JOSEPH
[CONTRIBUTION FROM
THE
Vol. 75
The Orthobaric Surface Tensions and Thermodynamic Properties of the Liquid Surfaces
of the n-AIkanes, C, to Cas
HY
JtjSEPII
J.
JASPER,
E. ROBERTKERR
AND ~REDERICKGREGORICH
I~CCEIVEU
APRILS, 1053
In the following paper there is briefly described the procedure for measuring orthobarically the surface tensions of the nalkanes, Cs to (2x8, furnished by the American Petroleum Institute Research Project 44. The capillary rise method was employed, and a precision capillarimeter, specially designed for this project, was used for the measurements. Surface tensiontemperature data are presented in a table together with the constants of the least-square equations which relate the variables.
From these data the entropies, latent heats and enthalpies of the liquid surface were calculated. The entropies and enthalpies are plotted graphically against the number of carbon atoms per molecule for the different compounds of the series.
The surface tension is a fundamental thermodynamic property of the liquid surface, which, due to
its origin in intermolecular attraction, has served as
a convenient and accurate index of the relative
magnitudes of other properties of liquids. It has
become of increasing importance in numerous aspects of theoretical and industrial chemistry, and
in recent years considerable study has been given to
its application in the determination of molecular
structure, and the structure of surface films on liquid substrates. Since the surface tension of a liquid
is influenced markedly by the presence of small
amounts of capillary-active impurities, reliable data
for its numerous applications can be expected only
from very pure compounds.
The purpose of this investigation was to obtain
orthobaric surface tension data of the n-alkanes,
Cg to (218, over an appreciable range of temperature,
and to formulate empirical equations relating these
variables. The compounds used were of a high
degree of purity, and were made available by the
American Petroleum Institute Research Project
44 at the Carnegie Institute of Technology from
the series of API research samples of hydrocarbons
purified by the American Petroleum Institute Research Project G from source materials supplied as
follows : n-tridecatie, n-pentadecanc and n-heptadecane, from the -4PI Research Project 42 a t the
Pennsylvania State College; n-pentane, n-hexane,
?I-heptane, n-octane, wnonane, n-decane, n-undecane, n-dodecane, n-tetradecanc, n-hexadecane and
n-octadecane from the API Research Project 6.
The uncertainties, inherent in the capillary rise
method and in all surface tension methods involving
curved liquid surfaces, are reflected in the capillary
constant. These can be reduced to negligible proportions by adhering rigorously to certain structural and dimensional specifications in designing the
capillarimeter. The accurate experiments of Richards and Carver indicate that the major errors in
the capillary constant can be reduced to a minimum
if (a) the radius of the capillary is sufficiently
small2 and (b) the reference surface of the liquid
differs but slightly from that of a geometric plane.
Experimental
Description of the Apparatus.-A capillarimeter was designedat o conform with the structural and dimensional requisites of a precision instrument and which possessed the addi(1) T.W. Richards and E. K.Carver, TRISJOURNAL, 48, 827 (1921).
(2) Under these conditions the shape of the liquid meniscus closely
approximates that of a hemisphere and can be treated as such in correcting the capillary rise.
(3) J. J. Jasper and K. R. Herrington, THISJ O U R N A L , 68, 2142
(19462.
