Designation: E 104 – 02

Standard Practice for

Maintaining Constant Relative Humidity by Means of
Aqueous Solutions1
This standard is issued under the fixed designation E 104; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.

This standard has been approved for use by agencies of the Department of Defense.

1. Scope 2.2 Other Document:

1.1 This practice describes one method for generating con- DIN50008 “Konstantklimate uber waesserigen Loseungen”
stant relative humidity (rh) environments in relatively small (Constant Climates Over Aqueous Solutions).
containers. Part 1: Saturated Salt and Glycerol Solutions.5
1.2 This practice is applicable for obtaining constant rela- 3. Terminology
tive humidities ranging from dryness to near saturation at
temperatures spanning from 0 to 50°C. 3.1 non-hygroscopic material—material which neither ab-
1.3 This practice is applicable for closed systems such as sorbs nor retains water vapor.
environmental conditioning containers and for the calibration 3.2 For definitions of other terms used in this practice refer
of hygrometers. to Terminology D 1356.
1.4 This practice is not recommended for the generation of 4. Summary of Practice
continuous (flowing) streams of constant humidity unless
precautionary criteria are followed to ensure source stability. 4.1 Standard value relative humidity environments are gen-
(See Section 9.) erated using selected aqueous saturated salt solutions.
1.5 Caution—Saturated salt solutions are extremely corro- 5. Significance and Use
sive, and care should be taken in their preparation and
handling. There is also the possibility of corrosive vapors in the 5.1 Standard value relative humidity environments are im-
atmospheres over the saturated salt solutions.2 portant for conditioning materials in shelf-life studies or in the
1.6 This standard does not purport to address all of the testing of mechanical properties such as dimensional stability
safety concerns, if any, associated with its use. It is the and strength. Relative humidity is also an important operating
responsibility of the user of this standard to establish appro- variable for the calibration of many species of measuring
priate safety and health practices and determine the applica- instruments.
bility of regulatory limitations prior to use. For more specific 6. Interferences
safety precautionary information see 1.5 and 10.1.
6.1 Temperature regulation of any solution-head space en-
2. Referenced Documents vironment to 60.1°C is essential for realizing generated
2.1 ASTM Standards: relative humidity values within 60.5 % (expected).
D 1193 Specification for Reagent Water3 6.2 Some aqueous saturated salt solutions change composi-
D 1356 Terminology Relating to Sampling and Analysis of tion following preparation by hydrolysis or by reaction with
Atmospheres4 environmental components (for example, carbon dioxide ab-
sorption by alkaline materials). These solutions should be
freshly prepared on each occasion of use.
1
This practice is under the jurisdiction of ASTM Committee D22 on Sampling
and Analysis of Atmospheres and is the direct responsibility of Subcommittee 7. Apparatus
D22.11 on Meteorology. 7.1 Container—The container, including a cover or lid
Current edition approved October 10, 2002. Published December 2002. Origi-
nally published as E 104 – 51. Last previous edition E 104 – 85(96). which can be secured airtight, should be made of corrosion
2
Opila, R., Jr., Weschler, C. J., and Schubert, R., “Acidic Vapors Above
Saturated Salt Solutions Commonly Used for Control of Humidity,” IEEE Trans.
Components, Hybrids and Manufacturing Technology, Vol 12, No. 1, March 1989,
5
pp. 114–120. Published by Deutsches Institut für Normung, 4-10 Burggrzfenstrasse Postfach
3
Annual Book of ASTM Standards, Vol 11.01. 1107, D-1000 Berlin, Federal Republic of Germany. Also available from ANSI
4
Annual Book of ASTM Standards, Vol 11.03. Publication Office, New York, NY.

