Solubility of Hydrogen, Oxygen, Nitrogen, and Helium in Water

1146 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 44, No. 5
TABLE lTIII. COMPARISON OF CYCLOP.4RAFFIN CONTENT OF cs AND HEAVIER
FRACTIONS
fractions. -4 serious discrepancy is shown in Table VI11 between
the paraffin-cycloparaffin splits in the CQ and heavier distillate
fractions boiling above 306" F. as calculated by the mass spec-
trometer and refractivity intercept methods. It is believed that
much of this difference is due to the presence of dicycloparaffins
and possibly tricycloparaffins which are shown in Table VI11 to
as high as 9% in one fraction. The data of Ward and Kurta (12)
show that the difference in refractivity intercept between paraffins
and dicycloparaffins is several times greater than that between
paraffins and monocycloparaffins. By correcting the value of the
refractivity intercept of cycloparaffins for the presence of dicyclo-
paraffins, a fair agreement was reached between the two methods
of analysis for paraffin content. Exact agreement can hardly be
expected since a small deviation in the mass spectrometer analysis
for dicycloparaffins produced a laigc
change in the refractivity interccpt de-
termination for paraffins.
(By mass spectrometer analysis and refractivity intercept method)
Volume % of Saphtha
LITERATURE CITED
Boiling Range Mono-
Uncorrected Corrected6
of Fraction, cyolo- Dicyclo- Cyclo- Cyclo-
(1) Bell, M. F., Anal. Chem., 22, 1005
F. Paraffins paraffins paraffinsa Paraffins paraffins Paraffins paraffins
(1950).
MAE^ SPECTROYETER ANALYSIS REFRACTIVITY INTERCEPT hf ETHOD
(2) Brown, R. A,, Zbid., 23, 430 (1951).
(3) Brown, R. A,, Taylor, R. C., Mel-
270-306
56 44 0 57 43 57 43
306-358 55 40 5 44 56 54
46
polder, F. W., and Young, W. S.,
358-391
54 40 6 33 67 46 54
Zbid., 20, 5 (1948).
391 and higher 53 38 9 25 75 45 55 14) Cady, W. E., AIarschner, R. F., and
a May also include small amounts of tricycloparaffins.
Cropper, W. P., payer presented at
b Refractivity intercept of the cycloparaffins corrected for the presence of dicycloparaffins indicated
119th Meeting, AM. CHEM. SOC.,
in mass spectrometer analysis.
Cleveland, Ohio, April 1951.
(5) Glaspow. A. 11.. Willinpham. C. B..
and Rossini, F. D.; IND. ENG.
CHEM., 41, 2282 (1949).
(6) Whir, B. J., J. Reseaich Natl. Bur. Standards, 34, 435 (1945).
(7) Noller, C. R., and Barusch, h.1. R., IND. ENG. CHmf., API'AL. ED.,
14, 907 (1942).
(8) Podbielniak, W. J., Zbid., 13, 639 (1941).
(9) Rampton, H. C., J. Znst. Petroleum, 35, 42 (1949).
(10) Starr, C. E., Tilton, J. A,, and Hockberger, W. G., END. KNG.
CREM., 39, 195 (1947).
(11) Taylor, W. J., Wagman, D. D., Williams, M. G., Pitzer, K. S.,
and Rossini, F. D., J. Rrseurch Natl. Bur. Stadwds, 37, 95
(1946).
(12) Ward, A. L., and Kurts. 8. S., IND. ENG. CHEY., .ANAL. ED., 20,
559 (1938).
RECEIVED for review May 2, 1951. -4CCEPTED December 31, 1961.
Presented as part of the Symposium cn Composition of Petroleum and Its
Hydrocarbon Derivatives presented before the Division of Petroleum Cliern-
istry at the 119th Meeting of the .4~E~lc.43 CHEYICAI. EOCIETY, Cleveland,
Ohio, April 1951.
