Equilibrium, frozen, excess and volumetric properties of dilute

solutions

Michael J. Blandamer
Department of Chemistry, The University, Leicester, UK LE1 7RH

The properties of aqueous solutions can be analysed in solvent interactions in determining the volume V(aq) of a
several ways leading to the identification of, for example, solution a useful procedure identifies the corresponding volume
frozen, equilibrium, relaxational, complex, sophisticated, V(aq;id) in the event that the properties of this solution are ideal.
delphic, isodelphic, ideal and excess contributions. These The difference [V(aq) 2 V(aq;id)] defines an excess volume.
terms are examined and illustrated in terms of increasing In the context again of eqn. (1-1), another challenge concerns
orders of partial differentials of Gibbs energies, volumes, understanding the dependences of volume V on temperature and
expansions and compressions. on pressure. These dependences are described in terms of
expansion E, compression K, expansivity a and compressibility
k. Closely linked to this new set of properties are the
1 Introduction corresponding instantaneous (frozen) and equilibrium proper-
ties.
The volume of a closed system is an important and, indeed,
comprehensible thermodynamic function of state defined,1a for
example, for a single phase by the set of independent variables 2 Gibbs energies
temperature T, pressure p and amount of each chemical The set of independent variables [T, p, ni] used in eqn. (1-1) also
substance j, nj; eqn. (1-1); equations are numbered according to defines the function of state called the Gibbs energy which for
the section in which they appear. systems at fixed T and p is the thermodynamic potential. For a
V = V[T, p, ni] (1-1) closed system at equilibrium the Gibbs energy is a minimum.
Chemistry is based on the assumption that across the whole
We note that temperature T and pressure p are intensive range of possible compositions (and organisations—see below),
variables. With reference to eqn. (1-1), the symbol ni represents the minimum in Gibbs energy G is unique.2 (All experience
the set describing the amounts of all chemical substances in the based on experiment supports this assumption.) If the state
system. Chemists are challenged by eqn. (1-1) in several defined by eqn. (1-1) is not at this minimum, spontaneous
interesting ways. There is the problem of understanding the chemical reaction/reorganisation takes place, driven by the
contributions made to volume V by each chemical substance j in affinity for spontaneous change A, the product of A and extent
the system. One way of tackling this problem probes the change of chemical reaction being positive;1c A dx ! 0, De Donder’s
in volume dV when dnj moles of substance j are added leading inequality where A = 2 (dG/dx)T,p.
to the definition of a partial molar volume Vj. The consequence Conceptually, we freeze-frame the thermodynamic state
of switching from a closed to an open system in this formalism defined by eqn. (1-1) in, by definition, state (I) where the
is not discussed here although it is an interesting point.1b For the affinity for spontaneous change is A(I) and the composition is
most part we confine our attention to aqueous solutions x(I). Again, conceptually, we perturb the system into a nearby
prepared by adding nj moles of substance j (e.g. urea) to n1 state by changes in pressure dp, temperature dT and amount of
moles of liquid water. We also confine our attention to solutes substance j dnj. There are two interesting constraints which we
which do not undergo solvolysis reactions. In order to probe, impose on this perturbation.
therefore, the role of solute–solute, solute–solvent and solvent– (A) Perturbation is to a near neighbouring state such that
affinity A remains constant.
(B) Perturbation is to a near neighbouring state at constant
Professor Michael J. Blandamer graduated from the University extent of reaction; i.e. at constant composition/organi-
of Southampton with BSc and PhD degrees in 1961. Following sation where x is constant.
post-doctoral research at NRC in Ottawa (Canada) he joined We are interested in the differential change in, for example,
the staff at the University of Leicester where he was appointed volume V under these two conditions. In fact, we direct our
to a Personal Chair in 1990. He is Visiting Professor in the attention to equilibrium states perturbed such that either (a) A
Department of Organic and = Aeq = 0, or (b) x = xeq.
Molecular Inorganic Chem- The keyword in the above two paragraphs is spontaneous. In
istry at the University of Gro- a typical kinetics experiment ni moles of reactants are added to
ningen, The Netherlands. His an aqueous solution at time t = 0 (at fixed T and p).
research interests concern the Spontaneous chemical reaction driven by the affinity for change
thermodynamic and kinetic leads the system to a minimum in Gibbs energy. The rate at
properties of solutes in aque- which this process occurs is examined using the formalism of
ous solutions. Otherwise, he is chemical kinetics. Similarly, when an aliquot of a solution
learning to play the piano, the containing micelles formed by an ionic surfactant is injected
plan being to attain a stan- into water, the micellar aggregates break up as the system
dard which is likely to be a spontaneously moves towards a minimum in Gibbs energy.3
pale shadow of that demon-
strated by the late Thelonius 3 Partial molar volumes
Monk. The distinction between the two types of perturbation is
illustrated using the following examples. A given closed

