J Solution Chem (2010) 39: 743–745
DOI 10.1007/s10953-010-9529-6
Response to: “Comments on ‘Ideal Behavior of Water
Solutions of Strong Electrolytes and Non-electrolytes
at High Concentrations’ by A.A. Zavitsas {Journal
of Solution Chemistry 39, 301–317 (2010)}”
by A. Apelblat
Andreas A. Zavitsas
Received: 14 April 2010 / Accepted: 16 April 2010 / Published online: 8 May 2010
© Springer Science+Business Media, LLC 2010
Apelblat and I agree that “non-ideality is often reduced to deviations from Raoult’s law.”
He also agrees that my treatment of the experimental data produces results consistent with
Raoult’s Law and “fulfills the purpose very satisfactorily.” He also states “However, if the
activity coefficient γ
1
(x
1
) is identically equal to unity for any x
1
, this does not mean that
the system is thermodynamically ‘ideal’ but only indicates the possibility of compensation
between the enthalpy and entropy terms as often is observed in organic mixtures.” Granting
that such fortuitous, but exact, compensation is conceivable so that the activity of water is
equal to unity over wide ranges of concentration, one has to consider the probability that
such fortuitous exact compensation occurs with every single one of the numerous cases
I have treated. It would seem unlikely that such lucky coincidence would occur in every
single case. Referring to organic mixtures that can show such compensation occasionally is
not relevant to solutions of table salt in water.
I certainly agree with Apelblat that “the hydration number is a rather inadequately defined
quantity.” This is why very different hydration numbers are obtained by different techniques,
e.g., diffraction studies (neutron diffraction, X-ray diffraction, EXAFS, etc.), dielectric re-
laxation, diffusion coefficients, electrostriction, spectroscopic measurements (IR, NMR),
colligative properties, molecular dynamics simulations, ion-water gas-phase clusters, etc.
This is emphasized in my article. To avoid confusion, I felt it appropriate to give H
T
some
kind of a different name. I gave it the designation “thermodynamic hydration number” not
to indicate that it is “more worthy and certain” than other hydration numbers, but because
H
T
values agree remarkably well with the number of water molecules adhering to the solute
by binding energies greater than about 56 kJ·mol
−1
. There was no attempt on my part to
imply that H
T
is better than “hydration numbers” reported by others, as Apelblat seems
to suggest. Apelblat asserts that it would be “strange” if we start calling hydration num-
bers “ ‘ultrasound’ hydration number” or “ ‘spectroscopic’ hydration number”, etc. Doing
A.A. Zavitsas ( )
Department of Chemistry and Biochemistry, Long Island University, University Plaza, Brooklyn,
NY 11201, USA
e-mail: zavitsas@liu.edu