J. Gem.

Thenno&~namics 1975, I, 185-190

Thermodynamic properties of organic

oxygen compounds
XXXVII. Vapour pressures of methanol,
ethanol, pentan-I-ol, and octan-l-01 from the
normal boiling temperature to the critical
temperature
D. AMBROSE, C. H. S. SPRAKE, and R. TOWNSEND
Division of Chemical Standards, National Physical Laboratory,
Teddington, Middlesex, TWII OLW, U.K.

(Received 24 June I974)

Vapour pressures greater than 200 kPa of methanol, ethanol, pentan-l-01, and octan-l-01
were measured. The results were fitted by equations in the form of Chebyshev polynomials,
and equations of this type were also used for representation of data already published for
the propyl and butyl alcohols extending to their critical temperatures. Great reliance cannot
be placed upon the results for pentan-l-01 and octan-l-01 because of decomposition, but
it is shown that in respect of some characteristics the vapour-pressure curves obtained for
these two compounds conform acceptably with those of the lower members of the series.

1. Introduction
Measurements of the vapour pressures of aliphatic alcohols in this laboratory have
been reported,(2-5) for some of them down to 0.15 kPa;@) this paper deals with
extension of the range upwards for methanol, ethanol, pentan-l-01, and octan-l-01.
Values are given for methanol from 180 to 3300 kPa (and these have been combined
with those reported by Skaates and Kay extending to the critical pressure),@)for
ethanol from 160 kPa to the critical pressure, for pentan-l-01 from 220 to 1220kPa,
and for octan-l-01 from 230 to 650 kPa. The quality of the results for the two last-
named compounds was relatively low becauseof decomposition of the samplesduring
the experiments, but equations are proposed to represent their behaviour up to their
critical points (the measurements of which are reported elsewhere)(‘) and these
equations are shown to be in accord, in respect of some characteristic features, with
equations for other compounds that are based on more reliable experimental results.
Equations of the sameform as those used in our current work are given to represent
values already reported from this laboratory for the propyl and butyl alcohols.

2. Experimental
The methods for measurement of vapour pressures have been described in earlier
publications.@-lO’ Measurements on methanol were made by the dynamic method;@)
the results were in good accord with somealready published’@ and, since the pressures
developed near the critical temperature approached and would perhaps have exceeded
186 D. AMBROSE, C. H. S. SPRAKE, AND R. TOWNSEND

the bursting limit of the apparatus, no static measurementswere made. Measurements

were made on ethanol by both dynamic(*) and staticCg)methods, on pentan-l-01 and
octan-l-01 by comparative ebulliometry,(lO) and on pentan-l-01 also by the static
method. The samplesused were drawn from the samebatches of the alcohols as were
used in earlier parts of this investigation.c4, 5,
In the measurements on methanol and ethanol, pressures less than 600 kPa were
determined with an air-operated piston pressure balance made from a standard
glass syringe.(ll)
3. Results
Temperatures are expressed as International Practical Kelvin Temperatures Tss,
which are considered as interchangeable with thermodynamic temperatures T. The
measured values are listed in table 1, which includes also, converted to the units used
in this paper, those reported by Skaates and Kay (Wfor methanol becausethey were
included in the set of values fitted by the equation following. The equation, which was
fitted to the results for all the compounds, is
TABLE 1. Observed vapour pressures and residuals A loglop = log,,p,,,, - iog,,p,,,,