Chemical Society Reviews, 1998, volume 27 73

aqueous solution of benzoic acid at specified temperature and The system described by eqn. (4-1) is perturbed by a change
pressure (close to ambient) contains at equilibrium (G = mini- in pressure dp. Two limiting perturbations of the Gibbs energy
mum, A = 0 and x = xeq) n1eq moles of water, neq (PhCOOH) are envisaged; (i) at constant affinity A, and (ii) at constant x,
moles of benzoic acid, neq (H+) moles of hydrogen ions and neq linked by the following calculus operation. At constant
(PhCOO2) moles of benzoate anions. Then the analogue of eqn. temperature eqn. (4-2) holds.
(1-1) has the following form.
 ∂G   ∂G   ∂A   ∂x   ∂G 
V = V[T,p,n1eq,neq(PhCOO2),neq(H+)] (3-1)   =  −      (4-2)
 ∂p  A  ∂p  ξ  ∂p  ξ  ∂A  p  ∂x  p
This volume V is readily measured by direct measurements of
density r and mass w. To this system we rapidly add The latter equation applied to the state where G is a minimum
dn(PhCOOH) moles of benzoic acid with consequent change in (i.e. at equilibrium) and ‘A = 0’. But1e the affinity A equals
volume from V to (V + dV). The two limiting conditions 2(dG/dx)T, . In other words, at equilibrium, (dG/dx)T,p is zero.
identified in the previous section are now considered. The Moreover, the partial differential (dG/dp)T equals volume V.
system is frozen such that the amount of benzoic acid in the new Hence eqn. (4-3).
system is [neq(PhCOOH) + dn(PhCOOH)]. In other words, the V(A = 0) = (∂G/∂p)T,A = 0 = (∂G/∂p)T,xeq = V(xeq) (4-3)
change in volume dV occurs at fixed extent of reaction xeq, the
perturbation being characterised by [dV/dn(PhCOOH)]T,p,xeq. Therefore the equilibrium and frozen volumes are the same
The latter quantity is the frozen partial molar volume of which is not unexpected because volume V is a function of state
PhCOOH in this aqueous solution; if j · PhCOOH, the defined being a property which is not path dependent; ‘volume’ is
quantity is Vj,T,p,xeq (aq). By adding dn(PhCOOH) moles of ‘volume’. Similar transformations [cf. eqn. (4-2)] with respect
benzoic acid the system is taken away from a minimum in G and to the dependences on temperature of G and G/T (at fixed
the affinity for spontaneous acid dissociation increased. Sponta- pressure) confirm that (a) S(A = 0) = S(xeq) and (b) H(A = 0)
neous (and, in this case, fast) chemical reaction allows the = H(xeq); thus entropy S and enthalpy H are functions of state;4
system to regain after time Dt, an equilibrium state where A is Fig. 1.
zero. So an alternative name for the frozen partial molar volume
is an instantaneous partial molar volume.
In the other class of perturbations, the system responds such
that in the new state chemical equilibrium is established, the
amounts of benzoate and hydrogen ions increasing. The
increase in amount of PhCOOH in the solution when
dn(PhCOOH) moles are added is moderated. [Moderation is Fig. 1 Functions of state
not, however, universally true despite the widespread applica-
tion of Le Chatelier’s principle—see ref. 1(d)]. In other words, An important first differential of the Gibbs energy G is with
the change in volume dV occurs at constant affinity A, actually respect to the amount of substance j, namely (dG/dnj) at fixed T,
at ‘A = 0’ so that the perturbation is characterized by the partial p and ni ≠ j. This important partial differential is the chemical
quantity [dV/dn(PhCOOH)]T,p,A = 0. This is the equilibrium potential of chemical substance j. We return to eqn. (4-1) and
partial molar volume of PhCOOH in this aqueous solution. consider a freeze-frame description of the system at defined T
One more example is relevant. Consider an aqueous solution and p prepared with composition ni0; the superscript ‘0’ refers to
at specified T and p prepared using n1 moles of liquid water (l) time zero. Spontaneous chemical reaction occurs driven by the
and nu moles of urea(s). The volume of this system is specified affinity for spontaneous change. We freeze-frame the system
by eqn. (3-2); cf. eqn. (1-1). where the composition is x and the affinity equals A. This
V = V[T,p,n1, nu]eq (3-2) system is perturbed by adding dnj moles of substance j, one of
the i-substances. The analogue of eqn. (4-2) has the following
The superscript ‘eq’ (plus conditions that G = minimum and A form (at defined T and p): eqn. (4-4).
= 0) indicates that the organisation of the solution described by
xeq characterising water–water, water–urea and urea–urea  ∂G   ∂G   ∂A   ∂x   ∂G 
interactions is unique to the system defined by eqn. (3-2).  ∂n  =  ∂n  −  ∂n   ∂A   ∂x  (4-4)
Conceptually, we add dnu moles of urea producing a change in  jA  jξ  jξ p nj
volume dV. The frozen (or instantaneous) partial molar volume We consider the case where the system being perturbed was at
of urea, (dV/dnj)T,p,n1,xeq describes the change in volume where equilibrium where ‘A = 0’, G is a minimum and, significantly
these intermolecular interactions remain unchanged. In con- (dG/dx) is zero. Therefore eqn. (4-5) holds.
trast, the equilibrium partial molar volume (dV/dnj)T,p,n1,A = 0
characterises the change in volume, urea–urea, urea–water and mj(A = 0) = (∂G/∂nj)A = 0 = (∂G/∂nj)xeq = mj(xeq) (4-5)
water–water interactions changing in order to hold the system at In other words, the chemical potential mj for substance j in this
equilibrium where ‘A = 0’; see, for example, data in ref. 4. In system at ‘A = 0’ equals the chemical potential mj for the
the latter case, although the Gibbs energies are different before condition x = xeq. Thus frozen (instantaneous) and equilibrium
and after addition of dnj moles of urea, the Gibbs energies are chemical potentials are equal, placing chemical potentials on a
at minima in both states. par with the function of state H, V and S in the thermodynamic
The above argument centres on volumes and partial molar hierarchy, these being first derivatives of the Gibbs energy;
volumes. But the question is raised as to which thermodynamic Fig. 1. Hammett reached the same conclusion by noting, in his
variables and related partial molar properties need be classified terms, that ‘sophisticated’ and ‘primitive’ chemical potentials5
along similar lines, namely frozen (instantaneous) and equi- are equal. In the context of describing the properties of
librium. solutions, Grunwald uses the terms6 isodelphic to describe the
partial molar properties of substance j when addition of dnj
4 Gibbs energies and potentials moles of solute j does not change the organisation of the solvent
Returning to eqn. (1-1) we replace variable V by the Gibbs network; lyodelphic describes the difference between iso-
energy G; eqn. (4-1). delphic and equilibrium partial molar properties. The lyo-
delphic contribution to the chemical potential of solute j is zero,
G = G [T,p,ni] (4-1) [cf. eqn. (4-4)]. In other words, the equilibrium chemical
We assert that eqn. (4-1) is valid over the range of compositions/ potential of solute j is equal to the isodelphic chemical
organisations described by the variable x. potential.7 In a similar context, Ben-Naim8 uses the terms

