Thermodynamic Properties of

Hydrocarbons
The effects of pressure on specific heats
at constant pressure, entropy, and en-
W. C. EDMISTER thalpy are computed in reduced or gen-
Standard Oil Company (Indiana), Whiting, Ind. eralized units for hydrocarbons. These
calculations are based on a new correla-
tion of P-V-T data. The effect of tem-
perature on these thermodynamic prop-

T HERMODYNAMIC properties, such as deviation from

perfect gas laws, fugacities, specific heats, heats of
vaporization, entropies, internal energies, free energies,
and enthalpies or heat contents for petroleum hydrocarbons
erties can be computed by a new equation
for specific heat at one atmosphere, which
is based on a correlation of the data of
and their mixtures are of practical importance in engineering Beeck, of Eucken and Liide, and of
work associated with petroleum refinery operations. Re- Eucken and Parts.
search development of new processes and the design of plant By means of a table of generalized ther-
equipment require a knowledge of these properties over wide modynamic properties and equations pre-
ranges in temperature and pressure. The preparation of
tables or charts of these properties is complicated by the sented in this paper, it is possible to com-
multiplicity of the petroleum hydrocarbons and by the scar- pute all the thermal properties for any
city of reliable experimental specific heat and Joule-Thomson hydrocarbon for which critical data are
effect data. More P-V-T data are available, however, so available.
that the effect of pressure on the above thermodynamic prop-
erties can be computed by means of the first and second
laws of thermodynamics.
I n a previous paper (IO) a study of individual hydrocar-
bons was begun with two purposes: to make available more able attention in recent years from Lewis and co-workers (4,
complete thermodynamic data for one-component systems 7,19,SO, %’I), Newton and Dodge (S6,26), Watson and Nelson
and to prepare a background which would assist in the prepa- (34,and Watson and Smith (36). All of these investigations
ration of such thermodynamic data for multicomponent arrive a t the effect of pressure on enthalpy, Joule-Thomson
systems. The first publication on this project dealt with coefficients, etc., in round-about ways, and most of them re-
methane, for which the effects of pressure on the thermal sult in tedious methods of calculation. It is believed that a
properties were calculated graphically by means of the Lewis more direct method of arriving a t the effect of pressure on
and Randall (9.9) volume residual quantity, a,obtained from thermodynamic functions would be more precise and more
P-V-T data. Graphical methods of differentiation were useful from a practical standpoint. Such a direct method is
adapted and thermodynamic functions were integrated to this made possible by the graphical reduced equation of state de-
particular problem, and it was then discovered that a vast veloped and discussed here. ’I

m o u n t of work was involved in performing such calculations

precisely for each hydrocarbon individually. It became ap- Reduced Equation of State
parent, therefore, that the most expeditious method of pre-
paring tables and charts of thermodynamic properties for all The compressibility factor, P V / R T , which is the ratio of
the noma1 paraffinic, isoparafhic, olefinic, naphthenic, and actual to theoretical gas volume, has been in wide use during
aromatic hydrocarbons was a generalized method, by which recent years as a means of correlating P-V-T data. When
these computations could be made once for all single-com- plotted against reduced pressure, lines of constant reduced
ponent hydrocarbon systems-in other words, a method that temperature for different hydrocarbons are close together,
would result in ‘%educed” thermodynamic properties, which and in some cases coincide. Vapor volumes estimated from
wodd be functions of reduced pressure and temperature. this type of plot are of sufficient accuracy for most engineering
With such a method the tedious graphical differentiations design calculations. For thermodynamic calculations this
and integrations could be performed with great care once to correlation is not accurate enough and, in addition, is not well
obtain tbe reduced thermodynamic properties; then by means adapted t o graphical methods.
of the critical constants for any given hydrocarbon it would Instead of the ratio of actual to ideal gas volume, let us
be possible to compute the value of any desired thermody- consider their difference; this residual quantity is defined as
namic property. Such a correlation of reduced thermody- a = -RT
- v
namic functions would make it possible to estimate properties P (1)
of hydrocarbons for which there are few or no data available.
It should also be possible to apply these reduced functions to As pointed out by Deming and Shupe (8), this residual quan-
mixtures by the use of Kay’s pseudo critical constants for tity is well adapted to graphical methods. Since a =
c m o , P = P,Pc, and T = TrTo,Equation 1 may be rear-
mixtures (14).
The generalization of isothermal pressure corrections to ranged and written
such thermodynamic properties as enthalpy, internal energy,
and Joule-Thomson coefficients has been receiving consider-
352
MARCH, 1938 INDUSTRIAL AND ENGINEERING CHEMISTRY 353

1.3. I \\\ I
LIQUIDS
I
USE PR SCALE
~
I

P-V-T DATA CORRELATION

.o I I l l 1 1 / 1 1 1 1 1 1 1
3.5 4.0 4.5 0
R E D U ~ D P R E ~ U R E, pR3.0

which is essentially a reduced equation of state, where the well as in the unsaturated vapor region are given in Figure 1,
ratio RT,/P,a, is practically a constant as shown in Table 11, where the liquid curves are plotted against a different ab-
and aris a function of P, and Tr. scissa scale from that used for the vapor curves in order that
The a, function was determined from experimental P-V-T the two sets of curves may not overlap.
data collected from the literature. Table I shows the sources ACCURACY OF P-V-T CORRELATION. Using the critical
and ranges of the data used in making this correlation. constants given in Table 11, the a r correlation shown in Fig-
Values of a r were calculated and plotted for each hydrocar- ure 1 was used to calculate vapor volumes, which were com-
bon listed in Table I, and Figure 1 was constructed from pared with the experimental data. The same comparison
these plots. Values of in the unsaturated liquid region as was made with vapor volumes calculated by means of the
P V / R T correlation; the P V / R T plot used was practically
identical with Brown's z plot (6) and Lewis' p plot (19).
I. SOURCEof P-V-T DATA
TABLE The results of these comparisons are shown in Table 111,from
H ydrooarbon Pressure Range, PI Temp. Range, Tr Citation which it can be seen that the maximum deviations are smaller
LMethane 0.0218 -5.46 1.064 -2.478 for the a, correlation than for the PV/RT correlation in all
Methane 0.2182 -0.8735 1 . 4 3 -2.478
Ethylene 0.749 -2.96 0 . 9 6 6 -1.037 cases except that of n-pentane, for which the deviations for
, Ethylene
Ethane
0.0986 -2.96
0.2277 -3.892
1.055 -1.668
0.977 -1.714
both correlations are quite low. When average deviations
Propane 0.0238 -3.333 0.8196-1.647 are considered, the comparison is even more favorable to the
Isopentane 0.01564-2.18 0.701 -1.20 a, correlation. For most of the data, Figure 1 is within the
n-Pentane 0.0342 -2.26.8 0.709 -1.176 ,
Cyclohexane 0.1104 -2.62
0 . 3 1 5 -1.26
0.746 -1.035
0.872 -1.089
experimental error and is considered a sound basis for gener-
n-Hexane
n-Heptane 0.1081 -1.706 0.766 -1.016 alized thermodynamic calculations.

