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Surface Tension and Molar Surface Free Energy and Entropy of Water To - 27.2
Surface Tension and Molar Surface Free Energy and Entropy of Water To - 27.2
Surface Tension and Molar Surface Free Energy and Entropy of Water To - 27.2
Surface Tension and Molar Surface Free Energy and Entropy of Water to -27.2 O C
To remove a deficiency in the growing data base on supercooled water, the surface tension of water has been measured, using
a small-sample capillary rise method, down to -27.2 "C. The data do not accord with extrapolations of equations best fitting
data above 0 O C but show a more rapid increase with decreasing temperature. This distinguishes water from other
hydrogen-bonded fluids and focuses attention on weaknesses of classical interpretations of the temperature dependence of
the surface tension. The observations are related to recent molecular dynamics studies of water surface tension. The possibility
of an artifact in experimental studies, caused by anomalous gas solubility in the supercooled regime, is recognized.
-i
-18.5 69 5 15.645 78.32
-17.5 69 6 10.718 78.27
-1 5.8 67 7 10.67 1 78.17
- I 5.3 68 7 10.656 78.07 -Capillary Tube
-14.1 71 4 15.508 77.59 h
-1 3.5 71 5 15.540 77.81
-12.5 71 6 10.614 77.52 I
-1 1.1 69 3 15.736 76.87
- 10.6 68 1 41.315 77.77
-10.6 68 2 42.872 76.51
-10.5 69 7 10.549 77.29
-9.8
-9.1
-8.0
-7.6
-5.7
69
72
73
70
70
7
4
6
7
3
10.560
15.386
10.574
10.492
15.635
77.37
76.99
77.24
76.88
76.39
1 ,/511!:-4-25 ml Flask
-5.3 75 6 10.543 77.04 -
-5.0 68 1 40.884 76.96
-5.0 68 2 42.592 76.01 Figure 1. Schematic diagram of capillary rise apparatus used to deter-
-3.6 73 4 15.150 75.82 mine surface tension of supercooled water. Only uppermost 1 cm of
-3.4 70 7 10.433 76.45 water column is cooled.
-3.2 71 7 10.387 76.12
-1.8 73 5 15.150 75.87 Measurements were always made with a descending meniscus.
-1.0 70 3 15.453 75.50 After temperature equilibration the column of water was pumped
0.3 71 7 10.352 75.86 to a position a few millimeter higher than the equilibrium position
0.5 13 4 15.064 75.44 by gently applying pressure through the side opening of the
1.5 74 6 10.358 75.67 reservoir flask (see Figure 1) and then allowing the meniscus fall
1.6 70 3 15.453 75.50
2.3 73 4 15.001 75.07 back to the equilibrium position. This procedure was repeated
several times and the equilibrium position was never observed to
3.7
3.7
4.3
68
68
14
1
2
6
39.785
42.475
10.324
74.89
75.80
75.43
-
vary by more than 10 pm except when an attempt was made
to reduce the diameter of the capillary below approximately 20
4.8 71 7 10.291 75.42 pm to increase the depth of supercooling attainable. The major
5.6 73 5 14.946 74.85 source of error in these measurements was the reading of the
7.3 73 6 10.273 75.05 reference level in different sets of measurements. Within any one
7.4 73 4 14.827 74.20 series the scatter is less than the overall.
9.6 71 7 10.159 14.45 With the very small diameter tubing, results were irreproducible
12.1 73 5 14.768 73.96
14.0 71 7 10.090 73.94
because the movement of the meniscus in the long columns sup-
16.2 70 1 10.018 73.41 ported in the case of small-diameter tubings was very sluggish
24.8 71 5 14.380 72.00 (partly because of the r4 dependence of the Poiseuille flow times
24.9 71 6 9.858 72.00 and partly for reasons unknown). The reproducibility and the
24.9 71 4 14.390 72.00 flow time problems were largely solved by replacing the long fine
25.0 70 3 14.737 72.00 capillary by a composite of a short length of a fine capillary for
25.4 68 7 9.828 72.00 the meniscus sealed into the end of a long wide-bore tube, for
29.1 61 7 9.768 71.55 which the column of water supported was, of course, the same
33.3 69 6 9.648 70.45 height. Unfortunately, the increase in supercooling expected with
37.2 68 4 13.994 70.00
40.9 66 6 9.478 69.19
this column, in which only the fine bore part was really cold, was
43.0 62 7 9.487 69.46 not obtained, and no refinement of the modification was attempted.
