Solutions for Maintaining

Constant Relative Humidity

D. S. CARR AND B. L. HARRIS
The Johns Hopkins L'niversity, Baltimore 18, M d .

T h e aqueous tensions maintained bj twelve saturated
aqueous salt solutions in an enclosed space from room
temperature to 90" C. are given and the relative humidities
calculated therefrom. The salts include the halides of
potassium and sodium, the nitrate, nitrite, chromate, and
dichromate of sodium, and chromic oxide. The data
were obtained by a static method using a modification
of the isoteniscope of Smith and Menzies.
I N COYKECTIOK n l t h studies ot adsorption oi mater vapor
on silica gel it was desired to equilibrate samples of gel in air
a t various relative humidities a t a constant temperature. In-
asmuch as the static equilibration was to take months, the
simplest method was thought to be that of exposing the ad-
sorbents in a desiccator to air in contact Jqith saturated aqueous
salt solutions a t eonstant temperature. Lange's handbook
cock lubricant (silicone) was used on all submerged lubricatrti
surfaces.
The operational procedure was as follows. A solution was pre-
pared from C.P. chemicals and redistilled water, containing suffi-
cient salt, so that some would remain undissolved a t 90" C. The
Bask containing the solution was connected to the ap aratus and
cooled with dry ice until the solution was frozen. $hen all air
was evacuated from the entire apparatus and the stopcocks were
closed. The solution was allowed t,o melt and was stirred vigor-
ously to free dissolved gases. This procedure was repeated twict,
more, after which the t,hermostat was placed in position and set.rtt
a desired temperature. As t'he pressure of the water vapor in-
creased] the differential manometer was kept roughly balanced by
allowing air to flow slowly into the pressure-measuring syst,ein.
When vapor-liquid equilibrium was reached, t>he pressure was
TABLD
I. AQUEOCXTIWSIOX AKD PERC E ~ IZELATIVI~
T
HUNIDITY
O F SATURaTED SALT SVLETIoNS

(8) gives a list of such salt solutions, but this list is not very com- kin- .Igueoiis Relative Tern- Aqueous ltelativr
uerature, Tension, Humidity UeLature, Tension, Humidity.
plete and values for various salts arr given a t single temperatures C. Mm. Hg % C. hlin. Hg '%
or over very restricted temperature ranges. Reference to the Sodium Chloride, SRCI Potassium Iodide, K I
literature showed that the data are fragmentary and widely 15.5 10.03 75.Y 40.0 36.94 66.8
20.7 13.85 75.7 50.0 60.11 65.0
scattered, nor could data be found on several systems that the 30.2 24.10 74.9 60.0 94.30 63.1
authors wished to use. Some few studies were found for several $0.0 41.30 74.7 70.0 144.0 61.7
00.0 68 30 74 9 80.0 916.0 fin 8
salts (1, 5). 60.0 111 9 74 9 90.0 817.3 60 1
70.0 175.4 75.1
Accordingly, it was undertaken to nieabure the vapor pressure 80.0 271.0 76.4
of water over saturated salt solutions from room temperature to Sodirini Erornide hJaBr.2HsO 4
90" C. The salts chosen were the chlorides, bromides, and io- N a B r a t b0.6' C. Sodium Nitmte, NaKU,
dides of potassium and sodium, potassium fluoride, sodium 20.3 10.35 58.0 30.1 20.16 63.0
40.9 30.37 52.4 40.0 33.97 61.5
nitrate, nitrite, chromatp, and dichromate, and chromic olidr 50.0 46.02 49.7 30.0 55,30 59.8
60.0 74.50 49.9 60.0 88.61 ,59.3
70.0 118.4 R0.7 70.0 137.6 5 8 !4
EXPERIM EhT 4 L 80.0 181.0 50.9

