M-2415

J. Chem. Thermodynamics 1989,2 I, 115 1- 1157

The enthalpy of ethanol

M. D. VINE and C. J. WORMALD”
Schoolof Chemistry,University of Bristol,
Bristol, BS8 ITS, U.K.

(Received31 July 1989)

Measurements of the specific enthalpy increment of ethanol are reported; 139 measurements
cover the range 393.2 to 573.2 K at pressures from 0.1 to 10.05 MPa. The overall accuracy is 0.5
per cent. Values of the specific enthalpy of vaporisation derived from the measurements are in
good agreement with other work and are well fitted by a modification of the Watson equation.

1. Introduction
In a previous publication(‘) we reported measurements of the specific enthalpy
increment of methanol measured using a new enthalpy-increment calorimeter.‘2)
Similar measurements of the specific enthalpy increment of ethanol have now been
made. Most of the measured thermodynamic properties of ethanol in both liquid and
gaseous states are more consistent than those of methanol. Previous measurements
of the specific enthalpy increment of ethanol were made by Storvick and Smith(3)
using a Freon-l 1 boil-off calorimeter. (4)Their measurements cover the range 394.2 to
533.2 K at pressures up to 9.65 MPa. The uncertainty on the measurements is stated
to be between 6 and 20 kJ * kg-‘. The uncertainty on the measurements of the
enthalpy of gaseous ethanol is large and no comparison with ideal-gas enthalpies
was made. Radosz and Lydersen (5) have recently measured the enthalpy of
vaporization of ethanol over the range 414.2 to 470.2 K. The vapour-phase heat
capacity of ethanol at atmospheric pressure has been measured over the range 356.2
to 591.2 K.(@ At low densities the isothermal enthalpy-pressure coefficient has been
measured over the range 323.2 to 430.2 K, (‘) but the measurements are incorrect.
Ideal-gas enthalpies have recently been obtained from spectroscopic measurements
by Chao and Hall. (*I Density measurements have been made by Ramsay and
Youngtg) and by Tarasenkov and Afinogenov (lo) who measured vapour densities up
to 5.0 MPa. Bhattacharyya and Thodos (11) have published values of the density of
ethanol up to 923 K and 250 MPa.
High-pressure (p, V,, 7’) measurements on ethanol have been made by Tammann
and Ruhenbecko2’ over the range 293 to 673 K at pressures up to 25 MPa, and by
Lo and Stielo3) at temperatures from 473 to 623 K at pressures up to 70 MPa. Low
pressure (p, V,, T) measurements on ethanol vapour have been used to obtain
second virial coefficients B, by Hanks and Lambert,(14) Kretschmer and Wiebe,‘15’
Knoebel and Edminster,“@ and more recently by Wilson, Lindley, Kay, and

0021-9614/89/01 I1 151+07 $02.05/O 0 1989 Academic Press Limited

1152 M. D. VINE AND C. J. WORMALD

Hershey.‘17’ These measurements agree over the range 338 to 401 K. It is probable
that at low temperatures all the measurements are in error due to adsorption. The
vapour pressure of ethanol has been measured by Ambrose et uL,(l** 19) and more
recently by Mousa 120)whose measurements cover the range 0.02 MPa to the critical
pressure: 6.324 MPa. The two sets of measurements agree to within the combined
experimental errors.

2. Experimental
The flow calorimeter and experimental technique were the same as previously
described.‘2) The ethanol was initially 99.7 moles per cent C2H,0H, the main
impurity being water. After drying over calcium hydride and distillation the density
of the purified material was 786.21 kg. mm3 at 298.15 K (literatureJ2 ‘)
785.09 kg. m-3). Analysis by g.1.c. showed only a single peak and the purified
material was not less than 99.9 moles per cent ethanol. Freshly dried and distilled
ethanol was used for every run. Material which had been used at temperatures of
573.2 K was analysed by g.1.c. but decomposition was found to be negligible.
Measurements were made using mass flow rates of approximately 0.1 g. s- ‘.

3. Calculation of results
When a steady state had been reached a stream of ethanol at temperature Ti and
pressure p entered the water-cooled heat-exchange calorimeter and emerged as liquid
at temperature 7” and at the same pressure. Heat lost by the ethanol was gained by
the cooling water. Measurement of the water flow rate and the inlet and outlet
temperatures of the flowing water allowed calculation of the quantity Ah’, where
Ah’ = 4, Tl) - h(p, 72. (1)
The specific enthalpy increment Ah relative to 298.15 K and the saturation
pressure pS was calculated from the equation:
T1 P
Ah=Ah’+ c,dT+ ~(1 -crT)dp, (2)
s 298.15K s Pn
where cp is the specific heat capacity of ethanol at 298.15 KJ21) u is the specific
volume of ethanol at 298.15 K and at saturation pressure, and CI is the isobaric
expansivity at 298.15 K obtained from the density measurements listed in reference
22. The cooling-water flow rate was adjusted until T2 was close to 298.15 K so that
the cp term was small and the pressure and temperature dependence of cp could be
neglected. Corrections for heat leaks, for the rate at which kinetic energy entered the
calorimeter, and for differences between the desired temperature and actual fluid-
inlet temperature were made as previously described. (‘) At high temperatures ethanol
undergoes thermal dehydrogenation yielding ethanal and hydrogen. The extent of
this decomposition was examined by analysing the ethanol that had been used to
make measurements at the highest temperature 573.2 K and lowest pressure
 THE ENTHALPY OF ETHANOL 1153

