JOURNAL OF RESEARCH of the National Bureau of Standards - A.

Phys ics and Chemistry

Vol. 81 A , No.1 , January- February 1977

Humidity Fixed Points of Binary Saturated Aqueous Solutions

Lewis Greenspan
Institute for Basic Standards, National Bureau of Standards, Washington, D. C. 20234
(October 22, 1976)
An e valua ted compil ation of equilibrium rela ti ve humiditi es in a ir ve rsus tempe rature from pure phase to
a pproximatel y l OS pascal (1 a tm) in press ure is present ed fo r 28 bina ry saturated aqueous so luti ons . Th e relative
humiditi es of th e solutio ns ra nge from about 3 to 98 pe rcent. Using a da ta base from 2 1 sepa ra te in ves ti gati ons
compris ing 1106 indi vidu al meas ure me nts, fits we re made by the me thod of least s qua res to regula r po lynomia l
equ ati ons with two through four coeffi c ie nts. Equa ti ons a nd ta bles a re presented a long with the estima ted
uncert a inti es in the correla ted res ults.
Key words : aqueous so lution; equilibrium; humidit y; rela ti ve humidity; salt; satura ted salt so lut ion; va por press ure;
water va por.

1.

Introduction

Research, hygromete r calibration, testing a nd material

conditioning often req uire the acc urate control of humidity in
a working space . The common me thods of co ntrolling the
humidity acc urately use either a humidity ge nerator [lA]t or
the equilibrati on of a closed space with a che mi cal system
[lB] whi c h produ ces the des ired equilibrium vapor press ure .
Humidity ge nerators te nd to be ex pe ns ive a nd complex
whereas equilibrati on with c he mi cal syste ms that provide
fix ed points is a relati vely inexpe nsive a nd s im ple method of
humidity control. Among the c hemi cal sys tems used for thi s
purpose are aqueous sulphuri c ac id soluti ons, glyce rine and
water soluti ons a nd single a nd binary salt solutions . Eac h
such solution offe rs a degree of humidity adjus tme nt that can
be achieved by cha nging its concentra tion. On the other
hand, special problems are associated with the use of solutions because their concentrations must be mea sured and
controlled. Not only must the concentration of the solution be
determined initially but the presence of any humidity sources
or sinks in the controlled space and even the initial equilibration process of the space can alter the solution concentration.
An especially useful method of humidity control by chemical system involves the use of binary saturated aqueous
solutions (primarily of single salts) in which the solute is
highl y non- volatil e.
At any temperature , th e conce ntrati on of a saturated solution is fi xed and does not ha ve to be dete rmined . By providing excess solute, the soluti on will re ma in saturated even in
the presence of modest sources or s inks . Whe re the solute is
a solid in the pure phase, it is easy to de termine that there is
indeed saturation . Du e to the ease of its use, thi s is a popul a r
method of humidit y co ntrol.
Since a given saturated salt soluti on provides only one
relative humidity (RH) at an y des ired tempe rature, a different
relative humidity must be achie ved by selecting a nother
appropriate salt. Though muc h data on saturated salt solu1 Figures in brac kets indi cate the lite rat ure re ferencL'S al the end of this pape r.

tions have been produced and ma ny compilations of the

equilibrium relative humiditi es of selected saturated salt
soluti ons exi st, the re are no compilati ons for whi ch the d ata
have been criti cally analyzed a nd estimates of the un certa inti es involved give n, a step whi ch is abolutely essential to the
implime nta ti on of the concept of fi xed po ints.
We ha ve moved to fill thi s gap by compiling, from the
lite ra ture, data on a suffic ie nt vari ety of saturated salt soluti ons to cover the e ntire ra nge of relative humidity at reasonably close intervals. We have adjus ted th ese da ta [1- 21] to be
consiste nt with te mpe ra tures on IPTS-68 a nd the most rece nt
equati ons for the va por pressure of water [22] . We have also
a nalyzed the ex pe rimental techniques used in obta ining the
ori ginal da ta a nd have made estim ates of the uncerta inti es in
the ori ginal data . We have the n used these da ta to calcula te
" best" values of relative humidity in air as a fun c ti on of
temperature from pure phase to approximately 105 pascal (1
atm) in pressure for these saturated soluti ons .

2.

