Adiabatic compressibility and structure of

aqueous solutions of ethyl alcohol

Cite as: J. Chem. Phys. 89, 4325 (1988); https://doi.org/10.1063/1.454816
Submitted: 24 February 1988 . Accepted: 15 January 1988 . Published Online: 04 June 1998

G. Onori

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© 1988 American Institute of Physics.

Adiabatic compressibility and structure of aqueous solutions of ethyl alcohol
G. Onori
Dipartimento di Fisica, Universita degli Studi di Perugia, Via Elce di Sotto, 06100 Perugia, Italy
(Received 24 February 1988; accepted 15 January 1988)
The adiabatic compressibility of ethanol-water mixtures has been measured as a function of
temperature and alcohol mole fraction; the measurements were carried out at 5 ·C intervals
over the 100000·C range of temperature and over the entire range of cosolvent concentration.
The experimental results are compared with other physicochemical measurements available for
these mixtures and discussed in terms of possible mechanisms of molecular aggregation in the
various regions of ethanol concentration.

I. INTRODUCTION With these points in view, a systematic study of the com-

The thermodynamic and physical properties of alcohol-
water mixtures have been studied extensively, particularly in
the water-rich region where an anomalous behavior is often
observed. 1-3
In spite of the great deal of work performed on these
systems, complete information is still lacking and no satis-
factory quantitative description of such solutions is avail-
able. As a rule, these studies refer to qualitative descriptions
of the observed behavior, often in some limited concentra-
tion ranges.
Though most properties of alcohol-water mixtures have
been closely investigated little attention has been paid to the
adiabatic compressibility /3s as a function of temperature T
and of cosolvent mole fraction X 2• The adiabatic compress-
ibility in a liquid mixture is a function of composition and is
strongly dependent on the nature and intensity of molecular
interactions. This makes possible the use of adiabatic com-
pressibility measurements to obtain information on the na-
ture of the interactions that the molecules of system ex-
change.
This paper is a continuation of our investigation of the
adiabatic compressibility of aqueous mixtures of monohy-
dric alcohols as a function of temperature and cosolvent
mole fraction. The main goal of this research is an under-
standing of the interactions between the components at the
molecular level. Previous /3s investigations of dilute aqueous
solutions of methanol, 4 ethanoV I-and 2-propanol6 ,7 strong-
ly suggest the existence of time-average clathrate hydrates in
the water-rich region, this structure collapsing when the ra-
tio of alcohol to water exceeds that of clathrates.
A simple model, involving the solute-solvent intrac-
tions and the molecular aggregation of solute was used to
explain the observed behavior. In this way, we were able to
describe sufficiently accurately the experimental data for the
water-methanol system over the whole mole fraction range,
while an analogous description for the other mixtures was
possible only in the water-rich region.
The simultaneous existence of clathrate-like partial cage
structure and OH-water hydrogen bonds is assumed in the
model proposed. One should thus expect compressibility
changes resulting from two independent types of solute-sol-
vent interactions. The relative balance of the two different
types of interaction could be evaluated by comparing data
from alcohols having hydrophobic groups of different sizes.
pressibility behavior of aqueous mixtures of ethanol over the
whole concentration range and from 10 to 4O·C has been
carried out and is presented in this paper. Preliminary re-
sults in the water-rich region have been presented else-
where. s The experimental data are compared with the pre-
viously obtained /3s data for the water-methanol system and
with other physicochemical measurements available for
these mixtures. The results are discussed in terms of struc-
ture changes in the aqueous alcohol solutions.
II. EXPERIMENTAL
Ultrasonic velocities were measured by means of a sing-
around velocimeter, model 6080, available from Nusonic
Corp., New Jersey, USA. Some measurements were also per-
formed using a variable-path interferometer working at 2
Mhz; the values thus obtained are coincident with those of
the sing-around velocimeter within the experimental error
limits. The temperature control was better than 0.1 ·C and
the measurement of sound velocity was reproducible within
±O.l m/s.
From the values of sound velocity and density p, the
adiabatic compressibility /3s was calculated by means of the
relation /3s = l/v2p. The densitieS used to calculate /3. from
velocity measurements were taken from the literature. 8
Ethyl alcohol (1. T. Baker, analytical grade) was used with-
out any further purification. The water used was distilled
and all mixtures studied were prepared by weighing the com-
ponents.
The ultraviolet absorption spectra were recorded with a
model 360 Shimadzu spectrophotometer; quartz cells 0.1 cm
long were used.
Water is designated as component 1 and the cosolvent as
component 2. Thus in the water-alcohol mixtures XI is the
mole fraction of water and X 2 = 1 - X I is the mole fraction of
alcohol.
III. RESULTS AND DISCUSSION
A. Adiabatic compressibility
The observed values of adiab~tic compressibility for the
water-ethyl alcohol system are shown in Table I. Some re-
sults at selected temperatures are also pictured in Fig. 1 (at
20 ·C), Fig. 2 (at 20 ·C), and Fig. 3 (at 10 and 40 ·C). For
comparison Figs. 1 and 2 also show the data obtained at a

