in the H capacity (at p(H)2 = 0.2 MPa) with atom fraction Mn. A linear dependence of log p(H)2 upon H content is found in the single hydride phase for all of these alloys suggesting that DeltaH(H) and DeltaS(H) are also linear functions of r in this region. This is confirmed using the Pd(0.875)Mn(0.125) alloy which has no two-phase region (303 K). It is shown for the Pd(0.875)Mn(0.125) alloy and for Pd that the changes of partial enthalpies and entropies with H content are correlated so as to minimize changes of mu(H).