Background

The methods used by investi ga tors to d etermine the water

vapor in equilibrium with saturated salt soluti ons a re dive rse.
A short description of the vari ous me thods used in the
referenced papers is of interest.
(1) The direct measurement of the vapor pressure. A chamber containing a saturated salt solution a t a co ntroll ed temperature is first evac uated to remove all gases . E vapora tion
from the solution is then allowed to proceed until the a mbie nt
vapor, essentiall y all wate r, has come to equilibrium with the
solution and a direct de te rmination of the total pressure
within the cha mber is mad e by conve ntional pressure measure me nt tec hniques.
(2) Dew point measurement. The dew point of the gas within
a c hamber co nta ining a saturated salt solutio n at co ntrolled
temperature is meas ured by means of a cooled mirror within
the c ha mber. Us ing vapor press ure ta bles or equa ti ons, this
dew point is converted to the vapor pressure of wate r.
(3) Isopiestic vapor pressure measurement. The va por pres-

89

s ure of a saturated salt solution in one cell or chamber is

allowed to come to eq uilibrium with a cell or cham ber
co ntaining a refere nce solution at a fi xed temperature. The
refe re nce solution must be well characterized as to vapor
pressure as a fun ction of co nce ntration at the reference
te mperature. Under the eq uilibrium co ndition, the equilibrium vapor pressure of th e saturated salt soluti on is ide ntical
to th e eq uilibrium vapor press ure of the refere nce solution .
After the tw o cells have reac hed equilibrium , the conce ntration of the refe re nce solution is det e rmined (usually by
weighing) and th e vapor pressure is calc ulated .
(4) Relative vapor pressure measurement. A c hamber conta ining a saturated salt solution a nd a chamber containing
pure water or other well c harac terized solution are eac h
evac uat ed to re move all non-water vapor gases. The two
c hambers are maintain ed at the same te mperature and the
absolute pressure of the saturated salt solution is meas ured as
in the first me thod. In addition th e press ure diffe rence betwee n the two chambe rs and/or the press ure of th e refe re nce
solution is de termin ed. The ratio of the vapor press ure of the
saturated salt solution to th e vapor press ure of th e wate r is the
activity (or re lative humidit y) of th e satura te d salt solution.
(5) Measurement with a calibrated humidity sensor. A
c hambe r conta ining a saturated salt solution a nd a humidit y
sensor are brought to equilibrium at a co ntrolled te mpe rature.
Calibra ti on of th e se nso r before or/and after the meas ureme nt
provid es the means of determining the eq uilibrium vapor
pressure.
(6) Gravimetric determination . Dry gas is passed throu gh
th e binary sat ura ted solution at a fi xed te mpe rature. The
wate r va por in th e efflu e nt gas is absorbed by a d es iccant and
measured by weighing. The volume of th e gas is also de termin ed. From these the vapor pressure or th e mixing ra ti o can
be d etermined .
As one would imagin e , the e rrors associate d with th ese
me th ods diffe r as to so urce and magnitud e. The en'ors in any
of th e method s a re also fun c ti ons of the le vel of vapor
press ure be ing meas ured as well as th e tempe rature of the
saturated salt solution. The re is, the refore, probably no one
method that gives a bes t measureme nt und er all co nditions.

3.

Method

We have acc umul a ted expe rim e ntal data from various
researc he rs [1-21] and calc ulated " bes t" values of re la tive
humidit y a nd the associate d un certa inties of those values.
Typical me thods of calc ulatin g or recalc ulatin g th e rela ti ve
humidity and associated un certa inties for th e vari ous inves tigations are give n in the Appendix. Our data base consists of
21 inves ti gations and includes so me of the most c ited work in
the fi eld . In total , 1106 indi vidual calculations of relative
humidities and assoc iated un certainti es were made whic h
involve d 89 saturated solutions. Not all data nor all satura ted
solutions in this s tudy we re found sati s fac tory for use .
The original data were correc te d to be co nsistent with
te mperature on IPTS-68, with the mos t recent formulation for
th e vapor press ure of water [22] and with the most rece nt
eq uations for th e e nhan cement of water va por in air [23]. The
computed relative humidit y data we re the n collated and fitted
by the me thod of leas t squares to regular polynomials as a
fun ction of te mperature in degrees Celsius (IPTS-68). In the
fitting process, eac h datum was we ighted inversely proportional to the es timated un certainty of th e datum . The order of
th e polynomial used in the fit was determined by an F-tes t or

