Document Detail


δ(18) O analysis of organic compounds: problems with pyrolysis in molybdenum-lined reactors.
MedLine Citation:
PMID:  22976207     Owner:  NLM     Status:  In-Data-Review    
Abstract/OtherAbstract:
RATIONALE: Effective δ(18) O determinations of organic compounds have been made using high-temperature pyrolysis (HTP) units that employ molybdenum (Mo) foil as an oxidation barrier instead of glassy carbon. In this investigation we evaluated the performance of a Mo-lined reactor during δ(18) O determinations from benzoic acid using a standard high-temperature conversion elemental analyser (TC/EA) unit. Our Mo-lined reactor was associated with poor performance statistics. It was hypothesised that this was as a consequence of the partitioning of oxygen within our system.
METHODS: In order to test this hypothesis scanning electron microscopy energy-dispersive X-ray spectroscopy (SEM-EDX) and Raman spectroscopy was conducted on two Mo-lined reactors, which had been used for the analysis of benzoic acids.
RESULTS: The EDX analysis revealed that the Mo metal, which had become severely pitted and corroded in the region corresponding to the hottest part of the furnace, was associated with Mo-oxide patinas throughout its entire length.
CONCLUSIONS: A complex circular reaction between CO, Mo and C is likely to be responsible for the sequestering of a portion of sample oxygen into Mo-oxides, fractionating our sample. Accurate analysis of benzoic acid and other compounds can therefore only be achieved if sample oxygen is quantitatively returned to gaseous CO, preventing the buildup of Mo-oxides within the reactor over time. This is most likely to be achieved if sample gases have a sufficient residence time within the reactive glassy carbon bed, optimising the recovery of sample oxygen. However, such conditions are unlikely to have been met within our standard TC/EA system resulting in poor performance of the Mo-liner compared with other HTP units. Copyright © 2012 John Wiley & Sons, Ltd.
Authors:
Alex Lombino; Tim Atkinson; Steve Firth
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  Rapid communications in mass spectrometry : RCM     Volume:  26     ISSN:  1097-0231     ISO Abbreviation:  Rapid Commun. Mass Spectrom.     Publication Date:  2012 Oct 
Date Detail:
Created Date:  2012-09-14     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  8802365     Medline TA:  Rapid Commun Mass Spectrom     Country:  England    
Other Details:
Languages:  eng     Pagination:  2407-12     Citation Subset:  IM    
Copyright Information:
Copyright © 2012 John Wiley & Sons, Ltd.
Affiliation:
Department of Geography, University College London, Pearson Building, Gower Street, London, WC1E 6BT, UK. ucfaalo@live.ucl.ac.uk.
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