Micellization behavior and thermodynamic properties of cetyltrimethylammonium bromide in lithium chloride, potassium chloride, magnesium chloride and calcium chloride solutions

doi:10.1016/j.cjche.2024.12.019

Abstract

Abstract: The micellization behavior and thermodynamic properties of cetyltrimethylammonium bromide (CTAB) in single lithium chloride (LiCl), potassium chloride (KCl), magnesium chloride (MgCl₂) and calcium chloride (CaCl₂) solutions were investigated at 288.15-318.15 K. Result showed that the critical micelle concentration (CMC) values of CTAB in all solutions decreased to a minimum value around 298.15 K and then increased with further increasing the temperature. In all cases, the CMC values decreased with increasing salt concentration at each temperature. Additionally, the introduction of any single salt resulted in a reduction of CMC values for CTAB, attributed to the combined effects of counterions and entropy-driven interactions. The observed trend for CMC values was as follows: CMC_H₂O > CMC_KCl > CMC_LiCl > CMC_CaCl₂ > CMC_MgCl₂. Furthermore, standard thermodynamic parameters, including standard free energy of micellization (△G_m⁰), standard enthalpy of micellization (△H_m⁰) and standard entropy of micellization (△S_m⁰), were calculated based on the obtained CMC values. The negative values of △G_m⁰ indicated that the formation of CTAB micelles was a spontaneous behavior. The variations in △H_m⁰ and △S_m⁰ suggested that micellization was primarily entropy-driven at temperatures between 288.15 and 298.15 K, while it was influenced by both entropy and enthalpy from 298.15 to 318.15 K. Fourier transform infrared spectroscopy (FTIR) and transmission electron microscope (TEM) were employed to further explore the effects of salts on the micellization behavior of CTAB.

Key words: Surfactants, Solution, Thermodynamic properties, Micellization behavior

摘要： The micellization behavior and thermodynamic properties of cetyltrimethylammonium bromide (CTAB) in single lithium chloride (LiCl), potassium chloride (KCl), magnesium chloride (MgCl₂) and calcium chloride (CaCl₂) solutions were investigated at 288.15-318.15 K. Result showed that the critical micelle concentration (CMC) values of CTAB in all solutions decreased to a minimum value around 298.15 K and then increased with further increasing the temperature. In all cases, the CMC values decreased with increasing salt concentration at each temperature. Additionally, the introduction of any single salt resulted in a reduction of CMC values for CTAB, attributed to the combined effects of counterions and entropy-driven interactions. The observed trend for CMC values was as follows: CMC_H₂O > CMC_KCl > CMC_LiCl > CMC_CaCl₂ > CMC_MgCl₂. Furthermore, standard thermodynamic parameters, including standard free energy of micellization (△G_m⁰), standard enthalpy of micellization (△H_m⁰) and standard entropy of micellization (△S_m⁰), were calculated based on the obtained CMC values. The negative values of △G_m⁰ indicated that the formation of CTAB micelles was a spontaneous behavior. The variations in △H_m⁰ and △S_m⁰ suggested that micellization was primarily entropy-driven at temperatures between 288.15 and 298.15 K, while it was influenced by both entropy and enthalpy from 298.15 to 318.15 K. Fourier transform infrared spectroscopy (FTIR) and transmission electron microscope (TEM) were employed to further explore the effects of salts on the micellization behavior of CTAB.

关键词: Surfactants, Solution, Thermodynamic properties, Micellization behavior

Wenting Cheng, Qianqian Li, Ying Zhai, Huaigang Cheng, Fangqin Cheng. Micellization behavior and thermodynamic properties of cetyltrimethylammonium bromide in lithium chloride, potassium chloride, magnesium chloride and calcium chloride solutions[J]. Chinese Journal of Chemical Engineering, 2025, 81(5): 95-104.