11. CRITICALCONSTANTS
TABLE FOR HYDROCARBONS
Critical Vol. Residual. R To Peat*
Hydrocarbon Mol. W t Critical Temp.
K. R.
Critical Pressure
Lb./sq. in.
Critical Vol.
Cc./g. Cu.j t . Cc./g.
ac
Cu. ft./
zc=-k' ks = Pcac
G. cal./
Atm. ah. mole l b . mot', mole lb. mole 8. mole**
Methano 16.03 191.1 344 45.8 673 99 1.586 243.5 3.90 1.406 1.413 270.2
Acetylene 26.02 309.1 556 61.7 907 113.2 1.814 298.0 4.772 1.381 1.452 445.8
Ethylene 28.03 282.8 508.5 50.7 745 133.4 2.138 324.2 5.195 1.410 1.410 398.5
Ethane 30.05 305.2 549 48.8 717 137.0 2.195 376.0 6.020 1.365 1.457 444.8
Propylene 42.05 364.8 656 45.0 661 181.6 2.91 483.8 7.745 1.375 1.446 527.5
Propane 44.06 369.9 665.5 42.01 617 195.0 3.123 528.0 8.46 1.368 1.455 538.0
Isobutane 58.08 407.1 732.0 37.0 544 249.0 3.99 654.5 10.48 1.379 1.442 587.0
n-Butane 58.08 426.0 766.5 36.0 529 250.0 4.005 720.5 11.54 1.347 1.477 629.0
Isopentane 72.09 460.9 829.0 32.92 483.4 307.6 4.930 842.0 13.485 1.365 1.459 672.0
n-Pentane 72.09 470.3 846.0 33.0 485 310.9 4.98 860.0 13.77 1.359 1.463 688.0
Benaene 78.05 561.6 1010 47.7 701 256.2 4.106 709.5 11.36 1.361 1.460 820.0
Cyclohexane 84.09 554.1 997 40.6 596.5 308.7 4.946 811.5 13.00 1.382 1.440 798.0
Diisopropyl 86.11 500.5 901 30.6 449.5 357.1 5.72 986 15.795 1.362 1.460 731.0
n-Hexane 86.11 507.9 913.5 29.5 433.5 367.2 5.88 1045 16.74 1.353 1.472 747.5
n-He tane 100.12 540.0 972.0 26.8 393.7 427.0 6.84 1227 19.65 1.349 1.477 797.5
Diisoxut yl 114.14 549.9 989.0 24.5 360.0 482.0 7.72 1389 21.77 1.355 1.468 807.0
n-Octane 114.14 569.3 1024 24.6 361.4 490.0 7.85 1410 22.59 1.347 1.475 840.0
* Dimensionless ratio is either g. cal./g. mole C. or B. t. u./lb. mole F.
** Multiply by 1.8 t o convert t o B. t. u./lb. mole.
354 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 30, NO. 3

OF P-V-T CORRELATIONS
111. ACCURACY
TABLE
Max. Deviations of Max. Deviations of
Calod. from Obsvd. Calod. from Obsvd,
Val., % Val., % where AC, is the increase in isobaric specific heat from zero
Correlation
Methane
Ethylene
PV/RT
6.6
10.6
ur
5.6
8.0
Correlation
Isopentane
n-Pentane
PV/RT
14.5
2.8
ar
6.9
5.3
pressure to any pressure P,. The second derivative (:%),
Ethane 5.9 3.5 Cyclohexane 9.0 4.5 was determined graphically by the chord area method from a
Propane 13.6 9.8 n-Hexane 11.2 5.5
n-Heptane 12.0 8.0 large-scale plot of ( $ ) p , vs. T , isobars; the first deriva-
tives were also determined graphically by the chord area
method from a large-scale plot of a, vs. T , isobars, and
Calculation of Thermal Properties Equation 7 was integrated graphically for several reduced
The effect of pressure on the various thermodynamic prop- temperatures. Values of ACp,lkzare given in Table IV, and
erties will now be calculated hv means of the reduced equa- values of le2 are given in Table 11.
tion of state represented by Figure l . Efect of Temperature. The AC, values computed from
FUGACITIES OF VAPORS. The fugacities of hydrocarbon
Table IV give only the effect of pressure on the isobaric spe-
vapors have been computed by several investigators using dif- cific heat. The effect of temperature must be determined ex-
ferent methods. Brown and co-workers (31) and Lewis (19) perimentally. The specific heat data available in the litera-
calculated the fugacity-pressure ratio by integrating the ture were collected, and a suitable correlation was developed.
compressibility factor, P V / R T , against pressure. Newton The data of Beeck (3) for methane, acetylene, ethylene,
(66)computed it for a large number of gases by integrating ethane, propylene, propane, butylene, butane, pentane, hex-
the equation ane, and heptane from 0" to 300" C. were used, as well as
the data of Eucken and Lude (11)for methane and of Eucken
and Parts (11) for ethylene and ethane. Bryant's equation
R T PI =~ -~J P 01 dP (3) (6) for methane agrees with the data of Beeck and of Eucken
and Lude, but his values for acetylene are about 4 per cent
against pressure directly for each gas and correlating the re- lower a t 600" K. and about 4 per cent higher at 250"K. By
sulting "activity coefficients" as a general function of reduced means of the data of Beeck (3) and of Eucken and co-workers
pressure and temperature. (11, 11) and on the assumption of a linear relation between
The values of f / p have been computed from the correlation C, and T between 250" and 600"K., the constants A and B
of Figure 1 as follows. On the introduction of reduced units were computed for the equation
Equation 3 becomes
Cp = A + BT
where C, = molal heat catacity
(4) T = temperature, K.

