Colloid chemistry

Lecture 10: Surfactants

Applications of surfactants: cleaning/detergents (40%); textiles; cosmetics; pharmacy; paint; food; etc.

Etymology

Surfactant micelles
surfactant molecule spherical micelle

hydrophobic alkyl chain

self-assembling (association) hydrophilic head group hydrophilic shell hydrophobic core

30-100 molecules d-3-5 nm

cationic surfactant anionic surfactant nonionic surfactant

OSO3-Na+

surfactant = surface active agent

orientation energy minimum Hardy-Harkins principle

Soap molecules/micelles

Hydrophilic ( lyophobic, waterloving) head containing a charged functional group

Hydrophobic ( lyophilic, water-fearing ) tail containing a hydrocarbon chain

If enough soap is added to water the molecules arrange themselves into a structure called a micelle

How are soap produced?

Soaps are produced from complex esters:

animal fat The saponification of a triglyceride

Classification of Surfactants

Classification of Surfactants
Anionic
O O S O-Na+ O
Sodium dodecylsulfate (SDS) +

Cationic

N Cetylpyridinium bromide Br
O O O O Dipalmitoylphosphatidylcholine (lecithin) OCH2CH2N(CH3)3 P OO
+

Zwitterionic

Nonionic

O
Tetraoxyethylene lauryl ether

OH

Micellar shapes

Packing parameter affects micellar shape

Surfactant phases

Surfactants as biocolloids

Surfactants as biocolloids

plasma membranes are primarily lipid bilayers with associated proteins and glycolipids
(cholesterol is also a major component of plasma membranes)

Surfactants as biocolloids

Peptide micelles

Small, viral sized (10-50 nm) particles Similar to lipid micelles Composed of peptide core (hydrophobic part) and PEG shell (hydrophilic part) Peptide core composition allows peptide/protein solubilization Also good for small molecules

Diblock copolymer micelles

PB202-PEO360

molecule

micelle

Solution Properties
cmc

14 12 10 8 6 4 2 0 0

Concentration

unimers

CMC
micelles

Surfactant concentration1
Osmotic pressure

10 8 6 4 2 0 0 log

Surface tension

12
10 8 6 4 2 0 0

14

CMC

CMC

1 (surfactant concentration)

Surfactant concentration1

14 12 10 8 6 4 2 0 0

Molar conductivity

CMC

1 1/2 (Surfactant concentration)

14 12 10 8 6 4 2 0

Light scattering

CMC

Surfactant concentration1

Krafft point; cloud point; cmT

I. Above the Krafft point, the solubility is sharply increases due to the formation of micelles. II. Some surfactants (e.g. poly(ethylene)-poly(ethylene-oxide) = PEPEO = CmEn) - based surfactants) dehydrate and phase separate upon temperature elevation (cloud point). III. For pluronics; poly(propylene-oxide)-poly(ethylene-oxide) = (PPO-PEO) diblock copolymer surfactants, the micelles form as a result of the dehydration of the PEO segments (critical micelle temperature or CMT).

Factors affecting the cmc: molecular structure of the surface active agent

Factors affecting the cmc: effect of additives

HLB of surfactants

HLB and use of surfactants

Amphiphilic surfactants are characterized by the hydrophiliclipophilic balance (HLB): a relative ratio of polar and nonpolar groups in the surfactant HLB ca. 1 to 3: Antifoams / inverse micelles HLB ca. 3 to 8: Water-in-Oil Emulsifiers HLB ca. 7 to 9: Wetting and spreading agents HLB ca. 8 to 16: Oil-in-Water Emulsifiers HLB ca. 13 to 16: Detergents HLB ca. >15: Solubilizers

Griffins scale: it is an arbitrary (group additivity) scale of values serving as a measure of the HLB of surfactants

(polysorbates)

(sorbitan monooleates)

HLB of surfactant blends

Surfactant blends are commonly used to obtain desired emulsifying properties. What is the HLB of the mixture of 40 % Span 60 (HLB = 4.7) and 60 % Tween 60 (HLB = 14.9)? HLB of mixture: 4.7 x 0.4 + 14.9 x 0.6 = 10.8 In what proportion should Span 80 (HLB = 4.3) and Tween 80 (HLB = 15.0) be mixed to obtain required HLB of 12.0? 4.3.(1-x) + 15.x = 12 x = 0.72 72 % Tween 80 and 28 % Span 80

Solubilization
Spontaneous transfer of a compound insoluble in the bulk solvent into solution due to incorporation into the surfactant micelles:
normal micelles non-polar compound reverse micelles polar compound

in polar solvents

amphiphilic compound

in non-polar solvents

Detergency

(contact angle increases)

amount of substance solubilized

K-soap concentration, mol/L

elementary steps of washing

solubilization efficiency of K-soaps

(solubilization capacity: tg )