Dyeing, a critical process in textiles, relies on effective dye-fabric binding for optimal coloration. Surfactants play a key role in this binding, with auxiliaries capable of modulating their interactions and impacting dye adhesion. This study explores the aggregation between cetylpyridinium chloride (CPC) surfactant and crystal violet (CV) dye, by monitoring conductivity changes as a marker for micelle formation. The effects of ethanol (EtOH), 1-propanol (1-PrOH), iso-butanol (iso-BuOH), and urea on CPC micellization in aq. CV solutions were analyzed. The driving forces of micelle formation were assessed through assessment of the critical micelle concentration (CMC), counter-ion binding (<InlineEquation ID="IEq1"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10953_2025_1485_Article_IEq1.gif" Format="GIF" Height="17" Rendition="HTML" Resolution="72" Type="Linedraw" Width="15" /> </InlineMediaObject> <EquationSource Format="TEX">$\beta$</EquationSource> <EquationSource Format="MATHML"><math> <mi>β</mi> </math></EquationSource> </InlineEquation>), and thermodynamic parameters such as change in Gibbs free energy (<InlineEquation ID="IEq2"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10953_2025_1485_Article_IEq2.gif" Format="GIF" Height="21" Rendition="HTML" Resolution="72" Type="Linedraw" Width="38" /> </InlineMediaObject> <EquationSource Format="TEX">${\Delta G}_{\text{m}}^{0}$</EquationSource> <EquationSource Format="MATHML"><math> <msubsup> <mrow> <mi mathvariant="normal">Δ</mi> <mi>G</mi> </mrow> <mrow> <mtext>m</mtext> </mrow> <mn>0</mn> </msubsup> </math></EquationSource> </InlineEquation>), enthalpy (<InlineEquation ID="IEq3"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10953_2025_1485_Article_IEq3.gif" Format="GIF" Height="21" Rendition="HTML" Resolution="72" Type="Linedraw" Width="47" /> </InlineMediaObject> <EquationSource Format="TEX">${\Delta H}_{\text{m}}^{0})$</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <msubsup> <mrow> <mi mathvariant="normal">Δ</mi> <mi>H</mi> </mrow> <mrow> <mtext>m</mtext> </mrow> <mn>0</mn> </msubsup> <mrow> <mo stretchy="false">)</mo> </mrow> </mrow> </math></EquationSource> </InlineEquation> and entropy (<InlineEquation ID="IEq4"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10953_2025_1485_Article_IEq4.gif" Format="GIF" Height="21" Rendition="HTML" Resolution="72" Type="Linedraw" Width="43" /> </InlineMediaObject> <EquationSource Format="TEX">${\Delta S}_{\text{m}}^{0})$</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <msubsup> <mrow> <mi mathvariant="normal">Δ</mi> <mi>S</mi> </mrow> <mrow> <mtext>m</mtext> </mrow> <mn>0</mn> </msubsup> <mrow> <mo stretchy="false">)</mo> </mrow> </mrow> </math></EquationSource> </InlineEquation>. Results indicate that increased alcohol and urea concentrations, as well as temperature, lead to elevated CMC values. Negative <InlineEquation ID="IEq5"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10953_2025_1485_Article_IEq2.gif" Format="GIF" Height="21" Rendition="HTML" Resolution="72" Type="Linedraw" Width="38" /> </InlineMediaObject> <EquationSource Format="TEX">${\Delta G}_{\text{m}}^{0}$</EquationSource> <EquationSource Format="MATHML"><math> <msubsup> <mrow> <mi mathvariant="normal">Δ</mi> <mi>G</mi> </mrow> <mrow> <mtext>m</mtext> </mrow> <mn>0</mn> </msubsup> </math></EquationSource> </InlineEquation> values suggest that micelle formation for CPC + CV system is a spontaneous process, while the assessment of <InlineEquation ID="IEq6"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10953_2025_1485_Article_IEq6.gif" Format="GIF" Height="21" Rendition="HTML" Resolution="72" Type="Linedraw" Width="40" /> </InlineMediaObject> <EquationSource Format="TEX">${\Delta H}_{\text{m}}^{0}$</EquationSource> <EquationSource Format="MATHML"><math> <msubsup> <mrow> <mi mathvariant="normal">Δ</mi> <mi>H</mi> </mrow> <mrow> <mtext>m</mtext> </mrow> <mn>0</mn> </msubsup> </math></EquationSource> </InlineEquation> and <InlineEquation ID="IEq7"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10953_2025_1485_Article_IEq7.gif" Format="GIF" Height="21" Rendition="HTML" Resolution="72" Type="Linedraw" Width="36" /> </InlineMediaObject> <EquationSource Format="TEX">${\Delta S}_{\text{m}}^{0}$</EquationSource> <EquationSource Format="MATHML"><math> <msubsup> <mrow> <mi mathvariant="normal">Δ</mi> <mi>S</mi> </mrow> <mrow> <mtext>m</mtext> </mrow> <mn>0</mn> </msubsup> </math></EquationSource> </InlineEquation> reveal the roles of hydrophobic and electrostatic forces. Furthermore, thermodynamics of transfer (<InlineEquation ID="IEq8"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10953_2025_1485_Article_IEq8.gif" Format="GIF" Height="23" Rendition="HTML" Resolution="72" Type="Linedraw" Width="50" /> </InlineMediaObject> <EquationSource Format="TEX">${\Delta G}_{\text{m},\text{tr}}^{0}$</EquationSource> <EquationSource Format="MATHML"><math> <msubsup> <mrow> <mi mathvariant="normal">Δ</mi> <mi>G</mi> </mrow> <mrow> <mtext>m</mtext> <mo>,</mo> <mtext>tr</mtext> </mrow> <mn>0</mn> </msubsup> </math></EquationSource> </InlineEquation>, <InlineEquation ID="IEq9"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10953_2025_1485_Article_IEq9.gif" Format="GIF" Height="23" Rendition="HTML" Resolution="72" Type="Linedraw" Width="52" /> </InlineMediaObject> <EquationSource Format="TEX">${\Delta H}_{\text{m},\text{tr}}^{0}$</EquationSource> <EquationSource Format="MATHML"><math> <msubsup> <mrow> <mi mathvariant="normal">Δ</mi> <mi>H</mi> </mrow> <mrow> <mtext>m</mtext> <mo>,</mo> <mtext>tr</mtext> </mrow> <mn>0</mn> </msubsup> </math></EquationSource> </InlineEquation>, and <InlineEquation ID="IEq10"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10953_2025_1485_Article_IEq10.gif" Format="GIF" Height="23" Rendition="HTML" Resolution="72" Type="Linedraw" Width="55" /> </InlineMediaObject> <EquationSource Format="TEX">${\Delta S}_{\text{m},\text{tr}}^{0})$</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <msubsup> <mrow> <mi mathvariant="normal">Δ</mi> <mi>S</mi> </mrow> <mrow> <mtext>m</mtext> <mo>,</mo> <mtext>tr</mtext> </mrow> <mn>0</mn> </msubsup> <mrow> <mo stretchy="false">)</mo> </mrow> </mrow> </math></EquationSource> </InlineEquation> and enthalpy-entropy compensation parameters were evaluated and reviewed thoroughly, providing valuable insights for optimizing surfactant and additive usage in dyeing applications. Graphical Abstract

