ACS 2007
Stabilizes dispersions.
1
Adsorption at interfaces
Air-water surface
Air-oil surface
Oil-water interface
ACS 2007
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:
= = = = = =
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
(OCH2CH2)nOH
Alkanolamides:
HO HO
NCR
Alkylbenzene sulphonates
SO3Na
ACS 2007
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
Zwitterionic The surface-active portion bears both charges Long-chain amino acid salts
Betaines
Surfactant structure
ACS 2007
ACS 2007
70
(mN/m)
60
50
40
30 0 10 20 30 40 50 60 70
Age (msec)
ACS 2007
10
100
80
60
40
20
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
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
ACS 2007
12
ACS 2007
sucrose
~0.05% soap
concentration of solute
14
Detergency
8
Arbitrary units
Interfacial tension
0 0.0 0.2 0.4 0.6
15
16
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
ACS 2007
17
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
(a)
6
(b)
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
19
Surfactant phases
Middle Phase
These terms come from the old soap makers literature. Different liquid crystal phases look different.
Neat Phase
Water in between.
ACS 2007
20
(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
Concentration
Crystals
Micelles
CMC curve
Temperature
ACS 2007
Lecture 1 - Surfactant science and technology
23
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
26
The micelle core is highly polar. The diameters are 10s of nanometers.
ACS 2007
27
ACS 2007
28
nm
n c = nm K + c
nm is called the monolayer capacity and has units of moles per gram of solid.
K is called the Henrys law constant and is a measure of the solid-adsorbate interaction.
ACS 2007
29
Polymer Adsorption
Lost: polymer -solvent solvent - solid Gained: polymer solid solvent - solvent
+
ACS 2007
Lecture 1 - Surfactant science and technology
30
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
31
ACS 2007
32
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
33
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
Soukup, R.W.; Schmid, R. Metal complexes as color indicators for solvent parameters. J. Chem. Ed., 62, 459 462, 1985.
ACS 2007
35
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
36
37
ACS 2007
38
Reference material
ACS 2007
39
ACS 2007
40
Dispersants
ACS 2007
41
Typical Entries
ACS 2007
42
McCutcheons Handbook
ACS 2007
43
Typical Entry
ACS 2007
44
Chemcyclopedia
ACS 2007
45
Typical Page
ACS 2007
46