b y a nalys is of the res ult of fits to various orde rs. An arbi trary
d ec ision was made not to use any order higher than 3. Also,
no data at temperatures below 0 C or above 104C we re used
in the fits .
In the fittin g process, the standard deviation of the predic ted value was co mputed for each datum. These s ta nda rd
deviations were th emse lves fitt ed to a quadrati c equation , as
a function of te mpera ture, by the method of leas t squares. At
any desired te mpe ra ture for a given sat urate d salt solution ,
the standard deviation of th e predict ed value was calculated
using th e appropriate quad ra ti c equation . T hree tim es thi s
value was the n assigned as the es tim a te d un ce rtainty for the
corres ponding value of rela tive humidi ty, wi th ce rtain exce ption s discussed below. This is the value whi c h appears in
table 2.
Where a numbe r of inves ti gation s of th e sa me solution
exis ted and the re la tive humidit y vs te mpe rature results of
one inves tiga tion we re comple te ly inco nsis te nt with th e results of th e oth er inves tiga ti ons, th e data of the deviant
in ves tiga tion were eliminated and a ne w fit made .
The data used in this pape r me t one of the following
crite ria: (1) a large numbe r of inves ti gations we re included
and exhibited a s ma ll res idual stand a rd d ev iat ion of th e
relative humidity vs te mpera ture fit s; (2) although fe w investigati ons we re includ ed, the me thod of meas urement was
judged to be s upe ri or a nd es tim a tes of th e un ce rtainties of th e
ori ginal meas ure me nts the mselves we re s mall ; a nd (3) the
data were in a rel ative humidit y ra nge which was not a pprox imate d by a ny of th e oth e r binary saturated solutions.

4.

Results

Table 1 co nta ins coeffi cie nts for the data of the selec ted
salts fitted to an equation of th e form:
3

RH =

2: Ai
i=O

where RH is in perce nt a nd t is in C (IPTS-68). The salts a re

lis ted in ascending ord e r of RH a t 25C. Also incl uded in
table 1 is th e residual s ta ndard de via ti on of th e fit , the ran ge
of te mpe rature ove r whi c h th e fi t was pe rformed a nd refere nces for th e fundam e ntal data th a t were involved in that
partic ular fit.
Ta ble 2 gives the calc ul a ted rela tive humid ities for eac h of
the binary saturated solutions at 5-degree inte rvals along with
the es tim ated un ce rtainti es in rela tive humidit y at eac h of th e
tempera tures . The saturated salt solutions are prese nt ed in
the same order as in ta ble 1.

5.

Discussion

Although the me thod used for fittin g the data gave no

proble ms, the assignment of weights to eac h datum re quired
some judgmen t. Three methods of we ightin g were conside re d:
(1) we ights were ass igned in ve rsely proportional to th e vari ance of the individual datum where the varian ce was ta ke n as
the square of th e total un certa inty; (2) weights we re ass igned
inversely proportional to th e es tim ated total un ce rtaint y of the
individual datum ; and (3) weig hts of unity we re assigned to
all data.
All of the data were fitted three times, once for eac h type of
we ighting . The results were asse mbled into three tables of

90

TABL E

I.

S Wlllllar) of Le(",t Squares Fits to RH

:" A;t; for Selected Saturated Salt Solutions

i = 0

No.
Salt

A,

Ao

A2

a-

A3

of

I min

( ma x

5.0
0.0
5.0
5.0
15. 0
0.0
11. 2
5.0
11. 2
25.0
0.00
5.0
0.0
0.0
5.0
23.4
5.0
5.0
5.0
0.0
11.2
5.0
0.4
0.0
5. 0
0 .6
0.5
23.7

80.0
100. 0
70.0
70.0
75.0
100.3
25.0
70.0
3l.0
90.0
99.4
90.0
30.0
48.1
80.0
78.9
90.0
30.0
90.0
80.0
3l.0
80.0
48.0
90.0
25.0
48. 1
52 .3
50.8

Data Source (a)

Points
Cesium Fluoride
Lithium Bromid e
Zinc Bromide
Potassium H ydroxide
Sodium H ydrox id e
Lithium Chloride
Calc ium Brom ide
Lithium Iodide
Potassium Acetate
Potassium Fluorid e
Magnes ium Chloride
Sodium Iodid e
Potassium Carbonat e

'D
.......

