M- 1928

J. Chem. Thermodynamics 1986, 18. 719-726

The enthalpy of methanol

T. K. YERLETT and C. J. WORMALD a
School of Chemistry, University of Bristol,
Bristol BS8 ITS. U.K.

(Received 19 September 1985; in revised,form 9 December 1985)

Measurements of the specific enthalpy increment of methanol are reported; 131 measurements
cover the range 373.2 to 573.2 K at pressures from 0.1 to 13.6 MPa. The overall accuracy is
0.6 per cent. The specific enthalpy of the saturated liquid and the saturated vapour and the
enthalpy of vaporization are derived from the measurements.

1. Introduction
Thermodynamic quantities for methanol at high temperatures and pressures are not
as accurate as one would expect for a substance of such importance as a fuel and
feedstock. The difficulty is that at temperatures above about 450 K methanol begins
to decompose. For (p, I’, T) experiments in which the methanol is confined in the
apparatus for several hours even a slow rate of decomposition may cause significant
error. Petty and Smith”) made (p, V, T) measurements at pressures up to 1.03 MPa
and temperatures between 322 and 411 K, probably too low a temperature range
for decomposition to be a problem. Zubarev and Bagdonas@) made (pp. V, 7’)
measurements in the range 413 to 573 K between 0.4 and 20 MPa. Finkelstein and
Stielt3) made similar measurements from 473 to 573 K at pressures between 8.4 and
70 MPa. Ta’anif4) has made (p, I’, T) measurements between 298 and 623 K at
pressures up to 800 MPa. Liquid-phase compressibility measurements have recently
been made by Machado and Streett U) between 298 and 489 K at pressures up to
104 MPa. Of the high-temperature measurements(2,3*4) only Ta’ani reports evidence
of decomposition. Analysis of his sample showed the presence of hydrogen, carbon
monoxide, carbon dioxide, formaldehyde, methyl formate, and dimethyl ether. It is
likely that decomposition affected other measurements(2,3) though the
decomposition products may depend on the metals and metallic oxides in contact
with the vapour. w The extent of decomposition will depend on temperature and
residence time in the apparatus. High pressure is likely to favour the formation of
condensation products of high molar mass. The presence of a monolayer of
decomposition product on the walls of a (p, V, T) apparatus can only increase the
error due to adsorption.
a To whom correspondence should be addressed.

0021-9614/86/080719 +08 %02.00/O c, 1986 Academic Press Inc. (London) Limited

720 T. K. YERLETT AND C. J. WORMALD

Flow-calorimetric measurements of the enthalpy increment of methanol were

made by McCracken and Smith”) using a Freon-l 1 boil-off calorimeter. The
measurements cover the range 394 to 514 K at pressures up to 9.7 MPa. The
accuracy claimed is around 2 to 3 per cent and is limited by the calorimeter rather
than decomposition of the material. Flow-calorimetric measurements are of course
free from adsorption errors. Using a new enthalpy-increment calorimeter’s’ 131
measurements of the enthalpy increment of methanol in the range 373.2 to 573.2 K
have been made. The measurements extend up to 13.6 MPa and the overall
accuracy is 0.6 per cent.

2. Experimental
Methanol (B.D.H. Aristar grade) was dried with calcium hydride and distilled. The
density of the purified material was 786.68 kg ame3 at 298.15 K (literature:(9)
786.64 kg * m-“). Analysis by g.1.c. showed only a single peak and the purified
material was not less than 99.95 moles per cent CH,OH. Freshly dried and distilled
methanol was used for every run.
The flow calorimeter and experimental technique were the same as previously
described.“’ The calorimeter was tested using steam and the results were compared
with the 1984 NBS/NRC steam tables. (lo) The mean deviation of 90 measurements
of the specific enthalpy increment of steam from tabulated values was -0.03 per
cent and the standard deviation was 0.43 per cent. Runs on methanol were done
with a flow rate of approximately 0.2 g. s- ‘. For runs at temperatures above 400 K
the density of the used methanol was checked and g.1.c. analysis was carried out.

