April, 1931 INDUSTRIAL AND ENGINEERING CHEMISTRY 40 1

Solubility of Nitrogen in Water at High Pressures

and Temperatures'
John B. Goodmanz and Norman W. Krase
DEPARTMEKT
OF CHEMISTRY.UNIVERSITY
OF ILLINOIS, URBANA.
ILL

8 PART of the pro- A high-pressure gas-solubility apparatus has been in water and nitrogen-hydro-

A gram for the collection

of fundamental data
on compressed systems, this
developed which is suitable for the determination of
gas solubilities at ordinary and elevated temperatures,
and at pressures from 100 to 1000 atmospheres. Cer-
gen mixtures in liquid ammo-
nia show increasing solubility
with temperature. Helium
laboratory has begun a corn- tain developments in solubility technic are presented, in water exhibits a minimum
prehensive study of the solu- which are improvements over previous methods. solubility between 25" and
bilities of gases in liquids. The solubility of nitrogen in water has been measured 30" C. a t 1 atmosphere, and
Not only are such data in- at temperatures from 0' to 170" C. and at pressures hydrogen in water shows not
t e r e s t i n g in enlarging the of 100, 125, 200, and 300 atmospheres. only a minimum at 25" C.
scope and testing the ap- The coefficient in Henry's law has been calculated for but a very unusual relation-
plication of existing theories the several pressures and solubility theories tested ship with temperature.
over wider ranges of tem- with the aid of the new data. These facts are safIicient to
p e r a t u r e a n d pressure, call for further investigation
but they are also necessary in the intelligent design and from a theoretical viewpoint a t least. The development of
operation of many industrial processes employing high pres- high-pressure synthesis of ammonia and methanol and other
sures. Practically no systematic measurements are re- processes where products are separated by condensation
corded in the literature for even simple systems of industrial under pressure furnishes further pressing needs of solubility
interest. The existing, fragmentary data, however, point data. The volume of gas dissolved in such condensed prod-
to this field as possessing special importance because of ucts is often very large. Most efficient operation calls for
departures from the ordinary, ideal laws of gas solubility. an exact knowledge of such data.
Since 1803 Henry's law has been generally accepted as
describing the effect of pressure on the solubilit'y of a gas Previous Work
in a liquid. Dalton'a amplification of this law has also served
well for many purposes, although the number of exceptions Investigation of the literature has shown the previous
seems to grow as more measurements are reported. Cer- published work on pressure solubilities to be very meager.
tainly as 'ideal" laws, useful in cases where Po-
larity, association, chemical combination, and de-
viations from the perfect gas laws do not enter, they
will continue to find a place in textbooks.
1
The effect of temperature on gas solubility is
usually connected with the thermal changes in-
volved by means of tJhe Clausius-Clapeyron rela-
tion in such cases where it is considered valid.
Below the critical temperature of the gas, there-
fore, this always indicates diminishing gas soh-.
bility with increasing temperature. For gases
above their critical temperature no satisfactoq
generalizations are available, although it is cus-.
tomary to reach the conclusion just stated for suck
cases also. Travers (IO) makes the statement:
I'.,
i 1D -,o 20 30 44
The curves representing the change of solubility with Ty.m+.n -C1"iq3.

temperature, for gases under constant pressure, ap- Figure 1-Positive Temperature Coefficients of Solubility
pear to indicate that for each gas there exists a point
of minimum solubility and thaf the temperature corresponding to although many investigations have been carried out to test
this is in some way related to the critical point for the gas. the validity of Henry's law. The systems considered usually
were treated a t low temperatures and a t but small tcmpera-
Very few data are offered to support this astonishing con- ture intervals. The pressures were low and seldom exceeding
clusion, and none involve common solvents such 11s water or a few atmospheres.
gases considerably above their critical temperatures. It is The solubility characteristics have been determined for a
not generally recognized that the existence of minimum solu- number of the inactive gases at ordinary pressures by numer-
bility points is common. The logical interpretation of the ous investigators. Just (5) determined the solubility of
phenomenon is difficult and will be discussed subsequently. nitrogen and other gases in aqueous and non-aqueous sol-
For examples of systems showing radical departures from vents. Bohr and Bock (9)have shown data on the solubility
accepted theory, reference to Figure 1 is invited. Xeon of nitrogen, oxygen, hydrogen, and carbon dioxide in water
Received January '16, 1931. Presented before the Division of a t temperatures from 0" to 100" C . Besides the work of
Physical and Inorganic Chemistry at the 81st Meeting of the American Estreicher (4) and Von Antropoff ( I ) on the solubilities of
Chemical Society, Indianapolis, Ind., March 30 to April 3, 1931.
Submitted in partial fulfilment of the requirements f o r the degree
helium! neon, and argon a t atmospheric pressure, there exist
of doctor of philosophy in chemistry in the Graduate School of the Uni- many notations of repeated work on nitrogen in water and
versity of Illinois. in non-aqueous solvents.
402 INDUSTRIAL AND ENGINEERING CHEMISTRY
Comprehensive solubility
measurements a t higher pres-
sures are likewise 1a c k i ng .
The solubility measurements
of Larsen and Black (7) on
the system nitrogen-hydro-
gen-liquid ammonia are the
only instances of recent de-
terminations of high-pressure
solubility. These data, while
a t rather low temperatures,
included pressures up to 150
atmospheres. The work of
Cassuto (3) includes the solu-
bility measurements of nitro-
gen in water a t pressures up
to 10 atmospheres along with
solubility determinations of
hydrogen, oxygen, and car-
bon monoxide in water. In
the consideration of solubility
m e a s u r e m e n t s a t higher
pressures, the work of Sander
(9) on c a r b o n dioxide in
water might also be included.
This work embraced meas-
urements taken up to 170
atmospheres. Von Wroblew-
ski (1.9))in his determination
of the hydrates of c a r b o n
dioxide, took measurements
up to 60 atmospheres.
Experimental Method
The present method is
quite satisfactory for liquid-
phase determinations and is
briefly as follows: The gas is
stored in cylinders at a pres-
sure above that used in the
experiments, and is led, after
purification, to the solubility
apparatus proper. It first
enters the saturator, which
contains water saturated with
gas a t room temperature and
a t the particular pressure of
the experiment. A portion
of the solution is then
transferred from a connec-
tion in the bottom of the
saturator to the solubility
pipet, which is surrounded
by either a copper thermo-
stat for high temperatures
or an ice thermostat. While
in the solubility pipet, the
liquid solution is s t i r r e d
by means of a magnetic
stirrer, at the same time being
FiQure
- 2-Solubility - Pipet
. subjected to the desired pres-
sure. After sufficient time
has elapsed to bring the solution to equilibrium, a sample is re-
moved by means of a needle valve a t the bottom of the
solubility pipet. The sample removed is separated by means
of a cooled trap into the gaseous and liquid constituents.
The usual corrections for gas volume are applied to reduce
the results to standard conditions. A satisfactory apparatus
Vol. 23, No. 4
has been developed which permits the use of this procedure
in determining gas solubilities in water up to 1000 atmospheres
pressure and from 0" to 170" C.
Solubility Apparatus
The main portion of the apparatus is, of course, the solu-
bility pipet (Figure 2). This was constructed of chrome-
vanadium steel with R liquid chamber l/z inch (1.3 cm.) in
diameter and 5'/2 inches (14 cm.) long, the capacity being
about 19 cc. The whole pipet was machined to a smooth
finish and then completely copper-plated inside and out. The
inner surface of the chamber was further plated with silver.
These protective coatings were used in order to reduce corro-
sion and to prevent contamination of the solutions with
iron.
The magnetic stirrer was placed on top of the solubility
pipet. The present design of this stirring device is unique
as applied in this problem, although the original idea wm
derived from an all-glass gas-circulating pump described by
Porter, Bardwell, and Lind (8). The cylinder of the stirrer
was constructed from a bar of nichrome IV; this alloy
was chosen after experience with a manganese-bronze alloy
showed that electrolytic corrosion in this section was serious.
In the cylinder there was placed a piston of soft iron care-
Fi$ure 3-Assembled Apparatus
fully turned but fitting somewhat loosely, there being about
l/TZ-inch (0.8-mrn.) clearance. To insure free passage of
the gas past the piston, two longitudinal grooves were cut
in the piston; these grooves also permitted any liquid car-
ried up into the stirrer from the lower section of the pipet
to drain down again. At the lower end of the piston was
attached a small bronze rod, which passed through the con-
necting nipple between the stirrer and the solubility pipet.
At its lower end two small paddles were attached to induce
circulation of the liquid in the pipet as the piston was drawn
up into the cylinder. To actuate the magnetic stirrer a
motor-driven interrupter was designed.
In this work it was noted that measurements at the higher
temperatures were considerably affected by temperature
changes. The operation of a high-temperature thermostat is
often troublesome, for hot-oil, molten-salt, or metal baths are
a considerable hazard. To remove entirely the hazards
and to improve further the temperature control, a copper
April, 1931 INDUSTRIAL AND ENGINEERING CHEMISTRY 403

thermostat was used. The authors have used this style of
thermostat in previous problems and found it completely
satisfactory. The present thermostat was a cast block of
copper 5 by 6 by 7 inches (12.7 by 15.2 by 17.8 em.). Three
holes were bored through the block to accommodate the
solubility pipet, the electrical heating unit, and the ther-
solubility apparatus. By means of a needle valve any de-
sired quantity of gas could be admitted to the saturator.
This was a steel cylinder 2 feet (61 em.) long, 2l/2 inches (6.3
em.) inside diameter, with a wall thickness of 1 inch (2.5 cm.).
The solubility operations were facilitated by filling this vessel
with about 1.5 liters of distilled water and then bubbling
nitrogen through this liquid at a higher pressure than at which
the experiments were t o be run. This gave a saturated
solution of nitrogen in water at room temperature. When
this solution was run into the solubility pipet, it simply re-
mained to add or remove nitrogen in solution to correspond
to the temperature of the experiment. This presaturating
of the solution shortened the time of stirring in the pipet.
The pressure on the solubility apparatus was indicated by
a calibrated Bourdon tube gage. Although constanbreading,
the Bourdon gage was not sufficiently accurate for measuring
the pressures. The actual total pressures were measured by
means of the dead-weight piston gage which was connected
into the pressure line when so desired. This piston gage was
of the type developed at the Massachusetts Institute of
Technology (6).

0 10 to so 40 60 bo 10 10 so IW 110 110 I 3 0 lka IS0 160 I70

T.y&..-c."+"p&
Figure 4-Ahsorption Coefficient-Temperature Isohars for
Nitrogen-Water

mometer. The mass (of copper left after the necessary holes
were bored was approximately 40 pounds (18.2 kg.). For
measurements at 0" C. an ice thermostat was used, It was
simply a large galvanized iron container, heavily lagged with
hair felt and filled with cracked ice and water.
The sampling valve connected to the bottom of the solu-
bility pipet was of the usual design of high-pressure valve.
The exposed interior sections of the valve body and stem were
plated as much as was possible with copper to reduce cor-
rosion. A11 the high-pressure tubing carrying either liquid
solutions or gas was of chrome-molybdenum steel with copper
lining.
Figure 5-Absorption Coefficient-Pressure Isotherms of
Auxiliary Apparatus Nitrogen- Water

