Solutes Surface-active solutes Surface-active agents Surfactants Lecture 1

ACS 2007

Adsorption lowers the energy

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

Lowers surface tension.

ACS 2007

Stabilizes dispersions.
1

Lecture 1 - Surfactant science and technology

Adsorption at interfaces

Air-water surface

Air-oil surface

Oil-water interface

Strong adsorption, substantial lowering of surface tension.

Little adsorption, little lowering of surface tension.

Strong adsorption, substantial lowering of interfacial tension.

ACS 2007

Lecture 1 - Surfactant science and technology

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

ACS 2007

= = = = = =

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
Lecture 1 - Surfactant science and technology

Common surfactants

Air/Oil/Solid

Hydrophobic portion

Water

Hydrophilic portion

ACS 2007

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

ACS 2007

Lecture 1 - Surfactant science and technology

Classification of surfactants
Anionic The surface-active portion bears a negative charge
Alkane carboxylic salts (soap) Alkane sulfonic salts (detergents) Alkyl-aromatic sulfonic salts Others: Phosphates, phosphoric salts

Cationic The surface-active portion bears a positive charge Amine salts

Quaternary ammonium salts

Zwitterionic The surface-active portion bears both charges Long-chain amino acid salts
Betaines

Nonionic The surface-active portion contains no charge Long chain ethers

Fatty acid esters Amides
ACS 2007
Lecture 1 - Surfactant science and technology

Nature of hydrophobic group

The variation in chemistry of the hydrophobic group is less pronounced than that of the hydrophilic group:* Straight chain, long alkyl groups (C8 C20) Branched-chain, long alkyl groups (C8 C20) Long chain (C8 C15) alkylbenzene residues Alkylnapthalene residues (C3 and greater) Rosin derivatives High MW propylene oxide polymers Long-chain perfluoroalkyl groups Polysiloxane groups Lignin derivatives.
* Rosen, 3rd ed., p. 4
ACS 2007
Lecture 1 - Surfactant science and technology

Surfactant structure

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

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

ACS 2007

Lecture 1 - Surfactant science and technology

Effect of structure on surface tension

ACS 2007

Lecture 1 - Surfactant science and technology

Dynamic surface tension

70

(mN/m)

60

50

40

30 0 10 20 30 40 50 60 70

Age (msec)

Aerosol OT at 500 mg/l by the vibrating jet.

ACS 2007

Lecture 1 - Surfactant science and technology

10

Adsorption at a solid surface 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

Text p. 334

ACS 2007

Lecture 1 - Surfactant science and technology

11

Where do I start?
Surfactant suppliers providing on-line help
Byk Chemie Schibley Chemical Surfactants, Inc. http://www.byk-chemie.com/gbn/frame.cfm http://www.schibley.com/surfactants.html http://www.surfactantsinc.com/formulary.asp

Surfactant manufacturers providing on-line help

Akzo Nobel Arizona Chemical BASF Cognis DeForest Enterprises Dow Chemicals McIntrye Group Rohm and Haas http://www.akzonobel.com/com/Chemicals/Products.htm http://www.arizonachemical.com/products/ http://www.basf.com/performancechemical/bcperfapplications.html http://www.cognis.de/framescout.html?/BusinessUnits.html http://www.deforest.net/deforest1.htm http://www.dow.com/surfactants/products/ethylene.htm http://www.mcintyregroup.com/productfinder_web.cfm http://www.rohmhaas.com/directory/prototype/search.htm

ACS 2007

Lecture 1 - Surfactant science and technology

12

Micelles and liquid crystals

Surfactants self-associate at higher concentrations

ACS 2007

Lowering of surface tensions with surfactants

sucrose

~0.05% soap

concentration of solute

The surface tension drops but reaches a limit.

ACS 2007
Lecture 1 - Surfactant science and technology

14

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

ACS 2007
Lecture 1 - Surfactant science and technology

15

Surfactants can create their own surface - Micelles

Adsorption and micellization are competing processes.

ACS 2007
Lecture 1 - Surfactant science and technology

16

Solubilization below and above the CMC

Solubility gL x 102

The solubility of gas increases sharply after micelles form (at the CMC).

0 0 1 2 3 4 5 6 7 8 9

Percent potassium laurate

Solubility of 2-nitrodiphenylamine in aqueous solutions of potassium laurate.

ACS 2007

Lecture 1 - Surfactant science and technology

17

Effect of temperature on solubilization for nonionics

Solubilization of n-heptane in 1% aqueous solutions of POE(9.0) nonylphenyl ether (I) and PEO(9.2) dodecylphenyl ether (II). Filled circles are cloud points. Open circles are solubility limits (Rosen, p. 188).
ACS 2007
Lecture 1 - Surfactant science and technology

18

Effect of structure on micelle formation

Interfacial tension (mN/m)

(a)
6

(b)
K
+

The linear molecule (a) forms micelles easily.

K
+

C 16 H33O
-

C 8 H17O

SO 3

CH3

SO 3 OC 8H17

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

The branched molecule (b) does not form micelles so readily and therefore lowers surface tension more.

