Determination of the critical micelle concentration in simulations of surfactant systems
Abstract
Alternative methods for determining the critical micelle concentration (cmc) are investigated using canonical and grand canonical Monte Carlo simulations of a lattice surfactant model. A common measure of the cmc is the “free” (unassociated) surfactant concentration in the presence of micellar aggregates. Many prior simulations of micellizing systems have observed a decrease in the free surfactant concentration with overall surfactant loading for both ionic and nonionic surfactants, contrary to theoretical expectations from mass-action models of aggregation. In the present study, we investigate a simple lattice nonionic surfactant model in implicit solvent, for which highly reproducible simulations are possible in both the canonical (NVT) and grand canonical (μVT) ensembles. We confirm the previously observed decrease of free surfactant concentration at higher overall loadings and propose an algorithm for the precise calculation of the excluded volume and effective concentration of unassociated surfactant molecules in the accessible volume of the solution. We find that the cmc can be obtained by correcting the free surfactant concentration for volume exclusion effects resulting from the presence of micellar aggregates. We also develop an improved method for determination of the cmc based on the maximum in curvature for the osmotic pressure curve determined from NVT simulations. Excellentmore »
- Authors:
-
- Princeton Univ., Princeton, NJ (United States)
- Publication Date:
- Research Org.:
- Princeton Univ., NJ (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1469187
- Alternate Identifier(s):
- OSTI ID: 1236409
- Grant/Contract Number:
- SC0002128
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 144; Journal Issue: 4; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Santos, Andrew P., and Panagiotopoulos, Athanassios Z. Determination of the critical micelle concentration in simulations of surfactant systems. United States: N. p., 2016.
Web. doi:10.1063/1.4940687.
Santos, Andrew P., & Panagiotopoulos, Athanassios Z. Determination of the critical micelle concentration in simulations of surfactant systems. United States. https://doi.org/10.1063/1.4940687
Santos, Andrew P., and Panagiotopoulos, Athanassios Z. Thu .
"Determination of the critical micelle concentration in simulations of surfactant systems". United States. https://doi.org/10.1063/1.4940687. https://www.osti.gov/servlets/purl/1469187.
@article{osti_1469187,
title = {Determination of the critical micelle concentration in simulations of surfactant systems},
author = {Santos, Andrew P. and Panagiotopoulos, Athanassios Z.},
abstractNote = {Alternative methods for determining the critical micelle concentration (cmc) are investigated using canonical and grand canonical Monte Carlo simulations of a lattice surfactant model. A common measure of the cmc is the “free” (unassociated) surfactant concentration in the presence of micellar aggregates. Many prior simulations of micellizing systems have observed a decrease in the free surfactant concentration with overall surfactant loading for both ionic and nonionic surfactants, contrary to theoretical expectations from mass-action models of aggregation. In the present study, we investigate a simple lattice nonionic surfactant model in implicit solvent, for which highly reproducible simulations are possible in both the canonical (NVT) and grand canonical (μVT) ensembles. We confirm the previously observed decrease of free surfactant concentration at higher overall loadings and propose an algorithm for the precise calculation of the excluded volume and effective concentration of unassociated surfactant molecules in the accessible volume of the solution. We find that the cmc can be obtained by correcting the free surfactant concentration for volume exclusion effects resulting from the presence of micellar aggregates. We also develop an improved method for determination of the cmc based on the maximum in curvature for the osmotic pressure curve determined from NVT simulations. Excellent agreement in cmc and other micellar properties between NVT and NVT simulations of different system sizes is observed. In conclusion, the methodological developments in this work are broadly applicable to simulations of aggregating systems using any type of surfactant model (atomistic/coarse grained) or solvent description (explicit/implicit).},
doi = {10.1063/1.4940687},
journal = {Journal of Chemical Physics},
number = 4,
volume = 144,
place = {United States},
year = {Thu Jan 28 00:00:00 EST 2016},
month = {Thu Jan 28 00:00:00 EST 2016}
}
Web of Science
Works referenced in this record:
Transition in three-dimensional micellar systems
journal, March 2000
- Girardi, M.; Figueiredo, W.
- The Journal of Chemical Physics, Vol. 112, Issue 10
Critical micelle concentration and the size distribution of surfactant aggregates
journal, October 1980
- Ben-Naim, A.; Stillinger, F. H.
- The Journal of Physical Chemistry, Vol. 84, Issue 22
The Mass-Action-Law Theory of Micellization Revisited
journal, November 2014
- Rusanov, Anatoly I.