573.2 K

FIGURE 1. The specific enthalpy increment Ah of ethanol plotted against pressure. 0, 0, Points listed
in table 1 (circles and squares are used on alternative isotherms for clarity). The vertical lines drawn across
the two-phase region are at pressures obtained from the vapour-pressure measurements of Ambrose et
a/.“‘. I” A. Ideal-gas values.“’

0.1 MPa. Analysis by g.1.c. showed that the ethanol contained less than 0.05 mole per
cent of ethanal. The extent of decomposition was so small that correction for the
presence of ethanal was unnecessary.
Systematic errors were estimated to be no more than + 3 kJ . kg- I. Random errors
arose mainly from fluctuations in the operation of the metering pump supplying the
ethanol and were estimated to be f 2 kJ * kg- ‘. In the critical region small
fluctuations in the flow rate of ethanol, and in the pressure and temperature,
produced large fluctuations in the measured enthalpy. The random error in this
region was therefore larger, but was estimated to be no more than f 7 kJ. kg- ‘. The
results of 139 measurements of the specific enthalpy increment of ethanol are listed in
table 1 and are plotted against pressure in figure 1.

4. Comparison with other work

Only one of our isotherms was at the same temperature as measurements of Storvick
and Smith.‘3’ The agreement was poor, but since the accuracy of their measurements
was no better than +_6 kJ. kg-’ this was expected.
A good test of enthalpy measurements is to extrapolate them to zero pressure and
make comparison with ideal-gas enthalpies calculated from spectroscopic
1154 M. D. VINE AND C. J. WORMALD

TABLE 1. Measurements of the specific enthalpy of ethanol. The enthalpy increment Ah was calculated
using equation (2) as described in the text; Ah = 0 for liquid ethanol at 298.15 K and the saturation
pressure

T P Ah P Ah -A?-- Ah
K MPa kJkg-’ MPa kJkg-’ MPa kJkg-L

393.2 0.10 1062.1 0.24 1058.5 0.34 1052.5

0.83 286.7 5.22 284.6 9.76 286.3
423.2 0.10 1122.1 0.34 1109.4 0.67 1091.3
0.83 1073.9 1.48 399.6 3.72 399.0
6.09 399.5 9.93 400.3
453.2 0.10 1175.7 0.50 1165.1 0.84 1151.1
1.41 1119.1 1.63 1104.9 1.70 1096.2
2.63 522.9 4.64 521.7 7.06 518.9
9.87 515.5
473.2 0.10 1215.7 0.63 1207.3 1.43 1175.6
1.96 1147.7 2.38 1125.7 2.63 1107.7
3.77 614.6 5.18 610.7 7.29 606.4
10.05 606.9
493.2 0.10 1258.3 0.67 1242.0 1.36 1225.2
1.83 1208.5 2.50 1185.3 3.28 1149.9
3.81 1118.0 3.99 1109.3 4.94 714.7
5.73 710.3 8.07 701.5 9.79 691.6
503.2 0.10 1277.5 0.69 1264.4 1.38 1250.1
2.69 1209.8 3.89 1156.1 4.44 1121.3
4.88 1090.6 5.54 767.0 6.87 766.6
8.09 749.8 9.91 736.3 9.93 740.3
513.2 3.91 1189.4 4.99 1138.6 5.21 1128.0
5.46 1103.9 5.54 1086.1 5.61 1073.2
6.37 844.4 6.49 838.3 7.71 813.4
9.79 788.4
519.2 0.10 1310.1 0.65 1298.0 1.04 1291.0
1.40 1283.7 1.86 1270.7 2.74 1248.2
3.28 1235.3 3.96 1214.6 4.68 1192.5
5.27 1162.3 5.63 1140.4 5.90 1121.2
6.32 1068.6 6.41 1057.6 6.54 1047.6
6.75 1001.5 6.86 935.1 6.98 918.1
7.06 898.4 7.27 873.1 7.27 873.1
7.80 855.1 8.98 839.2 9.73 835.4
523.2 0.10 1318.2 0.81 1309.0 1.44 1294.0
1.97 1281.8 3.44 1246.3 4.37 1214.9
5.13 1190.3 5.30 1176.4 5.61 1160.8
6.47 1094.2 6.89 1046.8 7.09 1014.5
7.19 983.2 7.38 929.5 7.39 934.5
7.58 908.1 7.58 912.5 7.76 898.5
7.84 889.7
533.2 0.10 1342.5 0.74 1330.8 1.36 1319.6
1.90 1302.5 3.00 1277.5 3.96 1249.8
5.77 1189.9 6.84 1137.0 7.99 1042.9
9.08 943.3 9.17 934.2 9.90 914.9
553.2 0.10 1381.8 0.76 1375.2 1.48 1361.5
2.66 1331.9 4.90 1287.3 6.60 1234.4
7.96 1182.6 9.20 1130.4 9.93 1093.0
573.2 0.10 1424.8 0.74 1413.7 1.39 1403.6
2.43 1384.2 4.16 1356.4 5.97 1321.8
7.80 1277.3 9.73 1218.6
 THEENTHALPYOFETHANOL

