Surface-active solutes Surface-active agents Surfactants

Lecture 2

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Etymology
English oil water solvent both flow affinity lack-of-affinity nature science Greek lipohydrolyoamphirheo-philic -phobic -pathic -logy Latin oleoaquasolvo-

English meanings are not literal translations, but interpretations of how the words are understood in this branch of science. Technical terms (neologisms) are formed by combinations of these words, such as the following adjectives:

amphipathic amphiphilic hydrophilic lipophilic lyophilic lyophobic

= = = = = =

combining both natures (oil and water understood) with affinity for both (oil and water understood) with affinity for water with affinity for oil with affinity for the solvent lack of affinity for the solvent
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Classification of surfactants
Classified by the hydrophilic group: Anionic Carboxylic Sulfuric esters Alkane sulfonic acids Alkyl aromatic sulfonic acids Others: Phosphates, phosphoric acids, Cationic Amine salts (primary, secondary, and tertiary) Quaternary salts Nonionic Ethers Esters Amides Amphoteric

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Adsorption lowers the energy

At the air/liquid interface: At the solid/liquid interface:

Lowers surface tension.

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Stabilizes dispersions.
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Adsorption of surfactant decreases the work needed for:

Spreading and wetting.

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Emulsification and dispersion.

Surfactants on drops or particles

Ionic surfactants produce charged surfaces.

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Nonionic surfactants produce protective coatings.

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Adsorption at water and organic surfaces

Strong adsorption, substantial lowering of surface tension.

Little adsorption, little lowering of surface tension.

Strong adsorption, substantial lowering of interfacial tension.

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Lowering of surface tensions with surfactants

The surface tension drops but reaches a limit:

Surface tension ( mJ/m )

Sucrose

~0.05% Soap

Concentration of surfactant

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Surfactants can create their own surface - Micelles

Adsorption and micellization are competing processes.

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Physical properties of surfactant solutions

The critical micelle concentration.
10

Detergency
8

Density change Conductivity

Arbitrary units

Surface tension Osmotic pressure Equivalent conductivity

0.8

Interfacial tension
0 0.0 0.2 0.4 0.6

% Sodium dodecyl sulfate

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Surfactant phases
Middle Phase
These terms come from the old soap makers literature. Different liquid crystal phases look different.
Lamellar Liquid Crystal

Hexagonal Liquid Crystal Surfactant

Neat Phase
Water in between.

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Phase diagrams can be constructed

(Consider taking the ACS short course on emulsions for much more information.)
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Oil-soluble surfactants

A widely used additive that combines both high molecular weight and basic function is polyisobutylene succinimide, marketed as OLOA 1200 by the Chevron Chemical Co. It provides low-temperature sludge and varnish control in gasoline engines and effective dispersancy in diesel engine, natural gas engine, and marine cylinder lubricants.

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Oil electrolytes form inverse micelles

The micelle core is highly polar. The diameters are 10s of nanometers. Single polymer molecules may be sufficient.
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Linear conductivity of nonpolar electrolytes?

Conductivity of OLOA 1200 in dodecane ( 25o C )
100

The conductivity of weak electrolytes should vary with the square root of concentration.

80

Conductivity (pS/cm)

60

40 = 58.6 * concentration 20

0 0.0 0.5 1.0 1.5 2.0

Concentration (wt %)

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Creation of charged micelles:

Micelles exchange ions with each other and with surfaces.

The equilibrium is a dynamic balance.

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Adsorption is a slow process

120

Per cent of equilibrium monolayer adsorbed

100

80

The adsorption of surfactants is much! slower than is estimated by molecular diffusion.

60

40

20

Time is required for molecules to rearrange at the solid/liquid interface.

-4 -3 -2 -1 0 1 2 3 4 5 6

Log10 time, sec

0.1% C17H35CONHCH2CHOHCH2NH2 0.01% " 0.5% C18H37NH2 0.3% C17H35COOH 0.3% C18H37OH Diffusion time for a 0.5% solution

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Adsorption of ionic surfactants

At the air/liquid interface: At the solid/liquid interface:

Lowers surface tension.

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Charges the particle and stabilizes the dispersion.

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Model of a charged particle in suspension

The loosely held countercharges form the electrical double layer.

The electric potential between the particle surface and the liquid at infinite distance is called the zeta potential. The description of the charged particle contains the zeta potential and a measure of how thick is the electrical double layer.

