Table Of ContentWATER IN BIOLOGICAL SYSTEMS
STRUKTURA I ROL' VODY V ZHIVOM ORGANIZME
CTPYKTYPA VI POJlb BOllbI B )f{VlBOM OprAHVl3ME
WATER IN
BIOLOGICAL SYSTEMS
Volume 2
Edited by M. F. Vuks and A. I. Sidorova
Trans lated from Russian
®S PRINGER SCIENCE+BUSINESS MEDIA, LLC 1971
The present volume comprises the translation of selected papers from Volumes 1 and
2 of Struktura i Rol' Vody v Zhivom Organizme, the original Russian editions of
which were published in 1966 and 1968 by Leningrad University Press, The English
translation is published under an agreement with Mezhdunarodnaya Kniga, the
Soviet book export agency.
CTPYKTYPA VI POJlb BOD.bl B )f{VlBOM OprAHVl3ME
M. CP. BYKC, A. H. CUaOpoBa
Library of Congress Catalog Card Number 69-12513
ISBN 978-1-4757-6957-9 ISBN 978-1-4757-6955-5 (eBook)
DOI 10.1007/978-1-4757-6955-5
© 1971 Springer Science+Business Media New York
Originally published by Plenum Publishing Corporation, New York in 1971
All rights reserved
No pat of this publication may be reproduced in any
form without written permission from the publisher
CONTENTS
Concentration Fluctuations and Their Influence on Sound Absorption
V. P. Romanov and V. A. Solov' ev. . . . . . . . . . . . ... 1
Spectrum of Aqueous Urea Solutions in the Near-Infrared Region
I. N. Kochnev, L. V. Moiseeva, and A. I. Sidorova .... 12
Influence of the Effective (Local) Light-Wave Field on the Infrared
Absorption Spectrum of Liquid Water in Vicinity of the
Valence-Vibration Band
V. M. Zolotarev and N. G. Bakhshi ev. . . . . . . . . . . . . . 15
Raman Spectra of Water, Saturated Aqueous Electrolyte Solutions,
and Ice Crystals
Z. A. Gabrichidze ......................... . 19
The Germanium- Water Interface
V. M. Zolotarev ..... . 26
State of Water in Certain Perchlorate Crystal Hydrates Formed by
Elements of Periodic Group II
T. G. Balicheva and T. I. Grishaeva . . . . . . . . . . . . . . 30
Investigation of Aqueous Nonelectrolyte Solutions by the Spin Echo Method
Yu. I. Neronov and G. M. Drabkin .................... . 39
Temperature-Related Changes in the Infrared Absorption Spectrum of Water
in the Cerebral and Muscle Tissues of the Frog
A. I. Sidorova and A. I. Khaloimov .................. . 43
A Mass-Spectrometric Study of Disturbances of Water Exchange through
the Pulmonary Barrier in Animals
L. A. Kachur and A. N. Shutko . . . . . . . . . . . . . . . . . . . . . . . 47
Possible Role of Water in Neuromuscular Excitation
Yu. V. Dubikaitis and V. V. Dubikaitis ..... 51
Two-Structure Model and the Heat Capacity of Water
Yu. P. Syrnikov ...... , ............. . 56
Study of the Structural Characteristics of Water from the Infrared
Absorption Spectra of Aqueous Acetonitrile Solutions
B. N. Narziev and A. I. Sidorova ................ . 60
Concentration-Related Changes in the Spectra Characteristics of the
Libration Band of Liquid Water in Acetonitrile and Acetone Solutions
A. I. Sidorova and L. V. Moiseeva. . ........... . 68
v
vi CONTENTS
Investigation of Aqueous Electrolyte Solutions by the Deflected Total
Internal Reflection (DTIR) Method
L. V. Ivanova and V. M. Zolotarev ................ . 72
Concentration Fluctuations and Light Scattering in Aqueous Solutions of
Propyl Alcohols
M. F. Vuks, L. 1. Li snyanskii, and L. V. Shurupova . . . . . 79
Interpretation of the Spectrum of Ice and Water in the Valence- and
Deformation-Vibration Regions
B. A. Mikhailov and V. M. Zolotarev. . . . . . . . ...... . 83
Chemical Proton Shifts in H20 - D20 Solutions
V. M. Vdovenko, Yu. V. Gurikov, and E. K. Legin 89
Self-Diffusion in Aqueous Solutions of Amino Acids, Peptides, and Proteins
L. K. Altunina, 0. F. Bezrukov, N. A. Smirnova, I. A. Moskvicheva,
and V. p. Fokanov . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
Use of Infrared Absorption Spectroscopy to Investigate the Influence on Water
Structure of a Number of Compounds with a Protective Action during Freezing
of Human Erythrocytes
A. 1. Sidorova and A. I. Khaloimov ....... : .......... . 104
Accessibility of Water in Muscle Fibers to Molecules of Different Sizes
N. N. Nikol'skii .......................... . 106
Calculation of Binary Distribution Functions and Thermodynamic
Characteristics of Aqueous Solutions of Strong Electrolytes
by the Monte Carlo Method
P. N. Vorontsov-Vel'yaminov and A. M. EI'yashevich. 111
CONCENTRATION FLUCTUATIONS AND
THEIR INFLUENCE ON SOUND ABSORPTION·
v. P. Romanov and V. A. Solov'ev
Maxima are usually observed in the curves representing ultrasound absorption as a func-
