Micellization Behavior of Long-Chain Substituted Alkylguanidinium Surfactants
Abstract
:1. Introduction
2. Results and Discussion
Compound | T (°C) Cr→LC ΔH (kJ·mol−1) | T (°C) LC→I ΔH (kJ·mol−1) |
---|---|---|
DCG | Heating: 54.1 °C; −28.3 kJ·mol−1 | – |
DDGC | Heating: 65.2 °C; −34.7 kJ·mol−1 | Heating: 113.5 °C; −0.78 kJ·mol−1 Cooling: 112.3 °C; 0.79 kJ·mol−1 |
TDGC | Heating: 72.2 °C; −22.9 kJ·mol−1 | Heating: 169.2 °C; −0.37 kJ·mol−1 Cooling: 160.5 °C; 0.36 kJ·mol−1 |
CGC | Heating: 76.8 °C; −38.2 kJ·mol−1 | Heating: 189.9 °C; −0.62 kJ·mol−1 Cooling: 185.2 °C; 0.47 kJ·mol−1 |
2.1. Krafft Temperature, Critical Micelle Concentration, and Micelle Dissociation
Surfactant | Temperature (K) | CMC (mmol·kg−1) | β | ΔmicG° (kJ·mol−1) |
---|---|---|---|---|
DGC | 298 | 26 ± 1 | 0.71 ± 0.01 | −22.3 ± 0.6 |
DDGC | 298 | 6.2 ± 0.3 | 0.74 ± 0.01 | −28.3 ± 0.9 |
TDGC | 306 | 1.8 ± 0.1 | 0.72 ± 0.01 | −33.6 ± 0.9 |
2.2. Thermal Effects of Micelle Formation in Various Aqueous Media
Surfactant | Solvent | Temperature (K) | CMC (mmol·kg−1) | ΔmicH° (kJ·mol−1) |
---|---|---|---|---|
DTAC | H2O | 298 | 21.5 ± 0.1 | 5.1 ± 0.2 |
DTAC | 0.01 M NaCl | 298 | 18.1 ± 0.1 | 4.2 ± 0.1 |
DTAC | 0.1 M NaCl | 298 | 8.6 ± 0.1 | 3.6 ± 0.1 |
TTAC | H2O | 298 | 5.0 ± 0.1 | 2.2 ± 0.2 |
TTAC | 0.1 M NaCl | 298 | 3.3 ± 0.4 | 1.1 ± 0.2 |
TTAC | H2O | 318 | 6.0 ± 0.4 | −8.9 ± 0.2 |
DGC | H2O | 298 | 28.4 ± 0.1 | −4.5 ± 0.1 |
DGC | 0.001 M NaCl | 298 | 25.5 ± 0.6 | −4.2 ± 0.3 |
DGC | 0.01 M NaCl | 298 | 22.7 ± 0.2 | −4.0 ± 0.1 |
DGC | 0.1 M NaCl | 298 | 9.6 ± 0.3 | −6.4 ± 0.1 |
DDGC | H2O | 298 | 6.2 ± 0.2 | −7.8 ± 0.5 |
DDGC | 0.001 M NaCl | 298 | 5.7 ± 0.2 | −9.0 ± 0.1 |
DDGC | 0.01 M NaCl | 298 | 3.5 ± 0.1 | −9.5 ± 0.5 |
DDGC | H2O | 306 | 6.6 ± 0.4 | −12.3 ± 0.9 |
DDGC | H2O | 310 | 7.3 ± 0.4 | −13.0 ± 0.4 |
TDGC | H2O | 306 | 1.5 ± 0.3 | −17.5 ± 0.3 |
3. Materials and Methods
3.1. Chemicals
3.2. Synthesis and Characterization of the Guanidinium Surfactants
3.2.1. Decylguanidinium chloride (DGC)
3.2.2. Dodecylguanidinium chloride (DDGC)
3.2.3. Tetradecylguanidinium chloride (TDGC)
3.2.4. Cetylguanidinium chloride (CGC)
Surfactants | ||||
---|---|---|---|---|
DGC [C11H26N3]+ | DDGC [C13H30N3]+ | TDGC [C15H34N3]+ | CGC [C17H38N3]+ | |
(ESI+, m/z) [M]+ calc. | 200.2121 | 228.2434 | 256.2747 | 284.3060 |
(ESI+, m/z) [M]+ found | 200.2127 | 228.2434 | 256.2756 | 284.3061 |
3.3. Physical Measurements
3.3.1. Conductimetry
3.3.2. Surface Tension Measurements
3.3.3. Titration Calorimetry
4. Conclusions
- For DDGC, TDGC, CGC, the Krafft temperature ranges between 292 and 314 K, and it increases strongly with the addition of methylene units to the surfactant hydrophobic tail.
- The presence of DDGC, TDGC, and CGC units in the aqueous solution decreases its surface tension down to about 24 mN·m−1 above the CMC, irrespective of the surfactant structure and temperature.
- The binding of chloride counter-ions to the micelle is about 70%, similar to that in the micelles of alkyltrimethylammonium bromides and much greater than in the case of alkyltrimethylammonium chlorides; it appears hardly dependent on the tail length and temperature.
- Micellization of guanidinium cationics, especially those with long alkyl chains, may be described as both entropy and enthalpy-driven; the critical micelle concentration, CMC, decreases and the standard enthalpy of micellization per mole of surfactant, ΔmicH°, becomes more negative (the process is more exothermic) upon lengthening the hydrocarbon tail.
- The addition of the background NaCl electrolyte to the aqueous phase causes a steady decrease in the CMC and renders the micellization process more exothermic; depending on the tail length, the alkylguanidinium micelles may attain their optimum shape and size at a given NaCl content, and further salt addition may result in the formation of micelles likely differing in shape and size.
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Bouchal, R.; Hamel, A.; Hesemann, P.; In, M.; Prelot, B.; Zajac, J. Micellization Behavior of Long-Chain Substituted Alkylguanidinium Surfactants. Int. J. Mol. Sci. 2016, 17, 223. https://doi.org/10.3390/ijms17020223
Bouchal R, Hamel A, Hesemann P, In M, Prelot B, Zajac J. Micellization Behavior of Long-Chain Substituted Alkylguanidinium Surfactants. International Journal of Molecular Sciences. 2016; 17(2):223. https://doi.org/10.3390/ijms17020223
Chicago/Turabian StyleBouchal, Roza, Abdellah Hamel, Peter Hesemann, Martin In, Bénédicte Prelot, and Jerzy Zajac. 2016. "Micellization Behavior of Long-Chain Substituted Alkylguanidinium Surfactants" International Journal of Molecular Sciences 17, no. 2: 223. https://doi.org/10.3390/ijms17020223