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Electric charge on carbon black particles in oil

-40

Zeta Potential (mV)

-30 -20 -10 0 0.0 0.5 1.0 1.5 2.0

OLOA 1200 in dodecane (% weight)

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Zeta potential and adsorption

OLOA 1200 on Carbon black (2% vol) in Isopar 0

Zeta Potential (mV)

-5 -10 -15 -20 -25 -30 -35 0.0 0.2 0.4 0.6 0.8 1.0

Surface coverage
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Charging of particles in nonpolar liquids

+1

1
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Nonpolar, electrocratic applications:

Carbon in engine oils:
http://www.autoshop-online.com/auto101/eng1.html

Liquid immersion printing: HP Indigo Electrophoretic displays: E Ink / Philips

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Commonly used surfactants

Chemical Class 1. Anionic Alkyaryl sulfonates Fatty alcohol sulfates Lignosulfonates Alkali soaps of tall oil Alkali soaps of rosin Dialkylsulfosuccinates 2. Cationic Alkyltrimethylammonium chloride 3. Nonionic Alkanolamides Glyceryl esters Ethylene-oxide condensates of alkylphenols Ethoxylated alkylphenols Ethoxylated fatty esters Fatty esters Polyalkylsuccinimides Lecithins Metal soaps Detergents, foam stabilizers Emulsifiers Emulsifiers Detergents, wetting agents, emulsifiers, dispersants Food emulsifiers (oil in water) Food emulsifiers (water in oil) Oil-soluble dispersants Oil-soluble dispersants Oil-soluble dispersants Emulsifier, corrosion, inhibitor, textile softener, antibacterial agent, detergent Detergents, emulsifiers Detergents, emulsifiers Dispersants Anionic emulsifiers Anionic emulsifiers Wetting agents Application

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Large volume surfactants

Fatty alcohols and alkylphenol ethoxylates:
R OH
R OH

(OCH2CH2)nOH

Alkanolamides:
HO HO

NCR

Alkylbenzene sulphonates

SO3Na

Fatty alcohol and fatty alcohol ether sulphates:

R OSO3Na

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Surfactant structure

Structure affects adsorption, stability, solubility, and temperature dependence, etc.

http://surfactants.net/huibers/Huibers1997.pdf

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Effect of structure on adsorption and micellization

8

Interfacial tension (mN/m)

(a)
6

(b)
K
+

C C16H33O SO 3-

C C8H17O

The linear molecule is more effective at lowering interfacial tension at low concentrations, but forms micelles easily. The branched molecule is not as effective at lowering interfacial tension, but does not form micelles so readily and therefore gets to a higher concentration in solution.

CH3

SO 3 OC 8H17

(a) (b)
0.02 0.04 0.06 0.08 0.10 0.12

0 0.00

Concentration (%)

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Bancrofts Rule
The emulsifier stabilizes the emulsion type where the continuous phase is the medium in which it is most soluble.

A hydrophilic solute in an O/W emulsion.

A hydrophilic solute in a W/O emulsion.

The long tail on the surfactant is to represent the longer range interaction of a hydrophilic molecule through water.
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The HLB Schema

Variation of type and amount of residual emulsion with HLB number of emulsifier.

Optimum
O /W

Emulsion
breaker

for O/W

Volume and type of emulsion

10

HLB

W /O

Optimum
for W/O

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HLB Scale
Lipophilic End of Scale
Stearane Steric Acid Sodium Stearate Sodium Laurate

Hydrophilic end of scale Sucrose Sodium Sulfate

Soluble in oil; insoluble in water Nonspreading on water substrate

Soluble in oil; insoluble in water Spreads on water substrate

Soluble in oil; and in hot water Spreads on water substrate

Slightly oilsoluble; soluble in water Reduces surface tension of aqueous solutions Reduces interfacial tension at oil water interface

Insoluble in oil; soluble in water Does not affect the surface tension in aqueous solution Does not affect interfacial tension at oil water interface Does not stabilize emulsions

Insoluble in oil; soluble in water Increases surface tension in aqueous solution

Does not affect interfacial tension at oil water interface

Reduces interfacial tension at oil water interface

Reduces interfacial tension at oil water interface

Increases interfacial tension at oilwater interface

Does not stabilize emulsions

Stabilizes water in oil emulsions 1 ___________

Stabilizes either type of emulsion HLB Scale

Stabilizes oil in water emulsions

20 ___________

Decreases the stability of emulsions

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Phase inversion temperature

30oC 40oC 50oC 60oC 70oC 75oC 80oC 90oC 100oC

Water
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Emulsion
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Oil
www.bias-net.com/chimica/pdf/set_baglioni.pdf

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HLB and the Phase Inversion Temperature

16

HLB number (at 25oC)

12

Cyclohexane/Water

Water/Cyclohexane

0 0 30 60 90 120

Phase Inversion Temperature (oC)

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Particles as emulsion stabilizers

Liquid 1 (oil)
r h

Liquid 2 (water)
Almost all particles are only partially wetted by either phase. When particles are adsorbed at the surface, they are hard to remove the emulsion stability is high. Crude oil is a W/O emulsion and is old!!
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Polymer Adsorption

