Modeling the Formation of Cations in Oleum
A study is performed of the mechanisms of the formation of H 3 SO , HSO , and H 3 S 2 O cations. The cations can act as sulphurizing agents, due to dissociation and rearrangement in oleum. Modeling is done at the level of the density functional theory and the theory of coupled clusters with implicit...
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| Veröffentlicht in: | Russian Journal of Physical Chemistry A 2022-11, Vol.96 (11), p.2432-2440 |
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| container_title | Russian Journal of Physical Chemistry A |
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| creator | Degtyarev, A. A. Pavlinov, R. Yu Dyachkova, T. P. |
| description | A study is performed of the mechanisms of the formation of H
3
SO
, HSO
, and H
3
S
2
O
cations. The cations can act as sulphurizing agents, due to dissociation and rearrangement in oleum. Modeling is done at the level of the density functional theory and the theory of coupled clusters with implicit (COSMO) and combined explicit and implicit allowance for the solvent (sulfuric acid). The thermodynamic characteristics of the formation of sulphurizing agents are determined. The mechanism of the formation of HSO
cations via interaction between H
3
SO
cations and SO
3
molecules is studied along with the decomposition of H
3
S
2
O
cations. The constant of the autoprotolysis of pyrosulfuric acid in sulfuric acid (5.37 × 10
7
) is calculated. It is more likely to form from H
3
S
2
O
cations than from H
3
SO
cations, as was thought earlier. The equilibrium constant of HSO
forming from H
3
S
2
O
(
K
= 5.8 × 10
−8
, Δ
G
= 41.28 kJ/mol) is calculated. |
| doi_str_mv | 10.1134/S0036024422110073 |
| format | Article |
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3
SO
, HSO
, and H
3
S
2
O
cations. The cations can act as sulphurizing agents, due to dissociation and rearrangement in oleum. Modeling is done at the level of the density functional theory and the theory of coupled clusters with implicit (COSMO) and combined explicit and implicit allowance for the solvent (sulfuric acid). The thermodynamic characteristics of the formation of sulphurizing agents are determined. The mechanism of the formation of HSO
cations via interaction between H
3
SO
cations and SO
3
molecules is studied along with the decomposition of H
3
S
2
O
cations. The constant of the autoprotolysis of pyrosulfuric acid in sulfuric acid (5.37 × 10
7
) is calculated. It is more likely to form from H
3
S
2
O
cations than from H
3
SO
cations, as was thought earlier. The equilibrium constant of HSO
forming from H
3
S
2
O
(
K
= 5.8 × 10
−8
, Δ
G
= 41.28 kJ/mol) is calculated.</description><identifier>ISSN: 0036-0244</identifier><identifier>EISSN: 1531-863X</identifier><identifier>DOI: 10.1134/S0036024422110073</identifier><language>eng</language><publisher>Moscow: Pleiades Publishing</publisher><subject>Cations ; Chemistry ; Chemistry and Materials Science ; Density functional theory ; Modelling ; Physical Chemistry ; Structure of Matter and Quantum Chemistry ; Sulfur trioxide ; Sulfuric acid</subject><ispartof>Russian Journal of Physical Chemistry A, 2022-11, Vol.96 (11), p.2432-2440</ispartof><rights>Pleiades Publishing, Ltd. 2022. ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2022, Vol. 96, No. 11, pp. 2432–2440. © Pleiades Publishing, Ltd., 2022. Russian Text © The Author(s), 2022, published in Zhurnal Fizicheskoi Khimii, 2022, Vol. 96, No. 11, pp. 1630–1638.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-c268t-bfc3d27488e8aa41d10471a5a6907f317c5026c92fe018e1974064b2ab02f0413</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://link.springer.com/content/pdf/10.1134/S0036024422110073$$EPDF$$P50$$Gspringer$$H</linktopdf><linktohtml>$$Uhttps://link.springer.com/10.1134/S0036024422110073$$EHTML$$P50$$Gspringer$$H</linktohtml><link.rule.ids>314,776,780,27901,27902,41464,42533,51294</link.rule.ids></links><search><creatorcontrib>Degtyarev, A. A.</creatorcontrib><creatorcontrib>Pavlinov, R. Yu</creatorcontrib><creatorcontrib>Dyachkova, T. P.</creatorcontrib><title>Modeling the Formation of Cations in Oleum</title><title>Russian Journal of Physical Chemistry A</title><addtitle>Russ. J. Phys. Chem</addtitle><description>A study is performed of the mechanisms of the formation of H
3
SO
, HSO
, and H
3
S
2
O
cations. The cations can act as sulphurizing agents, due to dissociation and rearrangement in oleum. Modeling is done at the level of the density functional theory and the theory of coupled clusters with implicit (COSMO) and combined explicit and implicit allowance for the solvent (sulfuric acid). The thermodynamic characteristics of the formation of sulphurizing agents are determined. The mechanism of the formation of HSO
