September, 1946 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY 923

LITERATURE CITED
l j Baeyer, A., Ber., 5, 1094-1100 (1S72).
'2) Bailes, E. L., J . Chem. Education, 22, 122 (1945).
'3) Breckenridge, J. R., Can. Chem. Process I nd. , 28, 570-3 (1944;.
(4) Callahan, J . .I., Chem. &. Me t . Eng. , 51 ( l o) , 109-14 (1944).
'5) Campbell. G. d., and Vest. T. F. , Chem. Trade J. , 115, 196-6
6) Darling, S. F., J . Chem. Education, 22, 170 ( 1944.
(7) Flei.k, E. E.. and Haller, H. L., IND. ENG. CHmi., 38, 177-8
' 8 ) Fleck, E. E., and Preston. 11. K., Soap Sunit. ChemicaZs, 21,
19) Frankforter, G. E., and Kritchevsky, W., J . A m Chem. .%e.,
(1944).
(1946).
111-13 (1945).
36, 151 1-29 (1914).
. I O) Glinther. F. .A,. Ihi d. . 67, 189-90 (19453.
(11) Gunther, F. A, , J . Chem. Education, 22, 2 3 8 4 2 (1945).
(12) Haller, H. L., et al., J . Am. Chem. SOC., 67, 1691-1602 (1945).
(13) Iris, R. C., and Leyra, R. D.. Rea. inst. s al ubr khd enfermedadea
(14) Katz, A. , J . prakt . Chem., [2] 90, 311 (1914).
(15) J lueller, P. (to J . R. Geigy A-G.), U. S. Patent 2,329,074 (Sept.
(16) Rueggeberg, W. H., and Torrans. D. J ., IND. ESG. CEEM., 38,
(17) Sumerford, TV. T.. J . Am. Pharm. Assoc., 34, 259 (1945).
(18) Thorpe, E., "Dictionary of Applied Chemistry", Vol. 2, pp.
180-1, New York, Longmans, Green & Co., Inc., 1921.
(19) U. S. Dept. of Commerce, Office of Publication Board. Rep(.
360, 5 (1900).
20' Zeidler. 0.. Ber. . 7, 1180-1 (1874).
t r op. (J lex.), 5, 74 (1944).
7, 1943).
211-14 (1948).
Change of Latent Heat of
Vaporization with Temperature
Two new rules for change of latent heat of vaporization
with temperatures are presented, and their derivations
given. It is believed that the new rules have the advan-
tages of simplicity and general applicability to all liquids.
EVERAL investigators have reported results on the change
S of latent heat of vaporization with temperature (1, 2, 6, 7-
f2). This paper presents some new rules for calculating the
change of latent heat of vaporization with temperature. The
new rules are simple and seem to have general applicability to
all liquids.
For vapor-liquid equilibria, the C,lapeyron equation is
i l i
dP = L
n T(1., - Vf)
whrw
p =vapor pressure of a given liquid at temperature
L =latent heat of vaporization per mole
Vsr 1; =molal volumes of saturated vapor and liquid. re-
T ( O K.)
spectively
rf w P act
Equation I may be mi tten as follon-s:
L =s R(1 - r ) i 2?
I<quation 2 contains, 111 dtlition to the gas constant, R, three
factors--namely, the slope of the plot, In p us. l /T, for thc
change of vapor presbure of the liquid n-ith temperature; the
compressibility factor p to account for thci deviation of the vapor
Fromthe perfect. gas law: and T. the ratio of volumes of liquid and
vapor per unit mass.
The vapor pressure curve of log p plotted against 1j T is nearly
linear over wide ranges of temperature or preasure. Figure 1,
presented a few years ago by the author (If), show log T US. l/O
for twenty liquids, T being the reduced pressure ( p / p . ) and 8,
reduced temperature (T!' T?), ,411the vapor pressure data are
from International Critical Tubics (3) except the duta on w,ter,
which were taken from the steam tables of Iieenan and lieyes (4).
The individual lines are surprisingly linear, but the slopcp are
fairly different from 'one another; that is, at equal reducd tem-
peratures the reduced vapor pressures of various liquids are, in
general, far from being equal to one another.
The compressibility factor I.( changes with pressure as well as
with temperature and was shown to be a function of T and e (6)
The ratio, T, of liquid volume to vapor volume p"r unit mass pl uy
an important role only near the critical point for, at low or
moderate pressures, r is small and (1 - 7 ) is nearly equal to 1.
The data arc correlated as the ratio of two latent heats of va-
porization at any txo temperatures. The reduced temperature
and pressure are used as temperature and pressure measures.
If r e assume a reference temperature eo at this f ~~rnpr~~ti i rc
Equation 1 becomes, for the same liquid,
( 3 ) Lo =sa PO R(1 - To)
Dil iding Equation 1 by Equation 3,
4)
If the vitpor pressure CUI Y <:, 111p 1's. l j T , for the given liqiiitl is
linear-that is. i f .q =.sL =constant-Equation 4 hwomee
CASE I. I t is assunied that L/Lo is a function of r/O, tho
latter being ti measure of the reduced concentration of the satu-
rated vapor over the liquid in qiivtion :
16A)
The reference state is arbitrarily chosen as that point at which
the vapor conditions have the ratio
.-a/& =0.1
All latent heat values at other temperatures with respect to L(
are then referred to tho reference state.
924 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY Vol. 38, No. 9
L. egend
1 Et hyl Al cohol
2 n- Propyl Alcoho
3 Mefbyl Alcohol
4Acefrc Aci d
5 f l z 0
6 Acef one
7 Hexane
September, 1946 I N D U S T R I A L A N D E N GI N E E R I N G CHEMISTRY 925
The test of Equations 6A and 6B will be to
plot the available latent heat values of all
liquids to find whether a universal curve re-
sults. Figure 2 shows such a curve which was
prepared by the author a few years ago (11).
The solid line represents water, for which the
reference temperature is 396" F. At this tem-
perature r , , / Oo =0.1. The agreement of the
points for thirteen other liquids with the water
line is striking. The data are taken from
International Critical Tables (9) and steam
tables (4).
By means of Figure 2, in combination with
vapor pressure curves like those of Figure 1,
we can estimate the latent heats of vaporiza-
tion of the liquid in question throughout the
whole range up to the critical point, if only
one value of latent heat of vaporization at any
temperature is known. Thus, for a liquid at W l A
II/ U
any two reduced temperatures, e, and el, by us-
ing Equation 6B and dividing,
Figure 2. Change of Latent Heat of Vaporization wi th Temperature
or Pressure
(7)
L l/r
where and y~ are the values of the ordinates of Figure 2, corre-
aponding to e, and e: , respectively.
Rule I may be stated as follows: The ratio of latent heats of
vaporization at two equal reduced concentrations of the equilib-
rium vapor, expressed in terms of is the same for all liquids.
I t is believed that the average deviation of the points from the
water line is less than 3%.
If we assume that L/ L, is a function of reduced
temperature 0 only, then
CASE 11.
(84
L
or
When the data are replotted with Lo at eo BS the referenoe point,
Figure 3 results. The reference point for all the liquids is taken
at Be =0.577, which corresponds to the boiling temperature of
water (212" F.) at one atsmosphere. The accuracy of Figure 3
may be regarded as being of the same order as that of Figure 2;
the average deviation is believed to be less than 3%. For t he
uae of Figure 3 no vapor pressure data are required,
Vol. 38, No. 9 926 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
For simplicity, a second rule is recommended, which may be
stated as follows (rule 11) : The ratio of latent heats of vaporiza-
tion at any two equal reduced temperatures is the same for all
liquids. The method of using Figure 3 is the same as that for
Figure 2 (Equation 7).
The particular reference temperatui e for the constructioii of
Figure 3 is Bo =0.577, at which temperature the vapor pressures
are low (7r =0.001 to 0.01, Figure 1); therefore the vapor may
be;assumed to behave like a perfect gas-Mo =1. Furthermore,
because of Ion. vapor pressures at this reference temperature the
ratio of volume of liquid to volume of vapor per unit mays is
negligible, or 1 - ro =1. Thrrefore, Equation 8.4 bec0rne.i
The factor @ may vary a few per cent eyen nt the same reduct,cl
temperatures, due to the difference of vapor pressures :it a giver)
reduced temperature. Since the agreement shown iii Figure 3
is good, it is probable that the three terms on the right-hand Qidc
of Equation 9 have a compensating effect. I n thc family of
vapor pressure curves (Figure 1) the line for water happens 10
strike the mean position. From this st:indpoiiit, wter i, a
good reference substance.