74 Chemical Society Reviews, 1998, volume 27

‘freeze’ and ‘release’ in treating the thermodynamics of a reference chemical potential mj#(aq) at fixed temperature and
aggregation. pressure. In the event that the solution is ideal such that there are
no solute–solute interactions, gj = 1.0 and the chemical
5 Chemical equilibria potential for solute j, mj(aq;id) is given by eqn. (6-1).
Using an approach based on Henry’s Law, the chemical mj(aq;id) = mj#(aq) + RTln (mj/m0) (6-1)
potential of a neutral solute j [e.g. urea(s)] in aqueous solution Interestingly in the limit that mj tends to zero, mj(aq;id) [and
is related to the molality mj using eqn. (5-1) where gj is the mj(aq) for real solutions] tends to minus infinity.9 This means
activity coefficient; m0 = 1 mol kg21. that solute j is increasingly stabilised as the solution becomes
mj(aq;T;p) = mj(aq;id;mj = m0;T;p) + RTln(mjgj/m0) (5-1) more dilute. This is the thermodynamic reason for the problems
faced by industries which require solvents having very high
By definition, limit (mj ? 0; mi ? 0) gj equals 1.0 at all purity. To remove the last trace of solute presents an awesome
temperatures and pressures; mj(aq;id;mj = m0;T;p) is the task. Eqn. (5-1) and (6-1) are important equations because they
chemical potential of solute j in an ideal solution (gj = 1.0) provide the basis for equations which describe the dependences
having unit molality. on composition of other partial molar properties. For example,
Granted that mj(aq;T;p) is the same for frozen xeq, and the partial molar volume Vj(aq) of solute j is given by the partial
equilibrium properties, the question arises—does this same derivative (∂mj/∂p)T. Thus from eqn. (5-1) for simple solute j we
condition apply to mj#(aq;T;p) [·mj(aq;id;mj = m0;T;p)]? obtain eqn. (6-2).
Consider an aqueous solution prepared using n0x moles of
chemical substance X where again superscript ‘0’ indicates at Vj(aq) = Vj#(aq) + RT(∂lngj/∂p)T (6-2)
time zero. Experimental evidence indicates that two chemical Therefore from the definition of gj, limit (mj ? 0) Vj(aq) equals
substances, X(aq) and Y(aq) exist in chemical equilibrium (at Vj#(aq) which we may also write as VjH(aq), the limiting partial
G = minimum where A = 0 at defined T and p). Such molar volume. We make one further point in this connection
experimental evidence often arises because the two solutes have because it is always advisable to examine these and comparable
quite different UV–VIS absorption spectra. At equilibrium eqn. equations in terms of what happens in certain limits.9 For
(5-2) holds. example, the partial molar entropy Sj of solute j is given by the
m eq eq partial derivative 2(∂mj/∂T)p. Then eqn. (6-3) holds.
X (aq) = mY (aq) (5-2)
Eqn. (5-2) offers the link with the argument developed in Sj(aq) = Sj#(aq) 2 Rln (mjgj/m0) 2 RT(∂lngj/∂T)p (6-3)
conjunction with the chemical potential of substance X. For this Therefore from the definition of gj, limit (mj ? 0) Sj(aq) equals
aqueous solution we would record the same increment in Gibbs + H. In other words, the term SjH(aq) has no practical meaning
energy G when dnX moles of substance X are added irrespective whereas VjH(aq) does.
of whether only substance X is present in the solution or As preparation for some of the subject matter discussed in the
substance X is in equilibrium with substance Y. Using following sections we set down the basis of a definition for the
Hammett’s terminology5 the primitive and sophisticated chem- excess Gibbs energy of an aqueous solution containing the
ical potentials of solute X are identical. single solute, chemical substance j. For a solution with ideal
Using the primitive description of the above system, the properties (at fixed T and p), the chemical potential of solute j
chemical potential of substance X(aq) is related to the is given by eqn. (5-1) with gj = 1.0. Then eqn. (6-4) holds.
composition of the solution using the following equation [cf. mjE(aq) = mj(aq) 2 mj(aq;id) = RTlngj (6-4)
eqn. (5-1)] for fixed T and p: eqn. (5-3).
For the solvent water in this solution the chemical potential
mX(aq) = mX#(aq;prim) + RTln[m0Xg X(prm)/m0] (5-3) m1(aq) is related to mj and the practical osmotic coefficient f
Using the sophisticated description of the solution wherein the using eqn. (6-5) where m1*(†) is the chemical potential of water
composition is described by molalities meq eq
X (soph) and mY -
at the same time T and p, eqn. (6-5) applies.
(soph), combination of eqn. (5-1) and (5-2) yields eqn. (5-4) for m1(aq) = m1*(†) 2 fRTM1mj (6-5)
the solution at fixed T and p.
For an ideal solution f = 1 and gj = 1. The excess Gibbs energy
m #X(aq;soph) + RTln[m eq eq
X (soph)g X (soph)/m ]
0
is defined by eqn. (6-6) for a solution prepared using 1 kg of
#
= mY(aq;soph) + RTln[mY (soph)g eqr /m0]
eq
(5-4) solvent and mj moles of solvent.
By definition, equilibirum constant K is given by eqn. (5-5). GE = mjRT[1 2 f + lngj] (6-6)
K = mY eq
(soph)g Yeq(soph)/meq eq GE is an intensive property of the solution because it refers to a
X (soph)g X (soph) (5-5)
thermodynamic property of a solution prepared using a fixed
But m0X = [mY eq
(soph) + mXeq(soph)] so that mX 0
= {1 + mass of solvent. The link between the dependence of f and gj on
[Kg eq eq eq eq
X (soph)/g Y (soph)]} mX (soph)g X (soph). molality mj is provided by the Gibbs–Duhem equation.
Then using the formulations for the chemical potential of
substance X in solution we obtain eqn. (5-6). 7 Volumes
m #X(aq;prim) = m #X(aq;soph) In Section 3 we commented on the significance of equilibrium
2 RTln[{1 + [Kg eq eq
X (soph)/g Y (soph)]}/gIRX(prim)] (5-6) and frozen partial molar properties using volumetric properties
In the limit that the solutions have ideal properties under both of solutions as examples. Here we take up the story again but
descriptions we obtain eqn. (5-7). develop the argument along the lines given in Section 5. The
mX#(aq;prim) = m#X(aq;soph) 2 RTln[1 + K] (5-7) broad sweep of our analysis is set out in Fig. 2 starting with the
function of state, volume V.
Therefore the reference chemical potentials for a given solute We consider a solution prepared using nj moles of substance
are not identical. Consequently, all other reference partial molar j (e.g. urea) and n1 moles of water (†). The analogue of eqn.
quantities (e.g. limiting partial molar volumes and limiting (4-2) describes the change in volume dV when dnj moles of
partial molar enthalpies) characterising solutes in sophisticated chemical substance j are added to the solution (i) at constant
and primitive descriptions also differ. affinity A and (ii) at constant extent of reaction x, both at
constant T, p and n1, eqn. (7-1).
6 Limiting partial molar properties and excess properties  ∂V   ∂V   ∂A   ∂x   ∂V 
According to eqn. (5-1), the chemical potential of solute j in a  ∂n  =  ∂n  −  ∂n   ∂A   ∂x  (7-1)
solution, molality mj is related to the activity coefficient gj and  j A  j ξ  j ξ   n   n j
j

