Surfactants and Interfacial Phenomena, 3rd Edition

by Milton J. Rosen (Surfactant Research Institute, Brooklyn College, The City University of New York, USA)

• ISBN13: 9780471478188
• ISBN10: 0471478180
• Edition: 3rd
• Format: Hardcover
• Copyright: 2004-07-01
• Publisher: Wiley-Interscience

Summary

This book is the premier text on the properties and applications of surfactants. The third edition is completely updated and revised, including new information on gemini surfactants (a new type of powerful surfactant), superspreading (or superwetting) by aqueous surfactant solutions of highly hydrophobic surfaces (important in agricultural applications), and dynamic surface tension (an important interfacial property not covered in the first two editions). * Clearly explains the mechanisms by which surfactants operate in interfacial processes * Uses a minimum of mathematics in explanation of topics, making it easy-to-understand and very user-friendly * Problems are included at the end of each chapter * Includes many tables of data as reference that are not compiled elsewhere * Milton J Rosen is an expert in the field of Surfactant research

Author Biography

MILTON J. ROSEN is Director of the Surfactant Research Institute at Brooklyn College of the City University of New York.

Table of Contents

Preface	xiii
Characteristic Features of Surfactants	1	(33)
Conditions Under Which Interfacial Phenomena and Surfactants Become Significant	2	(1)
General Structural Features and Behavior of Surfactants	2	(2)
General Use of Charge Types	4	(1)
General Effects of the Nature of the Hydrophobic Group	5	(1)
Characteristic Features and Uses of Commercially Available Surfactants	6	(25)
Anionics	7	(1)
Carboxylic Acid Salts	7	(1)
Sulfonic Acid Salts	8	(4)
Sulfuric Acid Ester Salts	12	(3)
Phosphoric and Polyphosphoric Acid Esters	15	(1)
Fluorinated Anionics	15	(1)
Cationics	16	(1)
Long-Chain Amines and Their Salts	17	(1)
Acylated Diamines and Polyamines and Their Salts	17	(1)
Quaternary Ammonium Salts	18	(1)
Polyoxyethylenated (POE) Long-Chain Amines	19	(1)
Quaternized POE Long-Chain Amines	19	(1)
Amine Oxides	19	(1)
Nonionics	20	(1)
POE Alkylphenols, Alkylphenol ``Ethoxylates''	20	(1)
POE Straight-Chain Alcohols, Alcohol ``Ethoxylates''	21	(1)
POE Polyoxypropylene glycols	22	(1)
POE Mercaptans	22	(1)
Long-Chain Carboxylic Acid Esters	23	(1)
Alkanolamine ``Condensates,'' Alkanolamides	24	(1)
Tertiary Acetylenic Glycols and Their ``Ethoxylates''	24	(1)
POE Silicones	25	(1)
N-Alkylpyrrolidones	25	(1)
Alkylpolyglycosides	26	(1)
Zwitterionics	26	(1)
pH-Sensitive Zwitterionics	26	(2)
pH-Insensitive Zwitterionics	28	(1)
Newer Surfactants Based Upon Renewable Raw Materials	28	(1)
α-Sulfofatty Acid Methyl Esters (SME)	28	(1)
Acylated Aminoacids	29	(1)
N-Acyl L-Glutamates (AG)	29	(1)
N-Acyl Glycinates	29	(1)
N-Acyl DL-Alaninates	30	(1)
Other Acylated Aminoacids	30	(1)
Nopol Alkoxylates	30	(1)
Environmental Effects of Surfactants	31	(1)
Surfactant Biodegradability	31	(1)
Surfactant Toxicity To and Bioconcentration in Marine Organisms	31	(1)
Some Useful Generalizations	32	(2)
References	33	(1)
Problems	33	(1)
Adsorption of Surface-Active Agents at Interfaces: The Electrical Double Layer	34	(71)
The Electrical Double Layer	35	(3)
Adsorption at the Solid-Liquid Interface	38	(21)
Mechanisms of Adsorption and Aggregation	39	(3)
Adsorption Isotherms	42	(2)
The Langmuir Adsorption Isotherm	44	(3)
Adsorption from Aqueous Solution Onto Adsorbents with Strongly Charged Sites	47	(1)
Ionic Surfactants	47	(5)
Nonionic Surfactants	52	(1)
pH Change	53	(1)
Ionic Strength	53	(1)
Temperature	53	(1)
Adsorption from Aqueous Solution Onto Nonpolar, Hydrophobic Adsorbents	54	(2)
Adsorption from Aqueous Solution Onto Polar Adsorbents without Strongly Charged Sites	56	(1)
Effects of Adsorption from Aqueous Solution on the Surface Properties of the Solid Adsorbent	57	(1)
Substrates with Strongly Charged Sites	57	(1)
Nonpolar Adsorbents	58	(1)
Adsorption from Nonaqueous Solution	58	(1)