J. Chern. Phys. 89 (7), 1 October 1988 0021-9606/88/194325-08$02.10 @ 1988 American Institute of Physics 4325
4326 G. Onori: Solutions of ethyl alcohol

TABLE 1. Sound velocities and isentropic compressibilities of ethanol-water mixtures. The calculated values ofP. were obtained from Eqs. (7) and (8) with
the parameter values reported in Table II.

IO IIP. IO IIP. IO " P.

2 (cm 2 dyn- ' ) (cm 2 dyn- ' )
(cm dyn- ' )
T v v v
(OC) 102x2 (ms- ' ) exp calc 102x2 (ms- ' ) exp calc 102x2 (ms- ' ) exp calc

10 0.789 1466.6 4.67 4.67 1.604 1486.2 4.56 4.56 2.437 1505.4 4.45 4.46
IS 1482.5 4.56 4.56 1501.1 4.47 4.47 1518.5 4.39 4.38
20 1498.2 4.48 4.48 1514.1 4.40 4.40 1529.8 4.33 4.32
25 1510.9 4.41 4.41 1525.1 4.34. 4.34 1539.2 4.28 4.27
30 1522.0 4.35 4.35 1535.1 4.29 4.30 1547.6 4.24 4.24
35 1531.2 4.31 4.31 1542.3 4.26 4.26 1553.7 4.21 4.21
40 1539.4 4.27 4.27 1549.8 4.23 4.23 1559.7 4.19 4.19
10 3.280 1526.1 4.35 4.35 4.165 1546.8 4.25 4.25 5.058 1566.8 4.15 4.15
15 1537.2 4.29 4.30 1555.3 4.21 4.21 1573.1 4.12 4.12
20 1546.3 4.25 4.25 1562.3 4.17 4.17 1577.7 4.10 4.10
25 1553.6 4.21 4.21 1567.8 4.15 4.15 1582.0 4.09 4.09
30 1559.8 4.17 4.18 1572.0 4.13 4.13 1584.6 4.08 4.08
35 1565.1 4.17 4.17 1575.6 4.12 4.12 1585.9 4.09 4.09
40 1569.9 4.15 4.15 1579.1 4.11 4.11 1586.5 4.08 4.08
10 5.978 1586.1 4.06 4.05 6.930 1602.6 3.99 3.97 7.898 1617.6 3.92 3.91
IS 1598.3 4.05 4.04 1603.4 3.99 3.97 1615.9 3.94 3.93
20 1591.9 4.04 4.03 1603.7 3.99 3.98 1613.9 3.95 3.95
25 1593.3 4.04 4.03 1603.1 4.00 4.00 1611.0 3.98 3.98
30 1593.7 4.05 4.03 1601. 7 4.02 4.01 1608.8 4.00 4.00
35 1592.9 4.06 4.07 1599.1 4.04 4.05 1603.6 4.03 4.q5
40 1591.8 4.08 4.08 1596.0 4.07 4.07 1598.7 4.07 4.07
10 8.905 1630.8 3.87 3.87 9.927 1640.8 3.83 3.84 10.98 1645.8 3.81 3.82
IS 1626.6 3.89 3.90 1634.0 3.87 3.88 1638.1 3.86 3.87
20 1622.2 3.92 3.93 1627.7 3.91 3.92 1629.8 3.91 3.92
25 1617.2 3.95 3.97 1620.9 3.95 3.96 1621.4 3.96 3.97
30 1611.2 4.00 4.00 1613.6 4.00 4.01 1612.6 4.02 4.03
35 1606.1 4.03 4.05 1605.9 4.05 4.07 1603.8 4.07 4.09
40 1599.5 4.08 4.09 1597.8 4.10 4.11 1594.2 4.13 4.14
10 12.07 1549.2 3.81 3.81 13.19 1650.6 3.81 3.82 14.33 1649.8 3.83 3.83
IS 1639.4 3.86 3.87 1640.1 3.87 3.88 1639.0 3.89 3.90
92 1629.5 3.92 3.93 1628.2 3.94 3.95 1625.5 3.97 3.98
25 1619.9 3.98 3.99 1616.6 4.01 4.02 1612.1 4.05 4.06
30 1609.4 4.05 4.05 1604.6 4.08 4.09 1598.6 4.13 4.14
35 1599.7 4.11 4.13 1593.8 4.15 4.18 1585.5 4.21 4.23
40 1588.2 4.18 4.18 1582.0 4.23 4.23 1572.6 4.30 4.29
10 15.52 1644.9 3.86 3.88 16.70 1639.9 3.90 3.90 18.03 1630.5 3.96 3.97
15 1622.9 3.95 3.96 1624.1 3.99 4.00 1610.4 3.99 4.00
20 1614.7 4.04 4.04 1607.2 4.09 4.08 1593.2 4.18 4.15
25 1599.8 4.13 4.13 1591.1 4.19 4.18 1578.8 3.27 4.26
30 1585.8 4.20 4.21 1575.6 4.29 4.27 1564.6 4.36 4.35
35 1572.7 4.30 4.32 1561.6 4.38 4.39 1551.6 4.46 4.47
40 1560.5 4.38 4.38 1549.1 4.46 4.44 1538.2 4.55 4.54
10 19.32 1617.7 4.04 4.04 20.66 1605.2 4.12 4.12 22.05 1586.4 4.23 4.22
15 1594.9 4.17 4.16 1578.5 4.27 4.25 1562.4 4.38 4.35
20 1578.8 4.27 4.24 1562.9 4.38 4.35 1549.7 4.47 4.46
25 1563.5 4.37 4.35 1550.0 4.47 4.45 1536.8 4.57 4.56
30 1550.4 4.46 4.44 1536.6 4.57 4.55 1523.2 4.67 4.66
35 1537.0 4.56 4.58 1522.6 4.67 4.69 1508.9 4.78 4.80
40 1523.0 4.66 4.64 1509.3 4.77 4.75 1495.8 4.88 4.88
10 23.49 1565.6 4.37 4.34 24.97 1548.8 4.48 4.48 26.50 1353.0 4.58 4.63
15 1549.2 4.48 4.47 1535.8 4.58 4.59 1521.5 4.68 4.77
20 1535.9 4.57 4.56 1522.4 4.68 4.69 1507.8 4.79 4.88
25 1522.9 4.67 4.68 1509.3 4.78 4.80 1495.0 4.89 4.98
30 1509.3 4.78 4.79 1495.6 4.89 4.92 1481.8 4.00 5.10
35 1495.2 4.89 4.92 1481.6 5.00 5.04 1466.9 5.13 5.20
40 1480.8 5.01 5.02 1467.3 5.12 5.16 1456.6 5.25 5.34
10 28.02 1522.6 4.68 31.40 1496.1 4.89 35.06 1471.0 5.11
15 1509.2 4.78 1482.6 5.00 1456.1 5.24
20 1496.5 4.89 1469.0 5.12 1441.8 5.37
25 1482.6 5.00 1455.2 5.24 1427.4 5.50
30 1468.6 5.12 1440.4 5.38 1412.8 5.65
35 1454.2 5.24 1425.6 5.51 1397.3 5.80
40 1439.8 5.37 1411.0 5.65 1382.7 5.95