Solubility of Hydrogen, Oxygen,
Nitrogen, and Helium in Water
THE
AT ELEVATED TEMPERATURES
H. A. PRAY, C. E. SCHWEICKERT, AND B. H. R/IIYVIvICH1
Battelle iMemorial Institute, Columbus 1, Ohio
1 incidng application of high temperaturesand pressures
to various processes has made a knowledge of the solubilities
of compressed gases in water necessary for purpoises of engineering
design. A survey of the literature has revealed that considerable
data are available on the solubilities of gases under partial pressures
of more than 25 atmospheres and at relatively low temperatures.
Data in the region from about 5 to about 25 atmospheres
and from about 125' F. to temperatures near the critical point of
water are very meager and incomplete. A determination of the
solubilities of oxygen, hydrogen, helium, and nitrogen in water at
temperatures from 128" to 650" F. and at presmres up to about
500 pounds per square inch absolute was, therefore, undertaken.
EXPERIMENTAL PROCEDURE. For determining the solubilities
of gases in water, the apparatus shown in the schematic diagram
(Figure 1) was used. A typical example of the use of this apparatus
is as follows:
Valves A and B are closed, valves C and D are opened, and the
3-liter bomb contained in the rocking autoclave, E, is evacuated
by means of the vamum pump, F. Valve A is then opened and
about 1500 ml. of distilled water are admitted to the bomb from
1 Present address, Naval Ordnance Testing Station, Inyokern, Calif.
INLET
Figure 1. Diagram of Solrability Apparatus

May 1952 INDUSTRIAL AND ENGINEERING CHEMISTRY 1147
Figure 2. Solubility of Oxygen in Water with Varying
Pressure
0. Authors
A. Froblioh et 01. (I)
Figure 3. Solubility of Oxygen in Water with Varying
Temperature
MRTIAL PRESSURE, PS I A
Figure 4. Solubility of Hydrogen in Water with Varying
Pressure
A. Ipatieff and Teodorovish (2)
B. Authom
C. Wiebe and Gaddy (3)
TEMPERATURE, OF.
Figure 5. Solubility of Hydrogen in Water with Varying
Temperature

1143 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 44, No. 5
PARTIAL PRESSURE, PS.1 A
Figure 6. Solubility of Helium in Water with Varying
Pressure
A. Wiebe and Gaddy (4)
0. Authors
Figure 7. Solubility of Helium in Water with Varying
Temperature
the water buret, G. Valve A is then closed and the system is
evacuated to a pressure corresponding to the saturated vapor pres-
sure of water at room temperature. Valve C is then closed and
the rocking autoclave, which is heated electrically, is set in
motion and brought to some predetermined temperature. The
Figure 8. Solubility of Nitrogen in Water with Varying
Pressure
A. Frohlich et QZ. (I)
R. Wiebe and Gaddr (5)
Figure 9. Solubility of Nitrogen in Water with Varying
Temperature
temperature of the autoclave is controlled by a Leeds & Northrup
Micromax temperature controller and recorder, N. The telu-
perature inside of the bomb is determined by means of a chromel-
alumel thermocouple inserted in a stainless steel well inside of the
bomb. The electromotive force of the thermocouple is deter-

May 1952 INDUSTRIAL AND ENGINEERING CHEMISTRY 1149
TABLE I. SOLUBILITY OF OXYGEN IN WATER
OZ Partid
Pressure
Lb./'Sq. In.' Abs. Souroe Cc. OP/G. of Water Average
140 (1) . ,
295 ..
370 ..
77' F.
..
..
..
325' F.
200 loo
300
Authors
Authors
Authors
0. 14 0.16 0. 16
0.31 0.31 0.31
0.47 0.47 0.45
. ..
..
..
400' F.
100
150
Authors
Authors
0.19 0.18 0.17
0.30 0.28 0.27
. .
..
100
200
300
400
Authors
Authors
Authors
Authors
5000 P.
0.68 0.63 0.62 0.51
0.47 0.99 0.69 0.56
0.92 0.89 0 91
1.52 1.68 1.18 1:OQ
1.37 1.24
t .
1.80 1.63 1:70 ..
600' P.
..
. .
..
,.
..
loo
Authors 0.63 0.60 0.69 0.62 . ,
Authors 1.39 1 45 1.43
300 Authors 2.22 2:14 2.34 2:02 2:24
650' F.
