Thermodynamic Properties of Solid Binary Antimonides

Schlesinger, Mark E.

doi:10.1021/cr400050e

Cited by 36 publications

(19 citation statements)

References 200 publications

(406 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…5,21 The low-Li eutectic temperature observed, 460 o C, is slightly lower than those reported by Federov 8 and Nikitin et al, 3 466 o C and 472 o C, respectively; however, the eutectic composition of x Li ≈ 0.40 observed in the present study is much higher than was presented in previous work. 3,4,8 Evidence of the peritectic reaction of Li 2 Sb(s) decomposing into Li 3 Sb(s) + liquid was observed at a much lower temperature than that postulated by Sangster, et al 4 (580 o C vs. 825 o C).…”

Section: Resultscontrasting

confidence: 66%

Electrochemical Determination of the Thermodynamic Properties of Lithium-Antimony Alloys

Kane

Newhouse

Sadoway

2014

J. Electrochem. Soc.

View full text Add to dashboard Cite

The variation in the high temperature thermodynamic properties of the Li-Sb system with temperature (425-775 o C) and composition (x Li = 0.01-0.75) was determined by electromotive force (emf) measurements in a cell configured as follows: Li-Bi reference electrode (x Bi = 0.35) | eutectic of LiCl-KCl or LiCl-LiF | Li-Sb alloy. On the basis of these data the Li-Sb couple was deemed attractive for storage of electrical energy in a liquid metal battery. In addition, an updated Li-Sb binary phase diagram is proposed. © The Author(s) 2014. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. [DOI: 10.1149/2.0671503jes] All rights reserved. The lithium-antimony (Li-Sb) binary system is of interest for energy storage applications, specifically at high temperatures for liquid metal batteries, because of the mutual reactivity of these elements, their relative abundance in the earth's crust, and their comparatively low cost.1,2 Prior investigations of this system are limited and are generally focused on intermetallic characterization.3-5 Notably, two groups have studied the intermetallics Li 2 Sb(s) and Li 3 Sb(s) electrochemically, determining the thermodynamic electric potential and Gibbs free energy of formation of the compounds between 355 o C and 600 o C. 3,6,7 As for liquid alloys, Nikitin et al. 3 studied the deposition of lithium by cathodic polarization of liquid antimony and observed that electrode potential varied inversely with both current density and degree of lithiation, which they attributed to formation of composition gradients.In 1993 Sangster and Dalton presented a calculated Li-Sb phase diagram; 4 however, for liquid interactions they relied on data from the Li-Bi system due to a perceived lack of thermodynamic data for Li-Sb liquid alloys. Two years later Fedorov 8 published an alternate version of the Li-Sb phase diagram determined from cooling curves (cooling rate unknown), specifying that it was a non-equilibrium phase diagram, an opinion expressed by others. 9In the present study electromotive force (emf) measurements characterize the thermodynamic properties of Li in Li-Sb liquid alloys between 425 o C and 775 o C. Emf measurements have been used to accurately characterize similar lithium binary systems in the past. 10-14The Li-Sb system was studied in this work using the electrochemical cellwhere a Li-Bi two phase alloy served as the reference electrode (RE), the Li-Sb alloys of various concentrations served as the working electrode (WE), and either of the two eutectic binary molten salts as the electrolyte. The half cell reactions of this cell areand the full cell reaction iswhere the parentheses indicate the solvent metal. The open circuit potential (OCP) at equilibrium E cell is related to the Gibbs free energy of reaction r G via the Nernst equationwhere n is the ...

show abstract

Section: Resultscontrasting

confidence: 66%

Electrochemical Determination of the Thermodynamic Properties of Lithium-Antimony Alloys

Kane

Newhouse

Sadoway

2014

J. Electrochem. Soc.

View full text Add to dashboard Cite

show abstract

“…Summarizing, it is likely, when experimental inconsistencies are cleared up, the lattice specific heats of the group IV elements with the diamond lattice would be the same. This value is close to 29J mol −1 K −1 and is certainly away from the presumed exact value (32).…”

Section: E Specific Heat Of Compounds or On The Neumann-kopp Lawmentioning

confidence: 54%

“…The vast number of new compounds were discovered and studied. Extensive data of modern measurements show that many compounds do not obey the Neumann-Kopp rule, for example, the overview of solid binary antimonides [32] states that "the Neumann-Kopp law is not a suitable substitute for experimentally obtained values of antimonide heat capacities". Likely this is the case for other classes of compounds.…”

Section: E Specific Heat Of Compounds or On The Neumann-kopp Lawmentioning

confidence: 99%

The field theory of specific heat

Gusev

2016

Russ. J. Math. Phys.