Chemical Society Reviews, 1998, volume 27 75

 this dependence12 is not defined by thermodynamics although,
in many cases, the dependence of f(Vj) on mj for dilute solutions
is linear. [For salt solutions, the Debye–Hückel limiting law
prompts analysis in the form of a dependence of f(Vj) on
1
(mj) .]
2

8 Isochoric conditions
An interesting set of independent variables defines the Helm-
holtz energy of a system, F; cf. eqn. (1-1): eqn. (8-1).
F = F[T,V,ni] (8-1)
Then all spontaneous processes under isochoric–isothermal
conditions lower spontaneously the Helmholtz energy of a
closed system. We do not develop this point further except to
note that in contrast to the set of independent variables given in
eqn. (1-1) and (4-1), the set in eqn. (8-1) involves two extensive
variables, volume and amounts, ni. The isochoric condition has
aroused controversy13–16 in analysis of kinetic data with respect
to the calculation of isochoric activation parameters.14,17,18 The
controversy centres on answers to the simple question—which
volume is held constant?13 The issue remains unresolved.

9 Isobaric expansions and isobaric expansibilities

We return to a consideration of thermodynamic variables
defined by the set of independent variables specified in eqn.
(1-1) and (4-1). The volume of an aqueous solution having
defined composition (e.g. n1 moles of water and nj moles of
solute j) depends on temperature at fixed pressure. There are
two limiting ways in which the volume of this solution may
Fig. 2 change as a result of a change in temperature; (a) at constant
affinity A, and (b) at constant extent of reaction/organisation x.
These two limiting changes are related (at defined T and p), eqn.
But (∂V/∂x)nj is not zero and so the equilibrium partial molar
(9-1).
volume of substance j, Vj(A = 0) is not equal to the frozen
partial molar volume, Vj(xeq). We recall our discussion in  ∂V   ∂V   ∂A   ∂x   ∂V 
Section 2 of the volumetric properties of urea(aq).   =  −      (9-1)
 ∂T  A  ∂T  ξ  ∂T  ξ  ∂A  T  ∂x  T
The volume of an aqueous solution comprising n1 moles of
water and nj moles of solute j is related to the equilibrium partial In particular case of a system at equilibrium we identify two
molar volumes Vj(aq) and V1(aq) using eqn. (7-2). limiting expansions; the equilibrium isobaric expansion Ep(A
= 0) [ = (∂V/∂T)p;A = 0] and the frozen isobaric expansion
V(aq) = n1V1(aq) + njVj(aq) (7-2)
Ep(xeq) [ = (∂V/∂T)p;xeq]. Further for the condition ‘A = 0’ then
However, an alternative form of eqn. (7-2) defines V(aq) in (∂V/∂T)p;x equals1f T (∂H/∂x)T,p. Hence eqn. (9-2).
terms of the apparent molar volume10 f(Vj), eqn. (7-3).
Ep(A = 0) = Ep(xeq) 2 T21 (∂x/∂A)T,p (∂V/∂x)T,p (dH/dz)T,p
V(aq) = n1V1*(†) + njf(Vj) (7-3) (9-2)
If the properties of the solution are ideal, eqn. (7-4). Equilibrium isobaric thermal expansions of aqueous solutions
can be directly measured dilatometrically.19 The analogue of
V(aq;id) = n1V1*(†) + njf(Vj)H (7-4)
eqn. (7-1) in which enthalpy H replaces volume V is a key
Here f(Vj [ =
)H VjH(aq)]is the limiting (indinite dilution) partial equation with respect to the temperature-jump fast reaction
molar volume of solute j. technique.20 Although at equilibrium (∂A/∂x)T;p is negative, the
Another form of eqn. (7-3) describes the volume of a solution sign of the product, (∂V/∂x)T;p (∂H/∂x)T;p is not predetermined.
prepared using 1 kg of water. So we have eqn. (7-5) where eqn. Therefore, the sign of Ep(A = 0) is not fixed. In fact, for water
(7-6) holds. below 277 K at ambient pressure, the temperature of maximum
density (TMD), Ep(A = 0) is negative;21 a similar feature is
V(aq) = (1/M1)V1*(†) + mjf(Vj) (7-5)
shown for many aqueous solutions22,23 in the region of 277 K.
V(aq;id) = (1/M1)V1*(†) + mjf(Vj)H (7-6)
As written in eqn. (9-2), Ep(A = 0) and Ep(xeq) are extensive
Therefore the excess volume VE is given by eqn. (7-7). variables but not functions of state because they characterise
pathways. We divide by the volume, an extensive function of
VE(aq) = mj[f(Vj) 2 f(Vj)H] (7-7)
state (see above), to define an isobaric equilibrium expansibility
An advantage of the latter equation is that VE is an intensive a(A = 0) [ = V21 Ep(A = 0)] and an isobaric frozen expansivity
variable. Eqn. (7-3) forms the basis of the experimental a(xeq) [ = V21 Ep(xeq)], two volume intensive properties of a
determination of f(Vj). The mass of the aqueous solution w solution, eqn. (9-3).
equals (w1 + wj) or (w1 + nj Mj) where Mj is the molar mass of
a(A = 0) = a(xeq) 2 (VT)21(∂x/∂A)T,p(∂V/∂x)T,p(∂H/∂x)T,p
the solute. The densities of the solution and the solvent are r(aq)
(9-3)
[ = w/V(aq)] and r1*(†) respectively. Hence11a eqn. (7-8)
holds. In these terms a(xeq) represents the volumetric response of a
system to a thermal shock as the temperature is increased in an
f(Vj) = (mj)21[r(aq)21 2 r1*(†)21] + (Mj/r) (7-8)
infinitesimal time. The extended product term describes the
Eqn. (7-8) does not determine the dependence of f(Vj) on mj; the relaxation of the system24 to the state characterised by
dependence is characteristic of the solution. In fact, the form of a(A = 0).