T’K plkpa 104A log,,p T/K p/@a 104A loglop T/K PlkPa lO*A loglop

Methanol
353.46 183.00 a 6 432.92 1747.8 a 0 443.18 2194.6 b -1
362.96 254.43 a 14 443.04 2189.7 a 3 453.18 2711.0 * -1
373.66 359.57 a 9 453.27 463.19 3319.1 b 0
383.28 481.81 a 462.90 2718.7
3310.8 0= 1: 473.19 4025.1 b -3
392.86 635.11 cz : 403.16 837.7 b -18 483.20 4844.9 b
403.38 846.76 a 3 413.17 1088.0b -6 493.20 5797.1 b z:
413.11 1087.9 = -1 423.17 1392.0” -2 503.20 6897.4 b -2
423.19 1393.4 = 0 433.18 1758.1 b 0 512.64 e 8097.1 b 3
Ethanol
364.86 168.39 a 2 408.53 666.94 c -1 487.81 3894.9 c 1
373.29 226.23 = -2 418.68 873.15= -5 498.32 4697.0 c -2
383.14 313.89 a 2 428.88 1129.3C -1 503.21 5114.5 c -2
393.40 431.77 a 2 439.14 1440.5 c 0 508.01 5552.4 c
402.89 570.60 a 7 448.38 1773.6 c 1 508.67 5615.5 c 1;
379.10 275.24 = 2 458.70 2211.3 c 1 511.08 5846.9 = -3
389.18 379.00 c -6 468.80 2715.2 c 2 513.92 e 6148.4 c 8
398.47 501.14 c -4 477.94 3243.3 c 3
Pentan-l-01
437.8 226.8 d 10 474.0 555.5 d 32 492.0 811.9 c 52
443.5 265.1 d 13 481.7 502.3 988.3 c 50
448.3 300.0 6 15 472.6 655.2
538.9 dc i: 512.2 1187 c 52
454.5 351.1 d 19 472.8 540.7 = 38 513.8 1220 c 49
463.5 436.4 d 27 472.8 541.4 c 40
467.0 473.9 d 29 482.8 671.2 E 44
Octan-l-01
502.2 234.6 * 12 515.6 313.6 d 15 538.0 487.3 d 16
507.5 263.6 d 14 521.1 351.1 6 17 545.0 554.5 d 16
510.8 283.6 d 14 528.4 405.8 d 15 554.0 649.9 d 16
514.0 303.3 I3 16

LLDynamic method. b Values reported for methanol by Skaates and Kay.@) c Static method.
d Comparative ebulliometry. B Critical temperature.
 VAPOUR PRESSURES OF ALCOHOLS 187

where E,(X) is the Chebyshevpolynomial in x of degrees, and x = (2T- (T,,, + T,J}

/(Taxax-Tmin), Trn,, and Twin being two temperatures respectively just above and just
below the extreme measuredvalues.(*) Coefficients of the equations are given in table 2
and the residuals appear in table 1 as A log,, p = log,, pobs-loglO pcalo pcalc being
the value calculated from the appropriate equation. Table 2 also includes coefficients
of equations fitted to the previously published values, after their conversion to IPTS-68,
for the propyl and butyl alcohols.124)
TABLE 2. Coefficients
of equation(1)

Order Tmin/K T,,,/K czO aI a2 a3 a4 a5 a6

Methanol 6 288 513 2304.364 858.250 -6.674 2.002 0.230 0.138 0.038
Ethanol 6 292 514 2191.459 863.668 -14.865 2.168 0.504 0.111 0.008
Propan-l-01 5 333 537 2461.373 777.490 -16.716 2.781 0.582 0.094
Prooan-2-01 5 325 509 2363.473 704.873 -15.275 2.577 0.570 0.077
But&-o1 5 351 563 2545.209 794.967 -19.593 3.732 0.525 0.110
Butan-2-01 4 340 537 2463.622 731.747 -18.609 3.352 -0.042
2-Methyl-
propan-l-01 5 343 548 2479.981 767.604 -19.805 3.608 0.428 0.091
2-Methyl-
propan-2-01 4 329 507 2353.478 663.704 -16.344 3.259 0.150
Pentan-l-01 4 347 589 2457.990 906.763 -25.582 7.795 0.949
octan-l-01 4 386 653 2577.692 984.483 -25.226 10.749 O.lQh

