INFLUENCE OF HETEROVALENT SUBSTITUTION ON THE CONDUCTIVITY OF MxPb1-xSnF4±х AND MxPb0,86-xSn1,14F4±х (M=K, Rb, Nd, Sm) FLUORIDE-CONDUCTING PHASES

INFLUENCE OF HETEROVALENT SUBSTITUTION ON THE CONDUCTIVITY OF MxPb1-xSnF4±х AND MxPb0,86-xSn1,14F4±х (M=K, Rb, Nd, Sm) FLUORIDE-CONDUCTING PHASES

In this article was evaluated effect of partial substitution of lead cations with K+, Rb+, Nd3+, Sm3+ cations on the conductivity of the synthesized fluoride-conducting phases MxPb1-xSnF4±x and MxPb0.86-xSn1.14F4±x. The non-stoichiometric phase Pb0.86Sn1.14F4 is characterized by high conductivity, w...

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Дата:2025
Автори: Nahornyi, Anton, Omelchuk, Anatolii
Формат: Стаття
Мова:English
Опубліковано: V.I.Vernadsky Institute of General and Inorganic Chemistry 2025
Онлайн доступ:https://ucj.org.ua/index.php/journal/article/view/717
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Назва журналу:Ukrainian Chemistry Journal

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Ukrainian Chemistry Journal
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spelling oai:ojs2.1444248.nisspano.web.hosting-test.net:article-7172025-05-07T17:17:11Z INFLUENCE OF HETEROVALENT SUBSTITUTION ON THE CONDUCTIVITY OF MxPb1-xSnF4±х AND MxPb0,86-xSn1,14F4±х (M=K, Rb, Nd, Sm) FLUORIDE-CONDUCTING PHASES Nahornyi, Anton Omelchuk, Anatolii fluoride-conducting phases, complex lead fluorides, complex tin fluorides, heterovalent substitution, conductivity, charge transfer. In this article was evaluated effect of partial substitution of lead cations with K+, Rb+, Nd3+, Sm3+ cations on the conductivity of the synthesized fluoride-conducting phases MxPb1-xSnF4±x and MxPb0.86-xSn1.14F4±x. The non-stoichiometric phase Pb0.86Sn1.14F4 is characterized by high conductivity, which at 373 K is 2.9∙10-3 S/cm and is almost an order of magnitude higher than the conductivity of β-PbSnF4. In contrast to the stoichiometric β-PbSnF4 phase, the substitution of some lead cations with K+, Rb+, Nd3+, Sm3+ cations increases the electrical conductivity of said Pb0.86-xSn1.14F4 phase at both low and high temperatures. The phases formed by the partial substitution of lead cations by the said substituents with the highest conductivity values are as follows: K0.03Pb0.83Sn1.14F3.97 (σ373 = 0.12 S/cm, σ573 = 0.37 S/cm), Rb0.2Pb0.66Sn1.14F3.80 (σ373 = 7.72∙10-2 S/cm, σ573 = 0.34 S/cm), Pb0.69Nd0.17Sn1.14F4.17 (σ373 = 3.7∙10-2 S/cm,  σ573 = 0.33 S/cm) and Pb0.76Sm0.10Sn1.14F4.10(σ373 = 1.1∙10-2 S/cm, σ573 = 0.12 S/cm). On the other hand substitution of some lead cations with K+, Rb+, Nd3+, Sm3+ cations increases the conductivity of the initial β-PbSnF4 phase only in the high temperature region. At 573 K, the best substituents are K+ (x = 0.10) and Sm3+ (x = 0.15) cations. The conductivity values of the K0.1Pb0.9SnF3.9 and Sm0.15Pb0.85SnF4.15 phases are 7.95∙10-2 and 7.97∙10-2 S/cm, respectively. At 373 K, only the Nd3+ (0.06 ≤ x ≤ 0.14) and Rb+ (0.03 ≤ x ≤ 0.06) cations contribute to the increase in electrical conductivity. The highest conductivity (4.8∙10-3 S/cm) is observed in the phase of Nd0.10Pb0.90SnF4.10composition. K+ and Sm3+ cations form phases with lower conductivity compared to the original β-PbSnF4 phase. Charge transfer in the synthesized phases according to the results of the evaluation of the electronic component of the conductivity by the Hebb – Wagner method is provided by fluo­ride anions. V.I.Vernadsky Institute of General and Inorganic Chemistry 2025-05-25 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/717 10.33609/2708-129X.91.4.2025.72-87 Ukrainian Chemistry Journal; Vol. 91 No. 4 (2025): Ukrainian Chemistry Journal; 72-87 Украинский химический журнал; Том 91 № 4 (2025): Ukrainian Chemistry Journal; 72-87 Український хімічний журнал; Том 91 № 4 (2025): Ukrainian Chemistry Journal; 72-87 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/717/365