- Langmuir, Vol. 30, Issue 48
Problems Associated with the Treatment of Conductivity−Concentration Data in Surfactant Solutions: Simulations and Experiments
journal, August 2002
- Carpena, P.; Aguiar, J.; Bernaola-Galván, P.
- Langmuir, Vol. 18, Issue 16
Critical micelle concentration. Transition point for micellar size distribution
journal, November 1975
- Ruckenstein, E.; Nagarajan, R.
- The Journal of Physical Chemistry, Vol. 79, Issue 24
Monte Carlo Simulations for Micellar Encapsulation
journal, June 1997
- Talsania, Sameer K.; Wang, Yongmei; Rajagopalan, Raj
- Journal of Colloid and Interface Science, Vol. 190, Issue 1
Micelle Aggregation Numbers of Surfactants in Aqueous Solutions: A Comparison between the Results from Steady-State and Time-Resolved Fluorescence Quenching
journal, September 1998
- Alargova, R. G.; Kochijashky, I. I.; Sierra, M. L.
- Langmuir, Vol. 14, Issue 19
Effect of the Nature of the Counterion on the Properties of Anionic Surfactants. 1. Cmc, Ionization Degree at the Cmc and Aggregation Number of Micelles of Sodium, Cesium, Tetramethylammonium, Tetraethylammonium, Tetrapropylammonium, and Tetrabutylammonium Dodecyl Sulfates
journal, December 2003
- Benrraou, Mohamed; Bales, Barney L.; Zana, Raoul
- The Journal of Physical Chemistry B, Vol. 107, Issue 48
Implicit-Solvent Models for Micellization: Nonionic Surfactants and Temperature-Dependent Properties
journal, February 2011
- Jusufi, Arben; Sanders, Samantha; Klein, Michael L.
- The Journal of Physical Chemistry B, Vol. 115, Issue 5
Micellization Studied by GPU-Accelerated Coarse-Grained Molecular Dynamics
journal, October 2011
- Levine, Benjamin G.; LeBard, David N.; DeVane, Russell
- Journal of Chemical Theory and Computation, Vol. 7, Issue 12
Critical micelle concentration in three-dimensional lattice models of amphiphiles
journal, September 2001
- Bhattacharya, Aniket; Mahanti, S. D.
- Journal of Physics: Condensed Matter, Vol. 13, Issue 41
Error estimates on averages of correlated data
journal, July 1989
- Flyvbjerg, H.; Petersen, H. G.
- The Journal of Chemical Physics, Vol. 91, Issue 1
Carbon-13 NMR of micellar solutions. Micellar aggregation number from the concentration dependence of the carbon-13 chemical shifts
journal, November 1979
- Persson, Bert Ove.; Drakenberg, Torbjoern.; Lindman, Bjoern.
- The Journal of Physical Chemistry, Vol. 83, Issue 23
A Definition of the Degree of Ionization of a Micelle Based on Its Aggregation Number
journal, July 2001
- Bales, Barney L.
- The Journal of Physical Chemistry B, Vol. 105, Issue 29
Calculations of Critical Micelle Concentration by Dissipative Particle Dynamics Simulations: The Role of Chain Rigidity
journal, July 2013
- Lee, Ming-Tsung; Vishnyakov, Aleksey; Neimark, Alexander V.
- The Journal of Physical Chemistry B, Vol. 117, Issue 35
Osmotic pressure in colloid science: clay dispersions, catanionics, polyelectrolyte complexes and polyelectrolyte multilayers
journal, August 2007
- Carrière, David; Page, Miles; Dubois, Monique
- Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 303, Issue 1-2
Ternary oil—water—amphiphile systems: self-assembly and phase equilibria
journal, July 2002
- Kim, Seung-Yeon; Panagiotopoulos, Athanassios Z.; Floriano, M. Antonio
- Molecular Physics, Vol. 100, Issue 14
Prediction of the Critical Micelle Concentration of Nonionic Surfactants by Dissipative Particle Dynamics Simulations
journal, February 2013
- Vishnyakov, Aleksey; Lee, Ming-Tsung; Neimark, Alexander V.
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 5
Model Shape Transitions of Micelles: Spheres to Cylinders and Disks
journal, February 2012
- Daful, Asfaw Gezae; Avalos, Josep Bonet; Mackie, Allan D.
- Langmuir, Vol. 28, Issue 8
Comparison of the Calorimetric and van't Hoff Enthalpy of Micelle Formation for a Nonionic Surfactant in H 2 O and D 2 O Solutions from 15 to 40 °C
journal, August 1998
- Kresheck, Gordon C.