Lost: polymer -solvent solvent - solid Gained: polymer solid solvent - solvent

+
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Drago E and C Parameters for a Variety of Molecular Bases

Bases Pyridine Ammonia Methylamine Dimethylamine Trimethylamine Ethylamine Diethylamine Triethylamine Acetonitrile p-Dioxane Tetrahydrofuran Dimethyl sulfoxide Ethyl acetate Methyl acetate Acetone Diethyl ether Isopropyl ether Benzene p-Xylene Cb 13.09 7.08 11.41 17.85 23.6 12.31 18.06 22.7 2.74 4.87 8.73 5.83 3.56 3.29 4.76 6.65 6.52 1.452 3.64 Eb 2.39 2.78 2.66 2.33 1.652 2.80 1.771 2.03 1.812 2.23 2.00 2.74 1.994 1.847 2.018 1.969 2.27 1.002 0.851

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Drago E and E Parameters for a Variety of Molecular Acids

Acids Iodine Iodine monochloride Thiophenol p-tert-Butylphenol p-Methylphenol Phenol p-Chlorophenol tert-Butyl alcohol Trifluoroethanol Pyrrole Isocyanic acid Sulfur dioxide Antimony pentachloride Chloroform Water Methylene chloride Carbon tetrachloride Ca 2.05 1.697 0.405 0.791 0.826 0.904 0.978 0.614 0.922 0.603 0.528 1.652 10.49 0.325 0.675 0.02 0.00 Ea 2.05 10.43 2.02 8.30 8.55 8.85 8.88 4.17 7.93 5.19 6.58 1.88 15.09 6.18 5.01 3.40 0.00

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Adsorption of PMMA on Silica

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Gutmann Acceptor-Donor Numbers

Acidic Solvents Hexane (reference solvent) Diethyl ether Tetrahydrofuran Benzene Carbon tetrachloride Diglyme Glyme HMPA Dioxane Acetone N-Methyl-2-pyrrolidinone DMA Pyridine Nitrobenzene Benzonitrile DMF Dichloroethane carbonate PDC CH3CN DMSO Methylene chloride Nitromethane Chloroform Isopropyl alcohol Ethyl alcohol Formamide Methyl alcohol Acetic acid Water CF3COOH CH3SO3H SbCl5 as ref. in DCE

kcal mol-1

AN

Basic Solvents 1,2-Dichloroethane Benzene Sulfuryl chloride Thionyl chloride Acetyl chloride Tetrachloroethylene carbonate Benzoyl fluoride Benzoyl chloride Nitromethane Dichloroethylene carbonate Nitrobenzene Acetic anhydride Phosphorous oxychloride Benzonitrile Selenium oxychloride Acetonitrile Sulfolane (tetramethylene sulfone) Dioxane Propanediol 1,2-carbonate Benzyl cyanide Ethylene sulfite Isobutyronitrile Propionitrile Ethylene carbonate Phenylphosphonic difluoride Methyl acetate n-Butyronitrile Acetone Ethyl acetate Water Phenylphosphonic dichloride Diethyl ether

kcal mol-1

DN

Basic Solvents Tetrahydrofuran Diphenylphosphonic chloride Trimethyl phosphate Tributyl phosphate Dimethoxyethane Dimethylformamide N-Methyl-2-caprolactam N-Methyl-2-pyrrilidinone N,N-Dimethylacetamide Dimethyl sulfoxide N,N-Diethylformamide N,N-Diethylacetamide Pyridine Hexamethylphosphoramide Hydrazine Ethylenediamine Ethylamine Isopropylamine tert-Butylamine Ammonia Triethylamine

kcal mol-1

DN

0 3.9 8.0 8.2 8.6 9.9 10.2 10.6 10.8 12.5 13.3 13.6 14.2 14.8 15.5 16.0 16.7 18.3 18.9 19.3 20.4 20.5 23.1 33.5 37.1 39.8 41.3 52.9 54.8 105.3 126.3 100

0.1 0.1 0.4 0.7 0.8 2.3 2.3 2.7 3.2 4.4 10.5 11.7 11.9 12.2 14.1 14.8 14.8 15.1 15.1 15.3 15.4 16.1 16.4 16.4 16.5 16.6 17.0 17.1 18.0 18.5 19.2

20.0 22.4 23.0 23.7 24 26.6 27.1 27.3 27.8 29.8 30.9 32.2 33.1 38.8 44.0 55.0 55.5 57.5 57.5 59.0 61.0

W.B. Jensen The Lewis Acid-Base Concepts: An Overview Wiley-Interscience: NY; 1980

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Common Polymeric Stabilizers