PROPERTIES
OF LIQUIDSURFACES
OF WALKANES
Nov. 5 , 1053
TABLE
I
THESURFACE TENSIONS
A N D LEAST-SQUARE
FACTORS
a AND b
Temperature, "C,
30
40
50
Compound
10
20
n-Pentane
n-Hexane
n-Heptane
%-Octane
n-Nonane
n-Decane
n-Undecane
n-Dodecane
n-Tridecane
n-Tetradecane
n-Pentadecane
n-Hexadecane
n-Heptadecane
n-Octadecane
18.27
20.50
22.31
23.75
24.84
25.73
26.57
27.24
27.87
28.42
28.87
29.32
29.74
30.09
17.19
19.46
21.30
22.77
23.90
24.81
25.68
26.36
27.00
27.56
28.02
28.48
28.90
29.26
16.09
18.41
20.28
21.78
22.96
23.89
24.78
25.48
26.13
26.69
27.12
27.64
28.06
28.42
THELATENT
HEATO F THE SURFACE AND
15.00
17.37
19.27
20.80
22.01
22.98
23.89
24.60
25.26
25.83
26.32
26.79
27.22
27.59
THE
Compound
10
20
n-Pentane
n-Hexane
n-Heptane
n-Octane
n-Konane
n-Decane
n-Undecane
n-Dodecane
n-Tridecane
n-Tetradecane
n-P&tadecane
n-Hexadecane
n-Heptadecane
n-Octadecane
30.76
28.56
27.69
26.83
25.77
25.10
24.39
24.00
23.79
23.55
23.27
23.00
22.87
22.79
31.84
29.58
28.70
27.82
26.70
26.02
25.29
24.88
24.66
24.41
24.12
23.84
23.72
23.62
32.93
30.60
29.71
28.80
27.64
26.94
26.18
25.76
25.53
25.28
24.97
24.69
24.56
24.45
16.32
18.25
19.82
21.07
22.06
23.00
23.73
24.39
24.97
25.46
25.95
26.38
26.75
15.28
17.24
18.84
20.13
21.14
22.10
22.85
23.52
24.11
24.61
25.11
25.55
25.92
FOR THE
14.24
16.22
17.85
19.19
20.22
21.21
21.97
22.65
23.24
23.76
24.27
24.71
25.09
34.01
31.61
30.73
29.79
28.57
27.86
27.09
26.65
26.40
26.15
25.82
25.54
25.44
25.28
32.63
31.74
30.77
29.50
28.78
27.98
27.52
27.27
27.01
26.67
26.38
26.27
26 12
Results
The data were applied in the following form of the
capillary-rise equation
80
20.31
21.09
21.78
22.38
22.91
23.42
23.87
24.25
TABLE
I1
LEAST-SQUARE
FACTORS
C AND d
Temperature,
30
40
n-ALICANES, cs TO Cia
70
60
5253
19.42
20.21
20.90
21.52
22.06
22.58
23.03
23.42
FOR THE
18.27 0.10891
20.50
.lo439
20.31
.lo148
23.75
.09826
24.84
.09417
25.73
,09190
26.57
.Of3935
27.24
.08788
27.87
.08707
28.42
,08625
28.87
.08515
29.32
,08424
29.74
,08389
30.09
,08339
%-ALKANES,c, TO
OC.
50
33.65
32.75
31.76
30.43
29.70
28.88
28.40
28.14
27.88
27.52
27.23
27.11
26.95
60
34.67
33.76
32.74
31.37
30.62
29.77
29.28
29.01
28.74
28.37
28.07
27.95
27.79
70
30.67
30.16
29.88
29.60
29.22
28.91
28.79
28.62
80
31.56
31.04
30.75
30.46
30.08
29.75
29.63
29.45
30.76 0.1084
28.56
.I018
27.69
.lo12
26.83
.0985
25.77
.0933
25.10
.0920
24.39
,0897
24.00
,0881
23.79
.0871
23.55
,0864
23.27
.0851
23.00
,0844
22.91
,0840
22.79
,0832
W.R. KRIGBAUM
AND P. J. RORY
5254
O.O8Y, . , . . , ,
,
,
.
I 48
5 6 7 8 9 10 11 12 13 14 15 16 17 18
Number of carbon atoms.
Fig. 1.-A, the entropies of surface formation; B, the
enthalpies of surface formation as a function of the number
of carbon atoms per molecule.
,
VOl. 75
0.14024
The plot of the entropies calculated from this equation are shown in Fig. la, and the enthalpies are
shown in Fig. lb.
From reference to the tables it is evident that while
y decreases and Q increases with the temperature
for each of the compounds, h, the sum of these, and
s, which is (Q/T),are independent of the temperature. The curves (a) and (b) of Fig. 1 show that
the enthalpies increase and the entropies decrease
with increasing molecular weights of the compounds, and that the latter appears to be approaching a limiting value of about 0.0830.
DETROIT, MICH.
DEPARTMENTS
OF CHEMXSTRY, DUKEUNIVERSITY
Introduction
According to the statistical treatment of dilute
polymer solutions,2*athe second coefficient, A*, in
the virial expression for the osmotic pressure
T
RT[Aic
+ A d + AacS + . . . ]
(1)
(c*/v1)(i- e/T),w(x)
(2)
(1944).