5972
Langmuir 1996, 12, 5972
Correlation between Lewis Acid-Base Surface Interaction Components and Linear Solvation Relationship Solvatochromic R and β Parameters L.-H. Lee* Langmuir 1996, 12, 1681-1687. On p 1682, all GijAB should be ∆GijAB. The corrected section reads as follows: By the VCG’s approach, the intrinsic asymmetry (or complementarity) of the two molecules should be taken into account for the acid-base interactions or hydrogen bonding, and the geometric mean rule can also be applied to the acid-base components of the free energy of interaction ∆GijAB and the maximum work of adhesion WijAB between the i and the j phases. Thus,
∆GijAB ) -WijAB ) -2[(γi-γj+)1/2 + (γi+γj-)1/2] (5) Hence, the free energy of interaction and the maximum work of adhesion for a polar system becomes
∆Gij ) -Wij ) -2[(γilwγjlw)1/2 + (γi-γj+)1/2 + (γi+γj-)1/2] (6) Since ∆GijAB can also be derived from the Dupre´ equation
∆GijAB ) γijAB - γiAB - γjAB the interfacial tension γijAB can be expressed as
γijAB ) 2[(γi+γi-)1/2 + (γj+γj-)1/2 - (γi-γj+)1/2 (γi+γj-)1/2] (7) or
γijAB ) 2[(γi+)1/2 - (γj+)1/2][(γi-)1/2 - (γj-)1/2]
(8)
Finally, for a polar system, Young-Good-GirifalcoFowkes equation becomes
γlv(1 + cos θe) ) 2[(γiLWγjLW)1/2 + (γi-γj+)1/2 + (γi+γj-)1/2] (9) N,N-Diethyl-4-nitroaniline was mistakenly not labeled as compound 1. The appropriate paragraph from section 2.2 is shown below: In addition to R and β, the third parameter24 Π* is derived from solvent effects on Π-Π* absorptions of seven primary probe molecules (preferentially nitroaromatics). For example, the UV/vis spectrum of N,N-diethyl-4nitroaniline (1),20b a nonprotonic indicator in non-HBA solvents, is shifted bathochromatically (red) with increasing dipolarity of the solvent. From the Frank-Condon principle, the ground state and excited electronic states occupy the same volume. Thus, the solvent effect on the wavenumber ν (in 1000 cm-1) of the longest wavelength absorption (Π f Π*) peak of a dilute solution depends on Π*. For this case, the expression is given as
ν(1)max ) 27.52 - 3.18Π* (103 cm-1)
(11)
In general, the actual Π* is the mean value of the Π* values for several probes.27 Values of Π* of “select solvents”, nonchlorinated, nonprotonic, aliphatic solvents with a single dominant bond dipole, have been shown to be generally proportional to molecular dipole moments.20b LA9609377
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