The apparatus constructed was a modification of the isoteni- Sodium Iodide, NaI.2HsO -+
N a I a t 68. l o C . Sodiiini Nitrate, NaNOi
scope of Smith and Menzies (10). 30.2 11.71 36.4 :10.0 23.14 72.8
40.0 17.94 32.3 40.0 39.58 71.5
It consisted essentially of a differential manometei filled with 60.0 26.28 28.4 50.0 63.46 68.8
dibutyl phthalate] connected on one side t o the sample tube and 60.0 37.80 25.3 60.0 100.7 67.6
on the other to a pressure-measuring system. The entire appara- 70.0 52.28 42.6 70.0 153.5 65 .i
80.0 81.37 23.2 80 0 232.5 65 5
tus was connected t o a high vacuum system by suitable stopcocks 90.0 123.4 23.5 90.0 341.8 65,O
through cold traps, The ressure-measuring system was filled
with dry air at pressure sugcient to balance roughly the differen- Potasbium Fluoride, KF.2HzO 3 Sodium Chromate NasCr0a.-
K F a t -50' C. 4Hz0 -+ NapCrOa kt 64.8' C
tial manometer a t any point, Being thus isolated from any con-
densable vapor, the pressure could be measured by McLeod gages 30.4 8.91 27.4 30.2 20.80 64.6
40.0 12.62 22.8 40.0 34.19 61.8
Two such gages, one measuring from 0.01 to 10 mm. and one from 60.0 18.88 20.4 50.0 54.40 58.8
10 to 123 mm. of mercury, were provided. Pressures above 125 60.0 31.36 21.0 60.0 83.06 55.6
mm. were measured on a large-bore manometer. The difference 70.0 51.34 22.0 70.0 127.6 54.7
80.0 80,25 22.8 80.0 199,s 56.2
between the levels of the dibutyl phthalate in the two legs of the 90.0 122.8 23.4 90.0 302.9 57.6
differential manometer was measured by cathetometer and trans-
lated to millimeters of mercury a t 0" C. using the known density Sodium Dichromate, Na~Cr207.
of the fluid a t the operating temperature. The reading of the Potassium Chloride, KC1 2HzO -+ NazCrzOi a t 74 8' C .
gage was corrected by this amount. The pressure-measuring 20.2 14.91 85.0 30.0 17.26 54.2
system was provided with a large-volume float (2 liters) t o elimi- 30.3 27.36 84.5 40.0 29.61 53.6
40.0 45.19 81.7 50.0 50.30 54.4
nate corrections due to compression when the McLeod gages 50.0 74.20 81.2 60.0 82.49 55.2
were operated. 60.0 120.3 80.7 80,O 190.0 56.0
The flask containing the solution was attached to the appara- 70.0 187.0 80.0
80.0 382.4 79.5
tus by a standard-taper joint for ease in changing solutions. The 90.0 411.5 78.3
flask contained a glass-enclosed iron rod by which the contents
could be stirred magnetically from the outside during degassing Potassium Bromide, KBr Chromic Oxide, CrOa
evacuations. All parts of the system which came in contact with 40.0 44.0 79.6 15.0 5,81 45.4
water vapor, from the differential manometer, including the flask 50.0 73.26 . 79.2 30 0 14 18 44.6
60.0 117.0 79.0 40 0 25.00 45.0
and over to the stopcock used for evacuation, were immersed in a 70.0 185.0 79.2 .iO.O 42.01 45.4
water thermostat maintained to i-0.1' C. over a long period of 80.0 281.5 19.3 60.0 68.41 45 8
time. Values were read only when the temperature was constant 70.0 108.0 46.3
to better than ~ 0 . 0 . C5 ~for 0.5 hour A high temperature Stop-
2014
September 1949 INDUSTRIAL AND ENGINEERING CHEMISTRY
read, as was the difference in levels of the legs of the differential
manometer. The procedure was then repeated a t a higher tem-
perature.
RESULTS
The data are given in Table I. The per cent relative humidity
was calculated from the aqueous tension by dividing by the
vapor pressure of water at the same temperature, as given in
International Critical Tables (6). Clausius-Clapeyron plots
(log p vs. 1/T) were linear over the temperature ranges studied,
and existence of phase transitions was characterized on such plots
by abrupt changes of slope. Such transitions are discussed below.
CHLORIDE.The aqueous tension of saturated solutions
SODIUM
of sodium chloride increased uniformly over the range studied
(15.5' to 80.0"C.). No transition was observed, as was expected.
SODIUM BROMIDE.A break in the plot of log p us. l / T was ob-
served a t 50" C. This agrees fairly well with the transition tem-
perature of 50.6' C. re orted by Dingemans ( 8 ) . Below this
temperature the form o f the compound is NaBr.2H20 and the
transition is to NaBr.
SODIUM IODIDE. This compound was observed to have a break
in the plot at about 70" C., in agreement with the transition tem-
perature from NaI.2Hz0 t o NaI a t 68.08' C. reported by Dinge-
mans (2). A value of 68.9' C. is listed in Perry's handbook (9).
POTASSIUM FLUORIDE. This solution was studied from 30.4"
to 90.0" C. and a transition temperature was found to occur in the
neighborhood of 50" C. The transition from the dihydrate to the
anhydrous form is reported by de Forcrand ( 4 ) to occur a t 41 O C.
POTASSIUM CHLOBIDE. The aqueous tension of this solution
was found to increase linearly over the temperature range studied