cations via interaction between H
3
SO
cations and SO
3
molecules is studied along with the decomposition of H
3
S
2
O
cations. The constant of the autoprotolysis of pyrosulfuric acid in sulfuric acid (5.37 × 10
7
) is calculated. It is more likely to form from H
3
S
2
O
cations than from H
3
SO
cations, as was thought earlier. The equilibrium constant of HSO
forming from H
3
S
2
O
(
K
= 5.8 × 10
−8
, Δ
G
= 41.28 kJ/mol) is calculated.</description><subject>Cations</subject><subject>Chemistry</subject><subject>Chemistry and Materials Science</subject><subject>Density functional theory</subject><subject>Modelling</subject><subject>Physical Chemistry</subject><subject>Structure of Matter and Quantum Chemistry</subject><subject>Sulfur trioxide</subject><subject>Sulfuric acid</subject><issn>0036-0244</issn><issn>1531-863X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><recordid>eNp1kEFLxDAQhYMouK7-AG8Fb0J1Jpkm7VGKuwore1DBW0nbZO3SbdakPfjvbV3Bg3iaB-99b-Axdolwgyjo9hlASOBEnCMCKHHEZpgIjFMp3o7ZbLLjyT9lZyFsAYgIacaun1xt2qbbRP27iRbO73TfuC5yNsq_VYiaLlq3ZtidsxOr22Aufu6cvS7uX_KHeLVePuZ3q7jiMu3j0lai5orS1KRaE9YIpFAnWmagrEBVJcBllXFrAFODmSKQVHJdArdAKObs6tC79-5jMKEvtm7w3fiy4ErwJJESxJjCQ6ryLgRvbLH3zU77zwKhmCYp_kwyMvzAhDHbbYz_bf4f-gKdoV9E</recordid><startdate>20221101</startdate><enddate>20221101</enddate><creator>Degtyarev, A. A.</creator><creator>Pavlinov, R. Yu</creator><creator>Dyachkova, T. P.</creator><general>Pleiades Publishing</general><general>Springer Nature B.V</general><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20221101</creationdate><title>Modeling the Formation of Cations in Oleum</title><author>Degtyarev, A. A. ; Pavlinov, R. Yu ; Dyachkova, T. P.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c268t-bfc3d27488e8aa41d10471a5a6907f317c5026c92fe018e1974064b2ab02f0413</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>Cations</topic><topic>Chemistry</topic><topic>Chemistry and Materials Science</topic><topic>Density functional theory</topic><topic>Modelling</topic><topic>Physical Chemistry</topic><topic>Structure of Matter and Quantum Chemistry</topic><topic>Sulfur trioxide</topic><topic>Sulfuric acid</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Degtyarev, A. A.</creatorcontrib><creatorcontrib>Pavlinov, R. Yu</creatorcontrib><creatorcontrib>Dyachkova, T. P.</creatorcontrib><collection>CrossRef</collection><jtitle>Russian Journal of Physical Chemistry A</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Degtyarev, A. A.</au><au>Pavlinov, R. Yu</au><au>Dyachkova, T. P.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Modeling the Formation of Cations in Oleum</atitle><jtitle>Russian Journal of Physical Chemistry A</jtitle><stitle>Russ. J. Phys. Chem</stitle><date>2022-11-01</date><risdate>2022</risdate><volume>96</volume><issue>11</issue><spage>2432</spage><epage>2440</epage><pages>2432-2440</pages><issn>0036-0244</issn><eissn>1531-863X</eissn><abstract>A study is performed of the mechanisms of the formation of H
3
SO
, HSO
, and H
3
S
2
O
cations. The cations can act as sulphurizing agents, due to dissociation and rearrangement in oleum. Modeling is done at the level of the density functional theory and the theory of coupled clusters with implicit (COSMO) and combined explicit and implicit allowance for the solvent (sulfuric acid). The thermodynamic characteristics of the formation of sulphurizing agents are determined. The mechanism of the formation of HSO
cations via interaction between H
3
SO
cations and SO
3
molecules is studied along with the decomposition of H
3
S
2
O
cations. The constant of the autoprotolysis of pyrosulfuric acid in sulfuric acid (5.37 × 10
7
) is calculated. It is more likely to form from H
3
S
2
O
cations than from H
3
SO
cations, as was thought earlier. The equilibrium constant of HSO
forming from H
3
S
2
O
(
K
= 5.8 × 10
−8
, Δ
G
= 41.28 kJ/mol) is calculated.</abstract><cop>Moscow</cop><pub>Pleiades Publishing</pub><doi>10.1134/S0036024422110073</doi><tpages>9</tpages></addata></record> |
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| identifier | ISSN: 0036-0244 |
| ispartof | Russian Journal of Physical Chemistry A, 2022-11, Vol.96 (11), p.2432-2440 |
| issn | 0036-0244 1531-863X |
| language | eng |
| recordid | cdi_proquest_journals_2732556603 |
| source | Springer Nature - Complete Springer Journals |
| subjects | Cations Chemistry Chemistry and Materials Science Density functional theory Modelling Physical Chemistry Structure of Matter and Quantum Chemistry Sulfur trioxide Sulfuric acid |
| title | Modeling the Formation of Cations in Oleum |
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