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The relative humidities maintained over saturated and unsaturated salt solutions and of some salt hydrate
mixtures have been collated from the literature over a wide range of temperature. Results are presented for
38 saturated salt solutions, and details listed for salts which are recommended as suitable for humidity con-
trol. The control of humidity in the laboratory by the use of salt solutions is critically discussed.
lntroduction 4@-65% R.H. The published data for the best salts in this
A control of atmospheric humidity is frequently required in region (KzC03.2H20 and CrO,) are conflicting and for this
the laboratory where it is desired to condition materials to a reason are not included in Table 1.
standard water content, to study the adsorption and de- In compiling these graphs, results from the source re-
sorption of moisture on powders, fibres, etc. and to study ferences (Table 11) have been plotted and a smoothed curve
hydration reactions under reproducible conditions. The drawn through the points. The self consistency of data and
traditional, and most convenient, means of providing stand- their agreement with independent determinations are taken
ard relative humidities covering a wide range of values is the as a measure of their reliability, and curves are weighted
use of salt solutions, either saturated or unsaturated, in towards the more reliable values. Dashed curves are drawn
small, sealed containers. Any salt solution at a definite where less reliable data only are available for a particular salt.
concentration and at constant temperature, is in equilibrium Unsaturated salt solutions
with a fixed partial vapour pressure of water and hence
Curves are given for the variation of relative humidity
defines a fixed relative humidity.
with concentration (Figs. 2 and 3) and temperature (Fig. 4)
However, humidity data quoted in standard reference for a few salt solutions and for sulphuric acid solutions,
works such as ‘International Critical Tables” come from
which have often been used in humidity control. An ex-
very early sources and subsequent work shows quoted values haustive list has not been given since unsaturated solutions
to be largely inaccurate. More comprehensive lists of rela- are less attractive than saturated solutions for humidity
tive humidities over saturated salt solution^^-^ have ap- control.
peared in the literature to serve as a practical guide for
science and industry. Again these compilations prove in- Salt hydrate pairs
adequate for many purposes, data being given for only one A mixture of two salt hydrates has a fixed relative hu-
temperature or a narrow temperature range, and in some midity at any given temperature as long as both hydrates are
cases being of doubtful reliability. present. Some hydrate mixtures for which humidity values
In recent years there have been several independent deter- have been measured are listed in Table 111. Of a large num-
m i n a t i o n ~ ’ ~ , ~ ~of, ’ the
~ , ~relative
~ , ’ ~ humidities in equili- ber of hydrate pairs considered’ only a few are suitable as
brium over a large number of saturated salt solutions and humidifying agents.
covering a wide range of temperature. These results have
been collected together and collated with earlier results and
Factors affecting salt solutions as humidity controls
are represented in the accompanying graphs and tables to
enable research workers to choose the salt solutions that best The use of saturated salt solutions to control relative
suit their particular needs. Some data on the relative humidi- humidity is both a convenient and a cheap method. Most
ties in equilibrium over unsaturated salt solutions and salt reagents are readily available in reasonable purity, are safe
hydrate pairs are also presented. to handle and are involatile, thus avoiding contamination
of the specimen. Acheson18 considers that salt impurities
below I have little effect on the R.H. values; but im-
Relative humidity values purities in lithium chloride may cause variations in its
Saturated salt solutions equilibrium relative humidity of several per cent. l 6
The accompanying graphs (Fig. 1) show the variation Most salt solutions are quite stable; but care should be
of relative humidity with temperature over 38 saturated salt taken to avoid using solutions at temperatures near the
solutions. It is considered that all solutions for which useful transition points where new hydrates are formed, since
data is available have been included. From these graphs, temperature variations will not then be linear. The transition
salts can be chosen whose equilibrium relative humidities points for those salts which form other hydrates are listed
have a low temperature coefficient and a linear variation in Table IV.
