96

特 集 有機 反応 と高圧 カ
Molecular Theories of Partial Molar Volume

F. Hirata, T. Imai, and M. Irisa

Two main streamsin themoleculartheoriesfor partialmolar volumeare reviewed.The fast stream is based on the
soled particle theory of liquids and its extension to polyatomic molecules;this has been used successfully in
detemmining the solvation freeenergyof non-polarsolutes in water.The secondmethodemploys the Kirkwood-
Buff solution theory. This method is coupledto the integral equationtheoryof molecularliquids to calculatethe
partialmolar volumeof polyatomicmolecules.Thedependenceof the partialmolar volumeon the conformational
changeof butane anda tripeptideis examinedbasedon thesemethods.[partialmolarvolume, scaledparticletheory,
Kirkwood-Buftheory, RISM theory, butane,peptide,water]

1. Introduction general observations tell us that protein denatures by applying

pressure. There are a couple of misunderstandings in the
Increasing attention has been paid to chemical processes statement. First, the excluded volume of the native
under higher pressure from a wide variety of fields in science, conformation is not necessarily the least of all due to 'cavities'
indudiing organic cheanistry [1] and biophysics [2],[3]. The existing inside protein. Secondy, the 'volume' concerned
theoretical study of the response of chemical processes to should not be the 'excluded volume but the partial molar

pressure change requires analyses of the partial molar volume

volume; this is the more essential mistake in the naive
of the chemical species in solution, since the pressure consideration. Partial molar volume is the thermodynamic
dependence of equilibrium constants is closely related to the response of the chemical potential to pressure change, to which

difference •¢ V in the partial molar volumes between reactants many chemical processes contribute. For instance, some

and products, namely [1], residues in protein may dissociate upon denaturing to release
ions, which in turn reduce partial molar volume due to the so
called'electrostriction' of the solvent. If that is the case, protein
(1)
will unfold by applying pressure. Polar residues may
contribute to pressure denaturation in the same manner, if the

If chemical reactions areto be describedby the transition state residues are exposed to solvent upon unfolding. Hydrophobic
theory, even the pressure dependenceof the reaction rate canbe residues may cause a similar condition if the structural

predicted by just analyzing the change in the partial molar modification of the water around the residues is denser, or more
volumes of the species in reactantand transition states, that is, packed, than bulk water. Although it has not been well clarified
yet which effect is most dominant to the pressure denahhration,
it is safe to say that what leads to the pressure denaturation of
(2)
protein is change in the partial molar volume due to the
structural modification of water.
As an example of phenomena which demonstrate the There is a large volume of experimental work devoted to
importance of partial molar volume, let's look at the pressure partial molar volume [1],[5],[6], but relatively few theoretical
denaturation of protein [4]. Pressure denaturation is one of the studies have been reported [7],[8],[91,[10],[11]. In this brief
outstanding properties of protein, which refutes any naive article, we do not attempt a complete review of the subject, but
argument concerning 'volume'. If one just focuses on the confine ourselves to theoretical developments based on the
'exdudbd volume' of protein , a naive argument says that modem statistical mechanics of liquids, to be more specific,
applying pressure should stabilize its native confonnaton, the scaledparticle theory (SPT) [7],[12] andthe Kirkwood Buff
because native conformations usually have the most compact theory of solution coupled with a theory of molecular lidpidls
structure, thereby, the least excluded volume. However, based on the interaction-site model [9],[10],[11],[13]. Wealso

1 Department of Theoretical Study, Institute for Molecular Science, 38 Nishigonaka, Myodaiji, Okazaki 444-8585
2 Department of Functional Molecular Science, The GraduateUniversity for Advanced Studies, 38 Nishigonaka, Myodaiji, Okazaki
444-8585
3 Faculty of Computer Science and Engineering, KyushuInstitute of Technology, 680-4 Kawazulizuka 820-8502

高 圧 力 の 科 学 と技 術Vol.8,No.2(1998)
 97

confine ourselves to the partial molar volume in infinitely

dilute solutions, thereby, related topics concerning solute-
solute interactions are excluded.
Some preliminary results obtained from the theories of
the partial molar volume of polyatomic molecules will be
presented putting stress on the effect of the conformational
change of the solute [15],[16].