References

[1] H. Kumar, A. Katal, P. Rawat, FT-IR spectroscopic and micellization studies of cetyltrimethylammonium bromide in aqueous and aqueous solution of ionic liquid (1-butyl-3-methylimidazolium bromide) at different temperatures, J. Mol. Liq. 249 (2018) 227-232.
[2] A. Di Crescenzo, P. Di Profio, G. Siani, R. Zappacosta, A. Fontana, Optimizing the interactions of surfactants with graphitic surfaces and clathrate hydrates, Langmuir 32 (26) (2016) 6559-6570.
[3] N. Singh, R. Yeri, J. Chakraborty, Effect of ionic surfactants and alcohols on the morphology of CuSO₄·5H₂O crystals: combined use of factors and significance of threshold surfactant concentration, Ind. Eng. Chem. Res. 52 (43) (2013) 15041-15048.
[4] S. Javadian, F. Nasiri, A. Heydari, A. Yousefi, A.A. Shahir, Modifying effect of imidazolium-based ionic liquids on surface activity and self-assembled nanostructures of sodium dodecyl sulfate, J. Phys. Chem. B 118 (15) (2014) 4140-4150.
[5] C. Yang, X.F. Song, S.Y. Sun, Z. Sun, J.G. Yu, Effects of sodium dodecyl sulfate on the oriented growth of nesquehonite whiskers, Adv. Powder Technol. 24 (3) (2013) 585-592.
[6] H. Wei, Q. Shen, Y. Zhao, Y. Zhou, D.J. Wang, D.F. Xu, On the crystallization of calcium carbonate modulated by anionic surfactants, J. Cryst. Growth 279 (3-4) (2005) 439-446.
[7] Y.X. Wang, Basic research on additive-assisted preparation of MgO whiskers, Master Thesis, Shanxi Univ., China, 2020. (in Chinese).
[8] W.T. Cheng, Q.Q. Li, Y.X. Wang, L. Fang, F.Q. Cheng, Formation and phase transformation of MgCO₃·3H₂O whiskers in the presence of sodium dodecyl sulfate, ACS Omega 8 (16) (2023) 14621-14629.
[9] H.M. Zhou, Z.H. Yang, C.J. Yin, S.L. Yang, J. Li, Fabrication of nanoplate Li-rich cathode material via surfactant-assisted hydrothermal method for lithium-ion batteries, Ceram. Int. 44 (16) (2018) 20514-20523.
[10] H. Dhaouadi, H. Chaabane, F. Touati, Mg(OH)2 nanorods synthesized by A facile hydrothermal method in the presence of CTAB, Nano Micro Lett. 3 (3) (2011) 153-159.
[11] D.M. Li, J. Huang, Z.H. Ren, Y.J. Lu, Y.J. He, S.W. Liu, J.J. Huang, Interfacial properties and micellization of octadecyltrimethylammonium bromide in aqueous solution containing short chain alcohol and effect of chain length of alcohol, j dispers sci technol 41 (6) (2020) 856-862.
[12] R. Sheng, Q.Y. Ding, Z.H. Ren, D.N. Li, S.C. Fan, L.C. Le, X.F. Quan, Y. Wang, M.T. Yi, Y.X. Zhang, Y.X. Cao, H. Wang, J.R. Wang, Q.H. Zhang, Z.B. Qian, Interfacial and micellization behavior of binary mixture of amino sulfonate amphoteric surfactant and octadecyltrimethyl ammonium bromide: Effect of short chain alcohol and its chain length, J. Mol. Liq. 334 (2021) 116064.
[13] W.T. Cheng, Z.B. Li, F.Q. Cheng, Solubility of Li₂CO₃ in Na-K-Li-Cl brines from 20 to 90°C, J. Chem. Thermodyn. 67 (2013) 74-82.
[14] D. Kumar, M.S. Sheikh, J.M. Khan, B. Kumar, D.T. Jangde, Influence of additives on the interaction of antidepressant drug with TX-165 surfactant: Surface tension and FTIR analyses, J. Mol. Liq. 411 (2024) 125727.
[15] M.S. Sheikh, J.M. Khan, B. Kumar, D.T. Jangde, D. Kumar, Exploration of the effect of NaCl/urea on aggregation process of imipramine hydrochloride drug and TX-165 mixture: a surface tension and UV-visible study, Colloids Surf. A Physicochem. Eng. Aspects 694 (2024) 134102.
[16] J. Abedin, S. Mahbub, M.M. Rahman, A. Hoque, D. Kumar, J.M. Khan, A.M. El-Sherbeeny, Interaction of tetradecyltrimethylammonium bromide with bovine serum albumin in different compositions: Effect of temperatures and electrolytes/urea, Chin. J. Chem. Eng. 29 (2021) 279-287.