- The Journal of Physical Chemistry B, Vol. 102, Issue 34
Novel scheme to study structural and thermal properties of continuously deformable molecules
journal, March 1992
- Frenkel, D.; Mooij, G. C. A. M.; Smit, B.
- Journal of Physics: Condensed Matter, Vol. 4, Issue 12
Osmotic Pressure and Interparticle Interactions in Ionic Micellar Surfactant Solutions
journal, April 1998
- Amos, D. A.; Markels, J. H.; Lynn, S.
- The Journal of Physical Chemistry B, Vol. 102, Issue 15
Computational study of trimer self-assembly and fluid phase behavior
journal, April 2015
- Hatch, Harold W.; Mittal, Jeetain; Shen, Vincent K.
- The Journal of Chemical Physics, Vol. 142, Issue 16
New Monte Carlo technique for studying phase transitions
journal, December 1988
- Ferrenberg, Alan M.; Swendsen, Robert H.
- Physical Review Letters, Vol. 61, Issue 23
Monte Carlo Simulations of Micellization in Model Ionic Surfactants: Application to Sodium Dodecyl Sulfate
journal, April 2006
- Cheong, Daniel W.; Panagiotopoulos, Athanassios Z.
- Langmuir, Vol. 22, Issue 9
Explicit- and Implicit-Solvent Simulations of Micellization in Surfactant Solutions
journal, October 2014
- Jusufi, Arben; Panagiotopoulos, Athanassios Z.
- Langmuir, Vol. 31, Issue 11
Growth of Sodium Dodecyl Sulfate Micelles with Detergent Concentration
journal, November 1995
- Quina, Frank H.; Nassar, Patricia M.; Bonilha, Joao B. S.
- The Journal of Physical Chemistry, Vol. 99, Issue 46
Micellization and Phase Separation of Diblock and Triblock Model Surfactants
journal, April 2002
- Panagiotopoulos, Athanassios Z.; Floriano, M. Antonio; Kumar, Sanat K.
- Langmuir, Vol. 18, Issue 7
Phase behavior and structure formation in linear multiblock copolymer solutions by Monte Carlo simulation
journal, April 2008
- Gindy, Marian E.; Prud’homme, Robert K.; Panagiotopoulos, Athanassios Z.
- The Journal of Chemical Physics, Vol. 128, Issue 16
Thermodynamics of Micelle Formation as a Function of Temperature: A High Sensitivity Titration Calorimetry Study
journal, July 1995
- Paula, Stefan; Sues, Willy; Tuchtenhagen, Juergen
- The Journal of Physical Chemistry, Vol. 99, Issue 30
Adsorption of surface active agents in a non-aqueous solvent
journal, January 1975
- Couper, A.; Gladden, G. P.; Ingram, B. T.
- Faraday Discussions of the Chemical Society, Vol. 59
Implicit Solvent Simulations of DPC Micelle Formation
journal, August 2005
- Lazaridis, Themis; Mallik, Buddhadeb; Chen, Yong
- The Journal of Physical Chemistry B, Vol. 109, Issue 31
Molecular simulations of self-assembly processes of amphiphiles in dilute solutions: the challenge for quantitative modelling
journal, March 2013
- Jusufi, Arben
- Molecular Physics, Vol. 111, Issue 21
A model on the temperature dependence of critical micelle concentration
journal, March 2004
- Kim, Hong-Un; Lim, Kyung-Hee
- Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 235, Issue 1-3
Energy and size fluctuations of amphiphilic aggregates in a lattice model
journal, June 2000
- Bhattacharya, Aniket; Mahanti, S. D.
- Journal of Physics: Condensed Matter, Vol. 12, Issue 28
Aggregation number and critical micellar concentration of surfactant determined by time-dependent static light scattering (TDSLS) and conductivity
journal, January 2005
- Thévenot, Caroline; Grassl, Bruno; Bastiat, Guillaume
- Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 252, Issue 2-3
Phase Separation and Liquid Crystal Self-Assembly in Surfactant−Inorganic−Solvent Systems
journal, March 2003
- Siperstein, Flor R.; Gubbins, Keith E.
- Langmuir, Vol. 19, Issue 6
Communication: Effect of solvophobic block length on critical micelle concentration in model surfactant systems
journal, July 2014
- Nikoubashman, Arash; Panagiotopoulos, Athanassios Z.