2. Partial Molar Volume from the Scaled Particle

Theory
where y is the ratio of the volume occupied by solvent

molecules NA •~ v0 (NA, the Avogadro number; v0, the volume

2.1 Scaled Particle Theory
of a solvent molecule) to the molar volume V of pure solvent,

namely, y = (4/3)ƒÎ(a/2)3(NA/V) = ƒÎ a3p/6. One interesting

I f one could look at liquids at the atomic level, they
aspect of SPT is its similarity with its phenomenological
would find many different sized cavities, in which molecular
counterpart in terms of functional dependency upon the cavity
centers donot exist. Those cavities are cieatedagainstpressure
radius R, namely,
d ue to the surrounding molecules. A probability f(R) of a

cavity of radius R is related to the reversible work W(R)

required to create the cavity against the pressure by f(R)•`

exp[-W(R)/kT]. A physically essential assumption of SPT is

to equate the excluded volume of a solute with the volume of a

where ƒÁ and ƒÂ represent the surface tension and its curvature
cavity. In the case of a liquid system consisting of hard spheres,
correction, respectively. The SPT outlined above was
the free energy change associated with creating a solute is the
originally formulated for a system of hard spheres. However,
reversible work W(R) required to make a cavity of radius R,
the application has been extended even to aqueous solutions by
where R = (a+ƒÐ)/2 with a and ƒÐ being the diameters of the
Pierotti with great success [18]. The solution process of a
solvent and solute molecules, respectively. The reversible
solute molecule into a solvent an be conceptually decoupled
work W(ă) can be written in terms of 'microscopic' pressure
into two processes: a process to make a cavity in which a
P(ă) and a differential volume element dV(ă) as
solute molecule is to be accommodated, and a process to turn

on solute-solvent interaction after the solute is placed in the

cavity. If the free energy changes associated with the two

processes are •¢Gc and •¢Gi, respectively, then the free energy

where P(ă) denotes the microscopic pressure exerted on a change associated with the entire solution process is

cavity of radius ă due to solvent molecules. The microscopic

•¢G = •¢G+ •¢Gi. (11)

pressure can be expressed in terms of 'local' density pg(ă) as

P(ƒÉ) = ptTg(ƒÉ), in which ƒÏ is the average density of solvent

molecules and g(ƒÉ) is the radial distribution function of a Pierotti equated •¢Gc with the reversible work of cavity

solvent around the solute at r=ă. Thus, Eq. (3) is rewritten as, formation W(R) in Eq. (5).

The partial molar volume which is our main concern in

this review can be really obtained from Eq. (11) by taking

pressure derivative [7],[19].

Using the analytical expression for g(ă), W(R) an be Vo= Vc+ Vi + KTkBT, (12)
expressed as [17],

W(R) = K0 + K1R+ K2R2 + K3R3, (5)

where KTdenotes the isothermal compressibility of the solvent,

and the term, KTKBT,arses from the change in the standard state
between the gas and solution. The analytical forms of V can
be obtained from Eqs. (5) to (9) as

高 圧 力 の 科 学 と技 術Vol.8,No.2(1998)
98

Table 1. The partial molar volumes for mono-valent ions in Table 2. Solvent parameter for SPT.
water. (cm3/mol)

a. molar volume (cm3/mol).

b. isothermal compressibility (bar-1).
c. effective diameter (Angstrom).
d. propylene carbonate.

a. Theoretical results from the scaled particle theory.

b. Theoretical results from the Kirkwood-Buff Solution Theory formation and electrostriction.
and the RISM equation. Similar analyses for the partial volume of non-
c. Results from Eq. (14). electrolytes in a variety of solvents have been reported by
d. Results due to Vi= V (exp)- Vc-KTKBT.
French and Criss [22]. The parameters required for the
e. The partial molar volume of the ions without charge.
calculations are listed in Table 2. The parameters for the
f. •¢V= V-Vu.
hard-sphere diameter of solvent molecules have been
g. calculated from Eq. (37).
determined based on Pierotti's gas solubility technique with the
Vc= 2.52rX3 + A'rx2 + A"rX + A''', (14) exception of propylene carbonate which is taken from Kim
[23]. It should be noted that those parameters suffer from
inevitable ambiguity due to replacing a polyatomic molecule
(15) by a sphere. Their results are shown in Table 3. An interesting
observation here is that V's for non-electrolyte solutes in
water cb not necessarily show negative values. The physical
(16) process
of V isessentially
thevolume
change
associated
with
the reorganization of the solvent structure due to the solute-
solvent interaction. The results indicate the process is farmore
(17)
complicated than that just described in terms of the
'electrostriction' .

where a denotes the diameter of solvent molecules.