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 E 104 – 02
resistant, non-hygroscopic material such as glass. A metal or 9.2 The container should be small to minimize the influence
plastic container is acceptable if the solution is retained in a of any temperature variations acting upon the container and
dish or tray made of appropriate material. Refer also to 9.2 for contents. A maximum proportion of 25 cm3 volume/cm2 of
size restrictions. solution surface area is suggested, and overall container
headspace volume should be no larger than necessary to
8. Reagents and Materials confine a stored item.
8.1 Purity of Reagents—Reagent grade chemicals shall be 9.3 Measurement accuracy is strongly dependent on the
used for preparation of all standard solutions. Unless otherwise ability to achieve and maintain temperature stability during
indicated, it is intended that all reagents conform to the actual use of any solution system. Temperature instability of
specifications of the Committee on Analytical Reagents of the 60.1°C can cause corresponding instabilities in generated
American Chemical Society where such specifications are values of relative humidity of 60.5 %.
available.6 Other grades may be used, provided it is first 9.4 The compatibility of any constant relative humidity
ascertained that the reagent is of sufficiently high purity to system used for instrument calibration testing should be
permit its use without lessening the accuracy of the determi- confirmed by reference to the instrument manufacturer’s in-
nation. structions.
8.1.1 Saturated salt solutions may be prepared using either 9.5 Important considerations leading to stability should
amorphous or hydrated reagents (that is, reagents containing include (but are not necessarily limited to) the following:
water of crystallization). Hydrated reagents are often preferred 9.5.1 Elimination of leakage paths.
to amorphous forms for their solvating characteristics. 9.5.2 Elimination of heat sources or heat sinks, or both, for
8.2 Purity of Water—Reagent water produced by distilla- temperature stability.
tion, or by ion exchange, or reverse osmosis followed by 9.5.3 Limiting flow rate to preclude source carry-over.
distillation shall be used. See Specification D 1193.
8.3 Nomenclature for Salts—The proper nomenclature for 10. Preparations of Aqueous Solutions
the Humidity Fixed Point (HFP) salt chemicals and the 10.1 Caution—Some saturated salt-water systems should
corresponding acceptable temperature ranges are provided in be regarded as hazardous materials. Refer to 1.5 and 1.6 for
Table 1. The scale encompasses relative humidity ranges from guidelines.
2 % to 98.5 % and a temperature range from 5°C to 80°C. 10.2 Saturated Salt-Water Systems:
When the salt solutions are used at temperatures above 40°C, 10.2.1 Select a salt of characteristic value from Annex A1.
the risk of salt crystals settling on the surface rather than being The reference document by Greenspan7 contains information
immersed in the solution must be taken into account. on many other saturated salt solutions which may be used.
These additional systems, however, are less accurately or less
9. Technical Precautions completely defined in value. Also, some may only be used
9.1 Although a container capable of airtight closure is when freshly prepared (to limit the influence of chemical
described in Section 7, it may be desirable to have a vent under instability such as hydrolysis or acid gas absorption). The salts
certain conditions of test or with some kinds of containers listed in Annex A1 can be used for a year or more.
(changes in pressure may produce undesirable cracks in some 10.2.2 Place a quantity of the selected salt in the bottom of
types of containers). The vent should be as small as practical to a container or an insert tray to a depth of about 4 cm for low
minimize loss of desired equilibrium conditions when in use. rh salts, or to a depth of about 1.5 cm for high rh salts.
10.2.3 Add water in about 2-mL increments, stirring well
after each addition, until the salt can absorb no more water as
evidenced by free liquid. Although a saturated solution system
6
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory 7
Greenspan, L., “Humidity Fixed Points of Binary Saturated Aqueous Solu-
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia tions,” Journal of Research, National Institute of Standards and Technology, Vol.
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, 81A, 1977, pp. 89–96.
MD.
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TABLE 1 Humidity Fixed Point (HFP) Salt Solutions

HFP Designation Salt Name Chemical Symbol Temperature Range (°C)
HFP 4 Caesium fluoride CsF 15 to 80
HFP 7 Lithium bromide LiBr 5 to 80
HFP 12 Lithium chloride LiCl 5 to 80
HFP 23 Potassium acetate CH3COOK 10 to 30
HFP 33 Magnesium chloride MgCl2 5 to 80
HFP 43 Potassium carbonate K2CO3 5 to 30
HFP 59 Sodium bromide NaBr 5 to 80
HFP 70 Potassium iodide KI 5 to 80
HFP 75 Sodium chloride NaCl 5 to 80
HFP 85 Potassium chloride KCl 5 to 80
HFP 98 Potassium sulfate K2SO4 5 to 50

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 E 104 – 02
is defined when any excess quantity of undissolved solute is figures associated with each source value, as stated in the
present, it is preferred to keep the excess liquid present to a Annex tables. In actual use, lack of temperature equilibrium
minimum for ease in handling and for minimal impact on (60.5°C) and other functional losses can reduce the bias
stability should temperature variations occur. statement to 62.5 %. Precision is 60.5 % rh.
10.2.4 Close the container and allow 1 h for temperature
stabilization. 12. Keywords
10.2.5 The container may be used as a reservoir from which
quantities of slush can be transferred for use, or the entire 12.1 aqueous solution; constant relative humidity; control of
container may be used for conditioning tests. relative humidity; equilibrium relative humidity; humidity;
relative humidity; saturated salt solutions
11. Precision and Bias
11.1 Under ideal conditions, the bias (accuracy) of the
sources generated by this practice are equal to the uncertainty

ANNEX

(Mandatory Information)

