492
24 Water and Aqueous Solutions
flowing water dipoles, which adds a translational/rotational component to the
rotational/translational motion and hence raises the mobility of the dipoles to
promote the micro-circulation of human body fluid and blood.
Regarding the aqueous solutions, we have obtained quantitative information that may
complement to the premises of continuum thermodynamics, molecular dynamics:
(1) H 3 O
+ hydronium formation in acid solution creates the H↔H anti–HB that
serves as a point breaker to disrupt the HX solution network and the surface
stress. The X
− polarization dictates the O:H (from 200 partially to 110 and
300 cm
−1 ) and the H–O phonon (from 3200 to 3480 cm
−1 ) frequency cooperative shift. Acid solvation has the same effect of liquid heating on the O:H–O
bond network and phonon relaxation through, respectively, H↔H fragilization
and thermal fluctuation.
(2) OH
− hydroxide forms the O:⇔:O super–HB point compressor to soften the
nearest solvent H–O bond (from above 3100 cm
−1 to below), and meanwhile,
the solute H–O bond shortens to its dangling radicals featured at 3610 cm
−1 .
The Y
+ polarization effect has been annihilated by the O:⇔:O compression and
the solute H–O contraction. Base solvation has partly the effect of mechanical
compression that lengthens and softens the H–O bond and shortens the O:H
nonbond.
(3) Y
+ and X
− ions serve each as a point polarizer that aligns, stretches, and polarizes
the surrounding O:H–O bonds and makes the hydration shell supersolid. The
polarization transits the ω L from 200 to 100 cm
−1 and the ω H from 3200 to
3480 cm
−1 . Salt solvation has the same effect of molecular undercoordination
to form the supersolid states.
(4) The solute capability of bond transition follows: f H (C) = 0, f Y (C) ∝ f OH (C) ∝ C,
and f X (C) ∝ 1–exp(–C/C 0 ) toward saturation, which indicate the nonparaxiality
of protons, invariant hydration volume size of Y
+ and HO
− , and the variant
X
− –X
− repulsion, respectively, and hence evidence the high structure order
of H 2 O molecular in the solvent matrix. The concentration trends consistent
among the salt solution viscosity, surface stress, and the f YX (C) suggest their
common origin of polarization associated with O:H–O bond transition from
water to hydration shells.
(5) Solvation and compression have the opposite effect on O:H–O relaxation and
the shortened H–O bond by polarization can hardly elongated than the H–O
bond in pure water. At constant concentration, the P C shows the Hofmeister
sequences, but the involvement of the anion-anion repulsion alters the pattern
of the critical pressure for the phase transition for the concentrated salt solutions.
(6) Compression, confinement, and heating compensate one another other on the
critical pressure of phase transition at the ambient as compression always shortens the O:H nonbond while heating and confinement do oppositely in the QS
phase of negative thermal expansion—H–O undergoes liquid heating and compression elongation and O:H contraction but confinement does oppositely. The
Liquid-VI phase boundary is less mechanically stable than the VI-VII boundary
because the involvement of the anion-anion repulsion wakens the local electric
24 Water and Aqueous Solutions
flowing water dipoles, which adds a translational/rotational component to the
rotational/translational motion and hence raises the mobility of the dipoles to
promote the micro-circulation of human body fluid and blood.
Regarding the aqueous solutions, we have obtained quantitative information that may
complement to the premises of continuum thermodynamics, molecular dynamics:
(1) H 3 O
+ hydronium formation in acid solution creates the H↔H anti–HB that
serves as a point breaker to disrupt the HX solution network and the surface
stress. The X
− polarization dictates the O:H (from 200 partially to 110 and
300 cm
−1 ) and the H–O phonon (from 3200 to 3480 cm
−1 ) frequency cooperative shift. Acid solvation has the same effect of liquid heating on the O:H–O
bond network and phonon relaxation through, respectively, H↔H fragilization
and thermal fluctuation.
(2) OH
− hydroxide forms the O:⇔:O super–HB point compressor to soften the
nearest solvent H–O bond (from above 3100 cm
−1 to below), and meanwhile,
the solute H–O bond shortens to its dangling radicals featured at 3610 cm
−1 .
The Y
+ polarization effect has been annihilated by the O:⇔:O compression and
the solute H–O contraction. Base solvation has partly the effect of mechanical
compression that lengthens and softens the H–O bond and shortens the O:H
nonbond.
(3) Y
+ and X
− ions serve each as a point polarizer that aligns, stretches, and polarizes
the surrounding O:H–O bonds and makes the hydration shell supersolid. The
polarization transits the ω L from 200 to 100 cm
−1 and the ω H from 3200 to
3480 cm
−1 . Salt solvation has the same effect of molecular undercoordination
to form the supersolid states.
(4) The solute capability of bond transition follows: f H (C) = 0, f Y (C) ∝ f OH (C) ∝ C,
and f X (C) ∝ 1–exp(–C/C 0 ) toward saturation, which indicate the nonparaxiality
of protons, invariant hydration volume size of Y
+ and HO
− , and the variant
X
− –X
− repulsion, respectively, and hence evidence the high structure order
of H 2 O molecular in the solvent matrix. The concentration trends consistent
among the salt solution viscosity, surface stress, and the f YX (C) suggest their
common origin of polarization associated with O:H–O bond transition from
water to hydration shells.
(5) Solvation and compression have the opposite effect on O:H–O relaxation and
the shortened H–O bond by polarization can hardly elongated than the H–O
bond in pure water. At constant concentration, the P C shows the Hofmeister
sequences, but the involvement of the anion-anion repulsion alters the pattern
of the critical pressure for the phase transition for the concentrated salt solutions.
(6) Compression, confinement, and heating compensate one another other on the
critical pressure of phase transition at the ambient as compression always shortens the O:H nonbond while heating and confinement do oppositely in the QS
phase of negative thermal expansion—H–O undergoes liquid heating and compression elongation and O:H contraction but confinement does oppositely. The
Liquid-VI phase boundary is less mechanically stable than the VI-VII boundary
because the involvement of the anion-anion repulsion wakens the local electric