76 Chemical Society Reviews, 1998, volume 27

 For the aqueous solution described in eqn. (7-4), the isobaric 10 Isothermal compression and compressibility
thermal expansion is described by eqn. (9-4).
In addition to isobaric expansion, the other major component of
 ∂V   ∂V * (l)   ∂f (Vj )  Fig. 2 describes compressions and compressibilities of solu-
Ep ( A = 0 ) =   = N1  1  + nj   tions. There are two limiting ways in which the volume of a
 ∂T  P;A =0  ∂T  P;A =0  ∂T  p;A + 0 solution may change as a result of a change in pressure (at fixed
(9-4) temperature); (i) at constant affinity A, and (ii) at constant extent
of reaction/organisation x. Thus, at fixed temperature,
We define an apparent equilibrium molar isobaric expansion of
solute j, f(Ej) by the partial differential (∂f(Vj)/∂T)p;A = 0, an  ∂V   ∂V   ∂A   ∂x   ∂V 
intensive property of solute j. Similarly, for the solvent water,   =  −      (10-1)
 ∂p  A  ∂p  ξ  ∂p  ξ  ∂A  p  ∂x  p
E1*(†;A = 0) equals [∂V1*(†)/∂T]p;A = 0. Hence for a solution
prepared using 1 kg of solvent, where both E1*(†;A = 0) and The partial differential (∂A/∂p)T;x equals1g 2(∂V/∂x)T;p. In the
f(Ej) are intensive variables we have eqn. (9-5). case where the system was at equilibrium, the partial differential
2(∂V/∂p)T;A = 0 is the equilibrium isothermal compression
Ep(A = 0;aq;w1 = 1 kg) = (1/M1)E1*(†;A = 0) + mjf(Ej)
KT(A = 0) whereas 2(∂V/∂p)T;xeq is the frozen compression
(9-5)
KT(xeq). Hence from eqn. (10-1) we have eqn. (10-2).
For the corresponding ideal solution we have eqn. (9-6). eq eq 2
KT(A = 0) = KT(xeq) 2 (∂x/∂A)T;p [∂V/∂x)T;p ] (10-2)
Ep(A = 0;aq;w1 = 1 kg;id) eq
= (1/M1)E1*(†;A = 0) + mjf(Ej)H (9-6) The compressions KT(A = 0) and KT(x ) are extensive
properties of a solution. The volume intensive properties are
The equilibrium partial molar expansion of solute j Ej(aq) and of isothermal compressibilities kT(A = 0) and kT(xeq) defined by
solvent water E1(aq) are defined by [∂Vj(aq)/∂T]p and [∂V1(aq)/ eqn. (10-3) and (10-4).
∂T]p. These quantities are normally calculated from measured
dependences of Vj(aq) and V1(aq) [cf. eqn. (7-8) using f(Vj)] on kT(A = 0) = 2 (1/V)(∂V/∂p)T;A = 0 = + V21KT(A = 0) (10-3)
composition at a series of fixed temperatures. For urea(aq) f(Ej) kT(xeq) = 2 (1/V)(∂V/∂p)T;xeq = + V21KT(xeq) (10-4)
and f(Ej)H are positive4 at ambient pressure over the range 0 @ Then from eqn. (10-2) we have (10-5).
mj @10.0 mol kg21. For 2-methylpropan-2-ol(aq) in very dilute
eq eq 2
solutions,12 the dependence of Ej(aq) on mj and temperature is kT(A = 0) = kT(xeq) 2 (∂x/∂A)T;p [(∂V/∂x)T;p ] (10-5)
complicated. The second differential, [∂2VjH(aq)/∂T2]p has been But (∂A/∂x)T;p is negative for all stable phases. Hence,
used to classify solutes on the basis of their effect on water– eq
irrespective of the volume of reaction (∂V/∂x)T;p , kT(A = 0) is
water interactions.25 An (intensive—based on fixed mass of always greater than kT(xeq). In fact, eqn. (10-5) is the key
solvent) excess equilibrium isobaric expansion EEp is defined by equation for the pressure-jump fast reaction technique,20 the
eqn. (9-7); cf. eqn. (6-6). second (large) term on the right-hand side of eqn. (10-5) being
