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Stability of Microemulsions
Why are microemulsions thermodynamically stable?*
Gm
emulsion formation
+ve
D C
0
R*
Unstable
B A
Stable
Gm*
Gm = G1 + G2 + G3 - TS
-ve
Gm < 0 for A & B in certain R range microemulsion formation in that R range NOTE: Microemulsions form spontaneously only when IFT is small. (order of 10-3 mN/m)
*
Formation of Microemulsions*
G m = G1 + G 2 + G3 T S
Oil
Gm = free energy change for microemulsion formation G1 = free energy change due to increase in total surface area G2 = free energy change due to interaction between droplets G3 = free energy change due to adsorption of surfactant at the oil/water interface from bulk oil or water S = increase in entropy due to dispersion of oil as droplets
Proper selection of chemicals in formulating the surfactant slug. Surfactant formulation- surfactant, alcohol and brine with or without added oil. Correlation between interfacial tension and interfacial charge.
salinity Oil chain length Alcohol conc. Parameter increasing Temperature Total surfactant brine/oil ratio surfactant/oil ratio molecular Wt. of surfactant
Multiphase microemulsions A variety of phases can exist in equilibrium with each other.
Interfacial Tension
Interfacial tension
Partition coefficient
NaCl concentration
Effect of salinity on interfacial tension and partition coefficient. Minimum in ultra low interfacial tension occurs when the concentration of the surfactant monomers in aqueous phase is maximum.
Oil
Middle phase microemulsion behaves like a water continuous system with respect to the effect of counterions.
Solubilization
For middle phase microemulsion, 1 mol CaCl2 16-19 moles of NaCl and for oil-external microemulsions, 1 mol CaCl2 4 moles of NaCl Values of optimal salinity : LiCl > NaCl > KCl > NH4Cl At phase inversion, partition coefficient is near unity. Repulsion forces between micelles decreases due to the neutralization of surface charge of micelles by counterions.
Even at very low surfactant concentration, microscopic amount of middle phase remains. Oil recovery maximum near the optimal salinity of the system.
Interfacial tension
For high salinity reservoirs, mixed surfactants are promising for enhanced oil recovery.
Transient Processes
At optimal salinity
Fastest coalescence occurs Minimum in pressure jump Minimum in apparent viscosity
NaCl conc.
t=0.5 min
t=25 min
t=5 min
t=60 min
t= 10 min
t=90 min
The flattening time reflects the rate at which surfactant molecules accumulate at the oil-brine interface. Flattening time decreases drastically in the presence of alcohol.
De-Emulsification
Cotton, wool, glass fibers and teflon to promote coalescence Addition of acid/base neutralizes the particle charge and leads to coagulation Application of high voltages Heating of emulsion.
Surfactant Hydrocarbon Aqueous phase phase phase Microemulsion CTAB + I 1-butanol Microemulsion CTAB + II 1-butanol Weight fraction 29.25% n-octane (Y,Ba,Cu) nitrate soln. (0.3 N) Ammonium oxalate soln. (0.45 N) 11.33%
n-octane
59.42%
Drug
Oil
Water
Fatty Acid
1) Control
2) Bupivacaine
3) Bupivacaine + ME