with temperature. Table I lists the saturated salt solutions Saturated salt solutions can liberate or adsorb large
which are recommended for the best control of humidity; quantities of water without changing the equilibrium hu-
also included are temperature coefficients and the range of midity. However, the same is not true of unsaturated solu-
temperatures for which they can be used with reliability. tions where large changes in water content will appreciably
The list has been compiled to cover the complete range of alter the concentration and hence the relative humidity.
humidity values; but it should be noted that there is a lack This may cause difficulty in preparing solutions of exact con-
of salts with low temperature coefficients in the region centrations.28 Nevertheless, by varying concentration, a
J. appl. Chem., 1967,Vol. 17, September
A
242 Young: Humidity Control in the Laboratory using Salt Solutions-A Review
-20 -10 o Y) m 30 LO 50 60 m 80
TEMPERATURE ,t
30-
L
1 4
TEMPERATURE, Oc
(f)
Fig. 1. Variation with temperature of relative humidities over saturated salt solutions
(Dashed curves indicate that only data of uncertain reliability are available)
TABLE 111
-1 Salt
Na2S04
ZnSO,
SrCI,
Relative humidities over some hydrate pairs
Hydrates
0+ 10
I +6
2+6
"/.R.H. at d (RH),
25"c
81
58,55
35
dT
0.89
0.73
0.50
oc
References
16,24-26
16, 25
5 , 11, 16
CH3COONa 0+3 27 0.45 5, 16,26
BaBr, 1 +2 15-5 0.40 11
NaI Of2 11 0.19 5 , 16
zo
Oxalic acid 0+2 11 0.16 24, 26
OO 10 a LO M 6Q ?I 80 90 SrBr, 2+6 8.7 0.20 5, 11
SULPHURIC ACID. wt -% ZnBr, 0+2 7.5 0.13 16
Fig. 2. Relative humidities over sulphuric acid solutions at 25"c CdSO4 O f1 2.1 0.07 16
Data from: ( x ) Ref. 4, (0) Ref. 19, (0) Ref. 20, ( A ) Ref. 21 Mg(N03)z 2+6 2.1 0-03 10
TABLE 1V
Transition temperatures of hydrates
Temperature,
Salt Transition OC References
NaOH H,O+anhydrous 64-3 9
LiCl 2H,O+H,O 18.8 9
CaCI, 6HzO+4HzO 29.4 9,11
4H.O+2H,O
- - - ----- 45.5
. _ 9. I 1
NaI 2H,O+anhydrous 68-1 12'
Ca(N03)* 4HzO+3HzO 42.1 8
MB(NO~)~ 6H,0+2H20 30.0
ko I 1
ia
I I
20
I I
30
I I
40 50
I I
60
I I
70
, i 80 Na,Cr,O, 2H,O+anhydrous 74.8
10
12
SOLUTE, wt.-%
NaBr 2H,O+anhydrous 50.6 12
Sr(N0J2 4H,O+anhydrous 3 1.3 27
Fig. 3. Variation of relative humidity with concentration for some SKI, 6H2O+2H,O 61.5 11
salt solutions at 25'c SrBr, 6H,O+H,O 88.0 11
(a) NaOH. H20(Ref. 4), (b) MgC1,.6H20 (Ref. 22), (c) LiCl.H,O BaCl 2Hz0 +HZ0 101.9 11
(Ref. 23) BaBG 2HiO4H;O 107.9 11
cuso4 ~HzO+~H~O 95.9 11
Observing the above precautions, the relative humidity Collins, E. M., & Menzies, A. W. C., J. phys. Colloid Chem.,
above a salt solution can be considered to be at least within 1935, 40, 379
lZ Carr, D. S., & Harris, B. L., id.Engng Chem. ind. (int.) Edn.,
2 % of the nominal humidity, which should be sufficient for 1949,41, 2014
most purposes. When a inore accurate control of relative l 3 Wink, W. A., & Sears,G . R., TAPPI, 1950,33,96
humidity is needed, much more attention must be paid to l 4 Johnson, E. F., & Molstad, M. C., J. phys. Colloid Chem., 1951,
cc 1c7
the design of the chamber and t o the control of the experi- JJ, L J I
l3 Wexler, A., & Hasegawa, S., J. Res. natn. Bur. Stand., 1954,
mental variables. In such cases it is desirable t o measure the 53A, 19
actual relative humidity of the chamber under operating I h Wylie, R. G. in ‘Humidity and Moisture. Vol. 3. Fundamentals
conditions by some direct method. and Standards’, (Eds. Wexler, A., & Wildhack, W. A.), 1965,
p. 507 (New York: Reinhold Publ. Co.)
Chemistry Division, Hedlin, C. P., & Trofirnenkoff, E. N., Ref. 16, p. 519
I n Acheson, D. T., Ref. 16, p. 521
D.S.I.R., l 9 ‘international Critical Tables’, 1928, Vol. 111, p. 303 (New York:
Petone, McGraw-Hill Book Co.)
New Zealand zo Shankman, S., & Gordon, A. E., J. Am. chem. Sue., 1939, 61,
2370
Received 18 April, 1967. 21 Greenwalt, C. H., J. Ind. Engng Chem., 1925,13, 522
z 2 Stokes, R. H., Trans. Faruaizy Soc., 1945,51,642
23 Robinson, R. A., Trans. Faraday Sac., 1945,51,756
References 24 Baxter, G . P., & Lansing, J. E., J. Am. chem. Soc., 1920, 42,
‘International Critical Tables’, 1926, Vol. 1, p. 67 (New York: 419
McGraw-Hill Book Co.) 2 5 Wilson, R.E., J. Am. chem. SOC., 1921,43,704
Burns, R., Bell Teleph. Syst. tech. Publs, Monogr. 8-986,1937 2 6 Baxter, G. P., & Cooper, W. C., J. Am. chem. Suc., 1924, 46,
OBrien, F. E. M., J. scient. Instrum., 1948, 25, 73 923
(a) Stokes, R. H., & Robinson, R. A., Ind. Engng Chem. ind. 2 7 Sidewick. N. V
-
.3
.. ‘Chemical Elements and their Comoounds’.
(int.) Edn., 1949, 41, 2013; (b) Robinson, R. A., & Stokes, 1950, 901.I, p: 256 (London: Oxford Univ. Press)
R. H., ‘Electrolytic Solutions’, 1959, 2nd Edn, (London: 2 * Schlunder, E. W., Ref. 16, p. 535
Butterworths Scientific Publs) 2 9 Kawasaki, K., & Kanou, K., Ref. 16, p. 531
Richardson, G. M., & Malthus, R. S., J. appl. Chem., Lund., 30 Pray, R. E., & Schieltz, N. C., J. Colloid Interface Sci., 1966, 21,
1955,5,557 353
Edgar, G., & Swan, W. O., 1. Am. chem. Soc., 1922, 44, 570 st DArcy, R. L., &Watt, I. C., J. Text. Inst., 1966, 57, T416
Leopold, H. G., & Johnston, J., J. Am. chem. Soc., 1927, 49, 32 Menzies, A, W. C., & Hitchcock, C. S., J. phys. CoNoid Chem.,
1974 1931, 35, 1662
Ewing, W. W., J. Am. chem. SOC.,1927, 49, 1963 3 3 Martin, S., Ref. 16, p. 503
Adams, J. R., & Merz, A. R., J. ind. Engng Chem., 1929,21, 305 34 (a) Copeland, L. E., & Hayes, J. C., Bull. Am. SOC.Test. Mater.,
l o Ewing, W. W., Klinger, E., & Brandner, J. D., J. Am. chern. 1953, No. 194, 70; (b) Brunauer, S., Hayes, J. C., & Hass,
SOC., 1934,56, 1053 W. E., J. phys. Chem., Ithaca, 1954,58,279