Topic 3140

Volume; Liquid Mixtures

A given binary liquid mixture is prepared using n1 moles of liquid 1 and n2 moles of
liquid 2 at temperature T and pressure p. The term ‘mixture’ usually means that a
homogeneous single liquid phase is spontaneously formed on mixing characterised by
a minimum in Gibbs energy G where the molecular organisation is characterised by
ξeq. G Em measures the extent to which G /(n 1 + n 2 ) differs from this ratio in the event
that the mixing is, in a thermodynamic sense, ideal.
A given binary liquid mixture is displaced to a neighbouring state by a change in
pressure at constant temperature. The overall composition remains at (n1 + n2) but the
organisation changes to a new value for ξeq where ‘A = 0’. The differential
dependence of G Em on pressure at constant temperature T is the excess molar volume

VmE .

 ∂G (mix ) 
V(mix) =   (a)
 ∂p  T ,A =0

 ∂G Em 
VmE =   (b)
 ∂p  T , A =0

 ∂G m 
For the molar volume, Vm =   (c)
 ∂p  T ,A =0

The quantities, V(mix), Vm and VmE are interesting because they can be determined

[1] whereas the same cannot be said for G(mix) and Gm although G Em can be obtained
from vapour pressures of mixtures and pure components.
Vm = V(mix) /(n 1 + n 2 ) (d)
Density, ρ(mix) = (n 1 ⋅ M 1 + n 2 ⋅ M 2 ) / V(mix ) (e)
M1 and M2 are the molar masses of the two liquid components. By measuring ρ(mix)
as a function of mixture composition, we form a plot of molar volume Vm as a
function of mole fraction composition. The plot has two limits;
lim it ( x 1 → 1)Vm = V1* (l) (f)

lim it ( x 2 → 1)Vm = V2* (l) (g)

If the thermodynamic properties of the binary liquid mixture are ideal (i.e. VmE = 0) ,

Vm (id ) = x 1 ⋅ V1* (l) + x 2 ⋅ V2* (l) (h)

Or, Vm (id ) = (1 − x 2 ) ⋅ V1* (l) + x 2 ⋅ V2* (l) (i)

Hence, Vm (id ) = V1* (l) + x 2 ⋅ [V2* (l) − V1* (l)] (j)

The latter is an equation for a straight line. The molar volume of a real binary
liquid mixture is usually less than Vm(id). For a real binary liquid mixture,
Vm (mix) = x 1 ⋅ V1 (mix) + x 2 ⋅ V2 (mix ) (k)
The difference between the molar volume of real and ideal binary liquid mixture
is the excess molar volume VmE .

VmE = x 1 ⋅ [V1 (mix) − V1* (l)] + x 2 ⋅ [V2 (mix) − V2* (l)] (l)

Or, VmE = x 1 ⋅ V1E (mix ) + x 2 ⋅ V2E (mix ) (m)

A given mixture, mole fraction x2 at temperature T and pressure p, is perturbed by
addition of δn 2 moles of chemical substance 2. The system can be perturbed either at
constant organisation ξ or constant affinity A
 ∂V 
Here we are concerned with   , the (equilibrium)
 ∂n 2  T ,p ,n (1),A = 0
partial molar volume of substance 2 in the mixture, V2(mix) .The condition' A
= 0' implies that there is a change in organisation ξ in order to hold the system in the
equilibrium state. A similar argument is formulated for the (equilibrium) partial molar
volume V1(mix). Moreover according to the Gibbs-Duhem equation (at constant
temperature and pressure),
n 1 ⋅ dV1 (mix ) + n 2 ⋅ dV2 (mix) = 0 (n)
Further, V(mix ) = n 1 ⋅ V1 (mix ) + n 2 ⋅ V2 (mix ) (o)
The property V(mix) is directly determined from the density ρ(mix).
V(mix) = (n 1 ⋅ M 1 + n 2 ⋅ M 2 ) / ρ(mix) (p)
The important point is that the thermodynamic extensive property V(mix) is directly
determined by experiment whereas we cannot for example measure the enthalpy H(mix). The
excess molar volume is given by equation (l) .

dVmE dV (mix ) (q)

= [V1 (mix ) − V1* (l)] + x 1 ⋅ 1
dx 1 dx 1
dV2 (mix )
- [V2 (mix ) − V2* (l)] + x 2 ⋅
dx 1
Using the Gibbs -Duhem equation,
dVmE
= [V1 (mix ) − V1* (l)] − [V2 (mix ) − V2* (l)] (r)
dx 1

dVmE
Or, [V1 (mix ) − V1* (l)] = + [V2 (mix) − V2* (l)] (s)
dx 1

From equation (l) ,

dVmE
VmE = x 1 ⋅ + x 1 ⋅ [V2 (mix) − V2* (l)] + x 2 ⋅ [V2 (mix ) − V2* (l)] (t)
dx 1

dVmE
Hence, [V2 (mix ) − V (l)] = V - x 1 ⋅
*
2
E
m (u)
dx 1
The derivation leading up to equation (s) is the 'Method of Tangents'.
dVmE
Moreover at the mole fraction composition where is zero,
dx 1

[V2 (mix) − V2* (l)] equals VmE .

For liquid component 1 the chemical potential in the liquid mixture is related to the mole
fraction composition (at temperature T and pressure p).
p

µ1 (mix, T, p) = µ (l, T ) + R ⋅ T ⋅ ln(x 1 ⋅ f 1 ) + ∫ V1* (l; T ) ⋅ dp

*
1 (v)
p0

At temperature T and pressure p, V1 (mix) = V1* (l) + R ⋅ T ⋅ [∂ ln(f 1 ) / ∂p]T (w)

But V1E (mix) = V1 (mix) − V1* (l) (x)

Hence, V1E (mix) = R ⋅ T ⋅ [∂ ln(f 1 ) / ∂p]T (y)

Then, VmE (mix) = R ⋅ T ⋅ {x 1 ⋅ [∂ ln(f 1 ) / ∂p]T + x 2 ⋅ [∂ ln(f 2 ) / ∂p]T } (z)

Footnote
[1] R. Battino, Chem.Rev.,1971,71,5.
[2]
(a) CmH2m+2 as a solute in CnH2n+2 solvent; H. Itsuki, S. Terasowa, K. Shinora and
H. Ikezawa, J Chem. Thermodyn.,19897,19,555.
(b) 60[Fullerene} in apolar solvents; P. Ruella, A. Farina-Cuendet and
U.W. Kesselring, J. Chem. Soc. Chem. Commun.,1995,1161.