J. Chern. Phys., Vol. 89, No.7, 1 October 1988

 G. Onori: Solutions of ethyl alcohol 4327

TABLE I (continued).

10 lip, IO llp, 10 11p,

2 I
(cm 2 dyn- I
) (cm dyn- ) (cm2 dyn- I )
T v v v
(DC) 102X2 (ms- I ) exp calc lQ2x2 (ms- I ) exp calc lQ2x2 (ms- I ) exp calc

10 38.94 1446.6 5.34 43.15 1422.3 5.58 5.60 47.70 1397.0 5.85 5.81
15 1432.2 5.47 1407.6 5.73 5.79 1381.5 5.99 6.03
20 1417.5 5.61 1392.8 5.88 5.93 1366.2 6.16 6.19
25 1402.9 5.76 1377.7 6.04 6.08 1350.7 6.33 6.36
30 1388.2 5.91 1361.8 6.21 6.25 1334.9 6.51 6.54
35 1372.4 6.08 1346.1 6.39 6.42 1318.6 6.71 6.74
40 1357.1 6.25 1331.0 6.56 6.60 1302.6 6.91 6.94
10 52.65 1374.0 6.11 6.06 58.18 1349.7 6.40 6.35 64.01 1326.3 6.71 6.66
15 1358.2 6.29 6.27 1333.5 6.60 6.57 1309.7 6.92 6.89
20 1342.3 6.47 6.45 1317.3 6.79 6.77 1292.9 7.13 7.11
25 1326.4 6.66 6.64 1301.1 7.00 6.98 1277.1 7.36 7.34
30 1310.2 6.86 6.84 1284.5 7.22 7.20 1259.5 7.60 7.58
35 1293.9 7.07 7.05 1267.4 7.45 7.43 1242.4 7.85 7.83
40 1277.4 7.29 7.27 1251.2 7.69 7.67 1225.5 8.11 8.10
10 70.63 1302.3 7.04 7.03 77.84 1275.4 7.44 7.43 86.09 1245.9 7.90 7.91
15 1285.1 7.27 7.28 1257.4 7.69 7.70 1228.2 8.17 8.19
20 1268.1 7.51 7.51 1240.3 7.95 7.96 1210.8 8.45 8.47
25 1251.3 7.75 7.76 1223.3 8.22 8.23 1193.5 8.75 8.77
30 1234.0 8.01 8.02 1206.0 8.50 8.51 1176.2 9.05 9.07
35 1216.8 8.29 8.30 1188.4 8.80 8.81 1158.3 9.39 9.41
40 1199.6 8.57 8.59 1171.2 9.11 9.13 1141.0 9.73 9.75
10 95.05 1213.5 8.45 8.43 100 1195.6 8.77 8.72
15 1195.8 8.74 8.73 1177.8 9.08 9.03
20 1178.6 9.05 9.04 1160.3 9.41 9.35
25 1160.7 9.38 9.36 1143.1 9.75 9.68
30 1143.9 9.71 9.69 1125.7 10.11 10.03
35 1126.1 10.08 10.05 1107.9 10.49 10.41
40 1108.9 10.45 10.42 1090.8 10.89 10.79

temperature value of 20 ·C for the water-methanol4 and for
the water-2-propanoI 7 systems.
The P. of pure water decreases on addition of small
amounts of alcohol. Since alcohol has a higher P. than the
water, graphs of compressibility vs alcohol mole fraction ex-
hibit a minimum. The position of the P. minimum shifts to
lower alcohol concentrations as the hydrophobic group be-
comes larger (Fig. 2). Besides this, the concentration at the
compressibility minimum is temperature dependent and de-
creases as the temperature increases (Fig. 3).
There is also evidence for a point of intersection of the
compressibility isotherms (Fig. 3), i.e., for a composition at
which the temperature coefficient of isentropic compress-
ibility, dP.IdT, is zero; the concentration at dP.IdT = 0 de-
pends upon the temperature and decreases as the tempera-
ture increases.
Similar results were observed by other authors9-12: the
available literature values are mostly above X 2 = 0.1 and at
25 ·C, the agreement with our values being generally good.
To rationalize the "phenomenon" most authors suggest
that the added alcohol enhances water-water interactions
such that the liquid structure resembles an alcohol clathrate.
Some authors 13 relate the formation of pseudoclathrate
structures to the minima of compressibility isotherms, while
others l4 •1s relate the formation of such structures to the
point of intersection of compressibility isotherms.
In our previously published papers it hw; been shown
that neither the minima nor the point of intersection have
any special meaning for the structural properties of the mix-
ture and, in this context, it has been shown that deviations
from an ideal behavior are more significant than direct data
for obtaining information on the molecular processes in the
mixture.
B. Excess values
The adiabatic compressibility is a quantity which refers
to a volume unit of solution and which does not take account
ofthe number of the interacting molecules. To describe the
P. vs X 2 behavior on the basis of molecular interactions, it is
better to take into account quantities that refer to a fixed
number of molecules. Examples of such quanitites are the
mean molar volume of the mixture
(1)
(M1 and M2 being the molecular weights) and the quantity
P.V= - cavlap). (2)
which accounts for the change of the solutions molar volume
of the solution under the influence of pressure.
The mean molar volume mainly reflects the intrinsic
volumes of the components and contains only a minor con-
tribution due to changes in molecular interactions. On the
other hand, the quantity P. V is a sensitive function of sol-
ute-solute and solute-solvent interactions and, as such, is a