The following table gives values of these constants for all

The critical ratio RTc/P, acof Equation 2 appears here in
the hydrocarbons for which reliable data were available; the
Equation 4. If values of this critical ratio were strictly identi-
cal for all hydrocarbons, and if we assumed that a, is a func- constants for benzene were taken from an equation of Lindsay
tion of T rand P,, f / p would be a function of reduced tempera- and Brown (23):
ture and pressure only; but since they are only approximately A B A B
identical, f / p is only an approximate function of P, and T,. Methane
Acetylene
4.60
7.51
0.0133
0.01115
Butylene
Butane
4.60
4.60
0.0515
0.0562
Figure 1 was integrated graphically, the right-hand side of Ethylene 3.84 0.022 Pentane 5.11 0.0692
Ethane 3.84 0.0298 Hexane 6.62 0.0522
Equation 4 was computed for several reduced temperatures, Propylene 4.09 0.0372 Heptane 6.13 0.0952
and the values obtained are given in Table IV under the head- Propane 4.09 0.0432 Benzene 6.16 0.0526
ing "kl In f / p " where the constant k , = -RT,/P, ac. Values
of this critical ratio are given in Table I1 for seventeen hy- These constants indicate that for paraffinic and olefinic hy-
drocarbons. The average value of k, for the hydrocarbons is drocarbons A is a function of the number of carbon atoms
about -1.37, with only methane and ethylene deviating by only and increases 0.51 unit per carbon atom, above three
an appreciable amount. Where reliable critical data are carbon atoms; and that B increases 0.0130 unit per carbon
available, a value of kl = -RTo/Poac should be used rather atom for paraffins and 0.0143 unit per carbon atom for o l e
than the average value of -1.37. For the purpose of com- fins, above three carbon atoms. When both of these rela-
paring f / p ratios calculated from Table IV with those of tions are assumed, the following equation is developed for the
Lewis (19) and Newton (26)' the average value of -1.37 was heat capacity of paraffinic and olefinic hydrocarbons of three
used, however. The results of this comparison show less or more carbon atoms:
deviation from perfect gas laws a t low pressures and more a t C, = 2.56 +
0.51 n +
(0.0013n2 +
0.0044~~-
high pressures than do Lewis' or Newton's results. 0.00065mn
where n = number of carbon atoms
+0.00495~~ - 0.0057)T (8)
SPECIFICHEATAT CONSTANT PRESSURE.E$ect of Pres- m = number of hydrogen atoms
sure. The change of specific heat with pressure is given by
the following equation: The accuracy of this equation when applied to Beeck and
Eucken's data (3, 11, 12) is about 1 per cent. At 340" K.
Equation 8 gives a value 4 per cent higher than Haas and
Stegeman's value ( I S ) for ethylene; at 337.5"K. it gives 8
When expressed in terms of arand reduced units, Equation 5 value 3.5 per cent higher than Thayer and Stegeman's value
becomes : (39)for ethane, although it agrees with both a t 273" K. The
equation agrees with Sage and Lacey's propane data a t 298" K.
($99)but gives a value 4 per cent higher than theirs a t 371 " K.
The equation agrees with Sage and Lacey's butane data at
Integrating between the limits of P, and Pr = 0 a t different 356' K. (99) but gives a value 4 per cent lower than theirs a t
constant values of T , and defining the ratio P c a o / Tas
~ k2: 296 " K.
MARCH, 1938 INDUSTRIAL AND ENGINEERING CHEMISTRY 355
THERMODYNAMIC
TABLEIV. REDUCED FUNCTIONS
FOR HYDROCARBONS

