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Reactivity of hydroxyl radicals on hydroxylated quartz surface. 1. Cluster model calculations.

Authors
Konecny-R
Source
J Phys Chem B Condens Mater Surf Interfaces Biophys 2001 Jul; 105(26):6221-6226
NIOSHTIC No.
20032280
Abstract
The interaction of a hydroxyl radical with cluster models of a hydroxylated -quartz surface was studied by means of density functional calculations. Two molecular models representing isolated (Si-OH) and geminal (=Si(OH)2) silanol-terminated quartz surfaces were used. Two reactive sites of the silanol models were investigated: the hydrogen of the silanol group and the surface-approximating silicon atom. The OH binds weakly to the silanol hydrogen atoms in both models, with a reaction energy of about -7 kcal/mol. The silicon atom in the isolated silanol cluster is not reactive toward the OH. In contrast, the OH adsorbs on the Si in the geminal silanol cluster with a reaction energy of -4 kcal/mol. The Si-OSi bond in the resulting pentacoordinated silicon complex is weakened upon the OH adsorption and can be dissociated. The energy barrier to the dissociation is 4 kcal/mol, and the overall reaction energy is -4 kcal/mol. The dissociation of the Si-OSiH3 bond which mimics the Si-O subsurface bonding in the real quartz surface suggests a possibility of OH activated quartz surface layer disintegration. The calculated energy barrier in this OH radical activated process is significantly lower than the predicted energy barrier in the rate determining step in the OH- catalyzed quartz surface dissolution (19 kcal/mol). The Si-OSi bond rupture followed by formation of a Si-O radical on the surface may provide a plausible mechanism for reactivation of chemically inert, silanol terminated, aged quartz surfaces.
Keywords
Quartz-dust; Silica-dusts; Dusts; Dust-particles; Particulate-dust; Hydroxy-compounds; Hydroxyl-groups; Fibrosis; Lung-disorders; Lung-fibrosis; Respiratory-system-disorders; Pulmonary-system-disorders
Contact
NIOSH, 1095 Willowdale Road, Morgantown, WV 26505-2888
CODEN
JPCBFK
CAS No.
14808-60-7
Publication Date
20010705
Document Type
Journal Article
Fiscal Year
2001
NTIS Accession No.
NTIS Price
Issue of Publication
26
ISSN
1520-6106
NIOSH Division
HELD
Source Name
The Journal of Physical Chemistry, Part B. Condensed Matter, Materials, Surfaces, Interfaces & Biophysical
State
WV
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