J. Chern. Phys., Vol. 89, No.7, 1 October 1988

4328 G. Onori: Solutions of ethyl alcohol

11~----~----~----~----'-----~~
10

10
9

9
QJ 8
c:
>- q,
'0
Ne c:
>-
'0
~
Ne 8
at 7 2-
"0
~
at
I
"~ 7
6

6
5

o .2 .4 .6 .8
X,

FIG. 1. Adiabatic compressibility of water-methanol (A-A) and of wa-

ter--ethanol ( ..... ) mixtures as functions of cosolvent mole fraction. o .2 .4 .6 .8
T = 20 'C. The curves were obtained from Eqs. (7) and (8) with the pa- X,
rameter values reported in Table II.
FIG. 3. Adiabatic compressibility isotherms for the water--ethanol system
as a function ofx2 • The curves were obtained fromEqs. (7) and (8) with the
useful parameter for elucidating the structural interactions parameter values reported in Table II.
in the system. Letting V id be the ideal molar volume,
VI = MIlP and V 2 = M21P the molar volumes of the pure
components, we have
-id -
V = XlVI + X2-V2 (3)
(4)
for an ideal mixture. 16
Differentiating Eq. (3) with respect to pressure at con- Thus, PsV becomes linear in mole fraction if a system be-
stant entropy we have haves as an ideal solution. It is useful to divide the quantity
PsV into an ideal contribution, corresponding to Eq. (4),
and an "excess" quantity, (Ps V)E, representing the effect of
nonideality
(PsV)E=psV- (PsV)id. (5)
Nonideality usually arises from a difference in interaction
energies for like and unlike molecules. The excess quantity
(Ps V) E is predicted to become less positive and then increas-
ingly negative as the strength between unlike molecules in-
creases. 17,4
The excess quantity (Ps V)E calculated according to
Eqs. (5) and (4) is negative for all compositions in the wa-
ter-ethanol system (Fig. 4); the curve at 40 ·C is nearly sym-
metrical about X 2 = 0.5 but, on decreasing the temperature
D5 .1 .15 .2 .25 to 10 ·C, the curve shows a fairly complex shape and the
x,
minimum shifts to a lower X2 value. Moreover, the depen-
FIG. 2. Adiabatic compressibility of water-methanol (A-A). water--eth- dence of (Ps'V)E changes with temperature at x2>0.2, but
anol (..... ). and water-2-propanol ( ..... ) mixtures as a functions of co-
solvent mole fraction in the water-rich region. T = 20 ·C. The curves were
not at x2<0.2. Bearing in mind Eq. (5) this is equivalent to
obtained from Eqs. (7) and (8) with the parameter values reported in Table saying that in the 0-0.2 mole fraction and in the 10-40·C
II. temperature ranges

