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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| Datum: | 2025 |
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2025
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| Назва журналу: | Ukrainian Chemistry Journal |
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Ukrainian Chemistry Journal| _version_ | 1856543845701910528 |
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| author | Nahornyi, Anton Omelchuk, Anatolii |
| author_facet | Nahornyi, Anton Omelchuk, Anatolii |
| author_sort | Nahornyi, Anton |
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| collection | OJS |
| datestamp_date | 2025-05-07T17:17:11Z |
| 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. |
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| institution | Ukrainian Chemistry Journal |
| language | English |
| last_indexed | 2025-09-24T17:44:01Z |
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| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
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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 |
| 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 |
| 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_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_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_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 |
| topic_facet | fluoride-conducting phases complex lead fluorides complex tin fluorides heterovalent substitution conductivity charge transfer. |
| url | https://ucj.org.ua/index.php/journal/article/view/717 |
| work_keys_str_mv | AT nahornyianton influenceofheterovalentsubstitutionontheconductivityofmxpb1xsnf4handmxpb086xsn114f4hmkrbndsmfluorideconductingphases AT omelchukanatolii influenceofheterovalentsubstitutionontheconductivityofmxpb1xsnf4handmxpb086xsn114f4hmkrbndsmfluorideconductingphases |