Addressing Mixed Surfactant

Systems and HLD

Basis for characteristic curvatures of commercial detergents

Michael Taylor Warren

University of Oklahoma
Institute of Applied Surfactant Research
Acosta’s work on
mixed surfactants
• Found that as you increased non-
ionic surfactant concentration the
more hydrophilic the solution
behaved
• Can not really consider temperature
yet.. (refined αmix & its difficult)

• Fitted this behavior to AMA!

• Another equation to use!
• Looking back at Sweta’s and my work..
For anionic-anionics..

Highest error is 15%

How far off is this technique? *PIT work indicates similar trends (mol% > 25)

Largest Cc error for Acosta’s

group is 25% using coalescence
rate.
• (Anionic-Anionic reference
surfactants is 15%)
• Reduce by taking larger
scan(WI-II)**
• How far off is our Cc’s from EACN Scan K CC
Acosta? Surfactant CC Cc a
CcEACNscanb 841s 0.06 -2.4
Acosta’s

Warren’s
PIT Simpl. methodology
S20 4.1 3.5 3.5 1041s 0.06 -2.2
T20 −3.2 −4.4 −7.9 104s 0.08 -2.1
T80 −3.2 −3.0 −3.7 AMA 0.07 -1.5
AOT 0.11 1.5
T80 0.17 -3.7
T21 0.11 -3.2
T20 0.12 -3.1
Zarate‐Muñoz, S. , Texeira de Vasconcelos, F. , Myint‐Myat, K. , Minchom, J. and Acosta, E. (2016), A
TX100 0.15 -2.9
Simplified Methodology to Measure the Characteristic Curvature (Cc) of Alkyl Ethoxylate Nonionic
Surfactants. J Surfact Deterg, 19: 249-263. doi:10.1007/s11743-016-1787-x
AOT 0.4g/100ml
 k Cc S (g/100ml)X Solver
Measured using Surfactant SP* AMA 0.072 -1.5 6.903303 0.9 2.64E-07 USE -4.4E-16
AOT 0.11 1.5 0.431711 0.1 2.64E-07
Solution Guess
0.0758 -1.2 5.232035 1.65

6.1 g/100ml k Cc S (g/100ml)X Solver

AMA 0.072 -1.45 6.566625 0.9 3.99E-07 USE 0
AOT 0.11 1.5 0.431711 0.1 3.99E-07
Solution Guess
0.0758 -1.155 5.001813 1.61
k Cc S (g/100ml)X Solver
AMA 0.072 -1.45 6.566625 0.7 3.46E-07 USE 0
20% AOT 0.11 1.5 0.431711 0.3 3.46E-07
Solution Guess
0.0834 -0.565 2.902001 1.07
k Cc S (g/100ml)X Solver
AMA 0.072 -1.45 6.59954 0.5 0.0025 USE 0.0025
AOT 0.11 1.5 0.431711 0.5 -1.3E-07
Solution Guess0.091 0.025 1.687925 0.52
Nonionic reference surfactants
• “The linear correlations predicted by the HLD
equation, and the linear mixing rule were
confirmed by the high R2 values of the linear
regressions discussed above. However, for
highly hydrophobic or hydrophilic test
surfactants these linear relationships can
break down.”
• We see this too!!
• CC values above/below 3/-3 probably will not behave
ideally
• “In the case of highly hydrophobic surfactants
such as dodecanol and oleic acid (in acidic
media), these surface active species can also
partition into the bulk oil phase (i.e. behaving
like an oil co‐solvent), thus the added molar
fraction into the system may not be equivalent
to the molar fraction at the interface. The
same could occur with a highly hydrophilic
surfactant, but in this case, a good fraction of
the surfactant can act as aqueous co‐solvent,
or at least remain in micelle form, but not
adsorbed at the oil–water interface.” *Warren’s assumed K range for non-ionics: (.1-.2)