J. Chern. Phys .• Vol. 89. No.7. 1 October 1988

 G. Onori: Solutions of ethyl alcohol
Or------,------.------,------TI
.~
>-
'Q -40
~E
u
I>
cxr-60
.. . .
-80
40"C
-100 L ----±.25::-----.;-5------;.75;-----::---'
lt2
n
FIG. 4. Plots of the excess quantity (P. E vs X2 for the water-ethanol
system at 10 and 40 ·C. The curves were obtained from Eqs. (7) and (8)
with the parameter values reported in Table II.
(6)
that is, the thermal behavior of the mixture is similar to that
expected for an ideal mixture.
Note that the existence of an intersection point of the
adiabatic compressibility isotherms (Fig. 3), the value of
which is slightly temperature dependent, is also expected for
an ideal behavior of the mixture [Eq. (4) ]. This comes from
the fact that the temperature coefficient of the compressibili-
ty of water is negative and temperature dependent, while
that of ethyl alcohol is positive. Thus the existence of a com-
position at which the compressibility is independent oftem-
perature does not seem to be related to the formation of a
pseudoclathrate structure, as is sometimes claimed in the
literature but, rather, to the different behavior of the adiaba-
tic compressibility for alcohol and for water as the tempera-
ture varies. The same holds for the aqueous solutions of
methanol, I-and 2-propanol.
Plots of (P. V)E vs X 2 for the water-ethanol and water-
methanol systems at 20'C are shown in Fig. 5. As can be
seen, the character of the changes in (P. V) E is similar for the
two alcohols. Slight differences are present in the (0-0.50)
X 2 range, whereas the two curves are almost coincident in the
(0.50-1) x 2 range. It has been verified that, on the basis of
the data reported by Lara and Desnoyers,12 systems such as
water-2-propanol and water-tert-butanol also show the
same behavior as the water-methanol system in the 050-1
cosolvent concentration range.
The striking resemblance of the two curves shown in
Fig. 5 indicates that factors determining the excess quantity
.
(f3 V)E are not particularly sensitive to the hydrophobic .na-
ture of the alcohol. The data suggest that the effects assocIat-
ed with the interaction between water and nonpolar alkyl
group of the alcohol molecules are present only at low X2
values (x 2 <0.50) whereas at higher alcohol concentration
values the compressibility changes are due only to the inter-
J. Chem. Phys., Vol. 89, No.7, 1 October 1988
4329
.~
>-
'Q -40
~E
u
-80
o .25 .75
FIG. 5. Plots of the excess quantity (P. n E vs X 2 for the water-ethanol (e-
e) and water-methanol (A-A) mixtures at 20 ·C. The curves were ob-
tained from Eqs. (7) and (8) with the parameters values reported in Table
II.
action with the polar hydroxyl group of alcohol molecules.
In any case, the hydration of the hydroxyl group with
the formation ofless compressible structures is believed to be
the main contribution in the entire molar fraction range.
c. Apparent molar compresslbllty
Although the excess function (P.V)E analyzed above
gives information on the overall change in the local structure
of the system, it tends to minimize the phenomenon in the
dilute region where the more significant changes generally
occur. Partial and apparent molar quantities do not suffer
from this drawback and reflect more readily the characteris-
tic interactions and structural changes in both ends of the
mixtures.
Figure 6 shows the quantity (P. V)E /X2 as a function of
X 2 for the ethanol- and methanol~ater mixtures at 20 ·C.
This quantity is equal to <l>k - P.2 V2, where <l>k is the alco-
hol apparent molar compressibility.
-E
The observed concentration dependence of (P. V) /x 2
in the low concentration range has been widely discussed in
our previously published papers and an analogous behavior