institution Ukrainian Chemistry Journal
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datestamp_date 2025-05-07T17:17:11Z
collection OJS
language English
topic_facet fluoride-conducting phases
complex lead fluorides
complex tin fluorides
heterovalent substitution
conductivity
charge transfer.
format Article
author Nahornyi, Anton
Omelchuk, Anatolii
spellingShingle Nahornyi, Anton
Omelchuk, Anatolii
INFLUENCE OF HETEROVALENT SUBSTITUTION ON THE CONDUCTIVITY OF MxPb1-xSnF4±х AND MxPb0,86-xSn1,14F4±х (M=K, Rb, Nd, Sm) FLUORIDE-CONDUCTING PHASES
author_facet Nahornyi, Anton
Omelchuk, Anatolii
author_sort Nahornyi, Anton
title INFLUENCE OF HETEROVALENT SUBSTITUTION ON THE CONDUCTIVITY OF MxPb1-xSnF4±х AND MxPb0,86-xSn1,14F4±х (M=K, Rb, Nd, Sm) FLUORIDE-CONDUCTING PHASES
title_short INFLUENCE OF HETEROVALENT SUBSTITUTION ON THE CONDUCTIVITY OF MxPb1-xSnF4±х AND MxPb0,86-xSn1,14F4±х (M=K, Rb, Nd, Sm) FLUORIDE-CONDUCTING PHASES
title_full INFLUENCE OF HETEROVALENT SUBSTITUTION ON THE CONDUCTIVITY OF MxPb1-xSnF4±х AND MxPb0,86-xSn1,14F4±х (M=K, Rb, Nd, Sm) FLUORIDE-CONDUCTING PHASES
title_fullStr INFLUENCE OF HETEROVALENT SUBSTITUTION ON THE CONDUCTIVITY OF MxPb1-xSnF4±х AND MxPb0,86-xSn1,14F4±х (M=K, Rb, Nd, Sm) FLUORIDE-CONDUCTING PHASES
title_full_unstemmed INFLUENCE OF HETEROVALENT SUBSTITUTION ON THE CONDUCTIVITY OF MxPb1-xSnF4±х AND MxPb0,86-xSn1,14F4±х (M=K, Rb, Nd, Sm) FLUORIDE-CONDUCTING PHASES
title_sort influence of heterovalent substitution on the conductivity of mxpb1-xsnf4±х and mxpb0,86-xsn1,14f4±х (m=k, rb, nd, sm) fluoride-conducting phases
description In this article was evaluated effect of partial substitution of lead cations with K+, Rb+, Nd3+, Sm3+ cations on the conductivity of the synthesized fluoride-conducting phases MxPb1-xSnF4±x and MxPb0.86-xSn1.14F4±x. The non-stoichiometric phase Pb0.86Sn1.14F4 is characterized by high conductivity, which at 373 K is 2.9∙10-3 S/cm and is almost an order of magnitude higher than the conductivity of β-PbSnF4. In contrast to the stoichiometric β-PbSnF4 phase, the substitution of some lead cations with K+, Rb+, Nd3+, Sm3+ cations increases the electrical conductivity of said Pb0.86-xSn1.14F4 phase at both low and high temperatures. The phases formed by the partial substitution of lead cations by the said substituents with the highest conductivity values are as follows: K0.03Pb0.83Sn1.14F3.97 (σ373 = 0.12 S/cm, σ573 = 0.37 S/cm), Rb0.2Pb0.66Sn1.14F3.80 (σ373 = 7.72∙10-2 S/cm, σ573 = 0.34 S/cm), Pb0.69Nd0.17Sn1.14F4.17 (σ373 = 3.7∙10-2 S/cm,  σ573 = 0.33 S/cm) and Pb0.76Sm0.10Sn1.14F4.10(σ373 = 1.1∙10-2 S/cm, σ573 = 0.12 S/cm). On the other hand substitution of some lead cations with K+, Rb+, Nd3+, Sm3+ cations increases the conductivity of the initial β-PbSnF4 phase only in the high temperature region. At 573 K, the best substituents are K+ (x = 0.10) and Sm3+ (x = 0.15) cations. The conductivity values of the K0.1Pb0.9SnF3.9 and Sm0.15Pb0.85SnF4.15 phases are 7.95∙10-2 and 7.97∙10-2 S/cm, respectively. At 373 K, only the Nd3+ (0.06 ≤ x ≤ 0.14) and Rb+ (0.03 ≤ x ≤ 0.06) cations contribute to the increase in electrical conductivity. The highest conductivity (4.8∙10-3 S/cm) is observed in the phase of Nd0.10Pb0.90SnF4.10composition. K+ and Sm3+ cations form phases with lower conductivity compared to the original β-PbSnF4 phase. Charge transfer in the synthesized phases according to the results of the evaluation of the electronic component of the conductivity by the Hebb – Wagner method is provided by fluo­ride anions.
publisher V.I.Vernadsky Institute of General and Inorganic Chemistry
publishDate 2025
url https://ucj.org.ua/index.php/journal/article/view/717
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last_indexed 2025-09-24T17:44:01Z
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