Aqueous dispersions
Anchor polymer
Polystyrene Poly(vinyl acetate) Poly(methyl methacrylate) Poly(acrylonitrile) Poly(dimethylsiloxane) Poly(vinyl chloride) Poly(ethylene) Poly(propylene) Poly(lauryl methacrylate)

Stabilizing moieties
Poly(oxyethylene) Poly(vinyl alcohol) Poly(acrylic acid) Poly(methacrylic acid) Poly(acrylamide) Poly(vinyl pyrrolidone) Poly(ethylene imine) Poly(vinyl methyl ether) Poly(4-vinylpyridine)

Nonaqueous dispersions
Anchor polymer
Poly(acrylonitrile) Poly(oxyethylene) Poly(ethylene) Poly(propylene) Poly(vinyl chloride) Poly(methyl methacrylate) Poly(acrylamide)

Stabilizing moieties
Polystyrene Poly(lauryl methacrylate) Poly(12-hydroxystearic acid) Poly(dimethylsiloxane) Poly(isobutylene) Cis-1,4-poly(isoprene) Poly(vinyl acetate) Poly(methyl methacrylate) Poly(vinyl methyl ether)

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Sources of surfactants

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Surfactant Companies
1. Surfactant Producers 3M Corp. Air Products And Chemicals, Inc. Akzo Nobel Surfactants America Albemarle Corp. Arizona Chemical BASF Corp. BFGoodrich Personal Care (Noveon) CK Witco (Crompton) Clariant Corporation The Cognis Group Croda Inc. DeForest Enterprises, Inc. The Dow Chemical Co. Dow Corning DuPont EAC Chemicals Ethox Chemicals Goldschmidt AG (Degussa) Henkel KGaA (The Henkel Group) Heterene Inc. Huntsman Corp. ICI in North America Jeneil Biosurfactant Company Lambent Technologies Libra Chemicals Ltd LidoChem, Inc. Lonza Inc. MacDermid, Inc. McIntyre Group Ltd. Montello Inc. National Starch and Chemical Company Nikko Chemicals Novo Nordisk A/S Petroferm, Inc. PILOT Chemical Company Procter & Gamble Chemicals Rhodia Rohm and Haas Shell Chemical Stepan Co. Taiwan Surfactant Co. Tomah Products, Inc. Uniqema

2. Surfactant Distributors Barton Solvents The M.F. Cachat Company Casey Chemicals Dawn Chemical Corp. New Life Chemical & Equipment Norman, Fox & Co. Novo Pacific Corp. Schibley Chemical Company Spectrum Laboratory Products, Inc. Surfactants, Inc. Thornley Company Van Waters & Rogers (Vopak USA)

For this and other information, visit the Surfactants Virtual Library (http://www.surfactants.net/).

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Dispersants

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Typical Entries

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McCutcheons Handbook

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Typical Entry

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Chemcyclopedia

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Typical Page

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Bibliography for Surfactants

Becher, P., Ed. Encyclopedia of emulsion technology, Vol. 1 Basic Theory, 1983; Vol. 2 Applications, 1985; Vol. 3 Basic theory, measurement, applications, 1988; Vol. 4, 1996; Marcel Dekker: New York. Conley, R.F. Practical dispersion: A guide to understanding and formulating slurries; VCH Publishers: New York; 1996. Flick, E. W. Industrial surfactants; Noyes Publications: Park Ridge, NJ; 2nd ed. 1993. Karsa, D.R., Ed. Industrial applications of surfactants II; Roy. Soc. Chem.: Cambridge; 1990. Laughlin, R.G. The Aqueous phase behavior ofsSurfactants; Academic Press: New York; 1994. McCutcheon's: Emulsifiers & Detergents, American Edition, MC Publishing: Glen Rock, NJ; (An annual publication.) Mukerjee, P.; Mysels, K.J. Critical micelle concentrations of aqueous surfactant systems; Nat. Stand. Ref. Data Ser., 36; U.S. Government Printing Office: Washington, DC; 1971. Nelson, Jr., RD. Dispersing powders in liquids; Elsevier Publishing: New York; 1988. Rosen, M.J. Surfactants and interfacial phenomena; John Wiley & Sons: New York; 1st ed, 1978; 2nd ed., 1989. Schwuger, M.J., Ed. Detergents in the environment; Marcel Dekker; New York; 1997. Shinoda, K.; Nakagawa, T.; Tamamushi, B-I; Isemura, T. Colloidal surfactants, Some physicochemical properties; Academic Press: New York; 1963. Shinoda, K., Ed. Solvent properties of surfactant solutions; Marcel Dekker: New York; 1967. Shinoda, K.; Friberg, S. Emulsions and solubilization; John Wiley & Sons: New York; 1986. Tanford, C. The hydrophobic effect: Formation of micelles and biological membranes; John Wiley & Sons: New York; 1980.

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