Geometrical constraints of thermal dehydration of β-calcium sulfate hemihydrate induced by self-generated water vapor
The thermal dehydration of calcium sulfate dihydrate exhibits a complex reaction behavior, in which the reaction pathway and kinetics vary depending on water vapor pressure ( p (H 2 O)) applied as the atmospheric condition and generated in the course of the reaction. Under high p (H 2 O) conditions,...
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| Veröffentlicht in: | Physical chemistry chemical physics : PCCP 2021-10, Vol.23 (4), p.22972-22983 |
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| creator | Iwasaki, Shun Zushi, Yuto Koga, Nobuyoshi |
| description | The thermal dehydration of calcium sulfate dihydrate exhibits a complex reaction behavior, in which the reaction pathway and kinetics vary depending on water vapor pressure (
p
(H
2
O)) applied as the atmospheric condition and generated in the course of the reaction. Under high
p
(H
2
O) conditions, a crystalline hemihydrate is produced as an intermediate, which subsequently dehydrates to form anhydride. In this study, the thermal dehydration of calcium sulfate hemihydrate under different self-generated
p
(H
2
O) conditions was investigated to gain further insight into the reactions in the calcium sulfate-water vapor system. The thermal dehydration of the hemihydrate under two sets of sampling conditions, namely, in open and lidded (semi-closed) pans, was systematically investigated
via
thermogravimetry (TG) in different heating program modes. The experimentally resolved TG curves were analyzed using the formal kinetic calculation methods based on isoconversional and isothermal kinetic relationships. Under both the sampling conditions, the thermal dehydration reaction was significantly influenced by self-generated
p
(H
2
O), which regulated the reaction proceeding from the top surface of the sample bed to the bottom. Under higher self-generated
p
(H
2
O) conditions in a lidded pan, the thermal dehydration under different heating program modes exhibited an invariant kinetic behavior characterized by a single set of kinetic parameters, whereas in an open pan the kinetic behavior varied between the reactions under isothermal and other heating modes. Based on the results of the formal kinetic analysis, an advanced kinetic modeling based on a physico-geometrical consecutive reaction model was examined to describe in detail the specific kinetic features of the reaction under self-generated
p
(H
2
O) conditions.
Self-generated water vapor regulates the reaction geometry of the sample particle assemblage. |
| doi_str_mv | 10.1039/d1cp03824a |
| format | Article |
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p
(H
2
O)) applied as the atmospheric condition and generated in the course of the reaction. Under high
p
(H
2
O) conditions, a crystalline hemihydrate is produced as an intermediate, which subsequently dehydrates to form anhydride. In this study, the thermal dehydration of calcium sulfate hemihydrate under different self-generated
p
(H
2
O) conditions was investigated to gain further insight into the reactions in the calcium sulfate-water vapor system. The thermal dehydration of the hemihydrate under two sets of sampling conditions, namely, in open and lidded (semi-closed) pans, was systematically investigated
via
thermogravimetry (TG) in different heating program modes. The experimentally resolved TG curves were analyzed using the formal kinetic calculation methods based on isoconversional and isothermal kinetic relationships. Under both the sampling conditions, the thermal dehydration reaction was significantly influenced by self-generated
p
(H
2
O), which regulated the reaction proceeding from the top surface of the sample bed to the bottom. Under higher self-generated
p
(H
2
O) conditions in a lidded pan, the thermal dehydration under different heating program modes exhibited an invariant kinetic behavior characterized by a single set of kinetic parameters, whereas in an open pan the kinetic behavior varied between the reactions under isothermal and other heating modes. Based on the results of the formal kinetic analysis, an advanced kinetic modeling based on a physico-geometrical consecutive reaction model was examined to describe in detail the specific kinetic features of the reaction under self-generated
p
(H
2
O) conditions.