Determination of the Specific Surface Areas of Solids	59	(1)
Adsorption at the Liquid-Gas (L/G) and Liquid-Liquid (L/L) Interfaces	59	(46)
The Gibbs Adsorption Equation	60	(2)
Calculation of Surface Concentrations and Area per Molecule at the Interface By Use of the Gibbs Equation	62	(2)
Effectiveness of Adsorption at the L/G and L/L Interfaces	64	(18)
The Szyszkowski, Langmuir, and Frumkin Equations	82	(1)
Efficiency of Adsorption at the L/G and L/L Interfaces	83	(4)
Calculation of Thermodynamic Parameters of Adsorption at the L/G and L/L Interfaces	87	(8)
Adsorption from Mixtures of Two Surfactants	95	(2)
References	97	(6)
Problems	103	(2)
Micelle Formation by Surfactants	105	(73)
The Critical Micelle Concentration (CMC)	105	(2)
Micellar Structure and Shape	107	(6)
The Packing Parameter	107	(2)
Surfactant Structure and Micellar Shape	109	(1)
Liquid Crystals	110	(3)
Micellar Aggregation Numbers	113	(7)
Factors Affecting the Value of the CMC in Aqueous Media	120	(29)
Structure of the Surfactant	121	(1)
The Hydrophobic Group	121	(17)
The Hydrophobic Group	138	(1)
The Counterion in Ionic Surfactants: Degree of Binding to the Micelle	139	(5)
Empirical Equations	144	(1)
Electrolyte	144	(2)
Organic Additives	146	(1)
Class I Materials	146	(1)
Class II Materials	147	(1)
The Presence of a Second Liquid Phase	148	(1)
Temperature	149	(1)
Micellization in Aqueous Solution and Adsorption at the Aqueous Solution-Air or Aqueous Solution-Hydrocarbon Interface	149	(8)
The CMC/C20 ratio	149	(8)
CMCs in Nonaqueous Media	157	(1)
Equations for the CMC Based on Theoretical Considerations	157	(4)
Thermodynamic Parameters of Micellization	161	(6)
Mixed Micelle Formation in Mixtures of Two Surfactants	167	(11)
References	168	(7)
Problems	175	(3)
Solubilization by Solutions of Surfactants: Micellar Catalysis	178	(30)
Solubilization in Aqueous Media	179	(11)
Locus of Solubilization	179	(2)
Factors Determining the Extent of Solubilization	181	(1)
Structure of the Surfactant	182	(2)
Structure of the Solubilizate	184	(1)
Effect of Electrolyte	185	(1)
Effect of Monomeric Organic Additives	185	(1)
Effect of Polymeric Organic Additives	186	(1)
Mixed Anionic-Nonionic Micelles	187	(1)
Effect of Temperature	188	(1)
Hydrotropy	189	(1)
Rate of Solubilization	190	(1)
Solubilization in Nonaqueous Solvents	190	(3)
Secondary Solubilization	192	(1)
Some Effects of Solubilization	193	(5)
Effect of Solubilization on Micellar Structure	193	(1)
Change in the Cloud Points of Aqueous Solutions of Nonionic Surfactants	193	(4)
Reduction of the CMC	197	(1)
Miscellaneous Effects of Solubilization	198	(1)
Micellar Catalysis	198	(10)
References	202	(4)
Problems	206	(2)
Reduction of Surface and Interfacial Tension by Surfactants	208	(35)
Efficiency in Surface Tension Reduction	212	(2)
Effectiveness in Surface Tension Reduction	214	(15)
The Krafft Point	214	(1)
Interfacial Parameter and Chemical Structural Effects	215	(14)
Liquid-Liquid Interfacial Tension Reduction	229	(5)
Ultralow Interfacial Tension	230	(4)
Dynamic Surface Tension Reduction	234	(9)
Dynamic Regions	234	(3)
Apparent Diffusion Coefficients of Surfactants	237	(1)
References	238	(4)
Problems	242	(1)
Wetting and Its Modification by Surfactants	243	(34)
Wetting Equilibria	243	(12)
Spreading Wetting	243	(3)
The Contact Angle	246	(1)
Measurement of the Contact Angle	247	(2)
Adhesional Wetting	249	(2)
Immersional Wetting	251	(2)
Adsorption and Wetting	253	(2)
Modification of Wetting by Surfactants	255	(14)
General Considerations	255	(1)
Hard Surface (Equilibrium) Wetting	256	(2)
Textile (Nonequilibrium) Wetting	258	(10)
Effect of Additives	268	(1)
Synergy in Wetting by Mixtures of Surfactants	269	(1)
Superspreading (Superwetting)	270	(7)
References	273	(2)
Problems	275	(2)
Foaming and Antifoaming by Aqueous Solutions of Surfactants	277	(26)
Theories of Film Elasticity	278	(4)
Factors Determining Foam Persistence	282	(3)
Drainage of Liquid in the Lamellae	282	(1)
Diffusion of Gas Through the Lamellae	283	(1)
Surface Viscosity	284	(1)
