ACS Publications. Most Trusted. Most Cited. Most Read
Direct Alkalinity Detection with Ion-Selective Chronopotentiometry
My Activity
    Article

    Direct Alkalinity Detection with Ion-Selective Chronopotentiometry
    Click to copy article linkArticle link copied!

    View Author Information
    Department of Inorganic and Analytical Chemistry, University of Geneva, Quai Ernest-Ansermet 30, CH-1211 Geneva, Switzerland
    Other Access OptionsSupporting Information (1)

    Analytical Chemistry

    Cite this: Anal. Chem. 2014, 86, 13, 6461–6470
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ac500968c
    Published May 27, 2014
    Copyright © 2014 American Chemical Society

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    We explore the possibility to directly measure pH and alkalinity in the sample with the same sensor by imposing an outward flux of hydrogen ions from an ion-selective membrane to the sample solution by an applied current. The membrane consists of a polypropylene-supported liquid membrane doped with a hydrogen ionophore (chromoionophore I), ion exchanger (KTFBP), and lipophilic electrolyte (ETH 500). While the sample pH is measured at zero current, alkalinity is assessed by chronopotentiometry at anodic current. Hydrogen ions expelled from the membrane undergo acid–base solution chemistry and protonate available base in the diffusion layer. With time, base species start to be depleted owing to the constant imposed hydrogen ion flux from the membrane, and a local pH change occurs at a transition time. This pH change (potential readout) is correlated to the concentration of the base in solution. As in traditional chronopotentiometry, the observed square root of transition time (τ) was found to be linear in the concentration range of 0.1 mM to 1 mM, using the bases tris(hydroxymethyl)aminomethane, ammonia, carbonate, hydroxide, hydrogen phosphate, and borate. Numerical simulations were used to predict the concentration profiles and the chronopotentiograms, allowing the discussion of possible limitations of the proposed method and its comparison with volumetric titrations of alkalinity. Finally, the P-alkalinity level is measured in a river sample to demonstrate the analytical usefulness of the proposed method. As a result of these preliminary results, we believe that this approach may become useful for the in situ determination of P-alkalinity in a range of matrixes.

    Copyright © 2014 American Chemical Society

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    Additional information as noted in the text. This material is available free of charge via the Internet at http://pubs.acs.org.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai

    This article is cited by 28 publications.