0.830
0 . 8 0 0.05 0.055 -2.71 0.190 0 . 6 0 0.130 0.148 0,410 1.150 -0.02 -0.256 19.5 3.770 5.23
0.10 0.896 0.110 -3.00 0.33 1.25 0.274 0.307 0.351 1.239 +o. 01 -0.204 18.0 3.76 5.32
0.15 0.919 0.167 -3.40 0.60 1.97 0,435 0.480 0.304 1.317 0.04 -0.168 16.8 3.75 5.40
0.20 0.964 0.225 -3.93 1.23 2.80 0.615 0.675 0.265 1.383 0.06 -0,144 15.9 3.746 5.45
0.201 1.494 0.08 -0.108 14.6 3.709 5.54
0.85 0.05 0.752 0.044 -2.14 0.132 0.493 0.103 0.128 0.154 1.581 0.10 -0.078 13.75 3.68 5.62
0.10 0.761 0.088 -2.32 0.237 1.02 0.215 0,264 0.120 1.650 0.09 -0,060 13.10 3.65 5.66
0.15 0.776 0.133 -2.55 0.360 1.61 0.336 0.408 0,091 1.70 0.08 -0,050 12.6 3.60 5.70
0.20 0.797 0.180 -2.85 0.512 2.29 0.470 0.562 0.067 1.736 0.07 -0.042 12.1 3.58 5.72
0.25 0.829 0.226 -3.22 0.810 3.08 0.625 0.730
0.30 0.879 0,274 -3.74 1.20 4.07 0.800 0,925 0.419 0.018 -0,81 0.040 0.0657
0.90 0.05 0.649 0.036 -1.70 0.083 0.109 0.417 0.037 -0.83 0,081 0.132
0.10 0.655 0.072 -1.80 0.170 0,222 0,416 0.076 -0,86 0.165 0.268
0.15 0.664 0.108 -1.93 0.263 0.342 0.418 0.114 -n. gn 0.253 0.405
0.20 0.676 0.145 -2.10 0.364 0.470 0.421 0,152 -0.96 0.345 0.550
0.25 0.692 0.184 -2.33 0.474 0.604 0.426 0.190 -1.01 0.444 0,697
0.30 0.713 0.223 -2.65 0.600 0.750 0.431 0,230 -1.08 0.547 0.855
0.35 0.739 0.263 -3.05 0.740 0.915 0,437 0.269 -1.15 0.660 1.02
0.40 0.772 0.305 -3.58 0.734 5.40 0.900 1.095 0.444 0.309 -1,25 0.780 1,20
0,451 0.350 -1.37 0.910 1.39
0,460 0.392 -1.57 1.06 1.60
0.95 0 . 0 5 0.574 0.030 -1.31 0.066 0.0925 0.480 0.477 -2.07 1.42 2.075
0.10 0.576 0.060 -1.39 0.135 0.187 0.510 0.567 -2.56 1.88 2.69
0.15 0.580 0,090 -1.48 0.207 0.285 0.520 0.612 -2.72 2.15 3.01
0.2 0.587 0 122 -1.59 0.283 0.389 0.517 0.660 -2.78 2.41 3.31
0.25 0.595 0 . iSi -1.72 0.365 0.495 0.496 0.753 -1.70 2.84 3.81
0.3 0.605 0.184 -1.86 0.451 0.610 0.455 0.840 -1.0 3.11 4.15
0.35 0.617 0.216 -2.04 0.550 0.726 0,398 0.936 -0.46 3.27 4.40
0.40 0.630 0.248 -2.24 0.660 0.855 0.347 1.02 -0 23 3.38 4.56
0.45 0.646 0.282 -2.51 0.780 1.000 0.304 1.094 -0.10 3.42 4.70
0.50 0.665 0.316 -2.87 0.920 1.160 0.267 1.16 -0.04 3.44 4.80
0.55 0.687 0.362 -3.31 1.07 1.340 0.204 1.268 +0.04 3.43 4.97
0.60 0.717 0.390 -3.89 1.25 1.540 0.158 1.349 0.06 3.41 5.05
0.65 0.755 0.428 -4.67 1.46 1.775 0.124 1.411 0.06 3.39 5.14
0.70 0.812 0.467 -5.70 1.72 2.07 0.095 1.460 0.05 3.34 5.20
0.071 1.499 0.05 3.30 5.25
1.0 0.0.5 0.513 0.015 -1.08 0.053 0.079
0.10 0.513 0.051 -1.12 0.108 0.160 0.015 -0.62 -0.056 0.100 0.035 0.0605
0.2 0.518 0.103 -1.22 0.227 0.329 0.383
0.3 0.527 0.155 -1.35 0.355 0.507 0.381 0.032 -0.73 -0,043 0.205 0.071 0.121
0.4 0.537 0.208 -1.50 0.500 0.705 0.378 0.066 -0.76 -0,020 0.429 0.144 0.243
0.5 0.55 0.263 -1.71 0.660 0.920 0.377 0.099 -0.78 +0.002 0.676 0.220 0.369
0.6 0.575 0.320 -2.03 0.845 1.165 0.378 0.132 -0.81 4-0.015 0.960 0.300 0.495
0.7 0.603 0.378 -2.58 1.075 1.440 0.380 0.165 -0.84 +0.023 1.275 0.380 0.626
0.8 0.642 0.440 -3.88 1.38 1.810 0.382 0.198 -0.88 0.028 1.625 0.470 0.763
0.9 0.707 0.507 -6.70 1.89 2.39 0.389 0.265 -0.98 0.036 2.48 0,655 1.055
0 96 0.771 0.544 -12.0 2.30 2.87 0.396 0.312 -1.11 0,037 3.62 0.870 1.375
1.0 1.00 0.586 -30.0 3.00 3.95 0.403 0.402 -1.25 0.037 5.44 1,100 1.730
1.02 1.07 0.606 -24.0 3.50 4.50 0.410 0.473 -1.46 1.375 2.110
l.O!j 1.052 0.636 -14.0 3.95 5.15 0.415 0.545 -1.56 1.675 2.52
0.412 0.616 -1.46 1,985 2.97
. 1.1
1.15
1.2
1.007
0.955
0.906
0.690 -1.9
0.738 i-0.67
0.786 -0.16
4.15
4.20
4.20
5.55
5.73
5.80
0.399
0.369
0.686
0.769
-1.13
-0.74
2.25 3.35
2.48 3.70
1.3 0.823 0.873 -0.21 4.20 5.90 0.333 0.845 -0.42 2.62 3.94
1.4 0.755 0.952 0 4.20 5.99 0.296 0.913 -0.24 2.70 4.13
1.5 0.694 1.024 +O.ll 4.20 6.05 0.263 0.974 -0.14 -0.126 9.54 2.74 4.27
1.6 0.639 1.091 +O. 16 4.20 6.10 0.205 1.075 -0.03 -0.103 8.67 2.79 4.46
1.8 0.55 1.209 0.21 4.19 6.19 0.159 1.154 f0.01 -0.081 8.18 2.80 4.60
20 0,477 1.312 0.22 4.18 6.26 0.125 1.215 0.02 -0.064 7.88 2.80 4.69
2.28 0.405 1.442 0.19 4.15 6.33 0.096 1.263 0.03 -0,051 7.67 2.80 4.75
2.50 0.347 1.515 0.15 4.13 6.37 0.073 1.301 0.03 -0,043 7.50 2.79 4.81
2.78 0,299 1.595 0.14 4.11 6.41
3.0 0.259 1.666 0.15 4.Ib 6.44 0.348 0.014 -0,625 0.031 0.0555
3.50 0.192 1.78 0.16 4.05 6.48 0.346 0.027 -0.635 0.062 0.111
0,342 0.058 -0.660 0.127 0.222
1.0250 . 0 5 0.487 0.025 -1.01 -0.022 0.172 0.050 0,0745 0.341 0.086 -0.680 0.194 0.336
0.10 0.485 0.049 -1.04 -0.001 0.355 0.101 0.151 0.340 0.115 -0.700 0.263 0.453
0.2 0.488 0.095 -1.11 +0.038 0.760 0.208 0.309 0.341 0.143 -0.720 0.333 0.573
0.3 0,496 0.143 -1.20 0.071 1.27 0.324 0.474 0.342 0.171 -0.745 0.408 0.695
0.4 n. 50.5
... 0,192 -1.30 0.097 1.92 0.449 0.652 0,344 0.229 -0.800 0.560 0.940
0.5 0.516 0.241 -1.45 0.124 2.76 0.586 0.843 0.347 0.286 -0,860 0.725 1.210
0.6 0.530 0.292 -1.63 0.154 3.95 0.740 1.054 0.350 0.345 -0.930 0.906 1.495
0.7 0.547 0.344 -1.92 0.194 5.60 0.916 1.290 0.351 0.402 -1,020 1.10 1,800
0.8 0.569 0.400 -2.35 0.244 8.15 1.127 1.561 0.351 0.461 - 1 n7n 1.31 2.12
0.9 0.597 0.456 -2.99 0.326 12.8 1.39 1.886 0.349 0.519 -1,045 1.526 2.44
1.0 0.638 0.526 -4.2 0.560 23.0 1.745 2.298 0.344 0.577 -0.960 1.725 2.76
1.1 0.719 0.582 -8.9 1.02 65.0 2.40 2.993 0.329 0.648 - 0 , 8 0 0 1.94 3.10
1.15 0.770 0.618 -12.4 0.98 71.0 2.885 3.65 0.305. 0.714 -0.615 2.11 3.40
1.2 0.812 0,657 -8.8 0.600 63.0 3.23 4.18 0.280 0.774 -0,430 2.25 3.63
1.25 0.824 0.696 -4.6 -0.100 54.0 3.52 4.50 0.254 0.830 -0,280 2.35 3,80
1.30 0.800 0.737 -2.75 -0.549 47.1 3.70 4.77 0,201 0.924 -0.115 2.45 4.03
1.4 0 746 0.813 -1.15 -0.555 39.0 3.83 5.03 0.159 0.999 -0.050 2.48 4.18
1.5 0 690 0.884 -0.58 -0.546 34.0 3.89 5.20 0.125 1,058 -0.020 2.49 4.29
1.6 0.636 0.948 -0.30 -0,514 30.3 3.91 5.30 0.096 1.103 0 2.50 4.37
1.8 0.550 1.061 0 -0,394 25.8 3.92 5.49 0.073 1.140 +0.01 2.50 4.43
2.0 0.480 1.162 +0.10 -0.321 23.2 3.91 5.60
1.30 0.05 0.291 0.011 -0,495 -0.050 0.07
0.0246 0.046
1.05 0 . 0 5 0.464 0.021 -0.94 0.046 0.071 0.10 0.289 0.021 -0,500 -0,045 0.141
0.04950.0925
0.1 0 462 0,044 -0.96 0.094 0.143 0.2 0.285 0.044 -0.504 -0,033 0.289
0.09950.186
0.2 0 463 0.087 -1.00 0.192 0.292 0.3 0.282 0.069 -0.510 -0,022 0.447
0.150 0.280
0.3 0.467 0,132 -1.07 0.295 0.447 0.4 0.280 0.088 -0.520 -0.014 0.616
0.201 0.377
0.4 n 474 0.178 -1.15 0.406 0.610 0.6 0.279 0.131 -0,540 -0,006 0,995
0.308 0.570
0.5 0.482 0.223 -1.25 0.528 0.785 0.8 0.277 0.174 -0,560 -0,004 1.41
0.418 0.767
0.6 0.491 0.269 -1.38 0.657 0.970 1.0 0.276 0.216 -0.590 -0.005 1.88
0.530 0.970
0.7 0.503 0.315 -1.55 0.805 1.175 1.2 0.275 0,259 -0,615 -0,008 2.40
0.658 1.183
0.8 0.517 0.364 -1.77 0.97 1.40 1.4 0,272 0.301 -0,640 -0.011 2.98
0.780 1.40
0.9 0.535 0,415 -2.07 1.16 1.65 1.6 0.270 0.343 -0.660 -0,014 0.915 1.62
3.59
1.0 0.559 0,468 -2.58 1.40 1.96 1.8 0.267 0.384 -0.670 -0,018 1.048 1.85
4.20
1.1 0.596 0,523 -3.65 1.697 2.33 2.0 0.263 0.424 -0.670 -0,023 1.184 2.08
4.84
1.2 0.645 0.582 -5.22 2.13 2.87 2.25 0.266 0.475 -0.640 -0,033 1.35 2.36
5.60
1.25 0.673 0.612 -6.20 2.42 3.20 2.50 0.243 0.523 -0.585 -0.046 1.50 2.62
6.19
1.3 0.692 0,642 -5.40 2.715 3.52 2.75 0.228 0.568 -0.525 -0.058 1.635 2 . 8 8
6.39
1.35 0.700 0.674 -4.10 2.96 3.82 3.0 0.213 0 610 -n. 4.__
~ n -0.064 1.765 3.09
6.39
1.4 0.695 0,707 -3 07 3.12 4.03 3.50 0.181 0.686 -0.455 -0.064 6.10 1.94 3.42
1.5 0.663 0.772 -1.86 3.38 4.35 4.0 0,149 0.780 -0,125 -0.062 5.72 2.035 3.65
1.6 0.625 0.834 -1.21 3.527 4.60 4.5 0.120 0.801 -0.080 -0.055 5.34 2.090 3.78
1.8 0.550 0.947 -0.48 3.69 4.93 5.0 0,093 0.842 -0,045 -0.048 5.00 2.115 3.86
2.0 0.482 1.044 -0.14 3.746 5.11 5,s 0.072 0.869 -0,OZZ -0.043 4.75 2.125 3.92
i