3. Calculation of results
At pressure p a stream of methanol vapour at temperature TI enters the water-
cooled heat-exchange calorimeter and emerges as liquid at temperature T2 and at
the same pressure. Energy lost by the methanol is gained by the cooling water.
Measurement of the water flow rate and temperature rise allows calculation of the
quantity Ah’ where
Ah’ = h(p, T,)-h(p, T2). (1)
The specific enthalpy increment Ah relative to 298.15 K and the saturation pressure
ps was calculated from the equation:
P

Ah = Ah’+ =’ c,(T)dT + ~(1 -crT)dp, (2)

s 298.15 K s PS
where cP is the specific heat capacity of methanol,C”’ u is the specific volume, and 01
is the isobaric expansivity at 298.15 K. t9) The cooling-water flow rate was adjusted
until T, was close to 298.15 K so that the cP integral was small and the pressure
dependence of cp could be neglected. Corrections for heat leaks, for the rate at which
kinetic energy enters the calorimeter, and a small (0.02 per cent) correction for the
 THE ENTHALPY OF METHANOL 721
presence of dissolved air in the methanol pumped into the calorimeter were made as
previously described. G+)Systematic errors are the same as for the measurements on
n-hexane,“’ and are estimated to be no greater than 0.2 per cent. Random errors
arose mainly from fluctuations in the operation of the metering pump supplying the
methanol. In the critical region small fluctuations caused larger fluctuations in the
density and enthalpy of the fluid in the calorimeter, and the random error in some of
the measurements rose to 1 per cent.

4. The effect of decomposition products

Decomposition of methanol is greatest for the measurements at 573.2 K. Analysis of
the methanol from a run at 8.9 MPa showed that the main impurities were acetone
(0.29 mole per cent), methyl formate (0.18 mole per cent), and methyl acetate (0.02
mole per cent). From the flow rate, the volume of the hot zone and the specific
volume of methanol calculated using the Patel-Teja (PT) equation of state”” the
residence time in the hot zone was estimated to be 325 s. For runs at lower
pressures the residence time in the calorimeter was less and smaller amounts of
impurity were detected.
An estimate of the effect of impurities on the measured specific enthalpy
increment was made assuming that under all conditions the impurities were acetone
and methyl formate in the mole ratio 3/2. The molar enthalpy H,(x) of the mixture
is given by
H,(x) = H~+x,H,(l)+x,H,(2)+(1 --Xl -x,)H,(3), (3)
where H,(l) and H,(2) are the molar enthalpies of acetone and methyl formate
calculated using the PT equation together with ideal-gas enthalpies; H,(3) is the
molar enthalpy of methanol; and Hfi, was calculated using the PT equation with the
interaction parameters k, equal to zero. The amounts of impurity were taken to be
acetone: 0.3 moles per cent and methyl formate: 0.2 moles per cent. The measured
specific enthalpy was 1481.0 kJ. kg-‘, and the specific enthalpy of CH,OH was
calculated to be 1475.0 kJ . kg-‘, a difference of -0.4 per cent.
The maximum error due to decomposition products was for the run at 573.2 K
and 13.64 MPa for which the measured enthalpy increment was 1326.5 kJ. kg-’
and from which the enthalpy increment of CH,OH was calculated to be
1318.5 kJ . kg- ‘, a difference of -0.6 per cent. Analysis of the methanol from this
run was not made, and the amounts of impurity were estimated by scaling the
amounts detected for the run at 8.9 MPa by the ratio of the residence times in the
hot zone. The extent of decomposition diminished rapidly with decreasing
temperature. At 548.2 K and 13.04 MPa the error due to impurity was estimated to
be 0.2 per cent, at 523.2 K and 12.14 MPa it was less than 0.1 per cent, and below
498.2 K it was negligible. As the residence time in the hot zone of the calorimeter is
approximately proportional to the pressure, the uncertainty due to decomposition
under any conditions is easily calculated. The results of 131 measurements of the
specific enthalpy increment of methanol are listed in table 1 and are plotted against
pressure in figure 1.
722 T. K. YERLETT AND C. J. WORMALD

TABLE I. Measurements of the specific enthalpy of methanol. The enthalpy increment Ah was
calculated using equation (2) as described in the text. Ah = 0 for liquid methanol at 298.15 K and the
saturation pressure