0 0.00

Concentration (%)

ACS 2007

Lecture 1 - Surfactant science and technology

19

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

Hexagonal Liquid Crystal Surfactant

Neat Phase

Water in between.

Lamellar Liquid Crystal

ACS 2007

Lecture 1 - Surfactant science and technology

20

Phase diagrams can be constructed

(Consider taking the ACS short course on emulsions for much more information.)
ACS 2007
Lecture 1 - Surfactant science and technology

21

Packing parameters
The shape of a surfactant helps determine the shape of any structures formed. V is the volume of the core lc is the length of the surfactant a0 is the cross sectional at the interface
Value of
V l c a0 0 - 1/3 1/3 - 1/2 1/2 - 1 >1

V
lc

a0

Structure of micelle Spheroidal in aqueous media Cylindrical in aqueous media Lamellar in aqueous media Inverse micelles in nonpolar media
Lecture 1 - Surfactant science and technology

ACS 2007

22

Solubility of ionic surfactants The Krafft Point

Note: the rapid increase in apparent solubility of the ionic surfactant at a critical temperature!

Concentration

Crystals

Micelles

CMC curve

Solution Solubility curve Krafft point

Micelles form above this temperature.

Temperature
ACS 2007
Lecture 1 - Surfactant science and technology

23

Adsorption of ionic surfactants

At the air/water interface: At the solid/water interface:

Lowers surface tension.

ACS 2007

Charges the particle and stabilizes the dispersion.

24

Lecture 1 - Surfactant science and technology

Adsorption of nonaqueous surfactants

At the air/oil interface: At the solid/oil interface:

Little effect on surface tension.

ACS 2007

Stabilizes the dispersion.

25

Lecture 1 - Surfactant science and technology

Oil-soluble detergents

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.

ACS 2007

Lecture 1 - Surfactant science and technology

26

Oil surfactants form inverse micelles

The micelle core is highly polar. The diameters are 10s of nanometers.

ACS 2007

Lecture 1 - Surfactant science and technology

27

Adsorption from Solution

Titrate surfactant The moles adsorbed is the total number of moles added minus the concentration in solution after adsorption times the volume of the solution.

Since adsorption is spontaneous, the interfacial energies must be lower.

ACS 2007

Lecture 1 - Surfactant science and technology

28

Langmuir Adsorption Isotherm

Moles adsorbed per gram

nm

n c = nm K + c
nm is called the monolayer capacity and has units of moles per gram of solid.

Equilibrium concentration of adsorbate in solution

K is called the Henrys law constant and is a measure of the solid-adsorbate interaction.

ACS 2007

Lecture 1 - Surfactant science and technology

29

Polymer Adsorption

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

+
ACS 2007
Lecture 1 - Surfactant science and technology

30

Drago E and C Parameters

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

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

ACS 2007

Lecture 1 - Surfactant science and technology

31

Adsorption of PMMA on Silica

ACS 2007

Lecture 1 - Surfactant science and technology

32

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 AN
kcal mol-1

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

DN
kcal mol-1

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

DN
kcal mol-1

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

ACS 2007

Lecture 1 - Surfactant science and technology

33

The solvatochromic scale

XYZ = XYZ 0 + a + b + s * +...

Marcus, Y. The properties of organic liquids that are relevant to their use as solvating solvents. Chem. Soc. Rev., 22, 409-416, 1993. ACS 2007
Lecture 1 - Surfactant science and technology

34

Solvatochromic dyes as acid/base probes

Soukup, R.W.; Schmid, R. Metal complexes as color indicators for solvent parameters. J. Chem. Ed., 62, 459 462, 1985.

ACS 2007

Lecture 1 - Surfactant science and technology

35

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)

ACS 2007

Lecture 1 - Surfactant science and technology

36

Surfactant(SDS) Polymer Interaction

Polymer saturated with surfactant. Apparent CMC.

Onset of surfactant/polymer interaction.

Holmberg et al., p. 278
ACS 2007
Lecture 1 - Surfactant science and technology

37

Surfactant (SDS) Protein Interactions

The effect of gelatin on the surface tension of solutions of SDS (circles) and Triton-X100 (triangles). Without gelatin (filled) and with gelatin (open). For Triton X-100: no interaction with the nonionic. For SDS: a plateau corresponding to a protein/surfactant association.

ACS 2007

Lecture 1 - Surfactant science and technology

38

Reference material

ACS 2007

Lecture 1 - Surfactant science and technology

39

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.

ACS 2007

Lecture 1 - Surfactant science and technology

40

Dispersants

ACS 2007

Lecture 1 - Surfactant science and technology

41

Typical Entries

ACS 2007

Lecture 1 - Surfactant science and technology

42

McCutcheons Handbook

ACS 2007

Lecture 1 - Surfactant science and technology

43

Typical Entry

ACS 2007

Lecture 1 - Surfactant science and technology

44

Chemcyclopedia

ACS 2007

Lecture 1 - Surfactant science and technology

45

Typical Page

ACS 2007

Lecture 1 - Surfactant science and technology

46