Magnesi um Nitrate
Sodium Bromid e
Cobalt Chloride
Potassiulll Iodide
Strontium Chloride
Sodium Nitrat e
Sodium Chloride
Ammonium Chloride
Potassiu m Bromide
Ammonium Sulfat e

Potassi um
Strontium
Potassi um
Potassi um

Chloride
Ni tra te
Nitrat e
Sulfat e

Potassium Chromate

6.20938
7.75437
9.28455
16. 7049
11. 558 1
11.2323
23.5670
22.82 16
22.4388
65.7907
33.6686
42.6040
43.13 15
60.35 14
64.7190
73 .0330
74.5466
78.5322
79.5738
75.5 164
8 1. 8777
86.6424
8 1. 7794
88.6190
94.2127
96.3361
98.7792
103.934

(a) Numbers correspond to refe re nces.

0. 143381
0 .0654994
0 .0906508
0.51 1352
0. 132339
0.00824245
0. 136 11 7
0,232642
0. 156288
- 2.07303
- 0.00797397
0 .00854045
0.00147523
- 0.298153
-0.22 1990
0.0852795
- 0.253167
- 0.273114
- 0. 193 192
0.039832 1
- 0.1 3227 1
- 0.332271
- 0 .0715320
- 0.193340
- 0.366025
0.01l237 1
- 0.0590502
- 0.310 163

0.123037
0. 420737
0 . 11 8 143
0.796712

X
X
X
X

10- '
10- 3
10- '
10- 2 .

- 0.2 14890
- 0.5858.36
O. .1 32306
0.612868
0 .305676
- 0. J08988
- 0.933320

X
X
X
X
X
X
X

JO - "
10- 2

- 0.426364

- 0.168738

X JO- 4

JO- 2

0.761055

X JO - 4

- 0.402414
- 0.218455
o. J04383
- 0.135136
- 0. 122 102
- 0.265459

X 10- 2
X 10- 1
X 10- 2
X JO - 2
X 10- 2
X 10- 2

0.059033 1
0.2 18691
0. 174308
0.284800

X 10- 4
X 10- '

0.459734

X JO - 2

- 0. 199429

X JO - 4

0.899706

X JO - 3

]0 - 2
10- 2
JO -

10- 4

10- 2

-0.4845 14

10- 2

0.273023

10- 2

X
X

10- 4
10-

0.54
.22
.20
.28
.90
.67
.06
.05
.22
.36
.28
.50
.31
.34
.44
1.44
0.20
.02
.37
.21

.60
. 14
.40
.45
.19
.80
.47
.22

21
21
16
14
24
100
7
15
10
8
48
25
9
24
22
17

12
7
25
44
20
II

:ZI
39
5
22
18
7

2, J7
2, 14
2, 14
2
I, .1 6
I, 3, JO , 11 , J7 , 18, 20
11, 14
2, 14
11 , 14, 17
6, 14
1,7, 11 , 14,17, 19,2 1
1,6, JJ , .14
8, 14, 17
1, 8, 17,19,21
2,6, 11 , 17
6
1, 6
1, 17
1,6,9, 17
1, 6, 8, 11 , 12, 13, 15, 17, 19,2 1
9, 11
I , 6, 17
9, 18, 20
I, 6 , 8, 9, 12, 17
1
9, 17, 19,2 1
12, 19,21
12 , 17

TABLE 2.

EquilibriulII Relative HUlllidit y u/Selected Saturated Salt SoiutiulI.lj'rolll () tu

J()()

Relative Humi dity, %

T
C
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100

Cesium
Fluoride
5.52
4.89
4.33
3.83
3 .39
3.01
2.69
2.44
2.24
2.11
2.04
2.03
2.08
2.20
2.37
2.61

1.9
1. 6
1.4
1.1
0.94
0.77
0.63
0.52
0.44
0.40
0.38
0.40
0.44
0.52
0.62
0.76

Lithiulll
Bromid e
7.75 0.83
7.43 0.76
7.14 0.69
6.86 0.63
6.61 0.58
6.37 0.52
6.16 0.47
5.97 0.43
5.80 0 .39
5.65 0.35
5.53 0.31
5.42 0.28
5.33 0.25
5.27 0.23
5.23 0.21
5.200.19
5.20 0.18
5.22 0.17
5.26 O. J7
5.32 0.16
5.41 0 . 17

Zinc

Putassiutll

Sodiulll

Brun lide

Hydroxid e

Hydroxid e

8.86 0.89
8.49 0 . 74
8.19 0 .61
7.94 0.49
7.75 0.39
7.62 0.31
7.55 0.25
7.54 0.20
7.59 0.17
7. 700.16
7.87 0.17
8 .090.19
8.38 0.24
8.72 0.30