T P Ah P Ah P Ah P Ah P Ah
K MPakJkg-’ MPakJkg-’ MPakJkg-’ MPakJkg-’ MPakJkg-’
-
313.2 0.10 1284.6 0.34 1237.9 3.02 214.5 11.72 222.5
0.21 1213.9 0.74 212.1 5.07 213.2
398.2 0.10 1334.2 0.34 1311.6 0.59 1273.0 4.30 292.1
0.18 1326.9 0.46 1302.2 0.90 295.7 11.84 301.3
423.2 0.10 1367.8 0.68 1336.5 1.20 1282.2 1.89 389.4 7.16 388.3
0.27 1356.1 0.99 1314.7 1.32 1265.1 3.36 389.7 12.00 389.5
0.44 1358.3
448.2 0.10 1412.5 0.82 1381.7 1.85 1317.5 2.73 479.3 7.36 488.3
0.33 1400.2 1.20 1364.8 2.19 1288.4 4.78 490.1 11.25 484.8
0.56 1399.1 1.58 1337.8
473.2 0.10 1464.4 1.68 1402.0 3.30 1309.3 4.94 602.5 9.04 596.2
0.68 1447.9 2.20 1377.6 3.78 1272.4 4.98 605.7 11.83 591.9
1.27 1414.4 2.82 1342.1 4.23 606.9 6.63 602.8
498.2 0.10 1513.1 2.98 1422.0 5.20 1304.2 6.80 743.8 9.64 717.7
0.83 1495.5 3.38 1403.9 5.75 1254.0 7.39 741.2 11.70 711.2
1.47 1477.5 3.60 1389.4 6.25 1191.0 8.30 732.0 12.92 702.4
2.18 1449.9 4.30 1360.6 6.42 836.5
510.2 3.56 1433.4 6.45 1282.0 7.55 1163.1 8.60 825.2 10.05 793.6
4.86 1371.0 6.90 1236.4 8.12 847.9 8.95 815.8 11.35 781.3
5.88 1320.9 7.40 1192.7 8.37 838.2
515.2 5.42 1363.4 7.77 1201.8 8.58 1057.1 9.16 835.3 10.55 828.1
6.08 1336.2 8.22 1151.5 8.87 909.0 9.92 831.3 12.13 809.7
6.72 1294.2 8.54 1066.8 8.95 892.0
523.2 0.10 1554.8 4.94 1422.9 8.50 1218.3 10.33 931.4 11.29 883.6
1.91 1504.9 6.36 1355.7 9.12 1152.7 10.74 904.7 12.14 868.3
3.40 1473.3 7.58 1293.9 9.74 1036.6
548.2 0.10 1603.7 4.91 1498.9 7.60 1420.7 9.86 1331.5 11.42 1238.0
1.74 1572.9 6.18 1462.8 9.02 1365.6 10.64 1280.4 13.04 1150.4
3.30 1534.8
513.2 0.10 1653.0 4.74 1573.6 7.52 1512.2 10.28 1438.5 12.23 1375.3
1.80 1620.2 6.20 1550.6 8.90 1481.0 11.18 1413.0 13.64 1326.5
3.33 1604.4

5. Comparison with other work

As the enthalpy-increment measurements of McCracken and Smith”) were made at
different temperatures to ours, direct comparison is not possible. Although their
overall accuracy is claimed to be 2 to 3 per cent it is worse at low pressures, and
extrapolation of their measurements to zero pressure is subject to large uncertainty.
In constructing their enthalpy-pressure diagram the authors ignored their own low-
pressure results and drew curves joining their high-pressure results to zero-pressure
enthalpies determined independently.
Chen, Wilhoit, and Zwolinsky” 3, reviewed ideal-gas properties up to 1977. Chao
and Ha11’i4’ have calculated ideal-gas enthalpies from spectroscopic data. The solid
 THE ENTHALPY OF METHANOL 723

0 4 x
\)IMPa
FIGURE 1. The specific enthalpy increment Ah of methanol plotted against pressure. 0, 0. Points
listed in table 1 (circles and squares are used on alternate isotherms for clarity).

curve in figure 2(a) was calculated from a quadratic equation fitted to their values.
Extrapolation of our measurements to zero pressure gives values shown by circles.
Our zero-pressure enthalpies are on average 0.5 per cent larger than the calculated
values.
Wilhoit Chao, and Hall”15) have reviewed thermodynamic measurements on solid
and liquid methanol, and have published a table of enthalpies for the saturated
liquid up to 390 K. We have fitted their values to a quadratic equation (shown as
the solid curve in figure 2b) and extrapolated the curve to 450 K (the broken curve

,o’
,’
?’
8’
&,’ ”
i
/’
1
/’
/ I
I /’

x0 ’ !
I
r

’ L ’ I
400 420 440

T/K T/K
FIGURE 2. (a), The specific enthalpy Ah,,, of the ideal gas for methanol. __ Best line through
ideal-gas enthalpies calculated from spectroscopic data;““’ 0, obtained by exkapolating table 2
measurements to zero pressure. (b). The specific enthalpy Ah(l) of saturated-liquid methanol. ---.
Calculated from a quadratic equation fitted to the values reported in reference 13; - - -, extrapolation
of the solid curve beyond the reference 13 values; A. reference 13; 0, table 2; x, from (p, V. 73
measurements.“’
724 T. K. YERLETT AND C. J. WORMALD