400 450 500 550

T/K
FIGURE 2. The specific enthalpy Ahi,, of the ideal-gas for ethanol. -, Best line through ideal-gas
enthalpies calculated from spectroscopic quantities;“) 0, obtained by extrapolating the table 1
measurements to zero pressure.

measurements. At all temperatures we made measurements at as low a pressure

(approximately 0.1 MPa) as the apparatus would allow. These measurements
facilitated the extrapolation to zero pressure. Comparison with ideal-gas enthalpies
calculated by Chao and Hall(*) is shown in figure 2 where the curve was calculated
from a quadratic equation fitted to their values. The mean deviation from the curve
is -(0.6*2.1) kJ*kgg’. The largest deviation is for the measurement at 573.2 K
where it is 5 kJ . kg- ’ smaller than the spectroscopic value.

5. The enthalpy of vaporization

Specific 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 et al. u** lg) The vertical lines shown in figure 1
were drawn at values of the vapour pressure obtained from the work of Ambrose et
al. The difference (Ah(g) - Ah(l)} is the enthalpy of vaporization, A,,,h. The standard
deviation of our derived AYaph values is estimated to be f2 kJ * kg-‘, with a
maximum uncertainty of f4 kJ* kg-’ on our value at 503.2 K. Enthalpies of
vaporization taken from the International Critical Tables (I.C.T.),‘ZZ’ the
experimental measurements of Radosz and Lydersen,‘5) and the values determined
from the total enthalpy measurements of Storvick and SmithJ3) are compared with
our values in figure 3. The values of AVaphlisted in table 2 were fitted to the Watson
equation:
&A~) = A,,,htT,Ntl - T/W - WW1>“- (3)
1156 M. D. VINE AND C. J. WORMALD

T/K

FIGURE 3. Specific enthalpies of vaporization A& of ethanol. 0, Table 2; 0, reference 3;

A, reference 5; V, reference 22. -, Calculated from equation (4).

Using Tb = 351.6 K, T, = 516.3 K, and Avaph(Tb) = 867.0 kJ. kg-*,(23) the best value
of the adjustable parameter n was 0.4341. The Watson equation fitted the values of
AVBph for ethanol to within f 12 kJ -kg- ’ which is three times larger than the
maximum uncertainty on A,,,h. To fit the AVaphmeasurements with better accuracy
we used a new equation which has the same constraints as the Watson equation at
the temperature limits Tb and T, but has two additional adjustable parameters. The
new equation is,
A,,,h(T) = A,,,h(T,){ax+(l -4xm)“, (4)
where
x = CC-WK-T,), (5)
and a, n, and m are adjustable parameters.

TABLE 2. The specific enthalpy of vaporization A,,$ of ethanol. 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

T Ah(g) Ah(l) Avsph

ii Idkg-’ kJkg-’ kJ.kg-’

393.2 1049.7 286.1 763.6

423.2 1063.0 399.1 663.9
453.2 1081.6 524.1 557.5
413.2 1088.3 614.1 474.2
493.2 1094.9 718.5 316.4
503.2 1081.9 774.3 307.6
 THE ENTHALPY OF ETHANOL 1157
This new equation was tested by fitting 30 values of the enthalpy of vaporization
of water from Tb and 7’, obtained from the HGK steam tables.‘24) Whereas the
standard deviation obtained with the Watson equation was +26 kJ * kg-‘, the fit
obtained using equation (4) was +4 kJ . kg- ‘. For ethanol the least-squares analysis
of the values listed in table 2 yielded the parameters a = 0.04846, m = 2.3852, and
n = 0.20254. The standard deviation is t- 3.3 kJ*kg-‘, and the fit is as good as that
obtained using the 4-parameter equation of Radosz and Lydersen.“’
In figure 3 we compare the new equation with previously measured values of AVaph
for ethanol and with our own values. The agreement between the values listed in
table 2 and the direct measurements reported by Radosz and LyderserP is excellent.
The enthalpy increments reported by Storvick and Smithc3) yield values of A,,,h
which are systematically too high by an average of 16 kJ . kg- ‘, The values of Avaph
published in I.C.T.@” are too high at temperatures up to 470 K and too low at
higher temperatures.

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