Semi-empirical supported, Ab initio derived thermodynamic properties for ClO2 and its sub and extended species, applied in water treatment cycles
This paper describes a group of sixty (60) sub and extended chlorine oxide species with the general formulae of ClxOy (with x ≤ 2, y ≤ 8). Their role in water treatment cycles, behaving as key reactive species, is represented by a complex sequence of chemical inter-dependencies, exposed as a cohesiv...
Saved in:
| Main Authors: | , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Elsevier
2024-10-01
|
| Series: | Heliyon |
| Subjects: | |
| Online Access: | http://www.sciencedirect.com/science/article/pii/S240584402414827X |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1846170216495579136 |
|---|---|
| author | Natasha Misheer Patrick G. Ndungu Jan A. Pretorius |
| author_facet | Natasha Misheer Patrick G. Ndungu Jan A. Pretorius |
| author_sort | Natasha Misheer |
| collection | DOAJ |
| description | This paper describes a group of sixty (60) sub and extended chlorine oxide species with the general formulae of ClxOy (with x ≤ 2, y ≤ 8). Their role in water treatment cycles, behaving as key reactive species, is represented by a complex sequence of chemical inter-dependencies, exposed as a cohesive set of chemical reactions to demonstrate their cyclic role in aqueous media. An empirical/semi-empirical computational approach, supported by Ab Initio simulations, in accordance with open-shell character, has been followed to determine their optimum molecular geometries, to obtain their thermochemical properties. Besides a single molecular analysis, Grand Canonical Ensemble simulations, supported by a revised library of force field parameters, constituted a core component of the computational approach and proved to be invaluable in confirming thermochemical properties. This approach also offered finite estimates of optimum model sizes, a benefit with wider modelling application. Extended molecular species of ClO2 display a complex sequence of bonding character, with a variable charge dissipation (reported as partial charges), which complicates selection of basis sets in optimizing molecular geometries, during Ab Initio analyses.Optimum molecular geometries were obtained using Gaussian and MOPAC, which in turn resulted in reliable Heats of Formation. These correlated well with energies extracted from the open literature. Thermodynamic Analysis of the reaction of selected chlorine oxides with water using FactSage, predicted the production of known and two previously undetected chlorine species, [ClO4]- and [ClOH2]+. |
| format | Article |
| id | doaj-art-2aa6587348004b57b7b212c30c41b33a |
| institution | Kabale University |
| issn | 2405-8440 |
| language | English |
| publishDate | 2024-10-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Heliyon |
| spelling | doaj-art-2aa6587348004b57b7b212c30c41b33a2024-11-12T05:19:17ZengElsevierHeliyon2405-84402024-10-011020e38796Semi-empirical supported, Ab initio derived thermodynamic properties for ClO2 and its sub and extended species, applied in water treatment cyclesNatasha Misheer0Patrick G. Ndungu1Jan A. Pretorius2The Department of Chemistry, University of Pretoria. Private Bag X20, Hatfield, Zip Code 0028, South Africa; ESKOM Research and Innovation Centre, Rosherville, Private Bag 40157, Cleveland, Johannesburg, 2022, South AfricaThe Department of Chemistry, University of Pretoria. Private Bag X20, Hatfield, Zip Code 0028, South AfricaThe Department of Chemistry, University of Pretoria. Private Bag X20, Hatfield, Zip Code 0028, South Africa; Centre for the Advancement of Scholarship, University of Pretoria, Private Bag X20, Hatfield, Zip Code 0028, South Africa; Corresponding author. The Department of Chemistry, University of Pretoria. Private Bag X20, Hatfield, Zip Code 0028, South Africa.This paper describes a group of sixty (60) sub and extended chlorine oxide species with the general formulae of ClxOy (with x ≤ 2, y ≤ 8). Their role in water treatment cycles, behaving as key reactive species, is represented by a complex sequence of chemical inter-dependencies, exposed as a cohesive set of chemical reactions to demonstrate their cyclic role in aqueous media. An empirical/semi-empirical computational approach, supported by Ab Initio simulations, in accordance with open-shell character, has been followed to determine their optimum molecular geometries, to obtain their thermochemical properties. Besides a single molecular analysis, Grand Canonical Ensemble simulations, supported by a revised library of force field parameters, constituted a core component of the computational approach and proved to be invaluable in confirming thermochemical properties. This approach also offered finite estimates of optimum model sizes, a benefit with wider modelling application. Extended molecular species of ClO2 display a complex sequence of bonding character, with a variable charge dissipation (reported as partial charges), which complicates selection of basis sets in optimizing molecular geometries, during Ab Initio analyses.Optimum molecular geometries were obtained using Gaussian and MOPAC, which in turn resulted in reliable Heats of Formation. These correlated well with energies extracted from the open literature. Thermodynamic Analysis of the reaction of selected chlorine oxides with water using FactSage, predicted the production of known and two previously undetected chlorine species, [ClO4]- and [ClOH2]+.http://www.sciencedirect.com/science/article/pii/S240584402414827XNOM (natural organic matter)ClO2 (chlorine dioxide)GEMC (gibbs ensemble Monte Carlo)Semi-empirical quantumRadicalsIons |
| spellingShingle | Natasha Misheer Patrick G. Ndungu Jan A. Pretorius Semi-empirical supported, Ab initio derived thermodynamic properties for ClO2 and its sub and extended species, applied in water treatment cycles Heliyon NOM (natural organic matter) ClO2 (chlorine dioxide) GEMC (gibbs ensemble Monte Carlo) Semi-empirical quantum Radicals Ions |
| title | Semi-empirical supported, Ab initio derived thermodynamic properties for ClO2 and its sub and extended species, applied in water treatment cycles |
| title_full | Semi-empirical supported, Ab initio derived thermodynamic properties for ClO2 and its sub and extended species, applied in water treatment cycles |
| title_fullStr | Semi-empirical supported, Ab initio derived thermodynamic properties for ClO2 and its sub and extended species, applied in water treatment cycles |
| title_full_unstemmed | Semi-empirical supported, Ab initio derived thermodynamic properties for ClO2 and its sub and extended species, applied in water treatment cycles |
| title_short | Semi-empirical supported, Ab initio derived thermodynamic properties for ClO2 and its sub and extended species, applied in water treatment cycles |
| title_sort | semi empirical supported ab initio derived thermodynamic properties for clo2 and its sub and extended species applied in water treatment cycles |
| topic | NOM (natural organic matter) ClO2 (chlorine dioxide) GEMC (gibbs ensemble Monte Carlo) Semi-empirical quantum Radicals Ions |
| url | http://www.sciencedirect.com/science/article/pii/S240584402414827X |
| work_keys_str_mv | AT natashamisheer semiempiricalsupportedabinitioderivedthermodynamicpropertiesforclo2anditssubandextendedspeciesappliedinwatertreatmentcycles AT patrickgndungu semiempiricalsupportedabinitioderivedthermodynamicpropertiesforclo2anditssubandextendedspeciesappliedinwatertreatmentcycles AT janapretorius semiempiricalsupportedabinitioderivedthermodynamicpropertiesforclo2anditssubandextendedspeciesappliedinwatertreatmentcycles |