Assuming the constancy of the slopc, s =so =constant, tor a
given liquid, within the limit of variations of a few per rent
Equation 9 becomes
DISCUSSION
Watson (12) found that when Troutons constant ( L T) 16
plotted against 6, the resulting curves for different material3 have
the same shape and constitute an affine group. When the
values of the ordinates ( LI T) of any curve are multiplied by the
proper constant factorf, that cuive can be made to coincide 13 ith
any one of the other curves. The ordinates of each curve repre-
senting an individual compound can be multiplied by the proper
factor to superimpose the curves in the best agreement. A
graph of ( L/ T) j us. 6 is thus obtained, where f is the multiplying
factor, specific for a specific liquid.
E If Equation 2 is multiplied by T,/T and the term; are rear-
ranged
Therefore, Rjatsons f is proportional to 1, :s, n-hich is specific for
a specific liqqid. Equat,ion 10 states that M (1 - r ) is a function
of 8. i
Factor f *day be eliminated if we conipare the Trouton con-
stants for any liquid at two temperatures. A common reference
temperature eo can be taken for all liquids. At O, , for any given
liquid n-e may wj te Equation 11 as fol10v;s:
(121
Dividing Equation 11 by Equation 12, for the 3ame liquid,
I
A uni3ersal curve will result if the left-hand side of EquitiolJ
13A is plotted adainst 6. Watsons rule may be stated in an
alternative $ay as follows: The ratio of Troutons conbtant
LIT at any b o equal reduced temperatures is the same for all
liquids. That is, for any given liquid,
The ratio K is the same for all liquids, provided they are all com-
pared at the same two reduced temperatures 6, and 62.
The findings of Othmer (9) and Gordon (1) will be derived
in a general manner. They found that, when any two liquids are
compared at equal reduced temperatures, the following re-
lation holds:
_ _ =_ _ _ =- LTa =constant
l ogn dl og p
log z- d log p LIT,
(14)
irheie the primed quantities refer to the reference substance
For thc present treatment, if we set s = -
\ l /
d( i,) =hc d( :), Equation 2 may be written atsfollnn s
( 15)
I ( ~r auotlier liquid, used as a referrnce substance and cwnpwed
ti t the qame reduced temperature, the following equation applies.
[Tiw qii:intity p(1 - /.) is constant st the .-:imc 6. n-. in Eqnoti on
in. 1
(.:r~~lhllllitg the two equations,
(17)
\\ riting l<quation 2 for the refercnce substances at the same 6,
7, =J i* K ( l - T)
(18)
Uividing Equation 2 tiy Equstiori 18, and assuming the slope?
J and S I . respectively, to Iw <wnstmit for each of the two liquids,
since
rl l ug d - log ri
(1 log 71 log a
d log T - ,1 log p
rl log T r l log p
__ - --
120,
whi i ati il: the rt.iult of (1tlimc.r and Gordon.
LITER4TUKE CITED
(1) Gordon, D. H., IND. TXG. CHEV. , 35, 851 (1943).
(2) Hildehrand, J . A m . (hem. SOC., 37, 970 (1915).
(3) International Critical Tables, Sew l o r k , McGraw-Hill Book
Co., Inc., 1926-1930.
(4j Keenan, J . H., and Iceyes. F. G., Thermodynamic Proqertiep
of Steam. New York, J ohn Wiley & Sons, Inc., 1936.
( 5) Kistyakovskii, Z. phys i k. Chem., 107, 65 (1923).
(6) Lewis. T5. K., IWD. ENG. CHEM., 28, 257 (1936).
(7) Lewis, TI-. K., and Weber, H. C., I bi d. , 14, 485 (1922).
(8) Meissner, H. P., I bi d. , 33, 1440 (1941).
(9) Othmer, D. F., Ibi d. , 32, 841 (1941); 34, 1072 (1942).
(10) Seglin, L., Ibid., 38, 402 (1946).
(11) Su, G.-J ., thesis, Mass. Inst. of Tech., 1937.
(12) Katson, K. M., IND. ENG. CHEM., 23, 362 (1931); 35,
(1943).
398