Figure 3 shows all necessary apparatus. Compressed The solution sample, removed by means of the needle
nitrogen was expanded from the commercial gas cylinders valve a t the lower end of the pipet, was collected in a weighed
down to about 5 pounds (0.35 atm.) pressure and led into the and cooled glass trap. As the dissolved gas was evolved it
first stage of a Rix three-stage, water-cooled compressor, passed through a weighed calcium chloride tube and was col-
in which it was compressed to 4000 pounds (272 atm.) into lected over mercury in a buret. Several gas burets were
the low-pressure storage cylinders or into the low-pressure used, the size depending on the volume of gas to be measured.
cylinder of the high-pressure storage system. The compres- All the necessary measurements, such as barometric pressure,
sion mas continued in the high-pressure storage cylinders gas temperature, etc., were recorded.
using a water piston and hydraulic pump. These cylinders
were used to store the compressed nitrogen a t a pressure Results
always above that used in the experiments.
The connecting tubing used in the system is all of chrome- The experimental results, showing the solubility of nitrogen
molybdenum alloy steel, copper-lined. All gages used were in water a t 100, 125, 200, and 300 atmospheres and at tem-
calibrated against the laboratory piston gage taken as a peratures up to 169' C., are presented in Table I.
standard. Ordinary hydraulic gages calibrated up to 10,000
pounds per square inch (680 atm.) were used for all low-pres- Table I-Solubility of Nitrogen in Water a t Various Temperatures
sure readings. PRESSURE 0' C. 25' C. 50' C. 80' C. 100' C. 144' C. 169' C.
The gas was purified as it was drawn out of the high- Afm. Cc. Cc. Cc. Cc. Cc. Cc. Cc.
pressure cylinders by passing over heated copper wire a t 450" 100 1.46 1.07 1.003 0.934 0.954 1.025 1.08
125 1.76 1.44 1.24 1.15 1.17 1.30 1.52
C. It was then cooled by passing through a water-jacketed 200 3.19 2.76 2.49 2.27 2.25 2.68 3.29
300 3.60 3.25 2.99 2.86 2.91 3.46 3.83
tube before entering the purifying tower. The absorbent
used with nitrogen was soda lime, because this material l/T,'K. 0.00366 0.00336 0 . 0 0 3 1 0.00283 0 . 0 0 2 6 8 0 . 0 0 2 4 0 . 0 0 2 2 6
removes any water in the gas as well as small traces of carbon
dioxide. The data are shown graphically in Figure 4, where the
A line from the high-pressure storage system ran to the absorption coefficient, cubic centimeters of gas at standard
404 INDUSTRIAL A N D ENGINEERING CHEMIXTRY Vol. 23, N o . 4

conditions per gram of water, is plotted against temperature. viscosity and suggested also that the thermal expansion of
Figure 5 presents the solubility isotherms a t several tempera- the solvent as measured by its specific volume change with
tures. Figure 6 is t,he usual representation of the thermal temperature was a factor opposite in effect to viscosity. As
characteristics by plotting the logarithm of the solubility a result these opposing factors a t some point neutralized
coefficient against the reciprocal of the absolute tempera- each other and a minimum solubility point resulted. Careful
ture. study of these properties has convinced us that, while qualita-
tively the idea seems sound, the quantitative application
T a b l e XI-Henry’s Law Constant to a particular system doubtless involves other factors
ABSORPTION
TEMP. PRESSURECOEFFICIENT K v FUGACITY Kf also.
c. Aim. Afm.
0 100 1.46 0.0146 97.43 0.0150
200 3.19 0.0160 195.4 0.0163
300 3.60 0.0120 302.6 0.0119
50 100 1.003 0.0100 101.0 0,0099
200 2.49 0.0125 207.0 0.0120
300 2.99 0.0150 326.5 0,0092
80 100 0.934 0.00934 102.0 0.00915
200 2.27 0.0114 212.5 0.0107
300 2.86 0.0143 334.1 0.0086
100 100 0.954 0.00954 102.8 0.0094
200 2.25 0.0113 214.3 0.0105
300 2.91 0.0145 338.7 0.0086
169 100 1.08 0.0108 104 0.0104
200 3.29 0.0185 217.8 0.0151
300 3.83 0.0128 344.0 0.0111 ab5 3r.b 3lb 70s 215 26s 2tF 226
$. to+

