LEC

Partial molar volumes

02.05

Related concepts Support rod, l = 500 mm 02032.00 2

Principles of thermodynamics, ideal and non-ideal behaviour of Right angle clamp 37697.00 5
gases and liquids, volume contraction, molar and partial molar Universal clamp 37715.00 4
quantities. Pycnometer, calibrated, 25 ml 03023.00 9
Bottle, narrow neck, 100 ml 41101.01 9
Principle Funnel, glass, do = 55 mm 34457.00 9
Due to intermolecular interactions, the total volume measured Glass beaker, 50 ml, tall 36001.00 2
when two real liquids (e.g. ethanol and water) are mixed deviates Pasteur pipettes 36590.00 1
from the total volume calculated from the individual volumes of Rubber bulbs 39275.03 1
the two liquids (volume contraction). To describe this non-ideal Rubber tubing, di = 6 mm 39282.00 3
behaviour in the mixing phase, one defines partial molar quanti- Hose clip, d = 812 mm 40996.01 4
ties which are dependent on the composition of the system. The Wash bottle, 500 ml 33931.00 1
values of these can be experimentally determined. Ethyl alcohol, absolute, 500 ml 30008.50 1
Water, distilled 5 l 31246.81 1
Tasks
Measure the densities of different ethanol-water mixtures of Set-up and procedure
specified composition at 20C with pycnometers. Calculate the Set up the experiment as shown in Fig. 1.
real volumes and the mean molar mixing volumes of the investi- Prepare the ethanol-water mixtures in the narrow neck bottles
gated ethanol-water mixtures and also the partial molar volumes on the laboratory balance in the approximate mass composition
of each liquid for selected compositions. Compare them with the specified in Table 1, weighing ethanol into the predetermined
molar volumes of the pure substances at 20C. mass of water (weighing accuracy 0.001 g). Close the bottles
immediately when the desired mass has been reached. Fill dry
Equipment pycnometers of known empty mass completely with the mix-
Precision balance, 620 g 48852.93 1 tures. Cover them with aluminium foil and position them in the
Immersion thermostat, 100C 08492.93 1 temperature-controlled bath for about 30 min at 20C for tem-
Bath for thermostat, 6 l, Makrolon 08487.02 1 perature equilibration. Subsequently, remove the pycnometers
H-base -PASS- 02009.55 1 and weigh them after meticulous drying.

Fig. 1. Experimental set-up.

PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen P3020501 1
 LEC
Partial molar volumes
02.05

Calculate the masses of 25 ml of the respective mixtures as the The dependence of it on the composition is described by the
difference of the two weights. relationship

d 1MV2
1VA VB 2 1VA VB 2
m (C2H5OH) / g m (H2O) / g d Vr d Vid
(6)
30.6 1.35 dxA dxA dxA

29.35 2.85
27.90 4.70 under consideration of the Gibbs-Duhem equation.
Analogous correlations can be formulated for xB due to the fact
26.20 6.85 that xA = 1 - xB.
24.15 9.45 After substituting (6) in (5), the following relationships are
obtained:
21.60 12.65
18.35 16.75 d 1MV2
VB MV xA VB (7.1)
14.15 22.10 dxA
8.35 29.40
and

Table 1: Ethanol-water mixtures to be investigated d 1MV2

VA MV xB VA (7.2)
dxA
Theory and evaluation
The volume vid and the mean molar volume Vid of an ideal mix- According to this, the partial molar volumes of the components
ture of the components A and B can be calculated if the quanti- A and B for the specific compositions (xA, xB) can be determined
tative composition is known. if the molar volumes of the pure substances (VA, VB) and their
nA differential quotients d (M V) / dxA are known. These can be
xA (1.1) obtained as the tangent to the graphical plot of MV versus xA
nA nB (Fig.2). This is, however, better calculated by deriving the func-
tional correlation MV = f(xA) for selected values of xA.
nB
xB (1.2) The following procedure is recommended for this: First, calcu-
nA nB late the exact mole fractional compositions from the weighed-
out masses of ethanol (A) and water (B) using equation (1.1) or
xA, xB mole fraction of the components A and B, respectively (1.2). With the pycnometer data (m = mass of the liquid in the
nA, nB amounts of A and B respectively pycnometer; v = 25 ml = pycnometer volume), the densities
(r = m/v) of the mixtures and the volumes vr corresponding to
vid the total masses (mA + mB) can be determined. These values can
Vid VAxA VBxB (2)
nA nB be converted into the mean molar volume vr using equation (4)
and then into the mean molar mixing volume MV in accordance
However, the assumed additivity in equation (2) loses its validity with equations (2) and (5).
in cases of real mixtures (e.g. ethanol / water). The real volumes The molar volumes of the pure liquids required for these conver-
vr and Vr deviate more or less strongly from the ideal volumes sions are VA = 58.277 ml / mol (ethanol) and VB = 18.073 ml /
due to volume contraction but can still be calculated if the molar mol (water) at T = 293.15 K.
volumes of the pure components A and B are replaced by the Plot the dependence of the mean molar mixing volume MV on
partial molar volumes VA and VB which are independent of the the composition xA analogous to Fig.2, and determine the differ-
composition. ential quotients d(MV) / dxA from the slope of the tangents for
selected mole fractions xA and the corresponding estimated val-
VA a b
0vr
(3.1) ues for MV from the curve itself.
0nA T,p,nB
[Note: The correlation between the variables can also be approx-
imated by a polynomial of the second or higher degree using a
VB a b
0vr
computer-assisted method. By substituting arbitrary mole frac-
(3.2)
0nB T,p,nA tions xA in the polynomial or its first derivative, the correspond-
ing estimated value for MV and the differential quotients d(MV)
vr / dxA can be calculated.]
Vr VAxA VBxB (4)
nA nB The partial molar volumes of both components are now acces-
sible via equations (7.1) and (7.2).
The difference between the mean molar volumes defined Finally, calculate the mean molar volume Vr for a selected mix-
according to equations (2) and (4) is designated as the mean ture which corresponds well to the experimental conditions from
molar mixing volume MV and is an intensive measure of the the partial molar volumes determined according to equation (4)
deviation of the mixture from ideal behaviour. and compare it with your experimental results.

MV Vr Vid

3 1VA VB 2 1VA VB 2 4xA 1VB VB 2

(5)

2 P3020501 PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen
 LEC
Partial molar volumes
02.05

Data and results

Fig. 2 illustrates the volume contraction that occurs on mixing of
ethanol and water. From the corresponding polynomial and its
first derivate, e.g. for xA = xB = 0.5, one obtains the partial molar
volumes VA = 56.64 ml / mol (ethanol) and VB = 16.82 ml / mol
(water) by substitution in equations (7.1) and (7.2). These values
are definitely less than the molar volumes of the pure substances
at 273.15 K (VA = 58.277 ml / mol, VB = 18.073 ml / mol).
Substituting these values in eqn. (4), one obtains a mean molar
volume of Vr = 36.73 ml / mol. The perfect agreement with the
experimentally determined value (Vr = 36.73 ml / mol) confirms
the validity of the additivity shown in eqn. (4) and thus the utility
of the partial molar volumes for the calculation of the volume of
mixed phases of known composition.

Fig. 2: Dependence of the mean molar mixing volumes MV

on the composition of different ethanol-water mixtures
described by the mole fraction xA of ethanol (T =
293.25 K)

PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen P3020501 3
 LEC
Partial molar volumes
02.05

4 P3020501 PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen