230 I S D C S T R I A L A S D ESGIA-EERIXG CHEMISTRY
air with helium. Because carbon dioxide is cheap, available
in large quantities, and easily separated from helium, it was
decided to displace the air with this gas. This method of
inflation had previously been used on a test section of the hull
with good results. An attempt was made to carry out the
inflation in such a manner as to allow the carbon dioxide to
displace the air with as little mixing of the gases as was pos-
sible. Since there are two chief causes of the mixing of these
two gases-i. e., diffusion and turbulent flow of gas from the
containers-it was necessary to determine the conditions of
operation which would minimize the effect of these phe-
nomena. As turbulence is mainly caused by rapid movement
of the gas, an attempt was made to keep the velocity of the
incoming carbon dioxide well within the region of quiet flow.
Diffusion, on the other hand, depends upon a number of fac-
tors, among which are time, difference in density of the gasec,
and the diffusing area. Taking all these factors into account,
a rate of input of carbon dioxide of about 10,000 cubic feet
per hour way tried, found satisfactory, and maintained
throughout the inflation.
Stratification of the carbon dioxide and air was quite
complete. This was partially visible to the naked eye. Dur-
ing the inflation the interior of the ship was illuminated.
Through the peep holes one could observe the moirture con-
densing out of the air and lying as a blanket of fog on the layer
of cold carbon dioxide in the lower part of the ship. -1s the
carbon dioxide rose higher and higher in the hull, the layer of
fog preceded it. Results of the gas analysis also verified the
completeness of stratification as shown by Figure 4, which
gives the percentage of carbon dioxide a t various levels in
the hull plotted against time during the inflation. The lower
sampling tubes almost immediately indicated 100 per cent
carbon dioxide. The rise in percentage of carbon dioxide was
rapid, once appreciable quantities of the gas appeared in any
tube. About 33,000 cubic feet of carbon dioxide were lobt
in purging, which is extremely low.
During the helium inflation stratification was not nearly
so complete. This was due chiefly to the great difference in
density betv-een helium and carbon dioxide. The input could
A Derivation of Duhring’s Rule’
A. McLaren White
G E O R G IS~C H O O L
CRIKG the last few years the necessity for obtaining
D a simple yet accurate method of relating vapor pres-
sures and temperatures has led to the rediscovery of
Duhring’s rule. This relation has given valuable results
when applied to solutions of salts in water ( I ) , to solutions of
organic liquids (4), and to pure liquids. Duhring’s rule has
been regarded as entirely empirical, though from its wide
applicability and validity it would seem that it should have
some thermodynamic basis. It is the object of this paper to
point out how Drihring’s rule niay be reconciled with thermo-
dynamics.
Inasmuch as the Duhring relation inrolres vapor pressures
and temperatures, it seems logical to believe that it must be
connected with the Clausius-Clapeyron equation. This
equation in its approximate form may be stated as
d In p/dT = AH/RT2
where p is the vapor pressure, T the absolute temperature,
and AH the heat of vaporization. The vapor is here as-
1 Received November 29, 1929.
T’ol. 22, KO.
not be kept within the region of quiet flow without consider-
able diffusion. While the volume was small and the area ex-
posed to diffusion was not great, stratificationwas fairly com-
plete, as shown by Figure 4. When appreciable quantities
of helium had displaced the carbon dioxide, trouble began.
Some of the causes of the rapid rise of helium in the exhaust
before the scrubbing was started were as follows: The dif-
fusing area, which was about 6000 square feet, had been at its
maximum for some time; the gas came into contact with the
tops of the inflated ballonets, causing a surging motion;
the rate of input of helium had been increased. However,
it is doubtful if diffusion between carbon dioxide and helium
could have been prevented.
The insertion of a drier or refrigerator between the scrubber
and the hull would be a decided improvement. Spacing
the sampling tubes symmetrically above and below the
equator of the ship would give a more accurate check of the
progress of inflation. The rate of input of helium was about
10.000 rubic feet per hour.
Conclusions
The results show that the method employed i b relatively
simple and efficient for inflating this type of ship. One hun-
dred per cent ballonet could not be employed in a ship of this
size. In a large ship, where 100 per cent ballonet may be
used, the usual method of inflation can be carried out.
Final conclusions concerning the diffusion of helium from
this ship have not been reached, as it has been under study for
too short a time. However, approximately 100 cubic feet of
helium are added every 24 hours to replace leakage froin the
hull. The purity of the gas in the ship has not decreased due
to inward leakage of air. This fact is a decided advantage
over the fabric ship, which allows appreciable inward leakage
of air with a corresponding loss of lift.
Literature Cited
( 1 ) Fritsche, J l e c h . E n g , 61, 905 (1920), gives complete description of
design, construction, and erection of the Z M C - 2 .
OF TIXHKOLOGY,
ATLANT.4, GA.
sumed to be a perfect gas, and the volume of the liquid negli-
gible compared with that of the vapor. If the heat of vapori-
zation is assumed to be constant over a small range of teni-
perature, this equation may be integrated, obtaining
l n p = -AH/RT C + (2)
This equation proves experimentally to yield a straight line
over small ranges of temperature.
Now for t x o different substances, a and b, let the vapor
pressures be equal at absolute temperatures, T , and Tb.
Substituting in Equation 2 and equating the result<,
This may be rearranged to read:
(1) (4)
Equation 4 should aleo represent a straight line, as was sug-
gested by Cox ( 2 ) ,since in its derivation the heats of vaporiza-
tion were assumed constant over the small range of tempera-
 March, 1930 ISDUSTRIAL ; 1 S D E S G I S E E R I S G CHE-VISTRY 231