was observed for all the four alcohol-water systems exam-
ined (methanol, ethanol, 1- and 2-propanol). This quantity
is nearly CQnstant at a low alcohol concentration but in-
creases steeply as more alcohol is added to the solution. Two
distinct regions becomes evident: the experimental points
can be described quite well by the functional form
0'X2'X~
(7)
X~'X2'X~
,
wherex~ = lformethanol, :::::0.25 for ethanol, :::::0.10 for 1-
propanol, and :::::0.12 for 2-propanol.
The best fit constants a,b,x~ at various temperatures
and for all the four examined systems are reported in Table
II. These parameters strongly depend on the alcohol used.
4330 G. Onori: Solutions of ethyl alcohol

mole fraction a point is reached X2 = x~, at which there is

o
·100
o tems. 18 As for the water-ethanol system, x~ diminishes
E
t -200
"tJ
Eu
-500L-_ _ _...J....._ _ _----l_ _ _ _...l.-_ _ _- '
o ~
x,
FIG. 6. Plots of the quantity (P,V)E /X2 at 20 ·Cas a function ofx2• (A-A)
water-methanol and (.... ) water-ethanol. The curves were obtained from
Eqs. (7) and (8) with the parameters values reported in Table II.
To be precise, the x~ and x~ values shift to lower alcohol
concentrations, the a value decreases and the b value in-
creases as the hydrophobic group becomes larger.
Expression (7) for «(J.V>E can be understood in terms
of a clathrate hydrate mode1. 4 - 7 In fact, the second order
term with respect to the concentration in Eq. (7) (range x~­
x~) may be related to the mutual interactions between the
solute molecules themselves. Such interactions thus occur
only for concentrations X 2 > x~. We may suppose that in the
concentration range 0<;;X2<X~, the alcohol molecules inter-
act with the water molecules and are kept physically apart by
virtue of the clathrate shells but with increase in cosolvent
insufficient water to accommodate the cosolvent in a clath-
rate-like structure and, for X 2 > x~, two or more alcohol mol-
ecules come into contact.
Note that the values found for x~ (see Table II), are
close to those at which a minimum in the partial molar vol-
ume of the nonaqueous component occurs for the same sys-
slightly when temperature increases, assuming values close
to those which characterized a solid hydrate of type II hav-
ing the composition ethanol-17H 2 0.
The existence of time-average clathrate hydrate-like
structures of the type ethanol-17H 20 in ethanol-water mix-
tures was first proposed by Glew '9 to account for an anoma-
lous molar volume at about a 0.06 mole fraction of ethanol in
ethanol aqueous solutions. Moreover, dielectric data indi-
cate the existence below - 73 ·C of solid ethanol hydrate of
composition ethanol-17H 2 0 with the ethanol molecule
strongly hydrogen bonded to its water cage. 20 Our compress-
ibility data further support the existence of clathrate hy-
drate-like structures of type II in ethanol-water mixtures in
the water-rich region.
In the range 50-100 mol % ethanol, where the values of
the excess quantity «(3. V) E for the water ethanol and water
methanol are very similar (see Figs. 5 and 6), the experimen-
tal data can be described by the relation
(11 )
This functional form is like that for a random distribution
for the water-alcohol interactions. 4
The best-fit constant c at various temperatures is report-
ed in Table II. The curves shown in Figs. 1-6 and the calcu-
lated values of (3. reported in Table I were obtained from
Eqs. 7 and 8 with the parameter values reported in Table II.
The agreement between the experimental and calculated
compressibility is very good.
D. Hydrophobic solvation
The concentration dependence of the (3. of ethanol-wa-
ter mixtures in the water-rich region indicates that the nega-
tive excess compressibility «(3. V) E appears as the sum of two