104 Authors 1.17 1.26 . . . , . .
175 Authors 1.85 .. ..
205 Authors 2.39 2128 2:19 ..
2 80 Authors 2.96 ,. .. .
2 89 Authors 2.51 2:61 , , ..
309 Authors 2.99 . . . . , . . .
a At standrsrd temperature and pressure.
mined with the aid of a Leeds & Northrup
Semi-Precision potentiometer, H. The
thermocouple was calibrated against the
melting points of metals obtained from
the Bureau of Standards for that purpose.
The temperature during any one run is
held constant to within 2" F. After the
temperature inside of the bomb reaches
the deRired temperature, the outlet valve,
A, leading to the mercury U-tube is
opened and the saturated vapor pressure
of water is determined with the dead-
weight gage, J. The mercury U-tube
isolates the material in the bomb from the
oil in the dead-weight gage. The pres-
sure, as determined by the dead-weight
gage, is checked against the vapor pres-
sure of water given in the steam tables.
The gas under investigation is then ad-
mitted to the bomb by opening one side
of valve C. The pressure is allowed to
build up to slightly over the desired
partial preseure at which the solubility
of the gaa is to be determined. Valve C
is then closed and the system is allowed
to come to equilibrium. This is done by
keeping the autoclave in motion over-
night at the desired temperature. The
temperature is then readjusted, if neces-
sary, and the pressure of the gas is re-
adjusted to ita desired partial preasure.
When the temperature and pressure have
remained constant for about 2 hours, a
sample is taken. This is done by circu-
lating ice water through the condenser, K,
and then opening the purging line side of
valve B. After about 25 ml. of water
have been taken off, the purging line valve
0.28
0.56
0.70
0.15
0.31
0.46
0.18
0.28
0.64
0.91
1.35
1 71
0.63
1.42
2.19
1.22
1.85
2.29
2.96
2.56
2.99
Probable
Error
,.
..
..
0.01
0.00
0.01
0.01
0.01
0.04
0.02
0.06
0.03
0.01
0.02
0.04
0.01
0:03
0:03
..
Maximum
Deviation
...
...
...
t0.01 to -0.01
fO.OO to -0.00
t0.01 to -0.01
fO.O1 to -0.01
$0.02 to -0.01
f0.35 to -0.17
+0.01 to -0.02
t0.33 to -0.26
+0.09 to -0.17
-I-0.06 to -0.03
f0.03 to -0.03
+0.15 to -0.17
+0.04to -0.05
+o. lo'to' -0.10
+O.O5'to' -0.05
...
is closed and the sampling line side of
valve B is opened. About 25 ml. of water
containing an amount of gas which depends
on the partial pressure and water
temperature are then collected over mercury
in the measuring buret, L, which is
surrounded by a water thermostat. The
gas and water volumes are then measured
and the needle valve, M, is opened. This
allows the water that remained in the
sample line, because of capillary action,
to drain into the buret. After the total
amount of gas and water have been determined,
dry air is blown in through the
inlet at N and allowed to escape through
M. This procedure dries all of the sampling
lines in preparation for the next
sample. The solubility of the gas in water
is then determined by reducing the gas
and water volumes, as found in the
measuring buret, to cubic centimeters of
gas at normal temperature and pressure
per gram of water,
EXPERIMENTAL RESULTS
The present experimental results and
certain previously reported data for the
solubility of hydrogen, oxygen, helium,
TABLE 11. SOLUBILITY OF HYDROGEN IN WATER
Ha Partial
Pressure Probable Maximum
Lb./Sq. In: Abs. Source CO. Hia/G. of Water - Average Error Deviation
300
367
200
300
350
100
200
300
375
500
100
200
300
375
500
100
200
300
376
100
200
300
375
500
100
200
300
100
200
300
100
115
120
125
75' F.
. . , . . . . . . . . ,
(8)
Authors
Authors
Authors
. . . . . . . .
125°F. ''
0.38 0.32 0.32 0.31 0.37 0.30
0.41 0.42 0.40 0.41
0.47 0.44 0.44 0.44 0.'46 .:'
(3 h ::
. .
