Thermodynamics of the N2/N3- redox couple in a LiBr-KBr-CsBr melt

Katsutoshi Kobayashi; Hironori Nakajima; Takuya Goto; Yasuhiko Ito

doi:10.1021/jp053920i

Thermodynamics of the N2/N3- redox couple in a LiBr-KBr-CsBr melt

Katsutoshi Kobayashi, Hironori Nakajima, Takuya Goto, Yasuhiko Ito

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Abstract

Nitrogen electrode reaction has been investigated in a LiBr-KBr-CsBr melt containing Li₃N. The reaction N^3- → 1/2N₂ + 3e^- is confirmed by quantitative analysis of anodically evolved gas. The Nernst relation holds for the rest potential of Ni electrodes at a nitrogen gas pressure, p_N2, of 0.05-1.0 atm and an anion fraction of the N^3- ions, x_N3-, of 0.003-0.010 (anion fraction). Then, the standard formal potential of the N₂/N^3- couple, E_N2/N3-^′, is evaluated to be 0.251 ± 0.009 V versus Li⁺/Li (p_N2 = 1 atm, x_N3 = 1) at 673 K. The dependence of E_N2/N3-^′ on the temperature (570-730 K) gives a linear relation, whose slope is (-0.930 ± 0.117) × 10^-3 V K^-1. Thermodynamic quantities for the formation of Li₃N in the melt are also estimated.

Original language	English
Pages (from-to)	23972-23975
Number of pages	4
Journal	Journal of Physical Chemistry B
Volume	109
Issue number	50
DOIs	https://doi.org/10.1021/jp053920i
Publication status	Published - Dec 22 2005
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry

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@article{02674a03871047b997ebdbe177e78ae8,

title = "Thermodynamics of the N2/N3- redox couple in a LiBr-KBr-CsBr melt",

abstract = "Nitrogen electrode reaction has been investigated in a LiBr-KBr-CsBr melt containing Li3N. The reaction N3- → 1/2N2 + 3e- is confirmed by quantitative analysis of anodically evolved gas. The Nernst relation holds for the rest potential of Ni electrodes at a nitrogen gas pressure, pN2, of 0.05-1.0 atm and an anion fraction of the N3- ions, xN3-, of 0.003-0.010 (anion fraction). Then, the standard formal potential of the N2/N3- couple, EN2/N3-′, is evaluated to be 0.251 ± 0.009 V versus Li+/Li (pN2 = 1 atm, xN3 = 1) at 673 K. The dependence of EN2/N3-′ on the temperature (570-730 K) gives a linear relation, whose slope is (-0.930 ± 0.117) × 10-3 V K-1. Thermodynamic quantities for the formation of Li3N in the melt are also estimated.",

author = "Katsutoshi Kobayashi and Hironori Nakajima and Takuya Goto and Yasuhiko Ito",

year = "2005",

month = dec,

day = "22",

doi = "10.1021/jp053920i",

language = "English",

volume = "109",

pages = "23972--23975",

journal = "Journal of Physical Chemistry B Materials",

issn = "1520-6106",

publisher = "American Chemical Society",

number = "50",

}

TY - JOUR

T1 - Thermodynamics of the N2/N3- redox couple in a LiBr-KBr-CsBr melt

AU - Kobayashi, Katsutoshi

AU - Nakajima, Hironori

AU - Goto, Takuya

AU - Ito, Yasuhiko

PY - 2005/12/22

Y1 - 2005/12/22

N2 - Nitrogen electrode reaction has been investigated in a LiBr-KBr-CsBr melt containing Li3N. The reaction N3- → 1/2N2 + 3e- is confirmed by quantitative analysis of anodically evolved gas. The Nernst relation holds for the rest potential of Ni electrodes at a nitrogen gas pressure, pN2, of 0.05-1.0 atm and an anion fraction of the N3- ions, xN3-, of 0.003-0.010 (anion fraction). Then, the standard formal potential of the N2/N3- couple, EN2/N3-′, is evaluated to be 0.251 ± 0.009 V versus Li+/Li (pN2 = 1 atm, xN3 = 1) at 673 K. The dependence of EN2/N3-′ on the temperature (570-730 K) gives a linear relation, whose slope is (-0.930 ± 0.117) × 10-3 V K-1. Thermodynamic quantities for the formation of Li3N in the melt are also estimated.

AB - Nitrogen electrode reaction has been investigated in a LiBr-KBr-CsBr melt containing Li3N. The reaction N3- → 1/2N2 + 3e- is confirmed by quantitative analysis of anodically evolved gas. The Nernst relation holds for the rest potential of Ni electrodes at a nitrogen gas pressure, pN2, of 0.05-1.0 atm and an anion fraction of the N3- ions, xN3-, of 0.003-0.010 (anion fraction). Then, the standard formal potential of the N2/N3- couple, EN2/N3-′, is evaluated to be 0.251 ± 0.009 V versus Li+/Li (pN2 = 1 atm, xN3 = 1) at 673 K. The dependence of EN2/N3-′ on the temperature (570-730 K) gives a linear relation, whose slope is (-0.930 ± 0.117) × 10-3 V K-1. Thermodynamic quantities for the formation of Li3N in the melt are also estimated.

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U2 - 10.1021/jp053920i

DO - 10.1021/jp053920i

M3 - Article

C2 - 16375386

AN - SCOPUS:30544439505

SN - 1520-6106

VL - 109

SP - 23972

EP - 23975

JO - Journal of Physical Chemistry B Materials

JF - Journal of Physical Chemistry B Materials

IS - 50

ER -

Thermodynamics of the N2/N3- redox couple in a LiBr-KBr-CsBr melt

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