    1. Fabian Steininger, Johan Palmfeldt, Klaus Koren, Andrey V. Kalinichev. Exploiting the pH-Cross Sensitivity of Ion-Selective Optodes to Broaden Their Response Range. ACS Sensors 2024, 9 (9) , 4555-4559. https://doi.org/10.1021/acssensors.4c01481
    2. Colin Sonnichsen, Dariia Atamanchuk, Andre Hendricks, Sean Morgan, James Smith, Iain Grundke, Edward Luy, Vincent Joseph Sieben. An Automated Microfluidic Analyzer for In Situ Monitoring of Total Alkalinity. ACS Sensors 2023, 8 (1) , 344-352. https://doi.org/10.1021/acssensors.2c02343
    3. Fabian Steininger, Silvia E. Zieger, Klaus Koren. Dynamic Sensor Concept Combining Electrochemical pH Manipulation and Optical Sensing of Buffer Capacity. Analytical Chemistry 2021, 93 (8) , 3822-3829. https://doi.org/10.1021/acs.analchem.0c04326
    4. Ellen M. Briggs, Eric Heinen De Carlo, Christopher L. Sabine, Noah M. Howins, Todd R. Martz. Autonomous Ion-Sensitive Field Effect Transistor-Based Total Alkalinity and pH Measurements on a Barrier Reef of Ka̅ne’ohe Bay. ACS Earth and Space Chemistry 2020, 4 (3) , 355-362. https://doi.org/10.1021/acsearthspacechem.9b00274
    5. Elena Zdrachek, Eric Bakker. From Molecular and Emulsified Ion Sensors to Membrane Electrodes: Molecular and Mechanistic Sensor Design. Accounts of Chemical Research 2019, 52 (5) , 1400-1408. https://doi.org/10.1021/acs.accounts.9b00056
    6. Renjie Wang, Xinfeng Du, Jingying Zhai, Xiaojiang Xie. Distance and Color Change Based Hydrogel Sensor for Visual Quantitative Determination of Buffer Concentrations. ACS Sensors 2019, 4 (4) , 1017-1022. https://doi.org/10.1021/acssensors.9b00186
    7. Wenyue Gao, Stéphane Jeanneret, Dajing Yuan, Thomas Cherubini, Lu Wang, Xiaojiang Xie, Eric Bakker. Electrogenerated Chemiluminescence for Chronopotentiometric Sensors. Analytical Chemistry 2019, 91 (7) , 4889-4895. https://doi.org/10.1021/acs.analchem.9b00787
    8. Jiawang Ding, Nana Yu, Xuedong Wang, and Wei Qin . Sequential and Selective Detection of Two Molecules with a Single Solid-Contact Chronopotentiometric Ion-Selective Electrode. Analytical Chemistry 2018, 90 (3) , 1734-1739. https://doi.org/10.1021/acs.analchem.7b03522
    9. Ellen M. Briggs, Sergio Sandoval, Ahmet Erten, Yuichiro Takeshita, Andrew C. Kummel, and Todd R. Martz . Solid State Sensor for Simultaneous Measurement of Total Alkalinity and pH of Seawater. ACS Sensors 2017, 2 (9) , 1302-1309. https://doi.org/10.1021/acssensors.7b00305
    10. Majid Ghahraman Afshar, Gastón A. Crespo, and Eric Bakker . Flow Chronopotentiometry with Ion-Selective Membranes for Cation, Anion, and Polyion Detection. Analytical Chemistry 2016, 88 (7) , 3945-3952. https://doi.org/10.1021/acs.analchem.6b00141
    11. Sutida Jansod, Majid Ghahraman Afshar, Gastón A. Crespo, and Eric Bakker . Alkalinization of Thin Layer Samples with a Selective Proton Sink Membrane Electrode for Detecting Carbonate by Carbonate-Selective Electrodes. Analytical Chemistry 2016, 88 (7) , 3444-3448. https://doi.org/10.1021/acs.analchem.6b00346
    12. Nadezda Pankratova, Majid Ghahraman Afshar, Dajing Yuan, Gastón A. Crespo, and Eric Bakker . Local Acidification of Membrane Surfaces for Potentiometric Sensing of Anions in Environmental Samples. ACS Sensors 2016, 1 (1) , 48-54. https://doi.org/10.1021/acssensors.5b00015
    13. Eric Bakker . Electroanalysis with Membrane Electrodes and Liquid–Liquid Interfaces. Analytical Chemistry 2016, 88 (1) , 395-413. https://doi.org/10.1021/acs.analchem.5b04034
    14. Jacob Lester, Timothy Chandler, and Kebede L. Gemene . Reversible Electrochemical Sensor for Detection of High-Charge Density Polyanion Contaminants in Heparin. Analytical Chemistry 2015, 87 (22) , 11537-11543. https://doi.org/10.1021/acs.analchem.5b03347
    15. José A. Ribeiro, A. Fernando Silva, H.H. Girault, Carlos M. Pereira. Electroanalytical applications of ITIES – A review. Talanta 2024, 280 , 126729. https://doi.org/10.1016/j.talanta.2024.126729