ture. Experiiiieiitally this proves to be the rase, for a plot of

1, T for water agaimt 1/T for another substance at the same
vapor pressure is a straight line. This relation holds over If these quotients are constant, the products of such quo-
temperature ranges of 100 degrees or more for a wide variety tients as given in the last term of Equation 7 should be coil-
of substances, as is shown graphically in Figurc 1, where stant.
reciprocal temperatures for such widely different substances Computation of Slope of Duhring Line
as sulfur dioxide, ammonia, methyl formate, calcium chloride
solution, acetic acid. ethyl alcohol, bromobenzene, and carbon From Equation 8 it ohould be possible to predict the slope of
tetrachloride are plotted against reciprocal temperatures for the Duhring line. if the vapor pressureq and heats of vaporiza-
water. tion of the two substance. are known. Table I records the val-
The straig1itne.s of the line- in Figure 1 is rather wrprising. ue< thus computed for the substance indicated against water.
for it indicates that the done, which is the ratio of the heats In the case of acetic acid, though the Duhring and re-
of ~aporizatioiiof the two- ciprocal temperature line,
Yubstances, i s constant are straight, the calculated
over a wide range of 7 apor <lope (0.548) does not agrw
From the integrated approximate Clausius-Clapey-
pressures. C a l c u l a t iiig with the observed -lope
ron equation it is possible to derive a linear function re-
values for this ratio for (0.878). This is proliahlv
lating vapor pressure and reciprocal temperature for
aiiniioiija, over a pressure due to the fact that tlie
any two substances. This relation has been shown to
range from 400 to 900 mm., approximate Clausius equa-
be the product of two functions, the expression for
tlie v a l u e f o r (1H",/- tion gives a much largrr
Duhring's rule and that of Ramsay and Young, each
--\HH?O) varies only from hitherto empirically obtained. By means of the re-
heat of vaporization than I <
a p p r o x i m a t e 1y 0.5i5 to a c t u a l l y observed. Tlicl
ciprocal temperature relation it has been found pos-
0 5 i l . Similarly, for the sible to predict the slope of the Duhring line, if the heat
exact Clausius equation prv-
plot of ethyl alcohol against of vaporization and vapor pressures are known, and to
clicts values which agrw
water. the heat of vaporiza- calculate the heat of vaporization from the slope of the
closely with those calori-
tion ratio over a vapor pre+ Duhring line. It is found that the reciprocal tempera-
metrically determined. If
cure range of from 40 to 360 ture relation yields a line more nearly straight than
instead of the true heat of
inm. x aries only from ap- T nporization of acetic acitl,
the Duhrixlg relation.
proximately 1.023 to 1.039. we uqe the apparent heat
Diihring'j rule is ordi- of vaporization as coiiiputetl
narily e-iprc-etl as from t h e approximate
Clausius equation. good agreement is obtained- for the slolie
of the Dtihring line.
TIhere iii i. the -lope of the line and the temperatures are those Table I-Computed Slopes of Duhring Lines
of equal vapor presbure. If, now, Equation 4 is rearranged SUBSTAWE
PRESSLIRE
RANGE
SLOPE C . 4 L C D
F R O U EQ. 8
SLOPE
OBSD
into the same form. M m
Benzene 760 to 6000 0 806 0 803
Ammonia 150 to 1300 1 409 1 405
Ethyl alcohol 1 2 to 1200 1 091 1 090
Sulfur dioxide "00 to 1200 1 263 1 260
where i t is the slope, n e have two expressions, each the equa-
tion of a straight line, one in terms of differences in tenipera-
ture and the other in terms of differences in reciprocal tem-
perature. In order to develop the mathematical connection
b e b e e n Equations 5 a i d 6, rearrange Equation 6 as follows:
T,' - T,

But the first term of the right-hand side of Equation 7 is

identical with the left-hand side of Equation 5 . Making
this substitution, Equation 7 becomes

' I
1

' where m is the elope of the Diihring line, experimentally s h o ~ m

to be a constant. Lewis and Weber ( 5 ) have derived an ex- ' d r 5 .OL o 300*~
I
morn OOW5 00050
Y7.x Jubitarce
pression siiiiilar to thii. Figure 1-Plot of Reciprocal T e m p e r a t u r e s a t Equal Vapor Pressure
For Equations 5 and 6 to be compatible it is mathematically Data for these plots were taken from the International Critical Tables,
as were all data on heats of vaporization and vapor pressure
necessary that the denominator of Equation 8, the tempera- 1-Bromobenzene 5-Carbon tetrachloride
ture product quotient of the two substances a t two vapor 2-Acetic acid '?--Methyl formate
3-Calcium chloride (25 91 7-Sulfur dioxide
pressures, be a constant. This checks experimentally, for grams per 100 grams water) 8--4mmonia
in the case of benzene CIS. mater the values for the denominator 4-Ethyl alcohol
of Equation 8 over a vapor pressure range of 760 to 3520 mm.
Calculation of Heat of Vaporization
vary from approximately 1.113 to 1.081. For ammonia
against water, over a vapor pressure range of 400 t o 900 mm , The reverse operation, that of predicting the heat of vapori-
tlie denominator varies from 0.408 to 0.411. This constancy zation from the slope of the Duhring line, should also be
could be predicted from the rule of Ramqay and Young (S), possible. In addition, heats of vaporization should be corn-
which states that for related substances a and b, when com- putable from the slope of the reciprocal temperature line.
pared a t equal rapor pressures, I n some case? the Drihring line turns out to be somewhat
232 I S D V X T R I A L A S D ESGIiYEERISG C H E M I S T R Y 1-01. 22, No. 3
curved. In this event a straight-line tangent a t the point Further, the personal equation enters to a large extent in
a t which the heat of vaporization is deqired is used to give constructing these lines and in determining their slope, adding
the slope. Table I1 s h o w the heats of vaporization com- another source of error.
puted by means of Equations 6 and 8, with water as reference It is interesting to note the similarity between Equation 6
substance, a t the temperature of the boiling point. and the empirical equation of Schultz (6) for entropies of
Table 11-Heats of Vaporization Calculated from Duhring and
vaporization. This equation may be stated
Reciprocal Temperature Lines
AH A H CALCD. A H C4LCD
SUBSTANCE OBSERVED FROM 1 / T FROM DLHRING
n-Propyl acetate 8200 Si20 8450
Bromobenzene 9050 9060 9030 If for t’he mean heat of vaporization over the temperat’ure
Cyclohexane
Carbon tetrachloride
7210 7540 7340 range in question we substitute the actual heat of vaporization
7150 7340 6990
Methyl formate 6750 6760 6920 a t the given temperature, Equation 6 becomes identical x-ith
that of Schultz.
Formic acid, like acetic acid, does not give satisfactory checks
by this method, the observed heat of vaporization being 5510 Literature Cited
calories per mol, while the Ddhring relation predicts 8290 (1) Baker and Waite, Trans. A m . Znst. Chem. Eng., 13 (2), 223 (1921);
and the reciprocal temperature formula 8070. C h e n . N e t . Eng., 26, 1137 (1921).
Considering the assumptions made in integrating the (2) Cox, IND.ENG.CHEM.,16, 592 (1923).
Clausius equation, and in making use of it in its approximate (3) Getman, “Outlines of Theoretical Chemistry,” 4th ed., p . 78.
(4) Leslie and Cam, IND.ENG.CHEM.,17, 810 (1925).
form, it is surprising that checks as close as these can be ob- (5) Lewis and Weber, Ibid., 14, 486 (1922).
tained froin the reciprocal temperature and Duhring lines. (6) Schultz, Ibid., 21, 557 (1929).