EEp (A = 0) = Ep(A = 0;aq;w1 = 1 kg) the relaxational term.
2 Ep(A = 0;w1 = 1 kg;aq;id) (9-7) For an aqueous solution the isothermal equilibrium com-
Therefore eqn. (9-8) holds. pression KT(A = 0) is related to the isothermal differential of
eqn. (7-3) with respect to pressure, eqn. (10-6).
EEp = mj[f(Ej) 2 f(Ej)H] (9-8)
E  ∂V1* (l) 
In other words, the excess expansion Ep (A = 0) is a well- K T ( A = 0) = −(∂V / ∂p) T;A =0 = −n1  
defined property given by the product of solute molality mj and  ∂p  T;A =0
a difference in real and ideal apparent molar expansions.
However, a similar clear definition does not emerge if we turn  ∂f(Vj ) 
our attention to expansibilities. The starting point is the − nj   (10-6)
definition given above for aT(A = 0) [ = V21Ep(A = 0)]. Then  ∂p  T;A = 0
using eqn. (9-4) we have eqn. (9-9).
Thus KT(A = 0) is an extensive property of a solution. It is
ap(A = 0) = n1[V1*(†)/V(aq)][V*1(†)]21E*p(†;A = 0) convenient to define an equilibrium apparent molar isothermal
+ nj[f(Vj)/V(aq)][f(Vj)]21f(Ej) (9-9) compression f(KTj) { = 2(∂f(Vj)/∂p)T;A = 0}. For an aqueous
If for the pure solvent, a*p(A = 0) equals [V1*(†)]21E*p(A = 0;†)], solution prepared using 1 kg of solvent we relate the intensive
then the isobaric expansibility of the solution a*p(A = 0) is given compression KT(A = 0;aq;w1 = 1 kg) to the composition using
by eqn. (9-10). eqn. (10-7).
ap(A = 0) = n1[V1*(†)/V(aq)]a*p(†) + [nj/V(aq)]f(Ej) (9-10) KT(A = 0;aq;w1 = 1 kg) = (1/M1)K*1T(†;A = 0) + mjf(KTj)
(10-7)
The property of the solution ap(A = 0) is given by an equation
which only partly resembles eqn. (7-3) with the added For the solution whose properties are ideal, eqn. (10-8)
complexity of a volumetric ratio [V1*(†)/V(aq)]. There is no applies.
obvious quantity which could be described as an apparent molar KT(A = 0;aq;w1 = 1 kg) = (1/M1)K*1T(†;A = 0) + mjf(KTj)H
isobaric expansivity of the solute j. Consequently, there is no (10-8)
obvious route leading in an elegant manner to an excess isobaric
expansibility of the solution; cf. eqn. (9-8). Then the excess compression KET is defined by eqn. (10-9).
We end this section by returning to eqn. (9-9) written as eqn. KET = mj[f(KTj) 2 f(KTj)H] (10-9)
(9-11). Interestingly, the form of eqn. (10-9) resembles those for the
ap(A = 0)V = n1V1*(†)a1*(A = 0) + njf(Ej) (9-11) excess volumes [eqn. (7-8)] and excess isobaric expansions
The latter equation forms the starting point for the derivation of [eqn. (9-8)]. The general form of eqn. (10-7) describes the
eqn. (9-12) which shows how f(Ej) is calculated using measured extensive compression of a solution containing nj moles of
ap(A = 0) for a solution molality mj. solute j and n1 moles of water eqn. (10-10).
f(Ej) = [mjr(aq)r1*(†)]21 {[r1*(†)ap(aq;A = 0)] KT(A = 0) = n1K1T(†;A = 0) + njf(KTj) (10-10)
2 [r(aq)a1*(†;A = 0)]} + [a(aq)Mj/r(aq)] (9-12) Calculation of f(Ej) from compressibilities uses eqn. (10-11)
This equation closely resembles eqn. (7-9) and is a member of which is derived in a manner analogous to that used to obtain
the same family of volumetric equations (see below). eqn. (9-12).