The first application of the theory was made to the 2.2 Extended Scaled Particle Theory

partial molar volume of ions in water [7]. It has been well-

regarded that the partial molar volume of small ions in water is Many of interesting problems in chemistry and
often negative. The volume deaese upon the dissolution biophysics concern changes in molecular geometry, or
process of ions is attributed to so called 'electrostriction,' or isomerization, of a solute in solution. Typical examples of
volume contraction due to the ion-solvent interaction. such problems indude organic isomerization reactions and
However, it is a nontrivial problem to extract the actual protein folding. The original SPT theory, which concerns just
magnitude of the volume contraction ee to the ion-water spherical solute molecules, is obviously unable to hande the
interaction, because the positive contributions due to the partial molar volume of such a system. Great efforts have been
cavity formation to accommodate the ions are always made to extend SPT to non-spherical molecules [26],[27],
associated with the dissolution process. Many empirical which has taken final shape due to the work of Irisa et. al. [12].
methods have been proposed to evaluate the positive According to the theory, the work for cavity formation, which
contribution often nefe ned to as the 'intrinsic volume' [5],[20]. corresponds to Eq. (5) in the case of spherical molecules,
Hirata and Arakawaderived the microscopic expression for the becomes,
'intrinsicvolume'basedon SPT. The volumecontractionV
dire to electmstriction can be extracted from the experimental W(ă) = A+ Bă + 1/2 Că + PVx(ă), (18)
data and the theoretical'intrinsic volume' using Eq. (12). Table
1 shows the experimental data of the partial molar volume of
A = -kBT ln(1- ƒÏVx (0)), (19)
some mono-valent ions [21] and the contributions from cavity

高 圧 力 の 科 学 と技 術Vol.8,No.2(1998)
 99

Table 3. The partial molar volume for non-electrolytes in a variety of solvents. (cm3/mol)

a. Theoretical results from the scaled particle theory.

b. Experimental data estimated from the additivity rule. (ref. 22)
c. results from V V (exp)- Vc-tTkBT.

(20)
(27)

(21)
(28)
where Vx(ă) is the excluded volume of solute molecules, which

is expressed analytically in terms of the scaling parameter and

molecular parameters such as the atomic radii, bond lengths,

(29)
bond angles, anddihedral angles of solute molecules [28]. The

partial molar volume of a solute with attiitrary shape can be

expressed by essentially the same equation as Eq. (14) [15], but Fig. 1 shows the calculated results for the partial molar volume

with the following generalized VC. of butane in water, in which the dlhe kal angle is varied The

partial molar volume of the cis-form (ƒÓ =0) is the least of all

conformations. It increases monotonially with 0 until 0

reaches 120 degrees, and then it becomes constant in the range

ƒÓ= 120 to ƒÓ= 180 (traps-form) . The results dearly

(22)
demonstrate the ability of the method to discriminate the

partial molar volume of different conformations of a molecule.

(23) Also plotted in the figure is the excluded volume (Vx(0)), or the

van der Waals volume, of butane calculated just from

geometric consideration. The dominative contribution to the

(24)
volume difference in the simplest case originates from the

difference in the excluded volume between the two

conformations. It appeals also that the contribution from the

(25)
solute-solvent interaction (attraction) does not depend on the

conformation in this particular case.

(26) 3. Partial Molar Volume from the Kirkwood-Buff

Solution Theory

高 圧 力 の 科 学 と技 術Vol.8,No.2(1998)
100

elements are the density of constituent species, ƒÏMM' =ƒÏMƒÂMM,

and x(0) = limk•¨O x(k), where x(k) is the Fourier transform

of x(r) defined by

x(k) = •çe-1krx(r)dr. (35)