A1. EQUILIBRIUM RELATIVE HUMIDITY VALUES FOR SELECTED SATURATED AQUEOUS SALT SOLUTIONS

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TABLE A1.1 Equlibrium Relative Humidity Values for Selected Saturated Aqueous Salt Solutions
HFP values according to Greenspan (ref-more refs needed from pH table)
t HFP4 HFP7 HFP12 HFP23 HFP33 HFP43 HFP59 HFP70 HFP75 HFP85 HFP98
(°C) Caesium Lithium Lithium Potassium Magnesium Potassium Sodium Potassium Sodium Potassium Potassium
fluoride bromide chloride acetate chloride carbonate bromide iodide chloride chloride sulfate
5 — 7.4 6 0.8 13 (11.2 - 14.0) — 33.6 6 0.3 43.1 6 0.5 63.5 6 0.8 73.3 6 0.4 75.7 6 0.3 87.7 6 0.5 98.5 6 1.0
10 — 7.1 6 0.7 13 (11.3 - 14.3) 23.4 6 0.6 33.5 6 0.3 43.1 6 0.4 62.2 6 0.6 72.1 6 0.4 75.7 6 0.3 86.8 6 0.4 98.2 6 0.8
15 4.3 6 1.4 6.9 6 0.7 12 (11.3 - 13.8) 23.4 6 0.4 33.3 6 0.3 43.2 6 0.4 60.7 6 0.6 71.0 6 0.3 75.6 6 0.2 85.9 6 0.4 97.9 6 0.7
20 3.8 6 1.1 6.6 6 0.6 12 (11.1 - 12.6) 23.1 6 0.3 33.1 6 0.2 43.2 6 0.4 59.1 6 0.5 69.9 6 0.3 75.5 6 0.2 85.1 6 0.3 97.6 6 0.6
25 3.4 6 1.1 6.4 6 0.6 11.3 6 0.3 22.5 6 0.4 32.8 6 0.2 43.2 6 0.4 57.6 6 0.4 68.9 6 0.3 75.3 6 0.2 84.2 6 0.3 97.3 6 0.5

4
30 3.0 6 0.8 6.2 6 0.5 11.3 6 0.3 21.6 6 0.6 32.4 6 0.2 43.2 6 0.5 56.0 6 0.4 67.9 6 0.3 75.1 6 0.2 83.6 6 0.3 97.0 6 0.4
35 2.7 6 0.7 6.0 6 0.5 11.3 6 0.3 — 32.1 6 0.2 — 54.6 6 0.4 67.0 6 0.3 74.9 6 0.2 83.0 6 0.3 96.7 6 0.4
40 2.4 6 0.6 5.8 6 0.4 11.2 6 0.3 — 31.6 6 0.2 — 53.2 6 0.5 66.1 6 0.3 74.7 6 0.2 82.3 6 0.3 96.4 6 0.4
45 2.2 6 0.5 5.7 6 0.4 11.2 6 0.3 — 31.1 6 0.2 — 52.0 6 0.5 65.3 6 0.3 74.5 6 0.2 81.7 6 0.3 96.1 6 0.4
50 2.1 6 0.4 5.5 6 0.4 11.1 6 0.3 — 30.5 6 0.2 — 50.9 6 0.6 64.5 6 0.3 74.5 6 0.9 81.2 6 0.4 95.8 6 0.5
E 104 – 02

55 2.0 6 0.4 5.4 6 0.3 11.0 6 0.3 — 29.9 6 0.2 — 50.2 6 0.7 63.8 6 0.3 74.5 6 0.9 80.7 6 0.4 —
60 2.0 6 0.4 5.3 6 0.3 11.0 6 0.3 — 29.3 6 0.2 — 49.7 6 0.8 63.1 6 0.4 74.4 6 0.9 80.3 6 0.5 —
65 2.1 6 0.5 5.3 6 0.3 10.9 6 0.3 — 28.5 6 0.3 — 49.5 6 1.0 62.5 6 0.4 74.2 6 0.9 79.9 6 0.5 —
70 2.2 6 0.6 5.2 6 0.3 10.8 6 0.4 — 27.8 6 0.3 — 49.7 6 1.1 61.9 6 0.3 74.1 6 0.9 79.5 6 0.6 —
75 2.4 6 0.7 5.2 6 0.3 10.6 6 0.4 — 26.9 6 0.3 — 50.3 6 1.3 61.4 6 0.5 74.0 6 0.9 79.2 6 0.7 —
80 2.6 6 0.8 5.2 6 0.3 10.5 6 0.5 — 26.1 6 0.4 — 51.4 6 1.5 61.0 6 0.5 73.9 6 0.9 78.9 6 0.8 —

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