Self-generated water vapor regulates the reaction geometry of the sample particle assemblage.</description><identifier>ISSN: 1463-9076</identifier><identifier>EISSN: 1463-9084</identifier><identifier>DOI: 10.1039/d1cp03824a</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Atmospheric models ; Calcium sulfate ; Calcium sulfate dihydrate ; Calcium sulfate hemihydrate ; Dehydration ; Heating ; Sampling ; Thermogravimetry ; Vapor pressure ; Water vapor</subject><ispartof>Physical chemistry chemical physics : PCCP, 2021-10, Vol.23 (4), p.22972-22983</ispartof><rights>Copyright Royal Society of Chemistry 2021</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c314t-62c42f9e442bddfc08884a8cffc4afb67b44d854b3af7e8a8c350eb10e93e2ee3</citedby><cites>FETCH-LOGICAL-c314t-62c42f9e442bddfc08884a8cffc4afb67b44d854b3af7e8a8c350eb10e93e2ee3</cites><orcidid>0000-0002-1839-8163</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>Iwasaki, Shun</creatorcontrib><creatorcontrib>Zushi, Yuto</creatorcontrib><creatorcontrib>Koga, Nobuyoshi</creatorcontrib><title>Geometrical constraints of thermal dehydration of β-calcium sulfate hemihydrate induced by self-generated water vapor</title><title>Physical chemistry chemical physics : PCCP</title><description>The thermal dehydration of calcium sulfate dihydrate exhibits a complex reaction behavior, in which the reaction pathway and kinetics vary depending on water vapor pressure (
p
(H
2
O)) applied as the atmospheric condition and generated in the course of the reaction. Under high
p
(H
2
O) conditions, a crystalline hemihydrate is produced as an intermediate, which subsequently dehydrates to form anhydride. In this study, the thermal dehydration of calcium sulfate hemihydrate under different self-generated
p
(H
2
O) conditions was investigated to gain further insight into the reactions in the calcium sulfate-water vapor system. The thermal dehydration of the hemihydrate under two sets of sampling conditions, namely, in open and lidded (semi-closed) pans, was systematically investigated
via
thermogravimetry (TG) in different heating program modes. The experimentally resolved TG curves were analyzed using the formal kinetic calculation methods based on isoconversional and isothermal kinetic relationships. Under both the sampling conditions, the thermal dehydration reaction was significantly influenced by self-generated
p
(H
2
O), which regulated the reaction proceeding from the top surface of the sample bed to the bottom. Under higher self-generated
p
(H
2
O) conditions in a lidded pan, the thermal dehydration under different heating program modes exhibited an invariant kinetic behavior characterized by a single set of kinetic parameters, whereas in an open pan the kinetic behavior varied between the reactions under isothermal and other heating modes. Based on the results of the formal kinetic analysis, an advanced kinetic modeling based on a physico-geometrical consecutive reaction model was examined to describe in detail the specific kinetic features of the reaction under self-generated
p
(H
2
O) conditions.
Self-generated water vapor regulates the reaction geometry of the sample particle assemblage.</description><subject>Atmospheric models</subject><subject>Calcium sulfate</subject><subject>Calcium sulfate dihydrate</subject><subject>Calcium sulfate hemihydrate</subject><subject>Dehydration</subject><subject>Heating</subject><subject>Sampling</subject><subject>Thermogravimetry</subject><subject>Vapor pressure</subject><subject>Water vapor</subject><issn>1463-9076</issn><issn>1463-9084</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNpd0cFKxDAQBuAiCq6rF-9CwIsI1aRJu-lRVl2FBT3ouaTJxM3SNjVJV_a1fBCfydbKCl4yYeZjGPij6JTgK4Jpfq2IbDHlCRN70YSwjMY55mx_959lh9GR92uMMUkJnUSbBdgagjNSVEjaxgcnTBM8shqFFbi6bytYbZUTwdhmaH99xj2WpquR7yotAqAV1GY0gEyjOgkKlVvkodLxGzQwDBT66F-HNqK17jg60KLycPJbp9Hr_d3L_CFePi0e5zfLWFLCQpwlkiU6B8aSUiktMeecCS61lkzoMpuVjCmespIKPQPeT2iKoSQYcgoJAJ1GF-Pe1tn3DnwoauMlVJVowHa-SFJOEs5IlvT0_B9d2841_XWDojRnBA_qclTSWe8d6KJ1phZuWxBcDBEUt2T-_BPBTY_PRuy83Lm_iOg3T6-GTQ</recordid><startdate>20211020</startdate><enddate>20211020</enddate><creator>Iwasaki, Shun</creator><creator>Zushi, Yuto</creator><creator>Koga, Nobuyoshi</creator><general>Royal Society of