(30.3" to 90.0" C.)with no evidence of transition.
POTASSIUM BROMIDE.The a y e o u s tension of this solution was
studied only over the range 40.0 to 90.0" C. The relative humid-
ity was found to be nearly constant over this range.
POTASSIUM IODIDE. This solution exhibited no transition, the
aqueous tension increasing to give a linear plot.
SODIUM NITRITE. This compound has the greatest variation of
solubility with temperature of any salt investigated here. No
phase transitions were observed, and the relative humidity de-
creased uniformly.
SODIUMNITRATE. The aqueous tension was measured over a
Solubilities of Aliphatic
Dicarboxylic Acids in Water J
APPLICATION OF DUHRING5 RULE
EDWARD c. ATTANE AND THOMAS F. DOUMANI
U n i o n Oil Company of California, Wilmington, Calif.
'rhe solubilities of glutaric, adipic, and 6-methyladipic
acids in water have been determined at several tempera-
tures. Solubility data for oxalic, malonic, maleic, fumaric,
malic, tartaric, glutaric, adipic, and p-methyladipic acids
have been correlated by means of a modification of Diih-
ring's rule. With the exception of glutaric and @-methyl-
A iK EXAMINATION of the literature reveals that although
the solubilities of the three lower dicarboxylic acids-
oxalic, malonic, and succinic-have been reported by various in-
vestigators over a rather wide range of temperatures, only a few
solubility data have been reported for glutaric and adipic acids.
Henry(5) reported the solubility of glutaric acid a t 14" and t h a t of
adipic at 15" C. Lamouroux (8) has given the solubility of
glutaric acid in water from 0 to 65 ' C., but unfortunately his re-
sults were expressed in grams of acid per 100 cc. of solution and no
2015
range from 30.0" to 90.0' C. The relative humidity decreased
with rising temperature; no transition was observed.
SODIUM CHROMATE.This solution was found t o undergo transi-
tion from Na2CrOa.4H20 t o the anhydrous form at about 65 O C.,
agreeing with Dingemans' value of 64.8" C. for the transition
temperature (2).
SODIUM DICHROMATE. A transition was observed for this solu-
tion a t about 75" C. A value of 74.8" C. for the transition from
the dihydrate to the anhydrous form has been reported by Hart-
ford ( 5 ) ,whereas the value reported by both International Criti-
cal Tables (6) and Perry's handbook (9) is 84' c. The aqueous
tension of this solution was not measured above 80" C., but be-
cause International Critical Tables does not list a transition at
75' C.., i t is believed that the value is in accidental error and that
this has been copied into the handbook without checking.
CHROMIC OXIDE. No transition was observed in the case of
this solution, in agreement with a study by Kremann ( 7 ) .
Several of the salts exhibit equilibrium relative humidity
values which first decrease to a minimum value and then increase
slightly. These variations are due to slight deviations from
absolute linearity on the Clausius-Clapeyron plot, possibly due t o
associations in the solution.
LITERATURE CITED
(1) Am. Paper and Pulp Assoc., Instrumentation Program, Rept. 40
(Feb. 15,1945).
(2) Dingemans, P., Rec. traw. chim., 57,144-51, 703-9 (1938).
(3) Edgar, Graham, and Swan, W. O., J . Am. Chem. SOC.,44, 570-7
(1922).
(4) Forcrand, R. de, Compt. rend., 152,1073-7 (1911).
(5) Hartford, W. H., J . Am. Chem. SOC.,63, 1473-4 (1941).
(6) International Critical Tables, Vol. I, p. 68; Vol. 111, p. 211-12.
New York, McGraw-Hill Book Co., 1926.
(7) Kremann, R., Monatsh., 32,619-22 (1911).
(8) Lange, N. A., "Handbook of Chemistry," 5th ed., p. 1412.
Sandusky, Ohio, Handbook Publishers, 1945.
(9) Perry, J. H., "Chemical Engineers' Handbook," 2nd ed., p p .
456-72, New York, McGraw-Hill Book Co., 1934.
(10) Smith, A., and Menzies, A. W. C., J . Am. Chem. SOC.,32,907-14
(1910).
RECEIVED
August 26, 1948.
adipic acids, a straight line is produced when the t e m -
perature at which the acid has a given solubility is plotted
against the temperature at which succinic acid has the
same solubility. The danger of employing Diihring's
rule when only two or three values for the solubility of a
particular compound are known is stressed.
corresponding density data are given. The solubility of adipic
acid at 40" C. has been reported by Bancroft and Butler ( 1 )
and a t 100" by Schrauth ( 1 2 ) .
It was decided to determine the solubilities of glutaric, adipic,
and B-methyladipic acids a t several different temperatures and to
test the applicability of Duhring's rule t o the solubilities of sev-
eral dicarboxylic acids. For the latter purpose, solubility data
were taken from the literature for oxalic (7), malonic ( 6 ) , maleic,
fumaric, and i-malic ( 9 , 16), d- or 2-tartaric acid ( g ) , and succinic