48.0 63 6 9.333 68.1 1
48.4 60 7 9.340 68.37 Results
53.0 61 6 9.274 67.67 The experimental values of the surface tension of water under
55.4 63 4 13.401 67.00 its own vapor pressure obtained between -27.2 and 60.0 O C are
60.0 54 7 8.975 65.66 reported in Table I and displayed in Figure 2. In Table I are
60.0 57 6 9.030 65.86 also listed other values used in the calculation of u, including the
"The density was calculated assuming that 1 em of the total water density that was obtained as explained in the previous section,
column, h, was at temperature T while the rest was at room tempera- and the capillary diameters. In Figure 2 the thick solid line
ture, RT. using p = ( l / h ) u , + [(! - , I ) / h ] p , + where the densities represents values obtained from an interpolation equation due to
were taken from ref 1 Ib. b T h e capillaries were (number, radius/pm): Vargaftik et a1.6
I , 38.5; 2, 36.5; 3, 99.91; 4, 102.30; 5, 102.38; 6, 149.34; 7, 149.04.
'Difference between the level of water in the capillary, h. and in the
reservoir, see Figure I ,
level of water in the reservoir (the differences between which (6) (a) Vargaftik, N. B.; Volkov, B. N.; Voljak, D. L. J . fhys. Chem., ReJ
Data 1983, 12, 817 and earlier references therein. (b) Gittens, G. J. J. Colloid
establish h) were measured to f10 pm with a cathetometer lnrerfuce Sci. 1969,30,406. (c) Straub, J.; Rosner, N.; Grigull, V. Wiirme-
(Precision Tools and Instruments Co., Ltd., England). und Sroffiibergung; Springer-Verlag: New York, 1980; p 241.
Surface Tension of Water The Journal of Physical Chemistry, Vol. 94, No. 10, 1990 4201
Sutface Tension(mN/m)
0 100 2W 300 T,
I , , 1 8 1 1 I 1 1
-40 -20 0 20 40 60 80 100 120 140
T/'C
association factor x between 60 and -27.5 O C . x of eq I5 will literally and calls d u / d T its entropy, then the heat capacity per
go inversely as k which is plotted in Figure 3. The low-tem- mole of the surface phase would be negative, which is impossible
perature increases of k seen in Figure 3 suggests that the asso- since a heat capacity is connected, in statistical thermodynamics,
ciation in water, as opposed to other hydrogen bonded liquids, is to the square of an entropy fluctuation.16 Fortunately, as Widom
decreasing with decreasing temperature in the supercooled regime has stre~sed’~,’’the identification of du/dT as an entropy depends
where all other evidence suggests the contrarq. Clearly the on a special, and arbitrary, choice of the dividing surface (such
classical interpretation of deviations from the Eotvos rule is in- that excess mass per unit area is zero). Furthermore,” to interpret
adequate, as indeed has long been realized on other grounds.I2 the temperature dependence of d u / d T as a heat capacity would
An alternative and preferred interpretation of the anomalous require a more complicated, even temperature-dependent, choice
temperature dependence of water and other H-bonded liquids has of dividing surface. I n any case the surface cannot be considered
been suggested by G00d.l~ Good calculated the molar surface independently of the bulk and it is only the total heat capacity
entropy S, defined from the specific surface entropy s, = d c / d T of the system (which is dominated by the bulk value) which must
bY remain positive.”
da du These considerations should not lead us to dismiss the distinction
S, = s,A = l.10p/3N’/3- = l . 1 0 ( M / p ) * / 3 N - (6) between water and other hydrogen-bonded liquids at low tem-
dT dT peratures. We suspect this difference is related to the fact that,
for a large number of hydrogen bonded, polar, and nonpolar liquids at the surface of water, the open network structure, which is the
-
and showed that the hydrogen bonded liquids fell into a separate
group. This group had S, values of 10-1 5 J mol-’ K-’ (1.4-2R)
source of rapid entropy decrease in supercooling bulk water, is
missing. However there is another possibility to be considered.