TABLE II. Coefficients for the least-squares representations by Eqs. (7) and (8) of isentropic compressibility
of water-alcohol mixtures.

I lO"a lO"b 10" c

("C) lo"x; (cmSdyn-'mol-') (cmSdyn -'mol-') (cm'dyn - 'mol- , )

Methanol 20 9.0 -296 325.3 - 325.3

Ethanol 10 6.66 -496 1164 - 299.5
15 6.55 -498 1125 - 310.6
20 6.36 -484 1077 - 319.8
25 6.03 -483 1026 - 331.6
30 5.57 -489 997 - 342.7
35 5.27 -496 969 - 356.9
40 4.55 -510 961 - 371.9
I-Propanol 20 3.6 - 590 4138
2-Propanol 20 4.5 -717 3342

J. Chem. Phys., Vol. 89, No.7, 1 October 1988

 G. Onori: Solutions of ethyl alcohol 4331

tion that the total concentration range can be divided into

four partial ranges (0 - x~, x~ - x~, x~ - x~, and x~ - 1,
with x~:::: 1/18, x~:::: 1/6.75, x~ ::::0.50) in which distinct
-
,
o
and different structural effects predominate. The same sug-
gestion comes from other physicochemical properties of the
E mixture l - 3 and, in particular, from an ultraviolet absorption
'(I)
c: -10
study ofthis system recently performed in our laboratory.22
"0
>- In this contest, we should like to report succinctly the results
"'E obtained at 20 .c.

-u It is known that saturated alcohols in the gas phase be-

gin to absorb near 200 nm with the maximum of the first
band near 185 nm. 23 This band has usually been ascribed to a
n --+ u* transition,24 i.e., absorption of a photon in this spec-
-20 tral region results in the excitation of a nonbonding electron
of the hydroxyl oxygen to an antibonding u* orbital of the
alcohol. The involvement of the oxygen-unshared pairs of
electrons in hydrogen bonding exerts a great influence on the
o .1 absorption spectrum. 25 To be precise, the presence of such
bonds lowers the transition probability of the optical elec-
trons. In fact, the absorbance of alcohols is much lower in
FIG. 7. Plots of the quantity A, [seeEq. (13) 1for the water-ethanolsystem the neat liquid24 than in the gas phase23 and, besides, in the
at 20 and 40 ·C as a function of x 2 • liquid the absorbance increases strikingly on raising the tem-
perature. 22 The alcohol absorbance in the range 185-200 nm
is therefore a sensitive probe of alcohol-alcohol or water-
negative contributions: one, ~I associated with the interac-
alcohol hydrogen bonding in the water-alcohol mixtures.
tion between water and nonpolar alkyl group of the alcohol
Figure 8 shows the absorbance at 194 nm (A 194) of wa-
molecules (hydrophobic solvation) and the other ~2 asso-
ter~thanol mixtures at 20 ·C as a function of molar alcohol
ciated with the polar hydroxyl group (hydrophilic solva-
concentration. It is evident that the observed absorption co-
tion).
efficient of the mixture is markedly dependent on solute con-
Moreover, data suggest that in the 50-100 mol % eth-
centration. In the water-rich region, the absorbance in-
anol range ~1..(~2; then, taking into account Eq. (8)
(9)
for high ethanol concentration.
Assuming that Eq. (9) for ~2 does not change in the
entire molar fraction range, it is possible to evaluate the con- .05 .1 .15.2 .25 3 .4 .5 .6 .8 1
tribution of ~ 1 by means of
~I = (Ps V)E - CX 1X 2• (to) to
Figure 7 shows the value of ~I obtained from Eq. (to) for .9
the water~thanol system at to and 40 ·C. ~I is negtive and
characterized by a minimum at x~ ::::0.15 for a temperature .8
value of to .c. As the temperature increases, the ~I absolute
value decreases; moreover, there is a small shift of the mini- .7
mum towards lower concentration values (x~::::0.14 at
T=40·C).
Note that the molar concentration of 0.15 corresponds
.5
well to the observed maximum viscosity enhancement in su-
percooled solutions of ethanol and that, on the grounds of
.4
this result, it has been suggested that a stable type I hydrate . I
with formula C 2 H sOH-5.75 H 20 is present in solution at .3
ethanol concentrations of 15-20 mol %.22
For the water-methanol system experimental data fit .2
Eq. (8) well over almost the whole concentration range ..
(x~ .;;;x2 .;;;1). Thus, the contribution due to hydrophobic hy-
dration seems to be negligible for this system.
.1
.. ..-.-... .
•_•• - t
~