tion of concentration for mixtures of associated liquids, particularly aqueous solutions of sub-
stances with polar molecules [1]. They are due to relaxation processes caused by molecular
association. A qualitative interpretation of this type was proposed by Bazhulin and Merson (2]
in 1938. Attempts at a quantitative calculation of the additional absorption caused by associ-
ation have been made on the basis of the quasi-chemical model, treating the associates as mole-
cules of strictly defined stoichiometric composition [2-5]. This theory is a good approximation
if saturated bonds are formed between the molecules. It can be used only for very rough esti-
mates if the composition of the associate has not been unambiguously determined, and detailed
conclusions drawn from it are totally invalid.
Another possible approach to description of association processes lies in representing the
associates as regions of altered concentration, or concentration fluctuations. This model is
better justified when saturated bonds are absent, since it deals with associates of any composi-
tion. The fact that it cannot be used for a detailed description of the short-range ordering must
be regarded as a drawback. Conversely, the quasi-chemical model only permits consideration
of the short-range ordering and then on the basis of very arbitrary assumptions regarding its
character. The actual pattern should lie between these two models.
This paper is an attempt to calculate sound absorption in mixtures on the basis of the
theory of associates as concentration fluctuations. Vuks and Lisnyanskii [6,7] hypothesized
that there is a relationship between anomalous absorption and concentration fluctuations and
called attention to the correlation between sound absorption and light scattering in solutions.
In articles devoted to sound absorption in the critical region, Fixman [8,9] considered
absorption in fluctuations with the aid of a strict method of correlative distribution functions.
He took into account two energy-dissipation mechanisms: 1) by thermal conduction between
regions with different densities or concentrations (similar to the Ziner-Isakovich mechanism);
2) by diffusive concentration redistribution under the influence of the change in temperature in
the sound wave. It can be demonstrated that the contribution made to absorption by the first
effect is small, at least in regions not overly close to the critical region [10 J. In dealing with
the second effect, Fixman investigated only the influence of temperature on fluctuations and did
not give consideration to the influence of pressure. Moreover, Fixman's calculations cannot
* Translated from Struktura i Rol' Vody v Zhivom Organizme, 1:36-48 (1966).
1
2 V.P. ROMANOV AND V.A. SOLOV'EV
withstand direct comparison with experimental data. It should be noted that the problem of the
applicability of Fixman's theory outside the critical region requires special investigation.
The process of sound absorption in a solution can be represented in the following manner.
During passage of a sound wave, the density p and temperature T in each element of the solution
volume undergo periodic changes. Since the average magnitude of the concentration fluctuations
depends on p and T, it should also vary, in turn causing fluctuations in the excess energy E and
pressure p. However, the change in fluctuation magnitude is not instantaneous, being governed
by the diffusion rate. There is therefore a phase shift between the change in p and p, which
should lead to sound absorption.
In order to take into account the influence of fluctuations on sound propagation, the fol-
lowing additional relationships must be introduced into the system of acoustic equations: 1)
expressions for the thermodynamic functions representing the influence of the inhomogeneous
concentration distribution; 2) equations describing the change in the average fluctuation with
time.
The influence of fluctuations has often been considered in connection with the theories
of light scattering and critical opalescence [8,11,12,13,23], proceeding from hypotheses regard-
ing thermodynamic functions "at a point." This is not wholly consistent and, in addition, the
coefficients of the gradient terms (see below) are usually introduced formally, which hinders
discussion and evaluation. Debye [131 considered the gradient terms on the basis of a molecu-
lar model, but he made certain limiting assumptions. We will use the most general method of
correlative distribution functions, neglecting only the molecular orientation.
