Measuring the Rate Constants of Reactions Between OH− and Ketone/Acids by Proton Extraction Reaction Mass Spectrometry

Due to its characteristics of short response time (1-10 s), low limit of detection (LOD) (10−12 (V/V)), and self-quantitative measurement, proton transfer reaction mass spectrometry (PTR-MS) has become a powerful technique for real-time trace detection of volatile organic compounds (VOCs). Different...

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Main Authors: Yue PAN, Qiang-ling ZHANG, Xue ZOU, Cheng-yin SHEN, Yan-nan CHU
Format: Article
Language:English
Published: Editorial Board of Journal of Chinese Mass Spectrometry Society 2025-05-01
Series:Zhipu Xuebao
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Online Access:https://zpxb.xml-journal.net/article/doi/10.7538/zpxb.2024.0140
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author Yue PAN
Qiang-ling ZHANG
Xue ZOU
Cheng-yin SHEN
Yan-nan CHU
author_facet Yue PAN
Qiang-ling ZHANG
Xue ZOU
Cheng-yin SHEN
Yan-nan CHU
author_sort Yue PAN
collection DOAJ
description Due to its characteristics of short response time (1-10 s), low limit of detection (LOD) (10−12 (V/V)), and self-quantitative measurement, proton transfer reaction mass spectrometry (PTR-MS) has become a powerful technique for real-time trace detection of volatile organic compounds (VOCs). Different from traditional VOCs detection technology, PTR-MS is termed as self-quantitative detection, can provide empirical concentration of the analytes without calibration, which makes it more advantageous in the quantitative detection of multi-component VOCs. Self-quantitative measurement detects the concentration of VOCs by calculating the reaction rate constants of ion-molecule reactions, there is no need for prior calibration unless exceptionally high measurement accuracy is desired. In 2014, our research team developed a new method of proton-extraction-reaction mass spectrometry (PER-MS) with OH− anion as the reagent ions, which can be applied for the detection of VOCs and even inorganic compounds. Due to the lack of reaction rate constant data of OH− and VOCs, the ability for self-quantitative measurements is limited. Therefore, in order to expand the data on the reaction rate constants of OH− and VOCs and promote the self-quantitative measurement ability of PER-MS technique, a new method of proton extraction reaction mass spectrometry (PER-MS) was developed for measuring reaction rate constants of OH− and VOCs. The reaction rate constants were calculated based on the reaction kinetic equations after detecting the signal intensity of product ions and reactive ions by PER-MS and measuring the number density of VOCs and the reaction time. In this work, the pressure in the ion detection system was 7.4×10−5 Pa, the pressure in the drift tube was 200 Pa, and the temperature of drift tube was kept at 308 K. Acetonitrile was used as a reference to measure the reaction rate constants of acetone with OH−. The measured results are agreement with the data reported in the literature. The reaction rate constants of seven VOCs (acetone, 2-butanone, 2-pentanone, 2-hexanone, 2-heptanone, formic acid and acetic acid) reacting with OH− ion were measured by the proposed method. The results enrich the contents of the reaction rate constants between OH− and VOCs, and improve the capability of self-quantitative detection for PER-MS, and also provide a useful reference for the research of ion-molecular reactions.