[17] M.K. Sah, K. Edbey, Z.O. Ettarhouni, A. Bhattarai, D. Kumar, Conductometric and spectral analyses of dye-surfactant interactions between indigo carmine and N-alkyltrimethylammonium chloride, J. Mol. Liq. 399 (2024) 124413.
[18] D. Kumar, Z. Farkas Agatic, K. Popovic, M. Posa, Binary mixed micelles of hexadecyltrimethylammonium bromide-sodium deoxycholate and dodecyltrimethylammonium bromide-sodium deoxycholate: thermodynamic stabilization and mixed micelle solubilization capacity of daidzein (isoflavonoid), Ind. Eng. Chem. Res. 63 (7) (2024) 3336-3348.
[19] A. Alam, K.M. Anis-Ul-Haque, J.M. Khan, D. Kumar, M. Irfan, S. Rana, M.A. Hoque, S.E. Kabir, Assessment of the assembly behaviour and physicochemical parameters for the tetradecyltrimethylammonium bromide and promazine hydrochloride mixture: Impact of monohydroxy organic compounds, Colloid Polym. Sci. 302 (5) (2024) 721-734.
[20] A. Dutta, M.T.R. Joy, S.M. Ali Ahsan, M.K. Gatasheh, D. Kumar, M. Abdul Rub, M. Anamul Hoque, M. Majibur Rahman, N. Hoda, D.M. Shafiqul Islam, Physico-chemical parameters for the assembly of moxifloxacin hydrochloride and cetyltrimethylammonium chloride mixture in aqueous and alcoholic media, Chin. J. Chem. Eng. 57 (2023) 280-289.
[21] T. Hasan, J.M. Khan, S. Rana, M. Anamul Hoque, D. Kumar, M. Kumar Banjare, M. Majibur Rahman, M. Nurul Abser, Exploration of micellization and phase separation nature of surfactants in metformin hydrochloride + additives media: an experimental and DFT study, J. Mol. Liq. 413 (2024) 125961.
[22] S. Mahbub, M.A. Rub, M. Anamul Hoque, M.A. Khan, D. Kumar, Micellization behavior of cationic and anionic surfactant mixtures at different temperatures: Effect of sodium carbonate and sodium phosphate salts, J. Phys. Org. Chem. 32 (9) (2019) e3967.
[23] M.A. Hoque, M.M. Alam, M.R. Molla, S. Rana, M.A. Rub, M.A. Halim, M.A. Khan, A. Ahmed, Effect of salts and temperature on the interaction of levofloxacin hemihydrate drug with cetyltrimethylammonium bromide: Conductometric and molecular dynamics investigations, J. Mol. Liq. 244 (2017) 512-520.
[24] K. Roebuck, A.Y. Tremblay, The self-assembly of twinned boehmite nanosheets into porous 3D structures in ethanol-water mixtures, Colloids Surf. A Physicochem. Eng. Aspects 495 (2016) 238-247.
[25] F.L. Xu, C.H. Lu, Y.R. Ni, Z.Z. Xu, Synthesis by microwave irradiation process and controllable infrared absorptive property of oxyapatite-type samarium silicate, New Chem. Mater. 42 (4) (2014) 159-161, 169.
[26] P. Bhattarai, T.P. Niraula, A. Bhattarai, Thermodynamic properties of cetyltrimethylammonium bromide in ethanol-water media with/without the presence of the divalent salt, J. Oleo Sci. 70 (3) (2021) 363-374.
[27] N. Scholz, T. Behnke, U. Resch-Genger, Determination of the critical micelle concentration of neutral and ionic surfactants with fluorometry, conductometry, and surface tension-a method comparison, J. Fluoresc. 28 (1) (2018) 465-476.
[28] K. Kuperkar, L. Abezgauz, K. Prasad, P. Bahadur, Formation and growth of micelles in dilute aqueous CTAB solutions in the presence of NaNO₃ and NaClO₃, J. Surfactants Deterg. 13 (3) (2010) 293-303.
[29] Z. Ul Haq, N. Rehman, F. Ali, N. Mehmood Khan, H. Ullah, Effect of electrolyte (NaCl) and temperature on the mechanism of cetyl trimethylammonium bromide micelles, Sains Malays. 46 (5) (2017) 733-741.
[30] A. Ali, U. Farooq, S. Uzair, R. Patel, Conductometric and tensiometric studies on the mixed micellar systems of surface-active ionic liquid and cationic surfactants in aqueous medium, J. Mol. Liq. 223 (2016) 589-602.
[31] A. Ianiro, H. Wu, M.M.J. van Rijt, M.P. Vena, A.D.A. Keizer, A.C.C. Esteves, R. Tuinier, H. Friedrich, N.A.J.M. Sommerdijk, J.P. Patterson, Liquid-liquid phase separation during amphiphilic self-assembly, Nat. Chem. 11 (4) (2019) 320-328.
