Chemistry Reference
In-Depth Information
is less than for dioxane, but the disfavored mutual interactions, δ
x
′
WS
(min) = -0.045
near
x
S
= 0.35, are about the same as for this ether.
Formic
,
acetic
,
and
propanoic acids
(Figure 3.6).
The KBIs are inaccurate for
the formic acid system outside the range 0.1 ≤
x
S
≤ 0.9 due to the quality of the data.
Within this range, mutual association is favored, δ
x
′
WS
(max) = 0.033 near
x
S
= 0.15,
0.50
0.50
0.30
0.30
0.10
0.10
-0.10
-0.10
-0.30
-0.30
-0.50
-0.50
-0.70
0.00
0.20
0.40
0.60
0.80
1.00
0.00
0.20
0.40
0.60
0.80
1.00
x
(Formamide)
x
(N-Methylformamide)
0.50
0.50
0.30
0.30
0.10
0.10
-0.10
-0.10
-0.30
-0.30
-0.50
-0.50
0.00
0.20
0.40
0.60
0.80
1.00
0.00
0.20
0.40
0.60
0.80
1.00
x
(N-Methylacetamide)
x
(N, N-Dimethylformamide)
0.50
0.70
0.50
0.30
0.30
0.10
0.10
-0.10
-0.10
-0.30
-0.30
-0.50
-0.50
0.00
0.20
0.40
0.60
0.80
1.00
0.00
x
(CH
3
COOH),
x
(CH
3
CH
2
COOH)
0.20
0.40
0.60
0.80
1.00
x
(HCOOH)
FIGURE 3.6
Volume-corrected preferential solvation parameters
δ
x
′
WW
(
●
) for water-water
interactions and
δ
x
′
WS
(
▲
) for water-solute interactions in the first solvation shell of aque-
ous mixtures with solutes identified in the label of the abscissa. (From Y. Marcus, 2001,
Preferential Solvation in Mixed Solvents, Part 10, Completely Miscible Aqueous Co-Solvent
Binary Mixtures at 298.15 K,
Monatshefte für Chemie
, 132, 1387, by permission of the pub-
lisher, Springer.)
