{"title":"Broadband Complex Permittivity Spectra: Cole-Cole vs Circuit Models.","authors":"Farizal Hakiki, Chih-Ping Lin","doi":"10.1021/acsmeasuresciau.5c00065","DOIUrl":null,"url":null,"abstract":"<p><p>Hydraulic properties such as porosity, water, and clay content can be inferred from electrical parameters like permittivity, conductivity, and resistivity. Spectral data enhance this analysis by revealing features such as pore size and clay type in wet particulate media. In liquid samples, electrode polarization is clearly observed, as orientational polarization occurs only at higher frequencies (MHz to sub-GHz). In contrast, particulate media exhibit electrode polarization artifacts that obscure spatial polarization peaks within the Hz-MHz range, especially in highly conductive materials like wet clayey soils, making the Cole-Cole model insufficient for distinguishing these effects. Therefore, a general circuit model using a parallel form of a resistor and a constant phase element configuration more effectively separates inherent material polarization from electrode polarization. The electrode polarization limiting frequency (<i>f</i> <sub>EP</sub>) correlates with both material conductivity and electrode properties, even with low-polarization electrodes like Ag/AgCl. A novel method is introduced to estimate the effective constant phase element exponent ( <math><mover><mi>η</mi> <mo>~</mo></mover> </math> ) using the slope of log permittivity vs log frequency. Finally, the chargeability of kaolinite (<i>m</i> = 0.83-0.86), derived from the ratio of critical frequencies between the Cole-Cole and Pelton models, aligns with its fundamental definition: <i>m</i> = (σ<sub>∞</sub> - σ<sub>0</sub>)/σ<sub>∞</sub>, where σ<sub>0</sub> is the DC conductivity and σ<sub>∞</sub> is the high-frequency conductivity.</p>","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":"5 5","pages":"716-728"},"PeriodicalIF":4.6000,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12532061/pdf/","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Measurement Science Au","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1021/acsmeasuresciau.5c00065","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/10/15 0:00:00","PubModel":"eCollection","JCR":"Q1","JCRName":"CHEMISTRY, ANALYTICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Hydraulic properties such as porosity, water, and clay content can be inferred from electrical parameters like permittivity, conductivity, and resistivity. Spectral data enhance this analysis by revealing features such as pore size and clay type in wet particulate media. In liquid samples, electrode polarization is clearly observed, as orientational polarization occurs only at higher frequencies (MHz to sub-GHz). In contrast, particulate media exhibit electrode polarization artifacts that obscure spatial polarization peaks within the Hz-MHz range, especially in highly conductive materials like wet clayey soils, making the Cole-Cole model insufficient for distinguishing these effects. Therefore, a general circuit model using a parallel form of a resistor and a constant phase element configuration more effectively separates inherent material polarization from electrode polarization. The electrode polarization limiting frequency (fEP) correlates with both material conductivity and electrode properties, even with low-polarization electrodes like Ag/AgCl. A novel method is introduced to estimate the effective constant phase element exponent ( ) using the slope of log permittivity vs log frequency. Finally, the chargeability of kaolinite (m = 0.83-0.86), derived from the ratio of critical frequencies between the Cole-Cole and Pelton models, aligns with its fundamental definition: m = (σ∞ - σ0)/σ∞, where σ0 is the DC conductivity and σ∞ is the high-frequency conductivity.
期刊介绍:
ACS Measurement Science Au is an open access journal that publishes experimental computational or theoretical research in all areas of chemical measurement science. Short letters comprehensive articles reviews and perspectives are welcome on topics that report on any phase of analytical operations including sampling measurement and data analysis. This includes:Chemical Reactions and SelectivityChemometrics and Data ProcessingElectrochemistryElemental and Molecular CharacterizationImagingInstrumentationMass SpectrometryMicroscale and Nanoscale systemsOmics (Genomics Proteomics Metabonomics Metabolomics and Bioinformatics)Sensors and Sensing (Biosensors Chemical Sensors Gas Sensors Intracellular Sensors Single-Molecule Sensors Cell Chips Arrays Microfluidic Devices)SeparationsSpectroscopySurface analysisPapers dealing with established methods need to offer a significantly improved original application of the method.