121

View full text Add to dashboard Cite

Finite temperature quantum field theory in the heat kernel method is used to study the heat capacity of condensed matter. The lattice heat is treated a la P. Debye as energy of the elastic (sound) waves. The dimensionless functional of free energy is re-derived with a cut-off parameter and used to obtain the specific heat of crystal lattices. The new dimensionless thermodynamical variable is formed as the Planck's inverse temperature divided by the lattice constant. The dimensionless constant, universal for a class of crystal lattices, which determines the low temperature region of molar specific heat, is introduced and tested with the data for diamond lattice crystals.The low temperature asymptotics of specific heat is found to be the fourth power in temperature instead of the cubic power law of the Debye theory. Experimental data for the carbon group elements (silicon, germanium) and other materials decisively confirm the quartic law. The true low temperature regime of specific heat is defined by the surface heat, therefore, it depends on geometrical characteristics of a body, while the absolute zero temperature limit is geometrically forbidden. The limit on a growth of specific heat at temperatures close to critical points, known as the Dulong-Petit law, appears from the lattice constant cut-off. Its value depends on the lattice type and it is the same for materials with the same crystal lattice. The Dulong-Petit values of compounds are equal to those of elements with the same crystal lattice type, if one mole of solid state matter were taken as the Avogadro number of the lattice atoms. This means the Neumann-Kopp rule is valid only in some cases.

show abstract

“…EDS data for points shown in Figure 5 (at.%). The formation enthalpy of Ce-Sb compounds [12] and Fe-Sb compounds [13] can be used to explain these behaviors. The formation enthalpy of Ce-Sb system is more negative than Fe-Sb system, as shown in Table 5.…”

Section: Ce-sb-fe Diffusion Couplementioning

confidence: 99%

“…There are four known intermetallic compounds (Ce2Sb, Ce4Sb3, CeSb and CeSb2) in the Ce-Sb system [10], and one intermediate compound Fe1.27Sb and one intermetallic compound FeSb2 in the Fe-Sb system [11]. Based on the enthalpy of formation, there is a greater driving force to form Ce-Sb compounds compared to Fe-Sb compounds [12] [13]. However, simply comparing the enthalpy of formation cannot support the stability of Ce-Sb compounds.…”

Section: Introductionmentioning

confidence: 99%

Thermodynamic stability studies of Ce-Sb compounds with Fe

Xie

Zhang

Benson

et al. 2018

Journal of Nuclear Materials

View full text Add to dashboard Cite

Lanthanide fission products can migrate to the fuel periphery and react with cladding, causing fuelcladding chemical interaction (FCCI). Adding a fuel additive dopant, such as Sb, can bind lanthanide, such as Ce, into metallic compounds and thus prevent migration. The present study focuses on the thermodynamic stability of Ce-Sb compounds when in contact with the major cladding constituent Fe by conducting diffusion couple tests. Ce-Sb compounds have shown high thermodynamic stability as they did not react with Fe. When Fe-Sb compounds contacted with Ce, Sb was separated out of Fe-Sb compounds and formed the more stable Ce-Sb compounds.

show abstract

Thermodynamic Properties of Solid Binary Antimonides

Cited by 36 publications

References 200 publications

Electrochemical Determination of the Thermodynamic Properties of Lithium-Antimony Alloys

Electrochemical Determination of the Thermodynamic Properties of Lithium-Antimony Alloys

The field theory of specific heat

Thermodynamic stability studies of Ce-Sb compounds with Fe

Contact Info

Product

Resources

About