TABLE 2. The specific enthalpy of vaporization A“,rh of methanol. The specific enthalpies of the
saturated vapour Ah(g) and saturated liquid Ah(l) were obtained from the measurements listed in table 1
as described in the text. AYOphcwas calculated from equation (4). The uncertainty in Avrph is 4 kJ. kg-’

T Ah(g) Ah(l) Avwh Avs&

z kJ.kg-’ kJ.kg-’ kJkg-’ kJ.kg-’
-
313.2 1234.0 2135 1020.5 1011.6
398.2 1249.0 296.0 953.0 940.9
423.2 1265.0 389.0 876.0 859.7
448.2 1268.0 488.0 780.0 162.3
413.2 1250.0 606.0 644.0 636.8
498.2 1184.0 760.0 424.0 440.7
510.2 1096.0 866.0 230.0 230.0

in figure 2b). The circles shown in the figure are the saturated liquid enthalpies
listed in table 2. Agreement with the extrapolated curve is within 0.25 per cent.
Machado and Streettc5) have calculated saturated liquid enthalpies from their direct-
weighing (p, V, T) measurements. Their values lie below the extrapolated curve by
about 4 per cent.

6. The enthalpy of vaporization

Enthalpy increments Ah(g) for saturated vapour, and Ah(l) for saturated liquid,
listed in table 2, were obtained by extrapolating our measurements to the vapour-
pressure curve measured by Ambrose, Sprake, and Townsend.(‘@ The difference
gives the enthalpy of vaporization A &. The uncertainty on our values of AVaph is
estimated to be +4 kJ +kg- I. Enthalpies of vaporization have been measured by
McCurdy and Laidler,“‘) Wadso,“*) Polak and Benson,“‘) Counsel1 and Lee,@O)
and Radosz and Lydersen. (‘I) Comparison with our measurements is made in

O I I 1 I I

300 400 500

T/K
FIGURE 3. Specific enthalpies of vaporization A vaph fitted by the Watson equation. 0, Table 2; A,
reference 7; 0, reference 21: 0. reference 20; x . reference 17. p. Watson, equation (4).(22’
 THE ENTHALPY OF METHANOL 725
figure 3. The values of A,.& listed in table 2 together with values reported by the
above workers, were fitted to the Watson(22’ equation:
A,,,WJ{(1- T/7X- WT,)-‘1”. (4)
Using q = 337.85 K, T, = 512.6 K, and A,,,h(T,) = 1098.8 kJ.kg-‘, the best
value of the disposable parameter n was 0.3665. Equation (4) fits the measurements
with a standard deviation of 0.75 per cent. Silverberg and Wenze1’23’ fitted the
Watson equation to a different selection of points and obtained n = 0.366. Our
derived values of AVa,h agree with the directly measured values reported by Radosz
and Lydersen (21) to better than 0.5 per cent. The enthalpy increments measured by
McCracken and Smith”’ yield values of Avaph which are about 2 per cent too large
below 500 K and 10 per cent too small above this temperature.

7. Comparison with the Patel-Teja equation of state

A good fit to the properties of methanol can be obtained using the equation of state
developed by Baumgartner, Moorwood, and Wenzel.t24’ The equation assumes the
existence of up to 14 associated molecules and can be adjusted to fit the properties
of methanol only at the expense of a large number of parameters. It is not clear how
these parameters should be combined to predict mixture properties, and for this
purpose it is difficult to do better than use the simpler equation of Pate1 and
Teja. (12) In addition to T, and pc the equation has a parameter which is adjusted to
fit the vapour pressure and another to fit saturated-liquid densities. The equation
was shown(25’ to fit the saturated-liquid and -vapour densities of acetone better than
the equations of Peng and Robinson,‘26’ Soave,@‘) and Gibbons and Laughton.‘28’

FIGURE 4. The specific enthalpy increment Ah of methanol compared with the Patel-Teja””
equation of state. -, Best curve through the table 1 measurements; - - -. calculated using the
Pate&Teja”” equation; A, ideal-gas enthalpies calculated from spectroscopic data.‘14’
726 T. K. YERLETT AND C. J. WORMALD

The Patel-Teja equation fits the vapour pressure (I’) of methanol between 315.2 and
512.5 K to within 1 per cent. Addition of the ideal-gas enthalpy to the residual
enthalpy calculated from the equation of state generates the broken curves shown in
figure 4. Solid curves are drawn through the table 1 measurements. The overall
agreement is not as good as was obtained for acetone(25’ and is similar to the fit that
can be obtained for water.

The award of a British Gas Scholarship to one of us (TKY) is gratefully

acknowledged.

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