The relationship of structure to properties in surfactants. IV. Effectiveness in surface or interfacial tension reduction

doi:10.1016/0021-9797(76)90257-5

Journal of Colloid and Interface Science

Volume 56, Issue 2, August 1976, Pages 320-327

https://doi.org/10.1016/0021-9797(76)90257-5 Get rights and content

Abstract

Equations have been derived for the effectiveness with which a surfactant above its Krafft point depresses the surface or interfacial tension of a solvent. The effectiveness, defined as the interfacial tension reduction (or interfacial pressure, π_eme) attained at the critical micelle concentration, is shown to depend upon: (1) the maximum surface excess concentration of the surfactant, (2) its critical micelle concentration, and (3) the efficiency, log (1/C)π=20, with which it can depress the interfacial tension by 20 dynes/cm, and is related to the difference in the free energy changes involved in the transfer of the surfactant molecule to the micelle or to the air/liquid (or liquid/liquid) interface at π = 20.

For both nonionic and 1:1 ionic surfactants, π_eme is only slightly affected by change in the length of the hydrophobic group. Other structural changes in the hydrophobic group or in the counterion, however, can cause marked changes in the effectiveness. In polyoxyethylenated nonionics, π_eme reaches a maximum at about four oxyethylene units, and then decreases with increase in the number of these units above six due to the increase in the cross-sectional area of the molecule at the interface.

References (28)

J.A Caskey et al.
J. Colloid Interface Sci.
(1971)
P.H Elworthy et al.
J. Colloid Interface Sci.
(1966)
B.A Mulley et al.
J. Colloid Sci.
(1962)
J.E Carless et al.
J. Colloid Sci.
(1964)
M.J Schick
J. Colloid Sci.
(1962)
M.J Rosen
J. Amer. Oil Chemists Soc.
(1972)
M.J Rosen
J. Amer. Oil Chemists Soc.
(1974)
K Shinoda
Colloidal Surfactants
M.J Rosen et al.
J. Phys. Chem.
(1964)
L Hsiao et al.
J. Phys. Chem.
(1956)

E.H Crook et al.

J. Phys. Chem.

(1964)

P Mukerjee et al.

Critical Micelle Concentrations of Aqueous Surfactant Systems

H Lange

R.L Venable et al.

J. Phys. Chem.

(1964)

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The relationship of structure to properties in surfactants. IV. Effectiveness in surface or interfacial tension reduction

Abstract

J. Colloid Interface Sci.

J. Colloid Interface Sci.

J. Colloid Sci.

J. Colloid Sci.

J. Colloid Sci.

J. Amer. Oil Chemists Soc.

J. Amer. Oil Chemists Soc.

Colloidal Surfactants

J. Phys. Chem.

J. Phys. Chem.

J. Phys. Chem.

Critical Micelle Concentrations of Aqueous Surfactant Systems

J. Phys. Chem.