- The Journal of Chemical Physics, Vol. 141, Issue 4
Atomistic Simulations of Micellization of Sodium Hexyl, Heptyl, Octyl, and Nonyl Sulfates
journal, February 2012
- Sanders, Samantha A.; Sammalkorpi, Maria; Panagiotopoulos, Athanassios Z.
- The Journal of Physical Chemistry B, Vol. 116, Issue 8
Micelle Formation and the Hydrophobic Effect †
journal, May 2004
- Maibaum, Lutz; Dinner, Aaron R.; Chandler, David
- The Journal of Physical Chemistry B, Vol. 108, Issue 21
Monte Carlo simulation of a lattice model for micelle formation
journal, July 1994
- Bernardes, Américo T.; Henriques, Vera B.; Bisch, Paulo M.
- The Journal of Chemical Physics, Vol. 101, Issue 1
Theory of the kinetics of micellar equilibria and quantitative interpretation of chemical relaxation studies of micellar solutions of ionic surfactants
journal, April 1976
- Aniansson, E. A. G.; Wall, S. N.; Almgren, M.
- The Journal of Physical Chemistry, Vol. 80, Issue 9
Monte Carlo simulation of model amphiphile‐oil–water systems
journal, September 1985
- Larson, R. G.; Scriven, L. E.; Davis, H. T.
- The Journal of Chemical Physics, Vol. 83, Issue 5
Modeling Aggregation of Ionic Surfactants Using a Smeared Charge Approximation in Dissipative Particle Dynamics Simulations
journal, August 2015
- Mao, Runfang; Lee, Ming-Tsung; Vishnyakov, Aleksey
- The Journal of Physical Chemistry B, Vol. 119, Issue 35
Temperature-induced transition to a nonmicellar state
journal, January 1999
- de Moraes, J. N. B.; Figueiredo, W.
- The Journal of Chemical Physics, Vol. 110, Issue 4
Self-assembly of surfactants in a supercritical solvent from lattice Monte Carlo simulations
journal, January 2002
- Lı́sal, Martin; Hall, Carol K.; Gubbins, Keith E.
- The Journal of Chemical Physics, Vol. 116, Issue 3
Sphere-to-rod transitions of micelles in model nonionic surfactant solutions
journal, February 2003
- Al-Anber, Zaid A.; Bonet i. Avalos, Josep; Floriano, M. Antonio
- The Journal of Chemical Physics, Vol. 118, Issue 8
Thermodynamic Characterization of Temperature-Induced Micellization and Demicellization of Detergents Studied by Differential Scanning Calorimetry
journal, June 2001
- Majhi, Pinaki R.; Blume, Alfred
- Langmuir, Vol. 17, Issue 13
Percolation and cluster distribution. I. Cluster multiple labeling technique and critical concentration algorithm
journal, October 1976
- Hoshen, J.; Kopelman, R.
- Physical Review B, Vol. 14, Issue 8
Micellization in Model Surfactant Systems
journal, April 1999
- Floriano, M. Antonio; Caponetti, Eugenio; Panagiotopoulos, Athanassios Z.
- Langmuir, Vol. 15, Issue 9
Modeling of Nonionic Micelles
journal, October 1995
- Wijmans, Christopher M.; Linse, Per
- Langmuir, Vol. 11, Issue 10
Membrane osmometry of aqueous micellar solutions of pure nonionic and ionic surfactants
journal, September 1970
- Attwood, D.; Elworthy, Peter H.; Kayne, S. B.
- The Journal of Physical Chemistry, Vol. 74, Issue 19
Implicit Solvent Models for Micellization of Ionic Surfactants
journal, November 2008
- Jusufi, Arben; Hynninen, Antti-Pekka; Panagiotopoulos, Athanassios Z.
- The Journal of Physical Chemistry B, Vol. 112, Issue 44
Temperature Dependence of Equilibrium and Transport Properties of Decyldimethylbenzylammonium Chloride in Aqueous Solutions
journal, May 2001
- González-Pérez, A.; Del Castillo, J. L.; Czapkiewicz, J.
- Journal of Chemical & Engineering Data, Vol. 46, Issue 3
Anomalous Temperature Dependence of Surfactant Self-Assembly from Aqueous Solution
journal, April 2004
- Bock, H.; Gubbins, K. E.
- Physical Review Letters, Vol. 92, Issue 13
A Monte Carlo simulation of the micellar phase of an amphiphile and solvent mixture
journal, February 1996
- Desplat, J. -C.
- Molecular Physics, Vol. 87, Issue 2
Monte Carlo simulation of microstructural transitions in surfactant systems
journal, June 1992
- Larson, R. G.