Metallurgical Research from the Chemical Point of

View’
H. W. Gillett
BATTELLE IKSTITUTE,
MEMORIAL COLUMBUS,
OHIO

H E value of research is far better appreciated today invested, chemical and allied industries spend 2.4 per cent

T than ever before. Science is front-page news. That and the metal-working industries 2.1 per cent for this purpose.
it is, is very largely due to the efforts of the AMERICAN
CHEMIC.4L SOCIETY and to such interpreters of science as the
Importance of Metallurgy
late Edwin E. Slosson. Metallurgy is a key industry. Of the ten leading in-
Science is back-page news, too. Glance through the ad- dustries from the point of value of manufactures, eight are
vertising pages of the Saturday Evening Post, for example, metal-working and metal-using industries. Even those
and you will find shrewd advertisers using the words “re- industries which do not directly make metallic products
search,” “science,” “experiment,” “testing” to stress the are highly dependent on them. The food industry needs
fact that their products have reached their present perfectioii agricultural implements and tin cans; the lumber industry,
because of long and painstaking research. This means that, saws; the chemical industry, tanks and piping; and so on
not only do the manufacturers believe in research, but the down the line.
public does too, since it pays to impress the public that re- Transportation-by railway, steamboat, automobile, and
search is being carried on. aircraft-is today in vehicles that average some 90 per cent
There are today a thousand research laboratories in the or more metallic. Water, gas, electricity, and telephone
country, exclusive of college, university, and government and telegraph messages are transported by metallic pipes
laboratories, in addition to control and testing laboratories. or wires; even the radio waves depart from, and are collected
Statistics in regard to the amount expended in the research by, metallic apparatus.
activities of the nation are pretty much guesswork. The A normal household uses alloys of a t least twenty different
dividing lines between research in pure science, industrial metals. One finds them from the bathroom to the kitchen,
research, development work, plant “trouble-shooting,” on his person, in his mouth, and in his automobile. In hi,
attention t o customer complaints, and routine analysis and daily work and his daily life everyone is served by metals,
inspection are so hazy that, without a census in which all and is benefited by the search for better and cheaper alloys.
items of so-called research are clearly classified, one is at sea
in guessing the extent of research. It has been estimated Relation of Metallurgy t o Chemistry
that the United States spends 10 million dollars and has 3000 Metallurgy is a branch of chemistry. If we look a t the
workers in pure science and 200 million dollars with 30,000 industrially spectacular achievements of metallurgy in recent
workers in applied science. Since the Bell Telephone Labo- years, outside of purely mechanical developments, we might
ratories alone have a yearly appropriation of some 19 select such items as: the use of alloy steels such as those of
million dollars for research and development, and employ nickel, chromium , molybdenum, vanadium, tungsten, manga-
6000 people, the above estimate is probably of the right nese, silicon, copper, aluminum, zirconium, and titanium,
order of magnitude. KO one can state exactly what is ex- and the knowledge of their heat treatment; the development
pended for research by or for any one industry, but the De- of strong, heat-treatable light alloys-these two advances
partment of Commerce quotes a statement that chemistry having played a major role in the development of modern
and metallurgy are in the lead since, on a basis of capital automobiles and aircraft; stainless steel and other high-
1 Received January 22, 1930 Presented a t the meeting of the Detroit chromium alloys for corrosion resistance; flotation, which
Section of the American Chemical Society, December 10, 1929 has made possible the economical utilization of ores con-