Calorimetric measurements were conducted on aqueous solutions of sodium alkyl sulfates (SC
nS; H(CH
2)
nOSO
3Na,
n = 5–13) at 298.15 K. The solute partial molar enthalpy,
Hs, was evaluated referred to infinitely diluted state and compared for the SC
nS homologues. At low concentrations, the
Hs increased with the molality
m until the critical micelle concentration (CMC) was reached. In the concentration range between the CMC and about three times the CMC, the
Hs decreased with increasing log
m:
Hs = (17.9 - 1.8
n) - 14/(
n-4.6) log
m. The
Hs observed at the CMC was taken as the enthalpy of micelle formation, Δ
Hm, which was expressed as Δ
Hm / kJ mol
–1 = 21.3 - 1.7
n for SC
nS with
n from 7 to 13. The Gibbs energy of micelle formation, Δ
Gm, was estimated from the CMC values: Δ
Gm / kJ mol
–1 = 0.2 - 3.1
n. The entropy of micelle formation, Δ
Sm, was calculated as
TΔ
Sm / kJ mol
–1 = 21.1 + 1.4
n. The large positive entropy term was the driving force for micelle formation. An attempt was also made to calculate the concentration dependence of
Hs for SDS (SC
12S) from the concentrations and the apparent molar enthalpies estimated for the sodium ion, dodecyl sulfate ion, and the micelles.
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