Chemical Society Reviews, 1998, volume 27 77

f(KTj) = [mjr(aq)r1*(†)]21{[r1*(†)kT(aq;A = 0)] dependence of volume V on pressure at constant entropy and
2 [r(aq)k1*(†);A = 0)]} + [kT(aq);A = 0)Mj/r(aq)] (10-11) affinity using eqn. (11-3).
Further, just as for expansibilities, an elegant equation similar to  ∂V   ∂V   ∂S   ∂T   ∂V 
that used for excess volumes [eqn. (7-8)] cannot be used to  ∂p  =  −      (11-3)
define an excess isothermal compressibility. Similarly, there is   S;A  ∂p  T;A  ∂p  T;A  ∂S  p;A  ∂T  p;A
no analogue of a partial molar volume which can be identified We use eqn. (11-3) with the constraint that constant affinity A is
as a partial molar compressibility. Direct measurement of at ‘A = 0’. The last partial derivative in eqn. (11-3) is, therefore,
isothermal compressibilities of aqueous systems is, neverthe- the isobaric equilibrium expansion Ep(A = 0); cf. eqn. (9-2). A
less, not straightforward bearing in mind that k(aq) depends on Maxwell relationship1g shows that (∂S/∂p)T;A = 0 equals
composition, temperature and pressure. 2(∂V/∂T)p;A = 0, which is 2Ep(A = 0). Further, the partial
differential (∂S/∂T)p;A = 0 equals1h the ratio of the equilibrium
11 Isentropic compression and isentropic compressibilities isobaric heat capacity to the temperature, Cp(A = 0)/T.
Data describing equilibrium isothermal compressibilities of Moreover, Ep(A = 0) equals ap(A = 0)V; cf. eqn. (9-3).
aqueous solutions are not extensive. It may at first sight seem Therefore,30
surprising, therefore, that information concerning equilibrium KS(A = 0) = KT(A = 0) 2 {[ap(A = 0)V]2T/Cp(A = 0)} (11-4)
isentropic compressibilities (i.e. compression at constant en-
tropy, kS) is more extensive. The reason for this state of affairs Thus by definition the equilibrium isentropic compression
is the Newton–La Place equation relating isentropic compressi- KS(A = 0) equals 2(∂V/∂p)S;A = 0. In eqn. (11-4), KS(A = 0),
bility to the density of a solution r and the velocity of sound u KT(A = 0), V and Cp(A = 0) are extensive properties of the
in the solution; kS = (u2r)21. If the frequency of the sound solution. The ratio [Cp(A = 0)/V] is the equilibrium isobaric
wave is low (e.g. in the MHz range), the calculated quantity is heat capacity per unit volume of the solution, s(A = 0). Then
the equilibrium isentropic compressibility kS(A = 0). In other we have eqn. (11-5).
words, each microscopic volume of a solution is compressed at KS(A = 0) = KT(A = 0) 2 {[ap(A = 0)]2VT/s(A = 0)} (11-5)
constant entropy. Moreover, these compressibilities can be Similarly, in terms of isentropic compressibilities, eqn.
precisely measured.26,27 (11-6).
The isentropic condition raises problems from the stand-
points of both thermodynamic theory and the interpretation of kS(A = 0) = kT(A = 0) 2 {[ap(A = 0)]2T/s(A = 0)} (11-6)
derived parameters. From the outset we have to change the basis In the next stage we return to an equation for the volume of an
of the thermodynamic treatment. Thus in reviewing equilibrium aqueous solution prepared using n1 moles of solvent water and
isobaric expansions Ep(A = 0) and isothermal compressions nj moles of solute j; eqn. (7-3). The isobaric compression KT(A
KT(A = 0), the analysis developed in a straightforward manner = 0) is given by eqn. (10-6) in terms of the equilibrium isobaric
from the function of state called volume defined using eqn. compression of the solvent K*1T(†) and an equilibrium partial
(1-1). In the latter case, our interests centred on the T–p differential isothermal dependence of f(Vj) on pressure. Thus
composition domain for which the thermodynamic potential we have eqn. (11-7).
function is the Gibbs energy. In order to understand the
significance of isentropic compressibilities kS and isentropic KT(aq;A = 0) = n1K*1T(†;A = 0) 2 nj[∂f(Vj)/∂p]T;A = 0
compressions KS, we switch interests into the S-p-composition (11-7)
domain. This is not a trivial switch. All spontaneous processes The task at this stage is to write down a satisfactory equation for
in closed systems at fixed entropy and pressure lower the the isentropic equilibrium compression of the solution. In the
enthalpy H of a system such that thermodynamic equilibrium context of treating the thermodynamic properties of binary
corresponds to a minimum in enthalpy where the affinity for liquid mixtures, the way forward was signalled by Benson and
spontaneous change is zero. Thus the enthalpy of a closed Kumaran,31 by Reis28 and by Douhéret, Moreau and Viallard32
system is defined1e by eqn. (11-1). particularly in developing equations describing excess com-
H = H [S, p, x] (11-1) pressibilities and excess compressions. Here we comment on
the equilibrium isentropic compressions of aqueous solutions.
The volume of the system is given by the partial differential, Thus it follows from eqn. (11-4) that for the pure solvent, water:
(∂H/∂p)S;x. The analogue of eqn. (1-1) is eqn. (11-2). eqn. (11-8).
V = V [S, p, ni] (11-2) K*1T(†;A = 0) = K*S1(†;A = 0)
In other words, we have switched the set of independent + {[a*1p(†;a = 0)V*1(†)]2T/C*p1(†;A = 0)} (11-8)
variables defining the volume from [T, p, ni] to [S, p, ni], a For the solution, according to eqn. (11-4) we have eqn.
switch from ‘Lewisian’ to ‘non-Lewisian’ independent vari- (11-9).
ables.28 The key point to note is that in one set, T and p are both
intensive variables whereas in the other set [cf. eqn. (11-1) and KT(aq;A = 0) = KS(aq;A = 0)
(11-2)] the independent variable S is extensive making two + {[ap(aq;A = 0)V(aq)]2T/Cp(A = 0;aq)} (11-9)
extensive variables in this definition. This contrast between the In eqn. (11-8), K*1T(†;A = 0) and K*S1(†;A = 0) refer to a mole
two sets is not trivial indicating that the choice of independent of liquid water whereas in eqn. (11-9) V(aq) and Cp(A = 0;aq)
variables is more than a matter of convenience. are extensive properties of the solution described in eqn. (11-7)
Two equilibrium quantities are of interest in this section; (i) having compression KT(aq;A = 0). The analytical problem is
the equilibrium isentropic compression, KS(A = 0) and (ii) the highlighted by eqn. (11-8) and (11-9). The isentropic condition
equilibrium isentropic compressibility kS(A = 0). The corre- on K*S1(†;A = 0) is understandable in terms of the condition
sponding instantaneous properties are KS(xeq) and kS(xeq). The associated with compression by the sound wave. The isothermal
difference between these equilibrium and instantaneous proper- conditions on K*1T(†;A = 0) and KT(aq;A = 0) are under-
ties is at the heart of the ultrasonic fast reaction technique.20,29 standable in terms of the isothermal condition associated with
At low rates of compression (i.e. change in pressure) at constant measuring the dependence of volumes on pressure. Thus we can
entropy, solvent–solvent, solvent–solute and solute–solute arrange experimentally for these two temperatures to be the
interactions within each microscopic volume of an aqueous same in order to compare the isothermal compressions of water
solution change in order to keep the system at a minimum in the and an aqueous solution having defined molality. Unfortu-
enthalpy. The differential dependence of volume V on pressure nately, we cannot ensure in a comparison of K*1S(A = 0) for
at constant temperature and affinity is related to the differential water and KS(aq;A = 0) for an aqueous solution that the two