[32] M.S. Alam, A. Mohammed Siddiq, V. Mythili, M. Priyadharshini, N. Kamely, A.B. Mandal, Effect of organic additives and temperature on the micellization of cationic surfactant cetyltrimethylammonium chloride: Evaluation of thermodynamics, J. Mol. Liq. 199 (2014) 511-517.
[33] A. Pal, R. Punia, Mixed micellization behaviour of tri-substituted surface active ionic liquid and cationic surfactant in aqueous medium and salt solution: Experimental and theoretical study, J. Mol. Liq. 296 (2019) 111831.
[34] P.K. Banipal, S. Arti, T.S. Banipal, Influence of polyhydroxy compounds on the micellization behaviour of cetyltrimethylammonium bromide: Conductance and microcalorimetric investigations, J. Mol. Liq. 223 (2016) 1204-1212.
[35] M.A. Hoque, M.A. Khan, M.D. Hossain, Interaction of cefalexin monohydrate with cetyldimethylethylammonium bromide, J. Chem. Thermodyn. 60 (2013) 71-75.
[36] S. Chauhan, K. Sharma, Effect of temperature and additives on the critical micelle concentration and thermodynamics of micelle formation of sodium dodecyl benzene sulfonate and dodecyltrimethylammonium bromide in aqueous solution: a conductometric study, J. Chem. Thermodyn. 71 (2014) 205-211.
[37] S. Chauhan, M. Kaur, K. Kumar, M.S. Chauhan, Study of the effect of electrolyte and temperature on the critical micelle concentration of dodecyltrimethylammonium bromide in aqueous medium, J. Chem. Thermodyn. 78 (2014) 175-181.
[38] M.A. Hoque, M.M. Alam, M.R. Molla, S. Rana, M.A. Rub, M.A. Halim, M.A. Khan, F. Akhtar, Interaction of cetyltrimethylammonium bromide with drug in aqueous/electrolyte solution: a combined conductometric and molecular dynamics method study, Chin. J. Chem. Eng. 26 (1) (2018) 159-167.
[39] M.M. Alam, S. Rana, M.A. Rub, M.A. Hoque, S.E. Kabir, A.M. Asiri, Influence of various electrolytes on the interaction of cetyltrimethylammonium bromide with tetradecyltrimethylammonium bromide at different temperatures and compositions: Experimental and theoretical investigation, J. Mol. Liq. 278 (2019) 86-96.
[40] A. Bhattarai, H. Wilczura-Wachnik, Interaction between morin and AOT reversed micelles: studies with UV-vis at 25°C, Int. J. Pharm. 461 (1-2) (2014) 14-21.
[41] S.S. Berr, Solvent isotope effects on alkytrimethylammonium bromide micelles as a function of alkyl chain length, J. Phys. Chem. 91 (18) (1987) 4760-4765.
[42] P. Warszynski, W. Barzyk, K. Lunkenheimer, H. Fruhner, Surface tension and surface potential of Na n-dodecyl sulfate at the air-solution interface: model and experiment, J. Phys. Chem. B 102 (52) (1998) 10948-10957.
[43] S. Mahbub, M.R. Molla, M. Saha, I. Shahriar, M.A. Hoque, M.A. Halim, M.A. Rub, M.A. Khan, N. Azum, Conductometric and molecular dynamics studies of the aggregation behavior of sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) in aqueous and electrolytes solution, J. Mol. Liq. 283 (2019) 263-275.
[44] M.S. Alam, A.Z. Naqvi, Kabir-ud-Din, Surface and micellar properties of some amphiphilic drugs in the presence of additives, J. Chem. Eng. Data 52 (4) (2007) 1326-1331.
[45] B. Kumar, D. Tikariha, K.K. Ghosh, Effects of electrolytes on micellar and surface properties of some monomeric surfactants, J. Dispers. Sci. Technol. 33 (2) (2012) 265-271.
[46] M.A. James-Smith, D. Shekhawat, B.M. Moudgil, D.O. Shah, Determination of drug and fatty acid binding capacity to pluronic f127 in microemulsions, Langmuir 23 (4) (2007) 1640-1644.
[47] J. Du, B.Y. Jiang, J.Q. Xie, X.C. Zeng, Effects of metal ions on the micellization of ionic surfactants, J. Dispersion Sci. Technol. 22 (6) (2001) 529-533.