356 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 30, NO. 3

REDUCED
THERMODYNAMIC
FUNCTIONS
FOR HYDROCARBONS
(Continued)

Tr Pr (Z)T~ ACp LH
loa Tr Pt bi In P
1 (h)
bTr Pr
(+)
bPr Tr
+A LH
ar lo2 at loa loa
1.4 0.05 0.248 0.009 -0.390 -0.050 0.055 0.0196 0.040 2.2 0.8 0.047 0.020 -0.128 -0.020 0.219 0.105 0.280
0.10 0.245 0.016 -0.390 -0,046 0.109 0.0390 0.080 1.0 0.043 0.025 -0.126 -0,020 0,277 0,130 0,346
0.2 0.241 0.033 -0.400 -0.037 0.222 0.0786 0.160 1.2 0.039 0.028 -0.124 -0.018 0.333 0.155 0.410
0.3 0.238 0.051 -0.400 -0.030 0.337 0.118 0.240 1.4 0.036 0.032 -0.121 -0.015 0.391 0.180 0.474
0.4 0.235 0.068 -0.405 -0,024 0.456 0.158 0.322 1.6 0.034 0.035 -0.118 -0,012 0.448 0.202 0.535
0.6 0.231 0.102 -0.415 -0.016 0.715 0.240 0.488 1.8 0.032 0.038 -0.115 -0.010 0.500 0.228 0,595
0.8 0.229 0.135 -0,425 -0.012 .1 .oo 0.324 0.650 2.0 0.030 0.041 -0.112 -0.010 0.554 0.248 0.654
1.0 0.226 0.168 -0.440 -0.012 1.30 0.410 0.820 2.5 0.025 0.047 -0,106 -0.010 0.680 0.300 0,795
1.2 0.223 0.200 -0.450 -0.014 1.63 0.499 0.985 3.0 0.020 0.052 -0.100 -0.010 0.790 0.352 0.925
1.4 0.220 0.231 -0,460 -0.016 1.98 0.590 1.16 3.5 0.014 0.056 -0,097 -0.012 0.885 0.400 1.046
1.6 0.216 0.262 -0.466 -0.019 2.34 0.685 1.33 4.0 0.008 0.058 -0,093 -0,013 0.975 0,448 1.158
1.8 0.212 0.293 -0.477 -0 I022 2.72 0.778 1.50 4.5 f0.001 0.059 -0,090 -0.012 1.05 0.490 1.26
2.0 0.208 0.323 -0.480 -0.027 3.11 0.875 1.68 5.0 -0.004 0.059 -0.080 -0.010 1.12 0.530 1.35
2.25 0.200 0.359 -0.480 -0.031 3.60 0.990 1.90 5.5 -0.007 0.058 -0.076 -0,003 1.18 0.570 1.436
2.5 0.192 0.395 -0,460 -0.035 4.10 1.115 2.11
2.75 0.183 0.428 -0.425 -0.039 4.52 1.225 2.33 2.5 0.1 0.029 0.002 -0,111 -0,027 0,016 0.011 0,0300
3.0 0.173 0.460 -0.385 -0.042 4.84 1.32 2.51 0.2 0.027 0.003 -0,110 -0.026 0.032 0,022 0.059
3.5 0.154 0.518 -0.295 -0.046 5.11 1.49 2.85 0.4 0.022 0.005 -0.108 -0,022 0.064 0.0435 0.115
4.0 0.132 0.570 -0.200 -0.046 5.00 1.615 3.10 0.6 0.018 0.007 -0.104 -0.020 0.096 0.0645 0.169
4.5 0.108 0.612 -0.140 -0.045 4.80 1.69 3.285 0.8 0.014 0.009 -0,100 -0.017 0.128 0.0850 0.200
5.0 0.087 0.647 -0.095 -0.040 4.55 1.75 3.39 1.0 0.010 0.010 -0,096 -0.015 0.160 0.105 0.270
5.5 0.068 0.675 -0.090 -0.035 4.30 1.82 3.46 1.2 0.008 0.011 -0.093 -0,013 0.192 0.1235 0.320
1.4 0.006 0.011 -0.090 -0.010 0.224 0.142 0.369
1.50 0.05 0.212 0.007 -0.320 -0.503 0.043 0.016 0.035 1.6 0.004 0.012 -0.088 -0.008 0.255 0.160 0.415
0.1 0.210 0,013 -0.321 -0.048 0.085 0.0322 0.0695 1.8 0.003 0.012 -0.086 -0.007 0.288 0.178 0.460
0.2 0.206 0.026 -0.324 -0.040 0.170 0.065 0.1390 2.0 +0.002 0.012 -0,084 -0.007 0.319 0,195 0.502
0.4 0.198 0.063 -0,332 -0.029 0,344 0.130 0.2790 2.5 -0.002 0.012 -0.082 -0.008 0.395 0.236 0,607
0.6 0.194 0.080 -0.338 -0.021 0.530 G.199 0.420 3.0 -0.006 0.011 -0.080 -0.010 0.467 0.275 0.705
0.8 0.190 0.106 -0.344 -0.017 0.733 0.267 0.560 3.5 -0.011 0.009 -0.075 -0.010 0.535 0.314 0.797
1.0 0.187 0.132 -0.352 -0.016 0.950 0.334 0.700 4.0 -0.016 0.007 -0.070 -0.010 0.605 0.350 0.882
1.2 0.183 0.156 -0.360 -0.019 1.175 0.403 0.840 4.5 -0.020 10.003 -0.065 -0.010 0.665 0.385 0.960
1.4 0.178 0.180 -0.360 -0.022 1.420 0.475 0.980 5.0 -0,024 -0,001 -0,060 -0,006 0.725 0,415 1.031
1.6 0.174 0.204 -0.362 -0.024 1.67 0.550 1.125 5.5 -0.027 -0.007 -0.060 -0.002 0,785 0.446 1.095
1.8 0.169 0.226 -0.360 -0.024 1.94 0.624 1.265
2.0 0.164 0.249 -0.355 -0.026 2.21 0.700 1.410
2.5 0.152 0.302 -0.340 -0.028 2.90 0.880 1.750
3.0 0.138 0.350 -0,310 -0.028 3.55 1.040 2.075
3.5 0.124 0.394 -0.280 -0.030 3.97 1.175 2.35
4.0
4.5
0.108
0.091
0.433
0 466
-0.210 -0.034 4.11
-0.160 -0.035 4.09
1.290 2.60
1.380 2.80
ENTROPY.
The equation for the entropy
5.0 0.075 0.494 -0.135 -0.033 3.99 1.460 2.95

1.0
5.5
0.05
0.1
0.2
0.060
0.183
0.180
0.176
0.516
0.006
0.011
0.022
-0,090 -0.027 3.85
-0,272
-0.272
-0.274
-0.055 0.034
-0.050 0.067
-0.046 0.134
1.520 3.06
0.0134 0.031
0.0270 0.062
0.0547 0.124
dS = q d T - G), dP

0.4 0,169 0.044 -0.278 -0.031 0.268 0.110 0.248 becomes, on the introduction of arand reduced units,
0.6 0.164 0.065 -0.280 -0.023 0.410 0.165 0.370
0.8 0.160 0,085 -0.280 -0.019 0.563 0.221 0.493
1.0
1.2
0.156
0.151
0.105
0.124
-0.280
-0.282
-0.020 0.725
-0.022 0.890
0.278 0.616
0.331 0.740
dfJ = 5 dT --
Rdp +*p (’5)
dp,
(10)
1.4 0.146 0.143 -0.285 -0.023 1.07 0.390 0.860 T P Tc aTr Pr
1.6 0.141 0.160 -0,283 -0.023 1.24 0.449 0.980
1.8 0.137 0.177 -0.281 -0.023 1.43 0.505 1.10
2.0 0.132 0.195 -0.280 -0.023 1.62 0.564 1.22 If we integrate, change the sign of the third term, and replace
2.5 0.121 0.234 -0.265 -0.022 2.10 0.704 1.50 Pca./Tc with k2, an equation for the change of entropy re-
3.0 0.109 0.270 -0.245 -0,022 2.58 0.833 1.767

s-(”)
3.5 0,098 0.303 -0,225 -0.022 3.00 0.950 2.00 sults :
4.0 0.088 0.332 -0.200 -0,024, 3.29 1.057 2.22
4.5 0.076 0.358 -0.170 -0.030 3.42 1.150 2.40
5.0 0.061 0.379 -0.140 -0.029 3.43 1.230 2.55
5.5 0.048 0.399 -0.113 -0.022 3.40 1.300 2.69 AS=C,lnT - R l n P - k k , dP, (11)
aTv ~r
1.8 0.05 0.136 0.004 -0.205 -0.060 0.026 0.010 0.025
0.1 0.133 0.008 -0.205 -0.055 0.051 0.0202 0.050
0.2 0.128 0.015 -0.206 -0.048 0.100 0.0410 0.100 The first and second terms can easily be evaluated for any
0.4 0.120 0.028 -0.207 -0.033 0,200 0.0820 0.199
0.6 0.115
0.111
0.042
0.054
-0.208
-0.207
-0.024
-0.020
0.305
0.410
0,123 0.298
0.164 0.395
specific problem, but it is desirable to integrate the third term
0.8
1.0 0.107 0.066 -0,205 -0.021 0.515 0.205 0.490 in reduced units. If Equation 11is written
1.2 0.103 0.078 -0.204 -0.022 0.620 0.248 0.585
1.4 0.097 0.089 -0.201 -0.022 0.728 0,290 0.680
1.6 0.093 0.100 -0.200 -0.020 0.840 0.330 0.770 AX = (2,111 T - R l n P - A S ’ (12)
1.8 0,090 0.110 -0.195 -0.018 0.950 0.370 0.865
0.120 -0.190 -0.015 1,050 0.408 0.950
2.0
2.5
3.0
3.5
0.086
0.079
0.070
0.062
0.143
0.164
0.182
-0,178
-0,166
-0.155
-0.016
-0,016
-0.016
1.310
1:56
1.80
0.500 1.150
0.590 1.350
0.677 1.53
where .s’
kz = J P r - ($& dP, (13)
4.0 0.064 0.198 -0.144 -0.017 2.00 0.755 1.695
4.5 0.045 0.212 -0.130 -0.019 2.16 0.830 1.85
5.0 0.034 0.223 -0.108 -0.021 2.28 0.900 1.974 and Equation 13 is integrated, the result is shown in Table
5.5 0.026 0.231 -0,100 -0.013 2.36 0.960 2.086
I V under “A8’/k2.’’ By means of Equations 12 and 8, and
2.0 0.05 0,099 0.003 -0.162 -0.056 0.017 0.008 0.021 values of AS’,%, in Table IV, the change of entropy between
0.1 0.096 0,006 -0.161 -0.050 0,035 0.0161 0.042
0.2 0.092 0,009 -0.162 -0.040 0.070 0.032 0.084 any two conditions for hydrocarbon vapors may be estimated.
0.4 0.084 0.018 -0.161 -0.031 0.143 0,064 0,165 ENTHALPY. The equation for the enthalpy
0.6 0.079 0.026 -0.160 -0.023 0.218 0.096 0.247
0.8 0.075 0,034 -0.160 -0.021 0,295 0.128 0.326
1.0
1.2
1.4
0.071
0.067
0.063
0.041 -0.159
0.048 -0.158
0.055 -0.154
-0.020
-0.020
-0.019
0,373
0.450
0,528
0.160 0.404
0.191 0.480
0.221 0.554 dH = C,dT - [T ($)p -V] d P (14)
1.6 0.059 0.061 -0 152 -0.018 0,603 0.261 0.630
1.8 0.056 0.066 -0.148 -0.016 0 . 6 8 0 0.281 0.700
2.0 0.053 0.072 -0.142 -0.014 0,752 0.311 0.770 becomes, when a,.and reduced units are introduced,
2.5 0.048 0.084 -0.132 -0.011 0.935 0.381 0.935
3.0 0.042 0.096 -0.124 -0.012 1.10 0.446 1.088