78 Chemical Society Reviews, 1998, volume 27

entropies are the same. In each case, the compression is 2 F. Van Zeggeren and S. H. Storey, The Computation of Chemical
isentropic (cf. the Newton–Laplace equation) but we cannot be Equilibria, Cambridge University Press, Cambridge, 1970.
sure that the properties of solution and solvent are compared at 3 J. Bach, M. J. Blandamer, J. Burgess, P. M. Cullis, L. G. Soldi,
K. Bijma, J. B. F. N. Engberts, P. A. Kooreman, A. Kacperska,
the same entropy. Furthermore, in examining the dependence of
K. C. Rao and M. C. S. Subha, J. Chem. Soc., Faraday Trans., 1995, 91,
KS(aq;A = 0) on the composition of a solution (e.g. on molality 1229.
of solute j), we cannot be sure that comparisons can be made of 4 R. H. Stokes, Aust. J. Chem., 1967, 20, 2087.
the properties of these solutions at the same entropy. 5 L. P. Hammett, Physical Organic Chemistry, McGraw-Hill, New York,
There is merit in defining an apparent equilibrium isentropic 1970, 2nd edn., p. 16.
compression of solute j, f(KSj) in terms of 2[∂f(Vj)/∂p]S;A = 0. 6 E. Grunwald, J. Am. Chem. Soc., 1984, 106, 5414; 1986, 108, 1361;
Similarly, f(KTj) = 2[(∂f(Vj)/dp]T;A = 0. Granted therefore that 5726.
experiment yields kS(aq;A = 0) for an aqueous solution (at 7 M. J. Blandamer, J. Burgess, A. W. Hakin and J. M. W. Scott, Water and
defined T and p) and k*S1(†;A = 0) for the pure solvent water, Aqueous Solutions, ed. G. W. Neilson and J. E. Enderby, Colston Papers
No. 37, Adam Hilger, Bristol, 1986.
eqn. (11-10) yields the apparent molar isentropic compression
8 A. Ben-Naim, Hydrophobic Interactions, Plenum Press, New York,
of the solute f(KSj). 1980, p. 130.
f(KSj) = [1/mjr*1(†)][kS(aq;A = 0) 2 k*S1(†;A = 0)] 9 J. E. Garrod and T. M. Herrington, J. Chem. Educ., 1969, 46, 165.
+ kS(aq;A = 0)f(Vj) (11-10) 10 See, for example, G. N. Lewis and M. Randall, Thermodynamics,
revised by K. S. Pitzer and L. Brewer, McGraw-Hill, New York, 1961,
Indeed, this is a classic equation used by many authors who cite 2nd edn.
as the key reference the monograph by Harned and Owen,12b 11 H. S. Harned and B. B. Owen, The Physical Chemistry of Electrolytic
confidence being boosted by the strong similarity with equa- Solutions, Reinhold, New York, 1958, 3rd edn., (a) p. 358; (b)
tions for f(Vj), f(Epj) and f(Kpj) as described in the previous p. 376.
sections. So common practice has been to use eqn. (11-10) as a 12 F. Franks and H. T. Smith, Trans. Faraday Soc., 1968, 64, 2962.
13 M. J. Blandamer, J. Burgess, B. Clark, R. E. Robertson and
method of determining the apparent property of f(KSj) from J. M. W. Scott, J. Chem. Soc., Faraday Trans. 1, 1985, 81, 11.
measured kS(aq;A = 0) for a solution molality mj. 14 J. R. Haak, J. B. F. N. Engberts and M. J. Blandamer, J. Am. Chem. Soc.,
Then the patterns which emerge are discussed in the 1985, 107, 6031.
conceptually simpler context of isothermal compression. Lara 15 P. G. Wright, J. Chem. Soc., Faraday Trans. 1, 1986, 82, 2557.
and Desnoyers note33 that for 2-butoxyethanol(aq) at 298 K, 16 L. M. P. C. Albuquerque and J. C. R. Reis, J. Chem. Soc., Faraday
‘isothermal and isentropic compressibilities are quite similar Trans. 1, 1989, 85, 202.
and reflect the same kind of interactions’. Franks and co- 17 M. G. Evans and M. Polanyi, Trans. Faraday Soc., 1935, 31, 875.
workers34 discuss the dependence of f(Kj) on composition and 18 E. Whalley, J. Chem. Soc., Faraday Trans. 1, 1987, 83, 2901.
19 J. L. Neal and D. A. I. Goring, J. Phys. Chem., 1970, 74, 658.
structure for various sugars in aqueous solutions in terms of
20 E. Caldin, Fast Reactions in Solution, Blackwell, Oxford, 1964.
solute-hydration and solute–solute interactions although the 21 M. J. Blandamer, J. Burgess and A. W. Hakin, J. Chem. Soc., Faraday
measured quantity was f(KSj). In the context of aqueous salt Trans. 1, 1987, 83, 1783.
solutions, for example, Criss and co-workers35 compare f(KSi)H 22 F. Franks and B. Watson, Trans. Faraday Soc., 1967, 63, 329.
for ion i with the trend predicted by the Born equation for the 23 D. D. Macdonald and J. B. Hyne, Can. J. Chem., 1976, 54, 3073.
isothermal property. Quite generally, therefore, measured 24 See discussion by C. M. Davis and J. Jarzynski, Water and Aqueous
isentropic properties are understood in terms of models based Solutions, ed. R. A. Horne, Wiley-Interscience, New York, 1972, ch.
on isothermal properties. This approach has obvious practical 10.
merit. Nevertheless, this author has reservations concerning 25 L. G. Hepler, Can. J. Chem., 1969, 47, 4613.
26 R. Garnsey, R. J. Boe, R. Mahoney and T. A. Litovitz, J. Chem. Phys.,
what seems a somewhat cavalier approach to the isentropic
1969, 50, 5222.
condition. Perhaps there is a need for a new approach to the task 27 H. Høiland and E. Vikingstad, J. Chem. Soc., Faraday Trans. 1, 1976,
of understanding the significance of isentropic compressibilities 72, 1441.
of solution. 28 J. C. R. Reis, J. Chem. Soc., Faraday Trans. 2, 1982, 78, 1595.
29 M. J. Blandamer, Introduction to Chemical Ultrasonics, Academic
12 Acknowledgements Press, London, 1973.
30 G. Douhéret and M. I. Davis, Chem. Soc. Rev., 1993, 43.
I thank Professors H. Høiland (University of Bergen) and J. B. 31 G. C. Benson and M. K. Kumaran, J. Chem. Thermodyn., 1983, 15,
F. N. Engberts (University of Groningen) for valuable discus- 799.
sion. Also my long-suffering Secretary, Vikki, who has seen 32 G. Douhéret, C. Moreau and A. Viallard, Fluid Phase Equilibria, 1985,
this same paper (with alterations) more times than she cares to 22, 277, 289; 1986, 26, 221.
remember. 33 J. Lara and J. E. Desnoyers, J. Soln. Chem., 1981, 10, 465.
34 F. Franks, J. R. Ravenhill and D. S. Reid, J. Soln. Chem., 1972, 1, 3.
13 References 35 J. I. Lankford, W. T. Holladay and C. M. Criss, J. Soln. Chem., 1984, 13,
699.
1 I. Prigogine and R. Defay, Chemical Thermodynamics, trans. D. H.
Everett, Longmans Green, London, 1954: (a) p. 3; (b) p. 67; (c) p. 38; Received, 20th June 1997
(d) p. 266; (e) p. 52; (f) p. 59; (g) p. 54; (h) p. 48. Accepted, 5th August 1997

Chemical Society Reviews, 1998, volume 27 79