J. Biol. Chem. 1927, 72:545-548.

THE SOLUBILITY OF OS, COz, AND Nz IN MINERAL OIL

AND THE TRANSFER OF CARBON DIOXIDE FROM
OIL TO AIR.
BY LAWRENCE S. KUBIE.
(From the Department of Physiology, Johns Hopkins Medical School,
Baltimore.)

(Received for publication, January 6, 1927.)

During the summer of 1925, in association with Dr. D. Bruns-

wick and Dr. H. Davis of the Department of Physiology of the
Harvard Medical School, an attempt was made to control the dry-
ing of mammalian nerves during studies of their electrical behavior
by immersion in mineral oil. This led one of us to an investiga-
tion of the solubilities of 02, COZ, and N, in this oil, their rate of
transfer to aqueous solutions, and the rate of loss of CO2 from oil
to air. Although as a result of these tests, this application of the
oil to nerve physiology turned out not to be feasible, the lack of
any data more recent than those of Gniewosz and Walfisz (1)
in 1887 and the wide-spread use of mineral oil in studies of blood
chemistry warrant the publication of a part of our results.
The medicinal white oil examined was the Amalie brand of
extra heavy medicinal white oil furnished to the Johns Hopkins
Hospital pharmacy by the L. Sonneborn Sons, Inc., of New York.
This oil is prepared by fractional distillation from a naphthene
base, with subsequent removal of all unsaturated hydrocarbons
by treatment with concentrated HzSOd. The product is then
washed with NaOH, and decolorized with fullers earth, bone-
black, or silica gel. The resulting white oil has a specific gravity
of 0.890 to 0.895 at 15C. (manufacturers determination), or of
0.868 at 27C. (authors determination). Its viscosity (Saybolt)
is 285 at 100F. It congeals at about -37C., is guaranteed not
to cloud at a higher temperature than -8C., and meets the
United States pharmacopeial tests perfectly, in that it shows no
discoloration on prolonged boiling with concentrated HzS04 or
545
 Gas Solubility in Mineral Oil

HNOB and is shown to be free from S and S compounds in the

PbO test.
I. Gas Xolubilities in White Oil.

In all of these determinations, we used the constant volume

apparatus described by Van Slyke and Neil1 (2). To secure com-
plete extraction of the gasesfrom the oil in a reasonable period of
time, we found it necessary to make a new calibration mark at the
lowest point in the wide reservoir of the pipette, which gave our
instrument a total volume of 48.37 cc. The mercury was lowered
only as far as this calibration mark, so that as the pipette was
shaken, a little mercury slapped backwards and forwards, beating
the oil out into a thin film from which complete extraction could
occur in about 10 minutes.
For transfer of oil to the Van Slyke apparatus, a pipette (with
a wide bore tip) was constructed to deliver 1.990 A 0.007 cc. in
exactly 60 seconds between marks. The usual pipettes could
not be used because from them the delivery of the oil was too
slow.
The calculation of the amount of gas dissolved in a fluid from
the amount which is extracted in this instrument requires the
multiplication of the actual volume of gas extracted by two cor-
rection factors. The first of these is due to the fact that some gas
remains dissolved in the fluid; the second is due to the fact that in
bringing the gas to the volume at which its pressure is to be meas-
ured a certain amount of gas redissolves. This latter factor is
only of measurable magnitude in CO2 determinations. Because
we were working with an emulsion of water and oil whose solu-
bility, for the gas, we had to consider as unknown, we could not
use Van Slykes formula for the first correction. Nor could we
apply to this emulsion t,he reabsorption correction which he has
determined on known bicarbonate solutions. Therefore, we had
to determine an empirical correction for each gas, by comparing
the volume of gas absorbed after a single complete extraction with
that which could be obtained by extracting completely, expelling
the extracted gas, reextracting the oil, again expelling, and so on,
until a constant pressure reading was secured. By this method
we secured a factor which combined both corrections. For CO2
this factor lay between 1.07 and 1.09; and our error from this
 E. S. Kubie 547

source is thus seen to be about 2.0 per cent. For oxygen this fac-
tor was only about 1.02, and for nitrogen about 1.04, again with
an error of nearly 2 parts in 100. This calculation gives the actual
volume of gas per cc. of oil, reduced to standard temperature and
pressure. A further correction was made for the barometric
pressure under which the gas was saturated; but no corrections
were introduced for the vapor pressure of oil or water, nor for
the change in volume of the oil due to the gas absorbed.
Our figures indicate, therefore, the volume of gas at standard
temperature and pressure which dissolves in 1.0 cc. of oil (neglect-
ing the change of volume of the oil), under 1 atmosphere pressure
of the gas (neglecting the partial pressure of water and oil vapor
over the oil).
Saturation was secured by bubbling gas for several hours di-
rectly from a commercial cylinder through the oil. The oil was
in a closed bottle from which the gas escaped at atmospheric
pressure through an oil trap. No attempt was made to control
temperature accurately; but the oil bottle and the connections
were immersed in water and records were kept of the temperature
both of the oil and of the bath. The constancy attained in this
way is indicated in the table of solubilities given below.
Solubility in Mineral Oil.
C.
CO? at 24-25 0.841 It 0.011
02 24 0.134 It 0.004
N2 22-22.5 0.071 xk 0.002

These solubilities may be compared, with negligible error, to

the absorption coefficients (Bunsen) of these gases in water,-as
tabulated in Seidell (3) from the well known investigations of
Winkler, Bohr and Bock, Braun, Geffcken, and of Just.
20C. 25C.
coz. . . .. . 0.878 0.759
02. . .. . 0.0310-0.0317 0.02834.0290
Nz . . . . . . . . . . . 0.0154-0.0164 0.0143-0.015oi

In contrast to our solubilities, Gniewosz and Walfisz (1) report

the following absorption coefficients in Russian petroleum.
10C. 20C.
Nz.. .. ... ... ... . .. . . ... .. . . _. _. _. . 0.135 0.117
02. 1 . . . . . . . . . . . . . . . . . .. . 0.229 0.2Q.2
coz. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.31 1.17
 Gas Solubility in Mineral Oil
II. Escape of CO2 from Mineral Oil to Air.
A slow rate of diffusion of the gas through the oil is seen when
oil saturated with 1 atmosphere of CO2 is exposed to air. Five
cups of identical cross-section and depth (i.e. 900 sq. mm. X 3
cm.) were set up simultaneously, and at intervals samples of oil
were collected from the top and from the bottom of the cups and
analyzed.

Per cent saturation.

Time.
Top samples. Bottom samples.

min.
5 91
40 94
70 89
104 93
149 70
323 37
358 90
403 20

SUMMARY.

1. The solubilities of 02, COZ, and Nz in mineral oil are

determined.
2. The extremely slow diffusion rate of CO2 and presumably of
other gasesthrough mineral oil is seen to be the main protective
virtue of the oil when it is used to separate a physiological fluid
from air.

BIBLIOGRAPHY.

1. Gniewosz, S., and Walfisz, A., 2. physik. Chem., 1887, i, 70.

2. Van Slyke, D. D., and Neill, J. IV., J. Biol. C&m., 1924, lxi, 523.
3. Seidell, A., Solubilities of inorganic and organic compounds, New York,
2nd edition, 1919.