Young: Humidity Control in the hhoratory using Salt Solutions-A

Review

24 1

HUMIDITY CONTROL IN THE LABORATORY USING

SALT SOLUTIONS-A REVIEW
By J. F. YOUNG

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 control. The control of humidity in the laboratory by the use of salt solutions is critically discussed.

lntroduction
A control of atmospheric humidity is frequently required in

the laboratory where it is desired to condition materials to a

standard water content, to study the adsorption and desorption of moisture on powders, fibres, etc. and to study
hydration reactions under reproducible conditions. The
traditional, and most convenient, means of providing standard relative humidities covering a wide range of values is the
use of salt solutions, either saturated or unsaturated, in
small, sealed containers. Any salt solution at a definite
concentration and at constant temperature, is in equilibrium
with a fixed partial vapour pressure of water and hence
defines a fixed relative humidity.
However, humidity data quoted in standard reference
works such as International Critical Tables come from
very early sources and subsequent work shows quoted values
to be largely inaccurate. More comprehensive lists of relative humidities over saturated salt solution^^-^ have appeared in the literature to serve as a practical guide for
science and industry. Again these compilations prove inadequate for many purposes, data being given for only one
temperature or a narrow temperature range, and in some
cases being of doubtful reliability.
In recent years there have been several independent determ i n a t i o n ~ ~ , ~ ~of, the
~ , ~relative
~ , ~ humidities in equilibrium over a large number of saturated salt solutions and
covering a wide range of temperature. These results have
been collected together and collated with earlier results and
are represented in the accompanying graphs and tables to
enable research workers to choose the salt solutions that best
suit their particular needs. Some data on the relative humidities in equilibrium over unsaturated salt solutions and salt
hydrate pairs are also presented.
Relative humidity values
Saturated salt solutions
The accompanying graphs (Fig. 1) show the variation
of relative humidity with temperature over 38 saturated salt
solutions. It is considered that all solutions for which useful
data is available have been included. From these graphs,
salts can be chosen whose equilibrium relative humidities
have a low temperature coefficient and a linear variation
with temperature. Table I lists the saturated salt solutions
which are recommended for the best control of humidity;
also included are temperature coefficients and the range of
temperatures for which they can be used with reliability.
The list has been compiled to cover the complete range of
humidity values; but it should be noted that there is a lack
of salts with low temperature coefficients in the region
J. appl. Chem., 1967,Vol. 17, September
A

4@-65% R.H. The published data for the best salts in this

region (KzC03.2H20 and CrO,) are conflicting and for this

reason are not included in Table 1.
In compiling these graphs, results from the source references (Table 11) have been plotted and a smoothed curve
drawn through the points. The self consistency of data and
their agreement with independent determinations are taken
as a measure of their reliability, and curves are weighted
towards the more reliable values. Dashed curves are drawn
where less reliable data only are available for a particular salt.
Unsaturated salt solutions
Curves are given for the variation of relative humidity
with concentration (Figs. 2 and 3) and temperature (Fig. 4)
for a few salt solutions and for sulphuric acid solutions,
which have often been used in humidity control. An exhaustive list has not been given since unsaturated solutions
are less attractive than saturated solutions for humidity
control.

Salt hydrate pairs

A mixture of two salt hydrates has a fixed relative humidity at any given temperature as long as both hydrates are
present. Some hydrate mixtures for which humidity values
have been measured are listed in Table 111. Of a large number of hydrate pairs considered only a few are suitable as
humidifying agents.
Factors affecting salt solutions as humidity controls
The use of saturated salt solutions to control relative
humidity is both a convenient and a cheap method. Most
reagents are readily available in reasonable purity, are safe
to handle and are involatile, thus avoiding contamination
of the specimen. Acheson18 considers that salt impurities
have little effect on the R.H. values; but imbelow I
purities in lithium chloride may cause variations in its
equilibrium relative humidity of several per cent. l 6
Most salt solutions are quite stable; but care should be
taken to avoid using solutions at temperatures near the
transition points where new hydrates are formed, since
temperature variations will not then be linear. The transition
points for those salts which form other hydrates are listed
in Table IV.
Saturated salt solutions can liberate or adsorb large
quantities of water without changing the equilibrium humidity. However, the same is not true of unsaturated solutions where large changes in water content will appreciably
alter the concentration and hence the relative humidity.
This may cause difficulty in preparing solutions of exact concentrations.28 Nevertheless, by varying concentration, a

Young: Humidity Control in the Laboratory using Salt Solutions-A Review

242

-20

-10

Y)

30

LO

50

60

80

TEMPERATURE ,t

30
L

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)

J. appl. Chem., 1967, Vol. 17, September

Young: Humidity Control in the Laboratory using Salt Solutions-A

Review

243

TABLE
I
Saturated salt solutions recommended for humidity control

% R.H.

Temperature d(RH)
range, "c 2T' %per "'

Salt
Na0H.H 20

15-25
3045

LiC1.2Hz0

KNOT
Mg(N0,).6Hz0

Na2Crz0,.2H,0
NaBr.2H20
NaNO,

7.0
-

0.00

-0.07

- 10-15
20-70
50-80
-10-30
10-50
5-35
2040
0-50
G50
- 10-35
20-40
10-30

LiCI.H,O

at 25"c

-0.17

-0.01

11.3
22.2
32.7
39.2
48.2
52.8
53.7
58.2
644
68.4
75.1
80.2
84.2
86.5
90.3
92.7
97.0
97.2

+0.03

-0.12
- 0.06
-0.32
-0.18
- 0.29
- 0.27
- 0.28
-0.19
0.00
- 0.02
- 0.07
-0.16
- 0.06
- 0.08
-0.12
- 0.05

5-60

25-50

5-40

2040
5-60
2-5

15-60

- 0.05

2540

Comparisons of % R.H. at 2%
Ref. 1
Ref. 3
Ref. 4
-

15*

20*
-

45*

52
52*
58*
81
88*
88
93
-

6.5

13
19
33

45*
52
52*
57
66
75-76'5
81-89
84-5-89
88*
88
93
100

* "/, R.H. at 20"c

TABLEI1
Source references for relative humidities over saturated salt solutions
Compound

References

KZSOJ
CUSO4.5H,O

3, 7, 9, 15
11
13
2,4, 11, 18

(NH,)H,PO,
BaCIZ.2H,0

Compound
KI

NaNO,
SrBr2.6H,0
NaBr, .2H20

References
12, 18
3, 12, 13
11
2 4 12, 13,
17
-.

3-5, 10, 13,

17, 18
3, 6, 9
5,12,13,15

NaCl

4 7,9,
11-13, IS,

3,5, 13

18
~~

11
17
2-4,6,9,
18

Ca(N0,),.4H20
KNO2
18 K,CO,.ZH,O

18

CrO,
NaT.2H,O

K Br

NH,CI

CaCl,.6H ,O
18
2,4,12,18 CaBG.6H;O
3,4,6,9, 17 MgCI2.6H,O

CH,COO.Na.

3, 13

3HzO
SrCl .6H,O

11, 18

CH,COOK.
I .5H20
LiC1.H 20

NaNO

3.4.6.12.18
. ,

NaOH.H,O

2,3,8,9,17
3, 13
2-5, 13
12, 13
5, 12, 17, 18
2-5, 11, 18
5 , 17
2-5, 13, 15,
17, 18
5 , 13, 17
2-5, 13-15,
17, 18
3-5. I8

single salt solution can be used to maintain a wide range of

relative humidities.
Sulphuric acid solutions can provide solutions with
equilibrium relative humidity values from &95 % with low
temperature coefficients. Solutions are readily prepared
directly by dilution and the concentration checked by specific
gravity measurements. However, the corrosiveness of the acid
must be guarded against. Recent measurementsZ2have shown
a detectable volatility of sulphuric acid, especially at low
humidities, that can modify the properties of cement3' and
J. appl. Chem., 1967, Vol. 17, September

w00l.~' Therefore, when surface properties are to be investigated, the use of sulphuric acid must be avoided.
Salt hydrate pairs are a third alternative of controlling
relative humidities since systems can be chosen to cover the
full range (see Table 111). However there are disadvantages'
which limit the use of hydrate pairs to very low humidities
(<7%) or to special conditions where the presence of a
liquid phase might be undesirable.
Effect of samples on relative humidities
Although saturated salt solutions can, in theory, handle
large changes in water content without affecting their equilibrium values, it has been found in practice that where
samples absorb moisture a p p r e ~ i a b l y ,the
~ ~ actual relative
humidity over a salt solution remains lower than the true
equilibrium value. A rate of adsorption as low as 4 mg./h
will depress the relative humidity over saturated ammonium
nitrate at 20" (65% R.H.) by 2%33even when a circulation
of air is maintained. For strongly adsorbing materials the
relative humidity may initially be depressed by several tens
of percent and take several days or weeks to come to equilibrium. It has probably not been generally recognised that
these effects can be of such magnitude.
The time taken to achieve equilibrium is a major drawback
even when samples do not strongly adsorb (or liberate) water.
Fine powders have a large surface area and may consequently take a long time to equilibrate even though the rate
of adsorption or desorption is never large. Hardened cement
pastes which contain extensive networks of fine pores and
capillary spaces are an extreme example of this. Such
samples never reach a steady equilibrium at low humidities,34
although the rate of loss of water after one or two weeks is
less than 0.5 mg/g per day.
Design of a laboratory humidity chamber
Any conveniently sized, leak-proof container may be used
as a humidity chamber. Such a container is often an ordinary
desiccator, which has the advantage that it can be evacuated

