Designation: E104 – 02 (Reapproved 2012)

Standard Practice for

Maintaining Constant Relative Humidity by Means of
Aqueous Solutions1
This standard is issued under the fixed designation E104; 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 (´) 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 D1356 Terminology Relating to Sampling and Analysis of

1.1 This practice describes one method for generating con- Atmospheres
stant relative humidity (rh) environments in relatively small 2.2 Other Document:
containers. DIN50008 “Konstantklimate uber waesserigen Loseungen”
1.2 This practice is applicable for obtaining constant rela- (Constant Climates Over Aqueous Solutions).
tive humidities ranging from dryness to near saturation at Part 1: Saturated Salt and Glycerol Solutions.4
temperatures spanning from 0 to 50°C. 3. Terminology
1.3 This practice is applicable for closed systems such as
environmental conditioning containers and for the calibration 3.1 non-hygroscopic material—material which neither ab-
of hygrometers. sorbs nor retains water vapor.
1.4 This practice is not recommended for the generation of 3.2 For definitions of other terms used in this practice refer
continuous (flowing) streams of constant humidity unless to Terminology D1356.
precautionary criteria are followed to ensure source stability. 4. Summary of Practice
(See Section 9.)
1.5 Caution—Saturated salt solutions are extremely corro- 4.1 Standard value relative humidity environments are gen-
sive, and care should be taken in their preparation and erated using selected aqueous saturated salt solutions.
handling. There is also the possibility of corrosive vapors in the 5. Significance and Use
atmospheres over the saturated salt solutions.2
1.6 This standard does not purport to address all of the 5.1 Standard value relative humidity environments are im-
safety concerns, if any, associated with its use. It is the portant for conditioning materials in shelf-life studies or in the
responsibility of the user of this standard to establish appro- testing of mechanical properties such as dimensional stability
priate safety and health practices and determine the applica- and strength. Relative humidity is also an important operating
bility of regulatory limitations prior to use. For more specific variable for the calibration of many species of measuring
safety precautionary information see 1.5 and 10.1. instruments.

2. Referenced Documents 6. Interferences

2.1 ASTM Standards:3 6.1 Temperature regulation of any solution-head space en-
D1193 Specification for Reagent Water vironment to 60.1°C is essential for realizing generated
relative humidity values within 60.5 % (expected).
6.2 Some aqueous saturated salt solutions change composi-
1
This practice is under the jurisdiction of ASTM Committee D22 on Air Quality tion following preparation by hydrolysis or by reaction with
and is the direct responsibility of Subcommittee D22.11 on Meteorology. environmental components (for example, carbon dioxide ab-
Current edition approved April 1, 2012. Published July 2012. Originally
approved in 1951. Last previous edition approved in 2007 as E104 - 02(2007). DOI: sorption by alkaline materials). These solutions should be
10.1520/E0104-02R12. freshly prepared on each occasion of use.
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,
pp. 114–120.
3
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
4
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM Published by Deutsches Institut für Normung, 4-10 Burggrzfenstrasse Postfach
Standards volume information, refer to the standard’s Document Summary page on 1107, D-1000 Berlin, Federal Republic of Germany. Also available from ANSI
the ASTM website. Publication Office, New York, NY.

Copyright. (C) ASTM International. 100 Barr Harbor Dr., P.O. Box C700 West Conshohocken, Pennsylvania 19428-2959, United States

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 E104 – 02 (2012)
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

