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A Versatile and Easy Method to Calibrate a Two-Compartment Flow Cell for Differential Electrochemical Mass Spectrometry Measurements

[Image: see text] Online techniques for the quantitative analysis of reaction products have many advantages over offline methods. However, owing to the low product formation rates in electrochemical reactions, few of these techniques can be coupled to electrochemistry. An exception is differential e...

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Autores principales: Bondue, Christoph J., Koper, Marc T. M., Tschulik, Kristina
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10436368/
https://www.ncbi.nlm.nih.gov/pubmed/37600459
http://dx.doi.org/10.1021/acsmeasuresciau.3c00009
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author Bondue, Christoph J.
Koper, Marc T. M.
Tschulik, Kristina
author_facet Bondue, Christoph J.
Koper, Marc T. M.
Tschulik, Kristina
author_sort Bondue, Christoph J.
collection PubMed
description [Image: see text] Online techniques for the quantitative analysis of reaction products have many advantages over offline methods. However, owing to the low product formation rates in electrochemical reactions, few of these techniques can be coupled to electrochemistry. An exception is differential electrochemical mass spectrometry (DEMS), which gains increasing popularity not least because of its high time resolution in the sub-second regime. DEMS is often combined with a dual thin-layer cell (a two-compartment flow cell), which helps to mitigate a number of problems that arise due to the existence of a vacuum|electrolyte interface. However, the efficiency with which this cell transfers volatile reaction products into the vacuum of the mass spectrometer is far below 100%. Therefore, a calibration constant that considers not only the sensitivity of the DEMS setup but also the transfer efficiency of the dual thin-layer cell is needed to translate the signals observed in the mass spectrometer into electrochemical product formation rates. However, it can be challenging or impossible to design an experiment that yields such a calibration constant. Here, we show that the transfer efficiency of the dual thin-layer cell depends on the diffusion coefficient of the analyte. Based on this observation, we suggest a two-point calibration method. That is, a plot of the logarithm of the transfer efficiencies determined for H(2) and O(2) versus the logarithm of their diffusion coefficients defines a straight line. Extrapolation of this line to the diffusion coefficient of another analyte yields a good estimate of its transfer efficiency. This is a versatile and easy calibration method, because the transfer efficiencies of H(2) and O(2) are readily accessible for a large range of electrode–electrolyte combinations.
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spelling pubmed-104363682023-08-19 A Versatile and Easy Method to Calibrate a Two-Compartment Flow Cell for Differential Electrochemical Mass Spectrometry Measurements Bondue, Christoph J. Koper, Marc T. M. Tschulik, Kristina ACS Meas Sci Au [Image: see text] Online techniques for the quantitative analysis of reaction products have many advantages over offline methods. However, owing to the low product formation rates in electrochemical reactions, few of these techniques can be coupled to electrochemistry. An exception is differential electrochemical mass spectrometry (DEMS), which gains increasing popularity not least because of its high time resolution in the sub-second regime. DEMS is often combined with a dual thin-layer cell (a two-compartment flow cell), which helps to mitigate a number of problems that arise due to the existence of a vacuum|electrolyte interface. However, the efficiency with which this cell transfers volatile reaction products into the vacuum of the mass spectrometer is far below 100%. Therefore, a calibration constant that considers not only the sensitivity of the DEMS setup but also the transfer efficiency of the dual thin-layer cell is needed to translate the signals observed in the mass spectrometer into electrochemical product formation rates. However, it can be challenging or impossible to design an experiment that yields such a calibration constant. Here, we show that the transfer efficiency of the dual thin-layer cell depends on the diffusion coefficient of the analyte. Based on this observation, we suggest a two-point calibration method. That is, a plot of the logarithm of the transfer efficiencies determined for H(2) and O(2) versus the logarithm of their diffusion coefficients defines a straight line. Extrapolation of this line to the diffusion coefficient of another analyte yields a good estimate of its transfer efficiency. This is a versatile and easy calibration method, because the transfer efficiencies of H(2) and O(2) are readily accessible for a large range of electrode–electrolyte combinations. American Chemical Society 2023-05-19 /pmc/articles/PMC10436368/ /pubmed/37600459 http://dx.doi.org/10.1021/acsmeasuresciau.3c00009 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/).
spellingShingle Bondue, Christoph J.
Koper, Marc T. M.
Tschulik, Kristina
A Versatile and Easy Method to Calibrate a Two-Compartment Flow Cell for Differential Electrochemical Mass Spectrometry Measurements
title A Versatile and Easy Method to Calibrate a Two-Compartment Flow Cell for Differential Electrochemical Mass Spectrometry Measurements
title_full A Versatile and Easy Method to Calibrate a Two-Compartment Flow Cell for Differential Electrochemical Mass Spectrometry Measurements
title_fullStr A Versatile and Easy Method to Calibrate a Two-Compartment Flow Cell for Differential Electrochemical Mass Spectrometry Measurements
title_full_unstemmed A Versatile and Easy Method to Calibrate a Two-Compartment Flow Cell for Differential Electrochemical Mass Spectrometry Measurements
title_short A Versatile and Easy Method to Calibrate a Two-Compartment Flow Cell for Differential Electrochemical Mass Spectrometry Measurements
title_sort versatile and easy method to calibrate a two-compartment flow cell for differential electrochemical mass spectrometry measurements
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10436368/
https://www.ncbi.nlm.nih.gov/pubmed/37600459
http://dx.doi.org/10.1021/acsmeasuresciau.3c00009
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