As can be understood from the theory outlined above, the

usefulness of the equations is largely dependent on whether the
pair correlation functions are available for a system of interests.
In fact, that is the main reason why the theory has not been
Fig. 1. The conformation dependence of the partial molar
implemented in real problems as much as it should be until
volume of butane in water calculated from the extended scaled
recently. As far as a system consisting of spherical molecules
particle theory. The relative value to the cis conformation (ƒÓ =
0) is plotted; solid line, the partial molar volume; dotted line, is concerned, theories for the pair correlation function have
the volume of cavity formation; dash dotted line, exclusion been well established. However, such an over-simplified model
volume. of liquids fails to account for the partial molar volume of
molecules of chemical interests, for example, amino acids, of
3.1 Kirkwood-Buff Solution Theory which specificities are characterized by their geometrical shape
and charge distribution. Two models have been proposed for
The Kirkwood-Buff theory describes thermodynamic describing interactions between non-spherical molecules with
atomic partial charges, and statistical mechanical theories have
properties such as the partial molar volume and the isothermal
compressibility of a solution in terms of the density pair been developed based on those two models. The first model
correlation function of constituent molecular species [13]. The employs spherical harmonic expansions to describe the
density pair correlation function is defined as a variance- orientational dependence of the molecular interactions and
covariance matrix of the local density (or concentration) related pair correlation functions [29]. The theory has been
fluctuation by successful in accounting for a system consisting of molecules
which are not very far from spherical shape, such as water.
X MM'(r,r')=((ƒÏM(r)-ƒÏM)(ƒÏM'(r')-ƒÏM')) (30)
However, due to an obvious mathematical reason associated
with the slow convergence of the spherical harmonics, the
where ƒÏM(r) and ƒÏM(r') denote the density of species M and M' method may not be applied to a system including highly
at positions r and r', respectively, and PM and PM' are the aspherical molecules such as biomolecules. The other model of
average densities or concentrations of respective species. The molecular liquids, which is referred to as the interaction site
angular bracket <•c> symbolizes the thermal average. By model (ISM) [30], sees the interaction between a pair of
defining the local density by ƒÏM(r) = ƒ°l ƒÂ(r - riM ), Eq. (30) molecules as the sum of site-site interactions, namely,
can be rewritten as
(36)

X MM' (r+r') = ƒÏMƒÂMM' + ƒÏMƒÏM'hMM' (r, r'), (31)

where 1,2 denotethe position and orientationof the pair of

or for the uniform liquids,
molecules.An integral equationtheory of molecularliquids
basedon ISM, referredto as RISM (referenceinteraction site
XMM'(r) = ƒÏMƒÂMM' +ƒÏMPM'hMM'(ƒÁ), (32)
method) [30] and its extendedversion (extendedRISM or
XRISM) [31] are very successful for dealing with highly
where ƒÂMM is the Cronecker ƒÂ-function, and r= |r-r'|. Then, the
asphericalmoleculesincludingpolypeptidesin water[32],[33]•
Kirkwood-Buff equations for the partial molar volume and the
Due to those reasons, we just focus below on the RISM
isothermal compressibility are written as
equationimplementedto the Kirkwood-Bufftheory. (Those
who might be interestedin the theoreticaltreatmentof the
(33)
partial molar volume of molecularliquids based on the first
modelmust consult the paperby Patey [9].)
(34) The partial molar volume and the isothermal
compressibility can be described by essentially the same
equationsas Eq.(33)and Eq. (34), but in terms of the site-site
In the above equations, p denotes a diagonal matrix of which
pair densitycorrelationfunctionsratherthan the molecularpair

高 圧 力 の 科 学 と技 術Vol.8,No.2(1998)
 101

Fig. 3. Structure of the alanine tripeptide.

Fig. 2. The conformation dependence of the partial molar
volume of butane in water calculated from the Kirkwood-
Buff-RISM method. The relative value to the cis conformation 3.2 Dependence of the partial molar volume on the
(0 = 0) is plotted. conformation of butane

correlation functions. Butane is the simplest system to study conformational

equilibrium; it has only one dihedral angle to be considered, but

(37) that one degree of freedom is essential for isomerization. Fig.

2 shows the dependence of the partial molar volume of butane
in water upon the dihedral angle, which is calculated from Eq.