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spelling doaj-art-1b9a75ea498342baa668446d60e17a942025-08-20T03:48:10ZengEditorial Board of Journal of Chinese Mass Spectrometry SocietyZhipu Xuebao1004-29972025-05-0146328629110.7538/zpxb.2024.01402024-140-d3Measuring the Rate Constants of Reactions Between OH− and Ketone/Acids by Proton Extraction Reaction Mass SpectrometryYue PAN0Qiang-ling ZHANG1Xue ZOU2Cheng-yin SHEN3Yan-nan CHU4School of Electronic Engineering, Chaohu University, Heifei 238024, ChinaAnhui Province Key Laboratory of Medical Physics and Technology, Institute of Health & Medical Technology, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, ChinaAnhui Province Key Laboratory of Medical Physics and Technology, Institute of Health & Medical Technology, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, ChinaAnhui Province Key Laboratory of Medical Physics and Technology, Institute of Health & Medical Technology, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, ChinaAnhui Province Key Laboratory of Medical Physics and Technology, Institute of Health & Medical Technology, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, ChinaDue to its characteristics of short response time (1-10 s), low limit of detection (LOD) (10−12 (V/V)), and self-quantitative measurement, proton transfer reaction mass spectrometry (PTR-MS) has become a powerful technique for real-time trace detection of volatile organic compounds (VOCs). Different from traditional VOCs detection technology, PTR-MS is termed as self-quantitative detection, can provide empirical concentration of the analytes without calibration, which makes it more advantageous in the quantitative detection of multi-component VOCs. Self-quantitative measurement detects the concentration of VOCs by calculating the reaction rate constants of ion-molecule reactions, there is no need for prior calibration unless exceptionally high measurement accuracy is desired. In 2014, our research team developed a new method of proton-extraction-reaction mass spectrometry (PER-MS) with OH− anion as the reagent ions, which can be applied for the detection of VOCs and even inorganic compounds. Due to the lack of reaction rate constant data of OH− and VOCs, the ability for self-quantitative measurements is limited. Therefore, in order to expand the data on the reaction rate constants of OH− and VOCs and promote the self-quantitative measurement ability of PER-MS technique, a new method of proton extraction reaction mass spectrometry (PER-MS) was developed for measuring reaction rate constants of OH− and VOCs. The reaction rate constants were calculated based on the reaction kinetic equations after detecting the signal intensity of product ions and reactive ions by PER-MS and measuring the number density of VOCs and the reaction time. In this work, the pressure in the ion detection system was 7.4×10−5 Pa, the pressure in the drift tube was 200 Pa, and the temperature of drift tube was kept at 308 K. Acetonitrile was used as a reference to measure the reaction rate constants of acetone with OH−. The measured results are agreement with the data reported in the literature. The reaction rate constants of seven VOCs (acetone, 2-butanone, 2-pentanone, 2-hexanone, 2-heptanone, formic acid and acetic acid) reacting with OH− ion were measured by the proposed method. The results enrich the contents of the reaction rate constants between OH− and VOCs, and improve the capability of self-quantitative detection for PER-MS, and also provide a useful reference for the research of ion-molecular reactions.https://zpxb.xml-journal.net/article/doi/10.7538/zpxb.2024.0140proton extraction reaction mass spectrometry (per-ms)reaction rate constantsself-quantitative detectionoh−
spellingShingle Yue PAN
Qiang-ling ZHANG
Xue ZOU
Cheng-yin SHEN
Yan-nan CHU
Measuring the Rate Constants of Reactions Between OH− and Ketone/Acids by Proton Extraction Reaction Mass Spectrometry
Zhipu Xuebao
proton extraction reaction mass spectrometry (per-ms)
reaction rate constants
self-quantitative detection
oh−
title Measuring the Rate Constants of Reactions Between OH− and Ketone/Acids by Proton Extraction Reaction Mass Spectrometry
title_full Measuring the Rate Constants of Reactions Between OH− and Ketone/Acids by Proton Extraction Reaction Mass Spectrometry
title_fullStr Measuring the Rate Constants of Reactions Between OH− and Ketone/Acids by Proton Extraction Reaction Mass Spectrometry
title_full_unstemmed Measuring the Rate Constants of Reactions Between OH− and Ketone/Acids by Proton Extraction Reaction Mass Spectrometry
title_short Measuring the Rate Constants of Reactions Between OH− and Ketone/Acids by Proton Extraction Reaction Mass Spectrometry
title_sort measuring the rate constants of reactions between oh and ketone acids by proton extraction reaction mass spectrometry
topic proton extraction reaction mass spectrometry (per-ms)
reaction rate constants
self-quantitative detection
oh−
url https://zpxb.xml-journal.net/article/doi/10.7538/zpxb.2024.0140
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