244

Young: Humidity Control in the Laboratory using Salt Solutions-A

Review

TABLE
111
Relative humidities over some hydrate pairs

-1
zo

10

OO

LO

SULPHURIC ACID.

?I

6Q

80

90

wt -%

Salt

Hydrates

Na2S04
ZnSO,
SrCI,
CH3COONa
BaBr,
NaI
Oxalic acid
SrBr,

0+ 10

NaOH
LiCl
CaCI,

1
ia

I
20

I
30

40

50

, i

I
70

60

NaI
Ca(N03)*
MB(NO~)~
Na,Cr,O,
NaBr
Sr(N0J2

80

SOLUTE, wt.-%

Fig. 3. Variation of relative humidity with concentration for some

salt solutions at 25'c
(a) NaOH. H20(Ref. 4), (b) MgC1,.6H20 (Ref. 22), (c) LiCl.H,O
(Ref. 23)

L l
0'

10

20

40

TEMPERATURE.

70%
I

50

~
60

70

1
80

Oc

Fig. 4. Variation with temperature of relative humidity over lithium

chloride and sulphuric acid solutions

Figures on curves indicate percentage by weight of solutc

- - _ _ _ LiCI (from Ref. 14)
____HZS04(from Ref. 19)
to avoid contamination by atmospheric gases. It must be
borne in mind, however, that the presence of air over the
solution affects the water vapour pressure16 and therefore
there will be a difference between the equilibria relative
humidity values over any salt solution under vacuum or at
atmospheric pressure. The differences are only a few tenths
of a percent and may be ignored for all but precise work; but
the solution of gas in a salt solution which may react chemically, e.g. carbon dioxide, may appreciably affect the values.
It may be noted that many relative humidity measurements
have been made under practical operating conditions using
reagent grade salts and atmospheric pressure.

SKI,

SrBr,
BaCl
BaBG

cuso4

+2
2+6

2+6

0.89
0.73

15-5

0.45
0.40

11
11

Of2

Mg(N03)z

81
58,55
35

27

0+3
1 +2

0+2
O f1

Salt

ko I

I +6
2+6

ZnBr,

CdSO4

Fig. 2. Relative humidities over sulphuric acid solutions at 25"c

Ref. 19, (0)
Ref. 20, ( A ) Ref. 21
Data from: ( x ) Ref. 4, (0)

"/.R.H. at d (RH),
25"c
dT

8.7
7.5
2.1

2.1

0.50

oc

References
16,24-26
16, 25
5 , 11, 16
5, 16,26
11

0.19
0.16
0.20

24, 26

0.13
0.07
0-03

16
10

TABLE
1V
Transition temperatures of hydrates
Temperature,
OC
Transition

5 , 16
5, 11

16

References
9

H,O+anhydrous
2H,O+H,O

64-3
18.8

4H.O+2H,O
- - - -----

45.5
. _

9. I 1

6HzO+4HzO

2H,O+anhydrous
4HzO+3HzO
6H,0+2H20
2H,O+anhydrous
2H,O+anhydrous
4H,O+anhydrous
6H2O+2H,O
6H,O+H,O
2Hz0 +HZ0