-
compared to -24 J mol-’ K-’ (2.93R) for nonpolar liquids. The
deficiency of 1.6R entropy units for water was attributed by
Good to the hydrogen bonded ordering of a small number, 1.6R/R
It is possible that the upturn in d u / d T below 0 “C is an artifact
peculiar to water, as follows. There is some suggestion, in the
equations used to fit data on the solubility of gases in water,I8
In 2 (=2.3), of outer layers of the water surface. The unusual that the solubility may increase anomalously in the supercooled
(large positive) temperature dependence of the S, for hydrogen- regime and perhaps tend to infinity near the -45 “C tran~ition.l~.*~
bonded liquids was then very reasonably interpreted in terms of Since our interface is exposed to nitrogen, the surface gas con-
the disordering of the inner layers with increasing thermal ex- centration could increase anomalously and, by providing the guest
citation. molecules for a clathrate-like structuring in the surface layers,
Good’s interpretation has been examined by Matsumoto and enhance the structure-related increase of the “pure” water surface
KataokaI4 in the light of their detailed molecular dynamics sim- tension. Indeed, Beagleholezl has recently reported anomalies in
ulation of the liquid-vapor interfaces of water (using the Car- the surface structure of water when subjected to a temperature
ravettaxlementi pair potential) and of the Lennard Jones system. gradient in the presence of gases, which are not present in rig-
Although they found S, of eq 6 to be in quite good agreement with orously degassed water. The effect on the measured surface
Good’s compilation (2.5R for LJ at 100 K vs the 2.93R inde- thermodynamic properties of surface concentrations of different
pendent of temperature for nonpolar liquids, compared with 1.3R gases will therefore have to be evaluated before the problems to
for water at 300 K increasing with increasing temperature) they which we have drawn attention can be fully assessed. The
were unable to support Good’s dipole orientation interpretation. measurement of surface tension in the absence of any foreign vapor
They found the entropy deficit due to orientation in the surface species would be more difficult but could in principle be performed
to be almost 1 order of magnitude less than that required to explain on the surface of a degassed evacuated sample of high-purity water
the observations. Matsumoto and Kataoka were unable to provide by light-scattering studies of the capillary waves.**
an alternative explanation but suggested that it might lie in “more
complicated structure due to the hydrogen-bonded network, Acknowledgment. This work has been supported by the Na-
perhaps analogous to hydrophobic structure-making”. tional Science Foundation under Chemistry Grant No.
That d u / d T is not a simple quantity to interpret is clear from CHE8318416. We are indebted to B. Widom for an enlightening
its behavior in water below 0 O C (Figure 3) (and in any liquid discussion on the complex relation between measured and inter-
near its critical temperat~re‘~).In these cases du/dT is increasing preted surface properties.
with decreasing temperature, so if one takes the “surface phase” Registry No. H 2 0 , 7732-18-5.
( I I ) (a) Sorensen, C. M . J . Chem. Phys. 1983, 7 9 , 1455. (b) Kell. G. S. ( I 6) Landau, L.; Lifschitz, E. M. Statistical Physics; Pergamon: London.
J . Chem. Eng. Data 1967, 12, 66. and Addison-Wesley: Reading, MA, 1958; Section 1 1 1, p 350.
(12) Harkins, W. D. Physical Chemistry of Surface Films; Rheinhold (17) Widom, 9. Private communication.
Publ. Carp.: N e w York, 1952. (18) Benson, B. 9.; Krause, D..Jr. J . Chem. Phys. 1976, 64. 489.
(13) Good, R. J. J . Phys. Chem. 1957, 61, 810. (19) Speedy. R . J.; Angell, C. A. J . Chem. Phys. 1976, 65, 851.
(14) Matsumoto. M.: Kataoka. Y. J . Chem. Phys. 1988, 88, 3233. (20) Speedy, R. J. J . Phys. Chem. 1982, 86, 982.
( I 5) Rowlinson. J. S.: Widom, B. Molecular Theory of Capillarity: Oxford (21) Beaglehole, D. J . Phys. Chem. 1987, 91, 5091.
University Press: London. 1982. (22) Cummins, H. E., Private communication.