The Existence and Thickness of the Electrical Double Layer	284	(1)
The Relation of Surfactant Chemical Structure to Foaming in Aqueous Solution	285	(9)
Efficiency as a Foaming Agent	285	(2)
Effectiveness as a Foaming Agent	287	(6)
Low-Foaming Surfactants	293	(1)
Foam-Stabilizing Organic Additives	294	(3)
Antifoaming	297	(1)
Foaming of Aqueous Dispersions of Finely Divided Solids	298	(5)
References	299	(2)
Problems	301	(2)
Emulsification by Surfactants	303	(29)
Macroemulsions	304	(13)
Formation	305	(1)
Factors Determining Stability	305	(1)
Physical Nature of the Interfacial Film	306	(2)
Existence of an Electrical or Steric Barrier to Coalescence on the Dispersed Droplets	308	(1)
Viscosity of the Continuous Phase	309	(1)
Size Distribution of Droplets	309	(1)
Phase Volume Ratio	309	(1)
Temperature	310	(1)
Inversion	311	(2)
Multiple Emulsions	313	(1)
Theories of Emulsion Type	314	(1)
Qualitative Theories	314	(2)
Kinetic Theory of Macroemulsion Type	316	(1)
Microemulsions	317	(2)
Nanoemulsions	319	(1)
Selection of Surfactants as Emulsifying Agents	320	(7)
The HLB Method	321	(3)
The PIT Method	324	(2)
The HLD Method	326	(1)
Demulsification	327	(5)
References	327	(3)
Problems	330	(2)
Dispersion and Aggregation of Solids in Liquid Media by Surfactants	332	(21)
Interparticle Forces	332	(9)
Soft (electrostatic) and van der Waals Forces: DLVO Theory	332	(6)
Limitations of the DLVO Theory	338	(1)
Steric Forces	339	(2)
Role of the Surfactant in the Dispersion Process	341	(2)
Wetting of the Powder	342	(1)
Deaggregation or Fragmentation of Particle Clusters	342	(1)
Prevention of Reaggregation	342	(1)
Coagulation or Flocculation of Dispersed Solids by Surfactants	343	(2)
Neutralization or Reduction of the Potential at the Stern Layer of the Dispersed Particles	343	(1)
Bridging	344	(1)
Reversible Flocculation	344	(1)
The Relation of Surfactant Chemical Structure to Dispersing Properties	345	(8)
Aqueous Dispersions	345	(4)
Nonaqueous Dispersions	349	(1)
References	350	(1)
Problems	351	(2)
Detergency and Its Modification by Surfactants	353	(26)
Mechanisms of the Cleaning Process	353	(9)
Removal of Soil from Substrate	354	(1)
Removal of Liquid Soil	355	(2)
Removal of Solid Soil	357	(2)
Suspension of the Soil in the Bath and Prevention of Redeposition	359	(1)
Solid Particulate Soils: Formation of Electrical and Steric Barriers: Soil Release Agents	359	(1)
Liquid Oily Soil	359	(2)
Skin Irritation	361	(1)
Dry Cleaning	361	(1)
Effect of Water Hardness	362	(3)
Builders	363	(1)
Lime Soap Dispersing Agents	364	(1)
Fabric Softeners	365	(2)
The Relation of the Chemical Structure of the Surfactant to Its Detergency	367	(12)
Effect of Soil and Substrate	367	(1)
Oily Soil	367	(3)
Particulate Soil	370	(1)
Mixed Soil	370	(1)
Effect of the Hydrophobic Group of the Surfactant	371	(1)
Effect of the Hydrophilic Group of the Surfactant	372	(2)
Dry Cleaning	374	(1)
References	374	(4)
Problems	378	(1)
Molecular Interactions and Synergism in Mixtures of Two Surfactants	379	(36)
Evaluation of Molecular Interaction Parameters	380	(4)
Notes on the Use of Equations 11.1-11.4	382	(2)
Effect of Chemical Structure and Molecular Environment on Molecular Interaction Parameters	384	(13)
Conditions for the Existence of Synergism	397	(8)
Synergism or Antagonism (Negative Synergism) in Surface or Interfacial Tension Reduction Efficiency	398	(2)
Synergism or Antagonism (Negative Synergism) in Mixed Micelle Formation in Aqueous Medium	400	(1)
Synergism or Antagonism (Negative Synergism) in Surface or Interfacial Tension Reduction Effectiveness	401	(4)
Selection of Surfactants Pairs for Optimal Interfacial Properties	405	(1)
The Relation between Synergism in Fundamental Surface Properties and Synergism in Surfactant Applications	405	(10)
References	410	(3)
Problems	413	(2)
Gemini Surfactants	415	(13)
Fundamental Properties	415	(5)
Interaction with Other Surfactant	420	(3)
Performance Properties	423	(5)
References	424	(2)
Problems	426	(2)
Answers to Problems	428	(5)
Index	433