(8) . .
(8) . .
::
. .
. .
, .
::
. .
, .
, ,
300' F.
:: ::
. . ,
. . , ,
. , . ,
345' F.
:'
, ,
, ,
,
390" F.
435O F.
(8) , . . . . . . , . . . ,
(a) , , . , . . . . . . , ,
yj . . . . . . . . . . ,
. . . . .
(8) , . . . , , . . , . , .
. . . . . . ,
500' F.
Authors 0.45 0.38 0.31 0.32 ..
Authors 0.98 0.91 0.84 0.92 , ,
Authors 1.24 1.23 1.28 . . , ,
600" F.
Authors 0.68 0.61 0.68 0.62 . . , .
Authors 1.24 1.31 1.34 1.41 . . . ,
Authors 2.05 2.06 1.98 1.94 . . . ,
650' F.
Authors . . . . . , . . . . , ,
Authors . . . . . . . . . . . .
Authors , . . . . , . . , . ,
Authors . . . . . . , . . . , .
At standard temperature and pressnre.
0.32
0.44
0.33
0.41
0.45
0.13
0.28
0.40
0.52
0.70
0.15
0.30
0.43
0.66
0.75
0.18
0.34
0.52
0.68
0.22
0.49
0.75
0 94
1.26
0.39
0.91
1.25
0.65
1.32
2.01
1.40
1.63
1.68
1.74
0.01 +0.05 to -0.03
0.00 +O.Ol to -0.01
0.01 +0.02 to -0.01
. .
..
..
..
..
..
..
0.02 +0.06 to -0.08
0.10 4-0.07 to -0.09
0.01 +0.03t0 -0.02
0.01 +0.03 to -0.04
0.02 +0.09 to -0.08
0.02 t0.05 to -0.03

11.50 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 44, No, 5
Figure 10. Solubility- Constant versus
Temperature near the Critical Point
and nitrogen are listed in Tables I, 11, 111, and IV, and are also
shown graphically in Figures 1 to 9. The probable error shown
in column 5 of tjhe tables was calculated from the usual formula
I .-."
probable error = 0.6745 LA'
-\in(n. - 1)
, TABLE IT'. SOL~BILITY OF NITROGEN xii WATER
h'l Partial
Pressure,
Lb./Sq. In.
Abs. Source Cc. Nna/G. of Water dverage
77' F.
Probable
Error
Maximum
Deviation
294
367
588
(1)
(6)
(1)
. .
. .
. ,
. .
. .
. ,
. .
. .
. .
0.28
0.35
0.55
..
..
..
...
.,.
..
1220 F.
367 (6) . . . . . . 0.27
167" F.
367 (6) . . . . . . 0.25
...
2120 F.
3 67
(6) . . . . . . 0.26 ,.
5000 F.
150 Authors 0.47 0.43 0.41 0.44 0.01 50 03 to -0.03
400 -4uthors 1.21 1.34 1.18 1.24 0.02 +O.lO to -0.06
600' F.
150 Authors 0.56 0.54 0.56 0.55 0.00 +O 01 to -0 01
300 Authors 1.56
400 Authors 2.40 2:29 2:26 2:32 0.'02 +0,08'tb'-0,06
6 standard temperature and pressure.
TABLE 1x1. SOLUBILITY OF HELIUM IX WATER
He Partial
Pressure, Lh./
Sq. In. Abs. Source Cc. He"/G. of Water- Average
Probable
Error
;\laximum
Deviation
TABLE v. HENRY'S LAW COSSTANT, x, FOR VARIOUS Gas~sa
Temp.,
E". Oxygen
Gas, K X 10-6
Hydrogen Helium Nitrogen
32
75
77
122
125
,.
6:56
..
11:o
..
8: 72
20.40
2i : 75
,..
...
13:io
16.M
167 ,. .. IS: io lS:&
212 .. .. ... 18.00
300 9.30 ...
325 8:oO 8.04
I . Si34
346
390
32' F.
(4) .. ...
367 . . . . . . . . . . 0.23
367
77' F.
(4) . . . . . . . . . . 0.22 I . ...