Discussion of Results Figure 6-Logarithmic P l o t of Isobars for Nitrogen-

The variation of these results from the ideal law of Henry
is shown in Table I1 and Figure 5. The Henry constant
calculated both for pressures in atmospheres and for fugaci-
ties shows wide variations and no significant trends.
In attempting to explain the peculiar properties of this
system, many theories have been tested. I n general it
seems best to attribute depaxtures from ideal behavior to
some property of the solvent rather than to look for explana-
tion in some peculiarity of nitrogen. I n this work the effects
of solvent density, viscosity, internal pressure, surface ten-
sion, association, and compressibility were investigated
with the help of such other data as were available. Interest-
ing theories have been proposed from time t o time correlating
one or the other of these solvent properties with solubility.
Only one, however, has definitely recognized the existence of
minimum solubility points for gases a t constant pressures.
Winkler ( I 1 ) developed a relation connecting solubility and
Water
e
The results, in so far as fundamental solubility theory
is concerned, lead one inevitably to the conclusion that many
more data are necessary for complete understanding of these
compressed systems.
Literature Cited
(1) Antropoff, v., 2. Elektrochem., 25, 269 (1919).
(2) Bohr and Bock, A n n . phys. chem., 44, 319 (1891).
(3) Cassuto, Nuooo cimcnfo, 6; 1903 (1913).
(4) Estreicher, 2. physik. Chem., 31, 176 (1899).
(5) Just, I b i d . , 37, 342 (1901).
(6) Keyes and Dewey, M. I. T. Publication 179 (1927).
(7) Larsen and Black, IND. END. CREM.,17, 715 (1925).
(8) Porter, Bardwell, and Lind, Ibid.. 18, 1086 (1926).
(9) Sander, 2. physik. Chcm., 7 8 , 513 (1911).
(10) Travers, “Experimental Study of Gases,” p. 255, Macmillan, 1901
(11) Winkler, Z . p h y s i k . Chem., 9, 171 (1899).
(12) Wroblewski, v . . W i d A n n . , 4, 268 (1879).

X-Ray Study of the Copper End of the

Copper-Silver System’
Roy W. Drier

DEPARTMBNT
OI MEIALLUROP.MICHlQAN COLLBQE OF MIXINGAND TECHNOLOGY,
HOUGHTON.
MICH.

URING an x-ray investigation of the plastic deforma- the eutectic temperature, 778” C., down to room tempera-

D tion of copper, it was noticed that both the Hull and

the Laue types of spectra contained lines other than
those of copper. Upon analysis these were found to be lines
from the silver spectrum. Inasmuch as the copper under
investigation did not contain enough silver to be beyond
the accepted solid-solution range for silver in copper, the
appearance of the silver lines seemed quite worthy of in-
vestigation.
Constitution diagrams (3, 4) of the copper-silver system
all show that silver is soluble in copper up to about 5 per cent
by weight. The diagram in the International Critical
Tables has the silver-in-copper solubility line dotted from
* Received June 26, 1930; revised paper received February 26, 1931.
ture, indicating that such solubility is questionable.
It is generally accepted t h a t there are two types of solid
solution. In the most common type the solute atoms
replace the solvent atoms on the lattice of the solvent.
Opinions differ as to whether the replacement is statistical
or random, but whichever condition obtains the resulting
solid solution is of the substitutional type. For a continuous
series of solid solutions i t is necessary that the two pure
components A and B crystallize on the same type of lattice.
According to the additive law of Vegard (1) the lattice
constant changes linearly with the composition in atomic
per cent between the limiting values of the pure components.
Copper and silver both crystallize on the face-centered