4. Discussion
The sets of observations fitted by the equations in table 2 included those made at
pressures below 200 kPa.(2J4)For the C1 to C4 compounds these observations were
given 10 times the weight of those made above 200 kPa, and the fit to the former of
the resultant equations is little, if at all, inferior to the fit of the third-order equations
fitted to them alone;(5) for methanol and ethanol, the overall fit in both the low and
high ranges is entirely satisfactory. The higher values for the propyl and butyl alcohols
were not as precise as those reported here for methanol and ethanol, and decom-
position was apparent in the experiments on the butyl alcohols, particularly
2-methylpropan-2-01; (3) the fit of the equations in the high range reflects the lower
quality of the data, but is otherwise satisfactory; in particular, the fit is as good as that
of the equation used over a shorter range in the original work, which was of somewhat
arbitrary form, being applicable only at reduced temperatures T, = T/T, 2 0.7.
For pentan-l-01 and octan-l-01 the effect of decomposition was much greater than
for the butyl alcohols. The values obtained for these compounds above 200 kPa were
erratic, differing from those obtained by extrapolation of curves fitting the values at
lower pressuresby larger amounts than are attributable to normal experimental errors
(the residuals in table 1 correspond to temperature differences of 0.1 to 0.5 K), and for
both compounds an inconsistency persists at the junction between the two sets of
values, i.e. at about 200 kPa, whatever fitting or extrapolation procedure is adopted.
Experiments had to be terminated shortly after the last point recorded in table 1
188 D. AMBROSE, C. H. S. SPRAKE, AND R. TOWNSEND
when useful results could no longer be obtained, and the equations in table 2 were
adjusted so that the fit was good to the relatively reliable points below 200 kPa and to
the two critical temperatures and pressures. Determination of these critical points,
however, was of rather low accuracy,(7) and it is not certain, therefore, that above a
reduced temperature of 0.75 the equations correctly represent the vapour pressures:
figures 1 and 2 are offered as demonstration that they are at least plausible.

FIGURE 1. AH/AZ obtained by differentiation of equations in table 2 for: A, methanol; B, ethanol;

C, propan-l-01; D, butan-l-01; E, pentan-l-01; F, octan-l-01; G, propan-2-01 (40 kJ mol-I);
H, butan-2-01 (80 kJ mol-I); J, 2-methyl propan-l-01 (80 kJ mol-I); K, 2-methylpropan-2-01
(40 kJ mol-I). For clarity some of the curves are displaced vertically downwards by the amounts
stated in parenthesis. (I, lower limit of the observed values on which the equations depend.

In figure 1 are plotted curves for AH/AZ, where AH is the enthalpy of evaporation
and AZ = Zv-Z, is the difference between the compression factors Z = RT/pV of
vapour and liquid. The quantity AH/AZ is given, by rearrangement of the Clapeyron
equation, as
AH/AZ = RT’d In p/dT, (2)
that is, the curves have been plotted by differentiation of the equations in table 2.
Waring showed that when AH/AZ obtained from thermal measurementsfor water is
plotted against T, the curve has a minimum at T, z 0.85,(12)and curves of similar
shape for other compounds have been shown.(13) The curves in figure 1 are qualita-
tively similar to them and, in the range supported by observation, show smooth
progressions in curvature with d2(AH/AZ)/dT2 positive, with the exception that curve
G for propan-2-01 appearsto waver slightly. Curves A and F for the C!r to C,, Cs, and
Cs primary alcohols form a fairly regular family. In figure 2 the zero-line represents
the approximate simple relation :
 VAPOUR PKESSURES OF ALCOHOLS 189
bkdJ’ = ~o&oP,+w~--1/T,)~ (3)
where pc is the critical pressure and b has been adjusted for each compound so that
the equation yields the observed value pobs, which is very close to pcalc defined above,
at T, = 0.7. The curves represent the differences between equation (3) and the actual
vapour pressures, as given by equation (l), as A log,,p’ = loglOpcalc-loglop’, and