(38) (37). The dependency is almost identical in general behavior

with the result from the extended scaled particle theory
although their magnitudes are somewhat different. The
where p is the blocked diagonal matrix consisting of density of
dominative contribution to the volume difference in the
sites (atoms), and the (ƒ¿M,ƒÁM)-elements of the site pair density
simplest case originates from the difference in the excluded
correlation function X is expressed by,
volume between the two conformations. The discrepancy in
the magnitudes between the two methods, the extended scaled
(39) particle theory and the Kitkwood-Buff-RISM method, is
essentially due to the difference in the model and partly due to
(40) the choice of the molecular parameters. More careful choice of
the molecular parameters will reconcile the inconsistency

Using the Kirkwood-Buff-RISM theory described above, between the two methods.

few problems concerning the partial molar volume have been

studied Those include the dependency of the volume upon 3.3 Dependence of the partial molar volume on the

conformational change of a tetraatomic molecule in a nonpolar conformation of a tripeptide

solvent; the study represents the first theoretical attempt to

analyze the conformational dependence of the partial molar The dependence of the partial molar volume of the

volume of a polyatomic solute molecule [10]. The partial alanine tripeptide (Fig. 3) on the ƒÓ and ƒÕ angles in water is

molar volume of the alkali-halide ions in water has also been depicted in a two dimensional map in Fig 4. The corresponding

Helmholtz free energy map is also shown in Fig. 5. According

studied by Chong and Hirata [11]. The theoretical results are
shown in Table 1 compared with those from experiments. The to the free energy map, the most stable conformation is located

results show good agreement with those from experiments for near ƒÓ =-160 and ƒÕ =+160 which correspond to a ƒÀ-strand

There are several less stable minima in the regions (ƒÓ =-160,
the anions, but exhibit some discrepancy for Na+ and K+. We
ƒÕ =-70), (ƒÓ=-70, ƒÕ=-80), (ƒÓ = -80, ƒÕ=-120)
suspect the disagreement is that the energy parameters for the , and (ƒÓ=
-160
ion-water interactions employed in the theoretical calculation , ƒÕ= -120). The one located at (ƒÓ = -70, ƒÕ = -80) is

might not be well-tuned for comparing with the experiments. characteristic of the right handed a-helix. The free energy

In what follows, we report the preliminary results difference between the most stable and the least stable

obtained for the volume change of butane and a tripeptide in conformations is about 4 kcal/mol. Roughly speaking, the

water associated with the conformational change of those volume contour map shows the opposite behavior to the free

molecules as an example of the application of the Kirkwood- energy map, namely, the volume is greater in the place where

Buff-RISM approach. the free energy is less. The conformations around ƒÓ = 0 and ƒÕ

= 0, which has the least volume, arenot accessible in terms of

free energy. The most stable conformation around ƒÓ =-160 and

高 圧 力 の 科 学 と 技 術Vol.8,No.2(1998)
 102

volume of protein.)

The treatment illustrated here suggests a general

procedure to predict the direction and rate of a pressure-induced

isomerization reaction among the local minima in the

conformational space of a biomolecule. In order to predict the

pressure effect on a reaction, one first has to find the free energy
surface along reaction coordinates properly chosen. The next

step consists of determining a reaction path from a reactant

conformation to a product conformation as well as the

transition state along the reaction path. Then, the reaction

volume, •¢VR = Vp-V, and the activation volume •¢VA =

Vt-Vr can be obtained by the method described above from

the partial molar volumes, Vr- Vp, and Vt, of the reactant,

product and transition state, respectively.

4. Concluding remarks

Fig. 4. The partial molar volume map of the tripeptide in

The partial molar volume of solute in an infinitely
waterr the ƒÓ and ƒÕ angles denoted in Fig. 3 are varied.
dilute solution has great significance for determining the
stability of the molecule under high pressure. The two
streams of the theoretical developments for partial molar
volume have been reviewed the scaled particle theory and the
Kirkwood-Buff method Recent progress in the both theories
have provided methods to analyze the dependence of the partial
molar volume upon the conformation of polyatomic solute
molecules. The latest methodological developments will open
new horizon for the study of the pressure effect on chemical
reactions and the protein conformation. As has been shown in
the review, there are still unresolved uncertainties in teens of
the consistency among those theories and experiments.
However, we are optimistic in this respect for two reasons:
firstly, problems that arise can be largely due to the molecular

parameter employed in the calculations, secondly, these

problems will not affect the qualitative aspects of conclusions
concerning the volume dependency on solute conformation,
which is of main interest in the studies of chemical reactions
Fig. 5. The Helmholtz free energy map of the tripeptide in and conformational equilibrium of protein under high pressure.
waterr the ƒÓ and ƒÕ angles denoted in Fig. 3 are varied.

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[Received 24 April 1998]
高 圧 力 の 科 学 と技 術Vol.8,No.2(1998)