Chemistry</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-1839-8163</orcidid></search><sort><creationdate>20211020</creationdate><title>Geometrical constraints of thermal dehydration of β-calcium sulfate hemihydrate induced by self-generated water vapor</title><author>Iwasaki, Shun ; Zushi, Yuto ; Koga, Nobuyoshi</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c314t-62c42f9e442bddfc08884a8cffc4afb67b44d854b3af7e8a8c350eb10e93e2ee3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Atmospheric models</topic><topic>Calcium sulfate</topic><topic>Calcium sulfate dihydrate</topic><topic>Calcium sulfate hemihydrate</topic><topic>Dehydration</topic><topic>Heating</topic><topic>Sampling</topic><topic>Thermogravimetry</topic><topic>Vapor pressure</topic><topic>Water vapor</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Iwasaki, Shun</creatorcontrib><creatorcontrib>Zushi, Yuto</creatorcontrib><creatorcontrib>Koga, Nobuyoshi</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><jtitle>Physical chemistry chemical physics : PCCP</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Iwasaki, Shun</au><au>Zushi, Yuto</au><au>Koga, Nobuyoshi</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Geometrical constraints of thermal dehydration of β-calcium sulfate hemihydrate induced by self-generated water vapor</atitle><jtitle>Physical chemistry chemical physics : PCCP</jtitle><date>2021-10-20</date><risdate>2021</risdate><volume>23</volume><issue>4</issue><spage>22972</spage><epage>22983</epage><pages>22972-22983</pages><issn>1463-9076</issn><eissn>1463-9084</eissn><abstract>The thermal dehydration of calcium sulfate dihydrate exhibits a complex reaction behavior, in which the reaction pathway and kinetics vary depending on water vapor pressure (
p
(H
2
O)) applied as the atmospheric condition and generated in the course of the reaction. Under high
p
(H
2
O) conditions, a crystalline hemihydrate is produced as an intermediate, which subsequently dehydrates to form anhydride. In this study, the thermal dehydration of calcium sulfate hemihydrate under different self-generated
p
(H
2
O) conditions was investigated to gain further insight into the reactions in the calcium sulfate-water vapor system. The thermal dehydration of the hemihydrate under two sets of sampling conditions, namely, in open and lidded (semi-closed) pans, was systematically investigated
via
thermogravimetry (TG) in different heating program modes. The experimentally resolved TG curves were analyzed using the formal kinetic calculation methods based on isoconversional and isothermal kinetic relationships. Under both the sampling conditions, the thermal dehydration reaction was significantly influenced by self-generated
p
(H
2
O), which regulated the reaction proceeding from the top surface of the sample bed to the bottom. Under higher self-generated
p
(H
2
O) conditions in a lidded pan, the thermal dehydration under different heating program modes exhibited an invariant kinetic behavior characterized by a single set of kinetic parameters, whereas in an open pan the kinetic behavior varied between the reactions under isothermal and other heating modes. Based on the results of the formal kinetic analysis, an advanced kinetic modeling based on a physico-geometrical consecutive reaction model was examined to describe in detail the specific kinetic features of the reaction under self-generated
p
(H
2
O) conditions.
Self-generated water vapor regulates the reaction geometry of the sample particle assemblage.</abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><doi>10.1039/d1cp03824a</doi><tpages>12</tpages><orcidid>https://orcid.org/0000-0002-1839-8163</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1463-9076 |
| ispartof | Physical chemistry chemical physics : PCCP, 2021-10, Vol.23 (4), p.22972-22983 |
| issn | 1463-9076 1463-9084 |
| language | eng |
| recordid | cdi_rsc_primary_d1cp03824a |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Atmospheric models Calcium sulfate Calcium sulfate dihydrate Calcium sulfate hemihydrate Dehydration Heating Sampling Thermogravimetry Vapor pressure Water vapor |
| title | Geometrical constraints of thermal dehydration of β-calcium sulfate hemihydrate induced by self-generated water vapor |
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