[ ar - T , (2)pr]
3.5 0.036 0.105 -0.119 -0.014 1.25 0.507 1.23
4.0 0,028 0.113 -0.113 -0.015 1.375 0.565 1.365
4.5 0.021 0.119 -0 108 -0.015 1.48 0.620 1.485 dH = C,dT - Pea, dP, (15)
5.0 0.014 0.124 -0.093 -0.014 1.56 0.675 1.596
5.5 0.008 0.126 - 0 , 0 8 6 -0.010 1.62 0.720 1.692
2.2 0.1 0.066 0,003 -0.139 -o,042 o,025 o,0135 o.0369 With temperature constant, the integral of the second term
0.2 0.062 0.006 -0.137
-0.133
-0.035
-0,027
0.051 0.0268 0.0730
0,105 0 0530 0.144
gives the effect of pressure on the enthalpy. Defining PCac
0.4 0.056 0.011
0.6 0.051 0.016 -0.130 -0.022 0,161 0,07900.213 asksandintegratingfromPrtoP, = 0,
MARCH, 1938 INDUSTRIAL AND ENGINEERING CHEMISTRY 357

The first column gives the experimental data of Sage, Webster,

and Lacey (SO); the second column gives values of AH com-
puted from a Watson and Nelson AH/T plot (34); and the
third column gives the values of AH computed from the data
where AH is the change of enthalpy from zero pressure to in Table IV, using the constants given in Table I1 and cor-
P , a t constant temperature. This integration wa3 performed recting the results to a reference pressure of one atmosphere.
graphically for different reduced temperatures; values of Since Watson and Nelson's method (34) is based on an ap-
AH/k3 are listed in Table IV. The effect of temperature on proximate equation of state derived from a PV/RT correla-
enthalpy may be determined by means of Equation 8. tion, it was expected that their results would deviate from the
The following example illustrates the use of the data of actual values. The agreement between their values and the
Table IV in computing the isothermal pressure correction to values calculated by the above method is not bad, however.
the enthalpy: Find AH (to be subtracted from the enthalpy The discrepancy between the experimental data of Sage,
a t atmospheric pressure) for propane a t 206" F. and 586 Webster, and Lacey (SO) and the values calculated by the
pounds per square inch absolute. The reduced temperature, above method is more difficult to explain, however. The
T,, is 1.O; the reduced pressure, P,, is 0.95; and the reduced computed pressure corrections to the enthalpy a t and near the
pressure a t atmospheric pressure, P,, is 0.024. At T , = 1.00 critical state are considerably higher than the experimental
and P, = 0.024 and 0.95, the values of AH/& are found to be values of Sage, Webster, and Lacey. The maximum devia-
2.87 and 0.037 from Table I V (0.037 was obtained by ex- tion of the arcorrelation for ethane is 3.5 per cent (it is even
trapolation). By means of constants from Table 11, AH lower a t the critical state), and the effect of pressure on en-
is found as follows: thalpy was computed by means of proved and accepted ther-
modynamic formulas and the arcorrelation. Therefore, the
A H = (2.87 - 0.0.37) 538 X 1.8 X 4m= 62.25 B. t. u./lb. discrepancy between the calculated and the observed values
of AH appears to be higher than one would expect.
BENZENE.Lindsay and Brown (23) obtained some iso-
DIFFERENCE
IN SPECIFIC
HEATS. The equation for the enthalpic expansion data on benzene and from it computed the
difference in specific heats effect of pressure on enthalpy. The following table gives a
comparison of AH (B. t. u. per pound to be subtracted from en-
thalpy a t P, = 0.03) for benzene a t three reduced temperatures :

----.TI 0.90-- 7- Tr = 1.0- -7 -----TI = 1.1--

Lindsay Watson Lindsay Watson Lindsay Watson
and and Ed- and and Ed- and and Ed-
PP Brown Nelson mister Brown Nelson mister Brown Nelson mister
becomes, on the introduction of ar and reduced 0.03 0 0 0 n n 0 n 0 0
units, 01 2.92 4.4 2.96 5.84 3.62 2.13 2.85 2.79 1.76
0.2 8.15 9.42 7.65 5.81 7.75 5.85 5.13 5.66 4.33
0.3 14.6 14.9 13.0 9.29 11.75 8.65 7.41 8.95 6.91
0.4 20.6 20.5 19.6 14.2 16.52 12.4 11.4 12.3 9.65
0.5 27.2 27.4 28.2 18.7 21.20 16.51 14,52 15.75 12.43
0.6 ...
...
...
...
.. .. .. 21.95
28.4
25.8
30.7
21.05
26.35
18.10
21.65
19.5
22.7
15.41
18.35
0.7
0.8 ,.. ... ... 32.9 36.2 33.11 25.05 27.6 21.95
0.9 , . . ... ... 40.0 43.2 44.2 29.90 30.4 25.5
1.0 ... ... .. 47.8 64.5 73.71 33.45 34.3 29.5
... ... ..
(z)
1.2 ,.. 42.7 42.5 38.4
1.3 ... ... .. 83.9 lO2'.0 110.5

(
The derivatives % ) p y and Trwere deter-

mined graphically by the chord area method from large- One column gives the experimental data of Lindsay and
scale plots of ar vs. T, isobars and ar vs. Pr isotherms, Brown (23); another gives values of AH computed from a
and are listed for several values of reduced pressures Watson and Nelson plot (84); and the third gives values of
and temperatures in Table IV. By means of Equation 18 AH computed from the data in Table IV, using the constants
and the data in Tables I1 and I V the difference in specific given in Table I1 and correcting the results to a reference pres-
heats may be estimated for hydrocarbon vapors. With C , sure of P, = 0.03.
estimated from Equations 7 and 8, C;, and C,/C, may also The disagreement a t and near the critical state of AH values
be estimated. computed from Table IV and the data of Lindsay and Brown
(2.9) is quite large. It seems reasonable to expect the iso-
Comparison of Results w i t h Experimental thermal enthalpy correction at the critical temperature to in-
Data crease more rapidly as the critical pressure is approached than
the data of Lindsay and Brown indicate.
ETHANE.Sage, Webster, and Lacey (SO) determined the Values of AH computed from Table IV for ethane are
effect of pressure on the enthalpy of ethane. The following higher than the data of Sage, Webster, and Lacey (SO) ; values
table gives a comparison of AH (to be subtracted from of AH computed from Table IV for benzene are lower (ex-
enthalpy a t atmospheric pressure to obtain enthalpy at higher cept near and a t the critical state where they are higher) than
pressure) in B. t. u. per pound a t three temperatures: the data of Lindsay and Brown (23). Since they are "re-
duced" thermodvnamic lsroDerties and are
-7O'F.-
Sage,
-- Sage,
100' F-.
*
Webster, Wat-
7-

Sage,
220' F
Webster, Wat-
.
-
I

obtained from generalized calculations, the

data in Table IV are consistent, whereas the
*

Webster, Wat-
Pres- and son and Ed- and son and Ed- and son and Ed- disagreements with the above-mentioned data
sure
-. Lacey Nelson mister Lacey Nelson mister Lacey Nelson mister are not consistent. Consistency in thermal
abs.
+b./sq.
2%. data is important in engineeringdesign calcu-
100 4.41 8.12 7.07 4.02 6.9 5.13 2.69 4.07 3.45 lations. It is desirable to have reliable and
300
500 17.25 54.8
38.0 27.9 23.08
51.38 15.44 23.3 18.70 9.78 13.58 11.88 consistent experimental data on the effect of
600 . .
.. .. ..
.. .. ..
.. 4i:43 50.3 48:77 2i:m 29:4 2i:2 pressure on enthalpy and other thermal prop-
erties .
1000 127.13 130.4 146.62 40.2 52.0 44.8
3500 .. .. .. .. 110.05 113.2 109.9
 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 30. NO. 3

Literature Cited Lewis, IND.ENQ.CHEM., 28,257 (1936).