7. Apparatus types of containers). The vent should be as small as practical to

7.1 Container—The container, including a cover or lid minimize loss of desired equilibrium conditions when in use.
which can be secured airtight, should be made of corrosion 9.2 The container should be small to minimize the influence
resistant, non-hygroscopic material such as glass. A metal or of any temperature variations acting upon the container and
plastic container is acceptable if the solution is retained in a contents. A maximum proportion of 25 cm3 volume/cm2 of
dish or tray made of appropriate material. Refer also to 9.2 for solution surface area is suggested, and overall container
size restrictions. headspace volume should be no larger than necessary to
confine a stored item.
8. Reagents and Materials 9.3 Measurement accuracy is strongly dependent on the
8.1 Purity of Reagents—Reagent grade chemicals shall be ability to achieve and maintain temperature stability during
used for preparation of all standard solutions. Unless otherwise actual use of any solution system. Temperature instability of
indicated, it is intended that all reagents conform to the 60.1°C can cause corresponding instabilities in generated
specifications of the Committee on Analytical Reagents of the values of relative humidity of 60.5 %.
American Chemical Society where such specifications are 9.4 The compatibility of any constant relative humidity
available.5 Other grades may be used, provided it is first system used for instrument calibration testing should be
ascertained that the reagent is of sufficiently high purity to confirmed by reference to the instrument manufacturer’s in-
permit its use without lessening the accuracy of the determi- structions.
nation. 9.5 Important considerations leading to stability should
8.1.1 Saturated salt solutions may be prepared using either include (but are not necessarily limited to) the following:
amorphous or hydrated reagents (that is, reagents containing 9.5.1 Elimination of leakage paths.
water of crystallization). Hydrated reagents are often preferred 9.5.2 Elimination of heat sources or heat sinks, or both, for
to amorphous forms for their solvating characteristics. temperature stability.
8.2 Purity of Water—Reagent water produced by distilla- 9.5.3 Limiting flow rate to preclude source carry-over.
tion, or by ion exchange, or reverse osmosis followed by 10. Preparations of Aqueous Solutions
distillation shall be used. See Specification D1193.
8.3 Nomenclature for Salts—The proper nomenclature for 10.1 Caution—Some saturated salt-water systems should
the Humidity Fixed Point (HFP) salt chemicals and the be regarded as hazardous materials. Refer to 1.5 and 1.6 for
corresponding acceptable temperature ranges are provided in guidelines.
Table 1. The scale encompasses relative humidity ranges from 10.2 Saturated Salt-Water Systems:
2 % to 98.5 % and a temperature range from 5°C to 80°C. 10.2.1 Select a salt of characteristic value from Annex A1.
When the salt solutions are used at temperatures above 40°C, The reference document by Greenspan6 contains information
the risk of salt crystals settling on the surface rather than being on many other saturated salt solutions which may be used.
immersed in the solution must be taken into account. These additional systems, however, are less accurately or less
completely defined in value. Also, some may only be used
9. Technical Precautions when freshly prepared (to limit the influence of chemical
9.1 Although a container capable of airtight closure is instability such as hydrolysis or acid gas absorption). The salts
described in Section 7, it may be desirable to have a vent under listed in Annex A1 can be used for a year or more.
certain conditions of test or with some kinds of containers 10.2.2 Place a quantity of the selected salt in the bottom of
(changes in pressure may produce undesirable cracks in some a container or an insert tray to a depth of about 4 cm for low
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
5
Reagent Chemicals, American Chemical Society Specifications , American after each addition, until the salt can absorb no more water as
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
6
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia Greenspan, L., “Humidity Fixed Points of Binary Saturated Aqueous Solu-
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, tions,” Journal of Research, National Institute of Standards and Technology, Vol.
MD. 81A, 1977, pp. 89–96.

2
 E104 – 02 (2012)
evidenced by free liquid. Although a saturated solution system figures associated with each source value, as stated in the
is defined when any excess quantity of undissolved solute is Annex tables. In actual use, lack of temperature equilibrium
present, it is preferred to keep the excess liquid present to a (60.5°C) and other functional losses can reduce the bias
minimum for ease in handling and for minimal impact on statement to 62.5 %. Precision is 60.5 % rh.
stability should temperature variations occur.
10.2.4 Close the container and allow 1 h for temperature 12. Keywords
stabilization.
10.2.5 The container may be used as a reservoir from which 12.1 aqueous solution; constant relative humidity; control of
quantities of slush can be transferred for use, or the entire relative humidity; equilibrium relative humidity; humidity;
container may be used for conditioning tests. 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

3
 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

E104 – 02 (2012)
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
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
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
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 —
 E104 – 02 (2012)

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