[48] X.K. Qu, L.Y. Zhu, L. Li, X.L. Wei, F. Liu, D.Z. Sun, Host-guest complexation of β-, γ-cyclodextrin with alkyl trimethyl ammonium bromides in aqueous solution, J. Solut. Chem. 36 (5) (2007) 643-650.
[49] M.A. Rub, D. Kumar, N. Azum, F. Khan, A.M. Asiri, Study of the interaction between promazine hydrochloride and surfactant (conventional/gemini) mixtures at different temperatures, J. Solut. Chem. 43 (5) (2014) 930-949.
[50] G. Para, E. Jarek, P. Warszynski, The Hofmeister series effect in adsorption of cationic surfactants: theoretical description and experimental results, Adv. Colloid Interface Sci. 122 (1-3) (2006) 39-55.
[51] K. Lunkenheimer, D. Prescher, K. Geggel, Role of counterions in the adsorption and micellization behavior of 1: 1 ionic surfactants at fluid Interfaces─Demonstrated by the standard amphiphile system of alkali perfluoro- n-octanoates, Langmuir 38 (3) (2022) 891-902.
[52] H. Kumar, A. Katal, Interaction of cationic surfactant cetyltrimethylammonium bromide (CTAB) with hydrophilic ionic liquid 1-butyl-3-methylimidazolium chloride [C4mim] [Cl] at different temperatures-Conductometric and FT-IR spectroscopic study, J. Mol. Liq. 266 (2018) 252-258.
[53] L. Justyna, C. Jungnickel, M. Joskowska, J. Thoming, J. Hupka, Thermodynamics of micellization of imidazolium ionic liquids in aqueous solutions, J. Colloid Interface Sci. 336 (1) (2009) 111-116.
[54] H. Kumar, C. Chadha, Conductometric and spectroscopic studies of cetyltrimethylammonium bromide in aqueous solutions of imidazolium based ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, J. Mol. Liq. 211 (2015) 1018-1025.
[55] Q. Zhang, Z.N. Gao, F. Xu, S.X. Tai, Effect of hydrocarbon structure of the headgroup on the thermodynamic properties of micellization of cationic gemini surfactants: an electrical conductivity study, J. Colloid Interface Sci. 371 (1) (2012) 73-81.
[56] D.N. Li, Y.X. Zhang, Z.H. Ren, L.C. Le, J. Huang, B.B. Li, Q.H. Zhang, M.T. Yi, X.F. Quan, Y.X. Wang, B.R. Wang, Z.B. Qian, J.R. Wang, H. Tian, J. Yuan, N. Wang, Q.L. Long, X.M. Zhang, Molecular interaction for quasi-binary mixture of N-acyl amino sulfonate amphoteric surfactant from castor oil and stearyltrimethyl ammonium bromide, J. Mol. Liq. 339 (2021) 116813.
[57] A. Pal, S. Chaudhary, Thermodynamic and aggregation behavior of aqueous tetradecyltrimethylammonium bromide in the presence of the hydrophobic ionic liquid 3-methyl-1-pentylimidazolium hexafluorophosphate, J. Mol. Liq. 207 (2015) 67-72.
[58] V.B. Wagle, P.S. Kothari, V.G. Gaikar, Effect of temperature on aggregation behavior of aqueous solutions of sodium cumene sulfonate, J. Mol. Liq. 133 (1-3) (2007) 68-76.
[59] R.K. Banjare, M.K. Banjare, S. Panda, Effect of acetonitrile on the colloidal behavior of conventional cationic surfactants: a combined conductivity, surface tension, fluorescence and FTIR study, J. Solut. Chem. 49 (1) (2020) 34-51.
[60] H. Kumar, A. Katal, Thermodynamic analysis of micelles formation of anionic surfactant SDS in the presence of aqueous and aqueous solution of ionic liquid 1-butyl-3-methylimidazolium chloride, J. Phys. Org. Chem. 34 (7) (2021) e4199.
[61] S. Chauhan, K. Negi, Insight of molecular interactions between short-chain tetraalkylammonium bromides and cetyltrimethylammonium bromide: a spectroscopic and thermodynamic approach, J. Surfactants Deterg. 26 (4) (2023) 505-515.
[62] H. Kumar, N. Sharma, A. Katal, Aggregation behaviour of cationic (cetyltrimethylammonium bromide) and anionic (sodium dodecylsulphate) surfactants in aqueous solution of synthesized ionic liquid [1-pentyl-3-methylimidazolium bromide] -Conductivity and FT-IR spectroscopic studies, J. Mol. Liq. 258 (2018) 285-294.