Lewis and Luke, Ibid., 25, 725 (1933).
Amagat, Ann. chim. phys., 29,58 (1893). Lewis and Luke, Trans. Am. SOC.Mech. Engrs., 54, 55 (1932).
Beattie, Hadlock, and Proffenberger, J . Chem.Phys., 3,93 (1935). Lewis and Randall, “Thermodynamics,” New York, McGraw-
Beeck, Ibid., 4, 680 (1936). Hill Book Co., 1923.
Brown, Lewis, and Weber, IND.ENQ.CHEM.,25,325 (1934). Iindsay and Brown, IND.ENO.CHEM., 27,817 (1935).
Brown, Souders, and Smith, Ibid., 24, 514 (1932). Massen and Dolley, Proc. Roy. SOC.(London), 103, 524 (1923).
Bryant, Ibid., 25, 820 (1933). Newton, IND.E m . CHEM., 27,302 (1935).
Cope, Lewis, and Weber, Ibid., 23, 887 (1931). Newton and Dodge, Ibid., 27, 577 (1935).
Deming and Shupe, Phys. Rev., 37, 638 (1931); 38, 2245 Perry and Herrman, J . Phvs. Chem., 39, 1189 (1935).
(1931). Rotinjanz and Nagornow, 2.physik. Chem., A169, 20 (1934)
Deschner, doctoral dissertation, Univ. Mirh., 1934. Sage and Lacey, IND.EXQ.CHEM.,27, 1484 (1935).
Edmister, IND.ENQ.CHEM.,28, 1112 (1936). Sage, Webster, and Lacey, Ibid., 29, 658 (1937).
Eucken and Liide, 2. physik. Chem., B5, 413 (1929). Selheimer, Souders, Smith, and Brown, Ibid., 24,515 (1932).
Eucken and Parts, IbiU., B20, 184 (1933). Thayer and Stegeman, J. Phys. Chem., 35, 1.505 (1931).
Haas and Stegeman, J . Phys. Chem., 36, 2126 (1932). Thomas and Young, Trans. Chem. SOC.,67, 1071 (1895).
Kay, IND.ENG.CHEM., 28, 1014 (1936). Watson and Nelson, IND.ENQ.CHBM., 25, 880 (1983).
Kay, unpublished data. Watson and Smith, Natl. Petroleum News. July 1, 1936.
Keenan, Steam Tables, New York, Am. Soc. Mech. Engrs., Young, Phil. Mag., [ 5 ] 47, 353 (1899).
1930. i37j Young, 2. physik. Chem., 29,193 (1899).
Keyes and Burke, J . Am. Chem. SOC.,49, 1403 (1927).
Kvalnes and Gaddy, Ibid., 53, 397 (1931). RBCEIVDD
September 29, 1937.

ORGANOLITES
Organic Base-Exchange Materials
HARRY BURRELL
Ellis-Foster Company, Montclair, N. J.

T HE phenomenon of base
exchange has been known
since 1850 (29) when Way
first showed that cations were
The suggestion is made that the or-
ganic counterparts of zeolites be called
sorganolites. types Of these
Adams and Holmes (1) con-
ceived the idea of purifying water
by synthetic resins prepared from
polyhydric phenols and formal-
absorbed by soils. However, the have been studied- They are dehyde. This is probably the
discovery that bases were mu- resistant to attack by waters of widely first instance of a truly synthetic
tually exchangeable (12, 19) is varying pH and are capable of hydrogen- organic base-exchange material.
usually credited t o Eichorn ion exchange if regenerated with acids. A similar product was reported
by Kirkpatrick (15A). Carleton
(1858)n Although the
Way
Of
applied to soils (in which
A comparison with inorganic zeolites is Ellis suggested that all base-ex-
both zeolites and humus a r e given. A theory of basemexchange ac- change substances of organic ori-
known to base exchange, 7 , 16, tivity is offered, and several applications gin i e called “organo~ites” to
22, 28)) commercial exploitation are suggested. distinguish them from the in-
of the reactions has been con- organic zeolites.
fined almost entirely to zeolites Researches carried out in this
of which the first commercial application for water softening laboratory have led to the development of synthetic organic
was patented by Gans (11) in 1906. Since that time the de- base-exchange materials which show certain advantages over
velopment of zeolites has progressed steadily until today their the phenol-aldehyde type and which possess qualities such as
use is widespread. cheapness, high exchange capacities, and resistance to aggres-
The organic or humus constituents of the soil have been sive waters which indicate that they may be of considerable
investigated by several workers (18) from a scientific stand- value industrially. These organolites are prepared by render-
point, especially as to effect of soil base exchange on plant life ing initially water-soluble wood extracts, especially those of
and soil acidity (16). Recently the use of humates for water the tannin type, insoluble by treatment with concentrated
purification was suggested by Fischer and Fuchs ( I O ) , who acids-for example, sulfuric acid. They will exchange either
stated that water can be softened by the sodium humates sodium or hydrogen ions for calcium or magnesium, and ex-
from humic acid of brown coal, and by Borrowman (6) who hibit some increase over initial capacity with each of the first
percolated water through a granular bed of lignite or brown few regeneration cycles.
coal and regenerated the bed in the usual manner with sodium
chloride brine. Modified humates, prepared by the action Theory of Organolites
of strong reagents such as sulfuric acid or zinc chloride on
peat, lignite, or wood, have also been described in several Why such materials exhibit base exchange is not definitely
foreign patents (60,68). The use of humates is, however, known. In the case of the polyhydric phenol-formaldehyde
not very satisfactory because of the rather low base-exchange resins, it is probable that large molecules are built up in the
capacity and a characteristic color throwing or imparting of a way usual for phenol-formaldehyde condensations (9) to
yellow to brown tint to the treated water. This latter defect produce substances which are capable of base exchanging in
may be overcome, according to Borrowman (6) who treated a manner similar to that of humus or lignin derivatives-that
the humic substance with sodium aluminate, and to Tiger and is, through functional phenolic groups (16, 17, 28).
Goetz (67) who used chromium salts as the color stabilizers. When tannins are treated with concentrated sulfuric acid,