- The Journal of Chemical Physics, Vol. 96, Issue 11
Monte Carlo Calculation of the Average Extension of Molecular Chains
journal, February 1955
- Rosenbluth, Marshall N.; Rosenbluth, Arianna W.
- The Journal of Chemical Physics, Vol. 23, Issue 2
Ion Specificity and Micellization of Ionic Surfactants: A Monte Carlo Study
journal, April 2014
- dos Santos, Alexandre P.; Figueiredo, Wagner; Levin, Yan
- Langmuir, Vol. 30, Issue 16
Self-assembly of coarse-grained ionic surfactants accelerated by graphics processing units
journal, January 2012
- LeBard, David N.; Levine, Benjamin G.; Mertmann, Philipp
- Soft Matter, Vol. 8, Issue 8
Surfactant Concentration Effects on Micellar Properties
journal, January 2012
- Jusufi, Arben; LeBard, David N.; Levine, Benjamin G.
- The Journal of Physical Chemistry B, Vol. 116, Issue 3
Reptation of a Polymer Chain in the Presence of Fixed Obstacles
journal, July 1971
- de Gennes, P. G.
- The Journal of Chemical Physics, Vol. 55, Issue 2
Aggregation Behavior of a Lattice Model for Amphiphiles
journal, September 1997
- Mackie, Allan D.; Panagiotopoulos, Athanassios Z.; Szleifer, Igal
- Langmuir, Vol. 13, Issue 19
Micellar Aggregation Numbers - A Fluorescence Study
journal, January 1998
- van Stam, Jan; Depaemelaere, Sigrid; De Schryver, Frans C.
- Journal of Chemical Education, Vol. 75, Issue 1
Surfactant association into micelles. An electrostatic approach
journal, November 1980
- Gunnarsson, Gudmundur; Joensson, Bengt; Wennerstroem, Haakan
- The Journal of Physical Chemistry, Vol. 84, Issue 23
Works referencing / citing this record:
Review of recent studies on interactions between polymers and nanotubes using molecular dynamic simulation
journal, September 2016
- Fatemi, S. Mahmood; Foroutan, Masumeh
- Journal of the Iranian Chemical Society, Vol. 14, Issue 2
Desorption of hydrocarbon chains by association with ionic and nonionic surfactants under flow as a mechanism for enhanced oil recovery
journal, August 2017
- Terrón-Mejía, Ketzasmin A.; López-Rendón, Roberto; Goicochea, Armando Gama
- Scientific Reports, Vol. 7, Issue 1
Self-assembly of spiral patterns in confined systems with competing interactions
journal, January 2019
- Pȩkalski, J.; Bildanau, E.; Ciach, A.
- Soft Matter, Vol. 15, Issue 38
Predicting low-temperature free energy landscapes with flat-histogram Monte Carlo methods
journal, February 2017
- Mahynski, Nathan A.; Blanco, Marco A.; Errington, Jeffrey R.
- The Journal of Chemical Physics, Vol. 146, Issue 7
Following the nucleation pathway from disordered liquid to gyroid mesophase
journal, April 2019
- Marriott, Maile; Lupi, Laura; Kumar, Abhinaw
- The Journal of Chemical Physics, Vol. 150, Issue 16
Non-equilibrium effects of micelle formation as studied by a minimum particle-based model
journal, May 2019
- Raschke, Simon; Heuer, Andreas
- The Journal of Chemical Physics, Vol. 150, Issue 20
Simulation of diblock copolymer surfactants. I. Micelle free energies
journal, July 2019
- Mysona, Joshua A.; McCormick, Alon V.; Morse, David C.
- Physical Review E, Vol. 100, Issue 1
Self-Assembly of Spiral Patterns in Confined System with Competing Interactions
text, January 2019
- Pekalski, Jakub; Bildanov, Eldar; Ciach, Alina
- arXiv
Aggregation Behavior of Medium Chain Fatty Acids Studied by Coarse-Grained Molecular Dynamics Simulation
journal, January 2019
- Hossain, Md Shakhawath; Berg, Staffan; Bergström, Christel A. S.
- AAPS PharmSciTech, Vol. 20, Issue 2
Desorption of hydrocarbon chains by association with ionic and nonionic surfactants under flow as a mechanism for enhanced oil recovery
preprint, January 2017
- Terrón-Mejía, Ketzasmin A.; López-Rendon, Roberto; Goicochea, Armando Gama
- arXiv