2HiO4H;O
~HzO+~H~O

29.4

68-1
42.1
30.0
74.8
50.6
3 1.3

61.5

88.0
101.9

107.9
95.9

9,11

12'
8
10

12
12
27
11
11
11

11
11

Wexler & Hasegawa15 list precautions which should be

observed in setting up humidity chambers with saturated
salt solutions in order that theoretical values may be used
with confidence, and that equilibrium shall be achieved in a
reasonable time. The following points are of importance:
(I) The chamber should be made of non-hygroscopic
materials to prevent adsorption of moisture by the walls
with a consequent delay in achieving equilibrium. It
should be remembered that concentrated salt solutions
should be kept out of contact with metals to avoid corrosion.
(2) The chamber should be leak proof.
(3) The whole chamber and its contents should be brought
to thermal equilibrium and kept at constant temperature.
Even for salt solutions with small temperature coefficients
it is important to keep the temperature constant.
(4) The salt solution should have as large a surface area as is
practical.
( 5 ) Some means of circulating the air should be provided;
alternatively the chamber should be evacuated. A fan
motor should be mounted outside the chamber to avoid
internal heating.
The principal factors determining the time to reach equilibrium are: (a) the ratio of free surface area of solution to
chamber volume, (b) the amount of air circulation, (c) the
absorbing properties of the sample, and (d) the agitation of
the salt solution-diffusion controlled mixing results in concentration gradients.
J. appl. Chem., 1967, Vol. 17, September

Young: Humidity Control in the Laboratory using Salt Solutions-A

Observing the above precautions, the relative humidity
above a salt solution can be considered to be at least within
2 % of the nominal humidity, which should be sufficient for
most purposes. When a inore accurate control of relative
humidity is needed, much more attention must be paid to
the design of the chamber and t o the control of the experimental variables. In such cases it is desirable t o measure the
actual relative humidity of the chamber under operating
conditions by some direct method.
Chemistry Division,
D.S.I.R.,
Petone,
New Zealand
Received 18 April, 1967.

References
International Critical Tables, 1926, Vol. 1, p. 67 (New York:
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Burns, R., Bell Teleph. Syst. tech. Publs, Monogr. 8-986,1937
OBrien, F. E. M., J. scient. Instrum., 1948, 25, 73
(a) Stokes, R. H., & Robinson, R. A., Ind. Engng Chem. ind.
(int.) Edn., 1949, 41, 2013; (b) Robinson, R. A., & Stokes,
R. H., Electrolytic Solutions, 1959, 2nd Edn, (London:
Butterworths Scientific Publs)
Richardson, G. M., & Malthus, R. S., J. appl. Chem., Lund.,
1955,5,557
Edgar, G., & Swan, W. O., 1. Am. chem. Soc., 1922, 44, 570
Leopold, H. G., & Johnston, J., J. Am. chem. Soc., 1927, 49,
1974
Ewing, W. W., J. Am. chem. SOC.,1927, 49, 1963
Adams, J. R., & Merz, A. R., J. ind. Engng Chem., 1929,21, 305
l o Ewing, W. W., Klinger, E., & Brandner, J. D., J. Am. chern.
SOC.,
1934,56, 1053

J. appl. Chem., 1967, Vol. 17, September

Review

245

Collins, E. M., & Menzies, A. W. C., J. phys. Colloid Chem.,

1935, 40, 379
lZ Carr, D. S., & Harris, B. L., i
d.Engng Chem. ind. (int.) Edn.,
1949,41, 2014
l 3 Wink, W. A., & Sears,G . R., TAPPI, 1950,33,96
l 4 Johnson, E. F., & Molstad, M. C., J. phys. Colloid Chem., 1951,
cc
1c7
JJ, L J I

Wexler, A., & Hasegawa, S., J. Res. natn. Bur. Stand., 1954,
53A, 19
I h Wylie, R. G. in Humidity and Moisture. Vol. 3. Fundamentals
and Standards, (Eds. Wexler, A., & Wildhack, W. A.), 1965,
p. 507 (New York: Reinhold Publ. Co.)
Hedlin, C. P., & Trofirnenkoff, E. N., Ref. 16, p. 519
I n Acheson, D. T., Ref. 16, p. 521
l 9 international Critical Tables, 1928, Vol. 111, p. 303 (New York:
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zo Shankman, S., & Gordon, A. E., J. Am. chem. Sue., 1939, 61,
2370
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
24 Baxter, G . P., & Lansing, J. E., J. Am. chem. Soc., 1920, 42,
419
2 5 Wilson, R.E., J. Am. chem. SOC.,
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2 6 Baxter, G. P., & Cooper, W. C., J. Am. chem. Suc., 1924, 46,
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2 7 Sidewick. N. V
.. Chemical Elements and their Comoounds.
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2 * Schlunder, E. W., Ref. 16, p. 535
2 9 Kawasaki, K., & Kanou, K., Ref. 16, p. 531
30 Pray, R. E., & Schieltz, N. C., J. Colloid Interface Sci., 1966, 21,

l3

.
3

353

DArcy, R. L., &Watt, I. C., J. Text. Inst., 1966, 57, T416

32 Menzies, A, W. C., & Hitchcock, C. S., J. phys. CoNoid Chem.,
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st