    16. Mariani Ahmad, Azrilawani Ahmad, Tuan Fauzan Tuan Omar, Rosmawani Mohammad. Current Trends of Analytical Techniques for Total Alkalinity Measurement in Water Samples: A Review. Critical Reviews in Analytical Chemistry 2024, 54 (8) , 2734-2744. https://doi.org/10.1080/10408347.2023.2199432
    17. Fabian Steininger, Klaus Koren. In Situ pH Modulation for Enhanced Chemical Sensing: Strategies and Applications. Analysis & Sensing 2024, 4 (5) https://doi.org/10.1002/anse.202400013
    18. Mehrdad Ghaemi, Leila Hajiaghababaei, Jamshid Najafpour, Ashraf Sadat Shahvelayati, Ramin M. A. Tehrani. Comparison of selectivity and sensitivity of various ferric selective electrodes prepared using N -((bis(dimethyl amino)methylene)carbamothioyl)benzamide. Physical Chemistry Chemical Physics 2024, 26 (27) , 18997-19007. https://doi.org/10.1039/D4CP01473A
    19. Andres F. Molina-Osorio, Alexander Wiorek, Ghulam Hussain, Maria Cuartero, Gaston A. Crespo. Modelling electrochemical modulation of ion release in thin-layer samples. Journal of Electroanalytical Chemistry 2021, 903 , 115851. https://doi.org/10.1016/j.jelechem.2021.115851
    20. Shoji Yamamoto, Hajime Kayanne, Nori Fujita, Yukari Sato, Haruko Kurihara, Saki Harii, Akihide Hemmi, Andrew G. Dickson. Development of an automated transportable continuous system to measure the total alkalinity of seawater. Talanta 2021, 221 , 121666. https://doi.org/10.1016/j.talanta.2020.121666
    21. Ziqi Sun, Yufeng Zhang, Xinyue Xu, Minglin Wang, Lijuan Kou. Determination of the Total Phenolic Content in Wine Samples Using Potentiometric Method Based on Permanganate Ion as an Indicator. Molecules 2019, 24 (18) , 3279. https://doi.org/10.3390/molecules24183279
    22. Xuemei Wang, Xue Bai, Zifu Li, Xiaoqin Zhou, Shikun Cheng, Jiachen Sun, Ting Liu. Evaluation of artificial neural network models for online monitoring of alkalinity in anaerobic co-digestion system. Biochemical Engineering Journal 2018, 140 , 85-92. https://doi.org/10.1016/j.bej.2018.09.010
    23. Sutida Jansod, Majid Ghahraman Afshar, Gastón A. Crespo, Eric Bakker. Phenytoin speciation with potentiometric and chronopotentiometric ion-selective membrane electrodes. Biosensors and Bioelectronics 2016, 79 , 114-120. https://doi.org/10.1016/j.bios.2015.12.011
    24. Majid Ghahraman Afshar, Gastón A. Crespo, Eric Bakker. Thin‐Layer Chemical Modulations by a Combined Selective Proton Pump and pH Probe for Direct Alkalinity Detection. Angewandte Chemie 2015, 127 (28) , 8228-8231. https://doi.org/10.1002/ange.201500797
    25. Majid Ghahraman Afshar, Gastón A. Crespo, Eric Bakker. Thin‐Layer Chemical Modulations by a Combined Selective Proton Pump and pH Probe for Direct Alkalinity Detection. Angewandte Chemie International Edition 2015, 54 (28) , 8110-8113. https://doi.org/10.1002/anie.201500797
    26. Stéphane Jeanneret, Gastón A. Crespo, Majid Ghahraman Afshar, Eric Bakker. GalvaPot, a custom-made combination galvanostat/potentiostat and high impedance potentiometer for decentralized measurements of ionophore-based electrodes. Sensors and Actuators B: Chemical 2015, 207 , 631-639. https://doi.org/10.1016/j.snb.2014.10.084
    27. Jiahong Lei, Jiawang Ding, Wei Qin. A chronopotentiometric flow injection system for aptasensing of E. coli O157. Analytical Methods 2015, 7 (3) , 825-829. https://doi.org/10.1039/C4AY02662D
    28. G. Mistlberger, M. Pawlak, E. Bakker, I. Klimant. Photodynamic optical sensor for buffer capacity and pH based on hydrogel-incorporated spiropyran. Chemical Communications 2015, 51 (20) , 4172-4175. https://doi.org/10.1039/C4CC07821G

    Analytical Chemistry

    Cite this: Anal. Chem. 2014, 86, 13, 6461–6470
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ac500968c
    Published May 27, 2014
    Copyright © 2014 American Chemical Society

    Article Views

    926

    Altmetric

    -

    Citations

    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.