167' F.
367 (4) . . . . . . . . . . 0.24
325' F.
100 Authors 0.20 0.20 0.19 , , . , . 0.20 0.00 iO.00 to -0.01
200 Authors 0.31 0.31 0.30 .. , , 0.31 0.00 io.00 to -0.01
300 huthors 0.39 0.37 0.37 . . , . 0.38 0.00 -0.01 to -0.01
600' F.
100 Authors 0.42 0.38 0.42 0.38 0.40 0.40 0.01 +0.02 to -0.02
200 Authors 0.58 0.60 0.64 0.59 0.60 0.01 iO.04 to -0.03
300 Authors 1.36 0.13 0.82 0.81 0:87
1.15 1.07 0.87 1.03 1.03 0:99 0:05 +0.37 tb'10.37
400 Authors 1.31 1 41 1 32 1.47 1.38 0.03 +0.09 to -0.07
500 Author8 1.74 1:64 1:86 1.70 1:85 1.76 0.03 +0.10to -0.12
600' F.
200
300
400
500
Authors
Authors
'Authors
Authors
0.92 0.95 0.89 0.93
1.64 1.61 1.70 1.66
2.44 2.37 2.59 2.31
2.84 2.37
2.72 3 12 8:07 3:i3
, ,
,.
2:82
0.92
1.66
2.'49
2.99
0.01
0.01
0:05
0 06
LO.03 to -0 04
+O.O4to -0 05
+0.35'tb'-0.18
+0.23to -0.27
.Z .kt standard temperature and preeaure.
6.98 ...
400 6: ... ...
435
4:98
500 2177 2.90 3:56 4: 18
GOO 1.74 1.86 2.20 2.38
650 1.22 0.885 ... ...
a K = 2, where PA = partial Pressure of gas, A, in pounds per 3~uar0
NA
inch and NA = mole fraction of gas, A, in solution.
which gives an indication of the preci-
sion of the data, where ZA = the
arithmetical sum of the deviations and
n = the number of measurements.
It is interesting to observe from the
tables and graphs that the solubilities of
these gases in water increase Kith in-
creasing temperature, in the high tem-
perature range, where= it has been estah-
lished that at temperatures in the
region from about 20" to ZOO" F. the
solubilities decrease with increasing tem-
perature.
Within experimental accuracy, the
solubilities of hydrogen, oxygen, helium,
and nitrogen appear to be linear func-
tions of pressure over the range investi-
gated. The resulting straight lines
(Figures 2, 4, 6, and 8) show that the
solubilities in question follow Henry's
law and may be predicted within the
limits of engineering accuracy over B
fairly wide range of temperatures and
pressures from the Henry's law con-
stants, which are listed io Table V.

May 1952 INDUSTRIAL AND ENGINEERING CHEMISTRY 11.51
At and above the critical temperature of water (705" F.), the
gases must be infinitely soluble and the Henry's law constant
must become relatively very small. The constants for the four
gases in the region of the critical temperature are plotted in
Figure 10. It is apparent that in this region the solubility con-
stants tend to converge and approach very low values at 705" F.,
thus indicating that the data are consistent with the fact that the
gases are miscible in all proportions at the critical point for water.
LITERATURE CITED
(1) Frolich et al., IND. ENG. CHEM., 23, 548 (1931).
(2) Ipatieff and Teodorovish, J. Gem. Chem. (U.S.S.R.), 4, No. 3, 396
(1934).
(3) Wiebe and Gaddy, J. Am. Chem. SOC., 55, 947 11933).
(4) Ibid., 56, 76 (1934).
(5) Ibid., 57, 847 (1935).
RECEIVED for review July 14, 1960. ACCEPTED December 31, 1951.
This work was csrried out under contract with the Atomic Energy Ccmmission,
Contract 7405-eng-92.
Selection of Surface Active Agents
for Detergent Applications
SUSPENDING POWEK AND MICELLAR SOLUBILIZATION
A. M. MANKOWICH
Paint & Chemical Laboratory, Aberdeen Proving Ground, Aberdeen, Md.