o 2 4 6 8 m ~ ~ ~ ~
E. Ultraviolet absorption spectra C (mol. 1- 1 )
The analysis we have performed of the adiabatic com- FIG. 8. Absorbance at 194 nm, A,.,., of the water-ethanol mixture at 20·C
pressibility of the ethanol-water system leads to the sugges- as a function of molar alcohol concentration.

J. Chern. Phys., Vol. 89, No.7, 1 October 1988

4332 G. Onori: Solutions of ethyl alcohol
creases linearly with the molar alcohol concentration, in
accordance with Beer's Law, up to a critical concentration of
x~ ::::;0.055. For X2>X~ a linear behavior is again observed
with a lower slope. This means a decrease in the molar ex-
tinction coefficient. Variations in the absorption coefficient
also appear in the 15-16 mol % and in the 50-60 mol %
ethanol ranges.
The anomalous behavior observed in the ultraviolet ab-
sorption coefficient, in agreement with what is suggested by
compressibility measurements, may reflect the change in the
state of association at the cosolvent mole fractions indicated
due to H bonding between alcohol-alcohol and alcohol-wa-
ter molecules.
IV. CONCLUSIONS
The analysis we have performed shows a complex de-
pendence of the adiabatic compressibility of water-ethanol
mixtures on cosolvent mole fraction. The Ps vs X 2 behavior
observed cannot be discussed in terms of a single molecular
mechanism throughout the entire concentration range. In a
first approximation the properties of these mixtures can be
understood by considering four mole fraction ranges defined
by "signpost" mole fraction x~, x~, xL with x~::::: 1/18,
x~::::: 1/6.75,x~ :::::0.50. This subdivision is also supported by
other properties of water-ethanol mixtures.
The observed compressibility behavior suggest that the
ethanol molecules are essentially dispersed and surrounded
by water molecules at low ethanol concentration (x 2 <x~)
and that they only come into contact when there is no longer
sufficient water to provide clathrate cavities for all the eth-
anol molecules. In the x~ 'X2'X~ range a number of possible
structures can be envisaged. For instance, we may suppose
the evolution of alternative clathrate structures involving
monomeric alcohol units or structures in which two alcohol
molecules occupy one larger cavity or, alternatively, struc-
tures in which alcohol molecules enter the mixtures in a non-
clathrated manner. In this respect it must be noted that wa-
ter is a remarkably versatile substance with regard to
hydrate formation being capable offorming a large variety of
cage-like structures. 26 In the case ofethanol-water mixtures,
there is evidence that in addition to a type II clathrate pres-
ent in the very dilute region, 19,20 a type I clathrate with stoi-
chiometric formula C 2 H sOH-5.75 H 20 is also present for
concentration of 15%-20% ethanol. 21 Our analysis of ex-
perimental data indicate that effects due to hydrophobic sol-
vation are still increasing for X 2 > x~ and become maxima for
J. Chern. Phys., Vol. 89, No.7. 1 October 1988
a concentratin of ::::: 15 mol % ethanol. This concentration
corresponds well with the type I clathrate C 2 H sOH-5.75
H 20 which is 14.8% ethanol. This finding, therefore, sup-
ports the hypothesis21 that on increasing the ethanol content
in the x~-x~ range the structure of the water-ethanol mix-
ture evolves towards a type I clathrate structure.
In the x~,x2,xi range effects due to hydrophobic sol-
vation becomes more and more smoother as X 2 increases. In
this range a gradual depolarization of the water structure
and, at the same time, the formation of aggregates contain-
ing H -bonded water and alcohol molecules, where the solute
molecules no longer fill the cages, is expected.
Finally, the data suggest a random distribution of mo-
lecular interactions in the x~ ,x2 ' 1 range. In this range ef-
fects due to hydrophobic solvation become negligible; solva-
tion of the polar group and associations of the solute
molecules are predominant in determining the concentra-
tion dependence of the adiabatic compressibility of concen-
trated solutions.
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