I
A liquid with an inhomogenous concentration distribution is in a nonequilibrium state.
According to the general rule of the thermodynamics of irreversible processes [14], the thermo-
dynamic functions for this state are identical to those for the analogous state brought to equi-
librium by an appropriate potential. Since the instantaneous concentration-distribution pat-
tern can always be expanded into a Fourier series, it is sensible to take the sine potential
uA=Asin/x, uB=-Bsln/x, (1)
where uA and uB are the potential energies of molecules of types A and B respectively and / is
the wave number. We will assume cyclic boundary conditions.
The concentration fluctuations are isobaric, since pressure inhomogeneities are usually
dissipated very rapidly (at the speed of sound). We must therefore impose on the potential in
Eq. (1) the condition that the total force acting on an element of the solution volume equals zero:
ANA BNB
-v-=-V-,
where NA and NB are the numbers of particles of types A and B in a macroscopic volume V.
The configuration integral for a solution in field (1) is
(2)
Expanding Eq. (2) into a series for powers NkT and B/kT and limiting ourselves to the quadra-
tic terms, we obtain
CONCENTRATION FLUCTUATIONS AND THEIR INFLUENCE ON SOUND ABSORPTION 3
Z* =Zo {I - ~A kAJ S[ Ff (r)-Ff (r)] slnj xdr + ~~ (:r rS [ Ff (r) + Ff (r)] sln2 j xdr+
(3)
Here Zo is the configuration integral of the unperturbed medium,* while Ft. Ft F~~ F{~
and F{-B are the first- and second-order correlative functions in the unperturbed medium [15,16],
which are defined by equations of the type
(4)
The linear term in Eq. (3) disappears, since F1 F~ == 1. The integral containing sin2jx
is readily calculated. The variables
must be substituted into the latter term. Introducing the function
we obtain
Z* = Zo { 1 + 4NV~(k AT2P [NVA + NVB + S[ '1AA (r)+~BB(r)-2vAB(r)] cos! x dr ]} . (5)
In view of the fact that the correlation functions vAA' v BB ' and vAB disappear at large r,
we expand cosjx into a series and limit ourselves to the quadratic term. Then
(6)
Here
12 = ---,,-----::f_"_r;-
V;2 _dr_-V;- ;-_ (7)
S' 1dr+ NA + N8
The function v in Eq. (7) reverts to zero if the correlation between the positions of the
heterogeneous molecules is the same as the average correlation in the pure components. It can
therefore be termed the true correlation function of the solution. The value of 1 reflects the
ordering distance, although it cannot, strictly speaking, be called the correlation radius [8].
*Here Zo is the integral over all states of the system, i.e., it actually takes into account all
possible fluctuations. Strictly speaking. we are oalculating not the contribution made to Zo
by the fluctuations but the influence of an addit ional imposed inhomogeneity. Since the fluctu-
ations are small, however, we can identify Zo with the configuration integral for the system
without fluctuations.
4 V.P. ROMANOV AND V.A. SOLOV'EV
The free energy of the solution in the field is
F* = FO- N4V~kAT2 l NVA + NVB + 5~ (r)dr ]( 1 --/62/-2) , (8)
where Fo is the free energy of the homogeneous solution. The value of F'* includes the poten-
tial energy of the molecules in the hypothetical field represented by Eq. (1). The free energy
of the inhomogeneous solution without the field differs from F* by the magnitude of this
potential energy: F = F* - U*. In order to calculate U'*, it is necessary to find the spatial
distribution of the molecules of each solution component. For example, the unary distribution
function for component A in the field is
(9)
As in calculating Z'*, we obtain
(10)
The corresponding expression for F * is found in the same manner. Calculating the potential
Bl
energy
and subtracting it from F'*, we find the free energy of the nonequilibrium solution:
(11)
We must now exclude from Eq. (11) the amplitude of the applied potential A. In order to
do so, we find the concentration distribution from Eq. (10) and the analogous formula for FBr:
(12)
Expressing A in terms of Cf and substituting this into Eq. (11), we finally obtain
VkTNfc}
(13)
The expression in the denominator can be represented in terms of thermodynamic func -
tions. According to the literature [16, 18], the average fluctuations in the number of particles
in solution are defined by the equations
t:.N2 V
SVB B dr = V -? - N .
NB B