ELECTION of surface active agents (sirfactants) for specific
S metal cleaning applications is usually made on a trial and
error basis, using laboratory detergency tests which have been
correlated with field test results. Experience plus the fragmentary
available information on such properties as molecular structure,
type and chemical stability of surfactant, surface and interfacial
tensions, and Draves and Clarkson sinking times (a)
may be used &s empirical screening media. It is imperative that
all possible combinations of compatible types of surfactants be
studied, since it is not possible at present to predict synergistic
combinations. Builder action varies with type of agent and soil,
which necessitates investigation of additional combinations, The
development of B laboratory detergency test that can be correlated
with field results is a problem. An obviously considerable
amount of research must be performed even when only a limited
number of surfactants are tested. This process has to be repeated
for every detergent application in which the soil and/or substratum
is varied.
The time-consuming, trial and error approach in determining
the suitability of various surfactants for use in cleaning coinpounds
intended for the removal of specific soils from specific
substrata is viewed unfavorably in this laboratory. It is believed
that the selection of surfactants for specific detergent applications
can be accomplished more scientifically and economically by determining
the fundamental or prime factors in the detergency
process; studying each factor to establish numerical criteria for
the various types of surfactants and builders under varying pH,
concentration, and temperature conditions; and classifying soils
with reference to the numerical values of the prime factors, obtaining
cofactors (minimum numerical criteria for each prime factor
necessary to accomplish soil removal in specific soil-surface
combinations).
Once the prime factors for various types of surfactants and the
cofactors for the soils are determined, an inspection of the data
will indicate appropriate surfactants or combinations of surfactants,
as well as suitable temperature, pH, concentration, and
builder data. This is done by selecting the surfactant, or combination
of surfactants, whose prime factors have equal or greater
numerical ratings than the corresponding cofactors. The principle
advanced is that detergency in a specific soil-surface application
is accomplished only if the numerical ratings of all the cofactors
are equaled or exceeded by the prime factors of the cleaning
solution. The need for utilizing more than one surfactant for a specific
detergency application will be readily apparent in those
cases where an otherwise! satisfactory agent is deficient in one or
more prime factors. When it is necessary to select two or more
surfactants, the maximum numerical rating for each prime factor
of the combination is estimated by adding the respective ratings
of the individual surfactants involved. Preliminary work indi-
cates that the numerical rating of a prime factor approaches a de&-
nite maximum which is not exceeded, regardless of the number of
surfactants combined for a specific detergent application. This
maximum is usually the highest value attained by any of the in-
dividual surfactants investigated. However, Bdditiveness of
numerical ratings of a combination of surfactants is obtained un-
til the maximum for the prime factors is reached. It is intended
to cover the determination of cofactors and classification of soils
and substrata in a later paper.
An advantage of the proposed method of selection is that it will
indicate a number of surfactants or combinations of surfactanta
for each soil-surface application, thus permitting a final selection
on an economic basis. No attempt is made to evaluate the rela-
tive importance of the various prime factors, and the method does
not depend on such evaluation. The proposed method is not to
be confused with the speculations ($1) that detergency will even-
tually be calculated from a formula containing weighted physico-
chemical factors. Assuming that these speculations are realized
eventually, they will not aid in the selection of surfactants for spe-
cific detergent applications. The formula will only give an index
of detergency. The proposed method indicates the minimum
physicochemical requirements for a detergent application, to-
gether with a number of surfactants or combinations of surfac-
tants capable of meeting the requirements. It is important to
realize that the proposed method indicates synergistic combina-
tions of surfactants.
PHYSICOCHEMICAL FACTORS OF DETERGENCY
Present-day knowledge indicates that detergency is the result-
ant of many factors (I, 22, 20, $2). It is understandable, there-
fore, that attempts to correlate detergency with one factor only
have been unsuccessful. Reich and Snell (18) emphasize a fur-
ther error made in attempting to evaluate detergency with one
factor. Detergency is dependent on three groups of variables
(13): those originating in the soil, in the surfactant, and in the
surface. A factor involving only one of the groups, such as sur-
face tension, or two of the groups, such as micellar solubilization,
is basically not in correlation with detergency.