0.7 0.8 0.9 1.0

T,
FIGURE 2. A log,,@ = log,,p,,,, - log& (equation 3) for: A, methanol; B, ethanol; C,
propan-l-01; D, butan-l-01; E, pentan-1-01: F, octan-l-01: G. 2.2.4-trimethvluentane: H. ethvlbenzene.
Curves for propan-2-01, but&-2-01, 2-methilpropan-l-61, %d-2-methyl&pan-2-&, ‘which are not
included, fall close to those for propan-l-01 and butan-l-01.

those for 2,2,4-trimethylpentane and ethylbenzene illustrate the behaviour of non-

associatedcompounds, i.e. a reversal of curvature at T x 0.85 and at higher tempera-
tures the observed pressure falling below the line of equation (3) so that there is a
steep rise in pressure as the critical temperature is approached. The curves for the
C, to C4 alcohols are quite different: there is no reversal of curvature and the curves
do not cross the zero-line, i.e. the rise in pressure as the critical temperature is ap-
proached is relatively slow. The curves for pentan-l-01 and octan-l-01 however,
although similar to those for the lower homologues near T, = 0.7, approach those for
the non-associated compounds at high reduced temperatures, suggesting that with
their larger molecules the effect of association is diminished near the critical tempera-
ture. The course of thesecurves for pentan-l-01 and octan-l-01 dependsupon the values
adopted for their critical temperatures and pressures which, as has been stated, are
not as firmly based as is desirable. However, to remove the dips below the zero-line
requires values for theseproperties differing more from those found than our estimated
errors.
Another point of interest in figure 2 is that all the curves for the C3 to Cs alcohols
cross the zero-line at about the same angle, i.e. at T, = 0.7 the slope d log,,p/dT
obtained from equation (1) exceedsthe slope d log,,p’/dT obtained from equation (3)
by 0.045 to 0.050, a difference corresponding to a difference between dp/dT and dp’/dT
of 10 to 12 per cent. This suggestsa generalization that may be useful in estimating
properties of other alcohols: that if the critical temperature is known an approximate
 190 D. AMBROSE, C. H. S. SPRAKE, AND R. TOWNSEND
value of the critical pressure may be calculated from equation (3) if a value of b is
obtained by appropriate adjustment of the observed slope of the vapour-pressure
curve at T, = 0.7.
Study of curves typified by those in figure 1 tends in general to support choice of a
lower order for equation (1) than would be chosen from examination of the fit to the
points except when the equation is controlled over a large range of temperature by
data of high accuracy. For example, an eleventh-order equation for water,(14) which
depends upon data between the triple and critical points of exceptional accuracy, gives
a satisfactory curve for AH/AZ, whereas for other compounds equations of fifth and
higher orders that are less well constrained may give AH/AZ curves diverging widely
from the expected shape, and it is then a matter of choosing between satisfying the
figure 1 criterion and the best possible fit to the data. If the latter is preferred, the
equation is clearly less suited for extrapolation than if the former is preferred. At low
temperatures Zv -+ 1 and Z, is negligible so that for reduced temperatures of 0.55 to
0.6 or less AH/AZ = AH. The variation of AH with T, is given approximately by
AH = a(1 - T,)“, (4)
where a is a constant for each compound and values for the exponent n ranging from
0.333 to 0.4 have been recommended(i5-“) (n = 0.38 is perhaps most commonly
used);(l’) according to equation (4) the curve will flatten somewhat as the temperature
is lowered when AH is plotted against T, rather than against (1 - T,)“. Such flattening is
obtained from the third-order equations recommended for these alcohols,(4, 5, which
tends to confirm their suitability for extrapolation to lower temperatures. For this
purpose, the higher-order equations in table 2 are less satisfactory, but on the other
hand they do not exhibit (figure 1) any gross anomalies between the lower limit of the
experimental results and T, = 0.4, and only in the range T, < 0.5 do some of them
tend to curve in what is probably the wrong direction.

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