Study of the Influences of Alcohol and Urea on the Self-assembly of Cetylpyridinium Chloride in the Presence of Crystal Violet Dye at Different Temperatures

期刊论文
发表日期：

2025年8月16日

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Tania Ferdous,
K. M. Anis-Ul-Haque,
Md. Newaz Sharif,
Muhammad Wajid Ullah,
Javed Masood Khan,
Mazhar Ul-Islam,
Md. Anamul Hoque,
Shariff E. Kabir

摘要

Dyeing, a critical process in textiles, relies on effective dye-fabric binding for optimal coloration. Surfactants play a key role in this binding, with auxiliaries capable of modulating their interactions and impacting dye adhesion. This study explores the aggregation between cetylpyridinium chloride (CPC) surfactant and crystal violet (CV) dye, by monitoring conductivity changes as a marker for micelle formation. The effects of ethanol (EtOH), 1-propanol (1-PrOH), iso-butanol (iso-BuOH), and urea on CPC micellization in aq. CV solutions were analyzed. The driving forces of micelle formation were assessed through assessment of the critical micelle concentration (CMC), counter-ion binding ( $\beta$ $β$ ), and thermodynamic parameters such as change in Gibbs free energy ( ${\Delta G}_{\text{m}}^{0}$ ${Δ G}_{m}^{0}$ ), enthalpy ( ${\Delta H}_{\text{m}}^{0})$ ${Δ H}_{m}^{0})$ and entropy ( ${\Delta S}_{\text{m}}^{0})$ ${Δ S}_{m}^{0})$ . Results indicate that increased alcohol and urea concentrations, as well as temperature, lead to elevated CMC values. Negative ${\Delta G}_{\text{m}}^{0}$ ${Δ G}_{m}^{0}$ values suggest that micelle formation for CPC + CV system is a spontaneous process, while the assessment of ${\Delta H}_{\text{m}}^{0}$ ${Δ H}_{m}^{0}$ and ${\Delta S}_{\text{m}}^{0}$ ${Δ S}_{m}^{0}$ reveal the roles of hydrophobic and electrostatic forces. Furthermore, thermodynamics of transfer ( ${\Delta G}_{\text{m},\text{tr}}^{0}$ ${Δ G}_{m, tr}^{0}$ , ${\Delta H}_{\text{m},\text{tr}}^{0}$ ${Δ H}_{m, tr}^{0}$ , and ${\Delta S}_{\text{m},\text{tr}}^{0})$ ${Δ S}_{m, tr}^{0})$ and enthalpy-entropy compensation parameters were evaluated and reviewed thoroughly, providing valuable insights for optimizing surfactant and additive usage in dyeing applications.

Graphical Abstract