14.34
12. 34
10.68
9.32
8 .23
7.38
6 . 73
6 .26
5.94
5.72
5.58
5.49
5.41
5.32

1. 7
1. 4
I. I
0.90
0.72
0.56
0.44
0.35
0.29
0.27
0 .28
0.32
0.39
0 .50

9.57
8.91
8.24
7.58
6.92
6.26
5.60
4.94
4.27
3.6.1
2.95
2.29
1.63

2.8
2.4
2.1
1.7
1.5
1.2
1.0
0 .85
0.73
0.65
0.60
0.60
0.64

Lithiulll
Ch loride
11.23 0.54
11.26 0.47
11.29 0.41
11. 30 0 .35
11. 31 0.31
11.30 0.27
11. 28 0.24
11.25 0.22
11. 2 1 0 .21
11..16 0.21
11.1O0.22
11.03 0.23
10.95 0.26
10.86 0.29
10.75 0.33
10.64 0.38
10. 51 0.44
10.38 0.51
10.23 0.59
]0.07 0.67
9.90 0.77

Calc ium

LithiulII

Putassiulll

Pulass illlll

Bro rlli ( jt'

Iodide

Acetate

Fluoride

2 1. 62
20.20
18. 50
16. 50

0 .50
0.50
0.50
0.20

2 1. 68
20.61
19.57
18.56
17. 56
16.57
105.57
14. 55
13.49
12.38
11.22
9.98
8.65
7.23

0.30
0.25
0.20
0.16
0.13
0.10
0.08
0.06
0.05
0.05
0.05
0 .06
0 .07
0.09

23.38
23.40
23.11
22.51
21.61

0.53
0.32
0.25
0.32
0.53

30.85
27.27
24.59
22.68
21.46
20.80
20.60
20.77
21.18
21. 74
22.33
22.85
23.20
23.27

1.3
I. I
0.94
0.81
0.70
0.62
0.56
0.53
0 .53
0.56
0 .61
0.69
0.80
0.93

\0
~

TABLE

2.

EquilibriulII Relative HUlllidi/ y ,!!Selecter! Saturater! Salt Sulutioll~j'rUIII () tu I()() C-Colltilluer!

Relative Humidit y, %

T
C

Magnesium

Chloride
0
5
10
IS
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100

33.66
33.60
33.47
33.30
33 .07
32. 78
32.44
32.005
31.60
31.10
30.54
29.93
29.26
28 ..54
27.77
26.94
26.05
25.11
24.1 2
23 .07
21. 97

0.33
0.28
0.24
0.21
0.18
0.16
0.14
0.13
0 .1 3
0.13
0.14
0.16
0.18
0.21
0.25
0.29
0.34
0 .39
0.46
0.52
0.60

Sodium
Iodid e
42.42
41.83
40.88
39.65
38.17
36.15
34.73
32.88
31.02
29.21
27.50
25.95
24.62
23.57
22.85
22.52
22.63
23.25

0.99
0.83
0.70
0.59
0.50
0 .43
0.39
0.37
0.37
0.40
0.45
0.52
0.62
0.74
0 .88
1.0
1.2
1.4

Potassiulll

Magnesium

Carbonate

Ni trat e

43 .1 3
43.13
43.14
43.15
43.16
43.16
43.17

0.66
0.50
0.39
0.33
0.33
0.39
0.50

60.35
58.86
57.36
55.87
54.38
52.89
5 1.40
49.91
48 .42
46.93
45.44

0.55
0 .43
0.33
0.27
0.23
0.22
0.24
0 .29
0.37
0.47
0.60

Sodium
Brumide

63.51
62 . 15
60.68
59. 14
57.057
56.03
54 ..55
53. 17
5 1. 95
50.93
50.15
49 .66
49.49
49.70
50.33
5 1. 43

0.72
0.60
0.5 1
0 .44
0 .40
0.38
0.38
0.41
0.47
0 .55
0.65
0.78
0.94
.1.1
1. 3
1.5

Coba lt
Ch loride

64 .92
6 1. 83
58.63
55.48
52.56
50.01
48 .02
46.74
46.33
46.97
48.80
52.0 1

3.5
2.8
2.2
1.8
1.5
1.4
1.4
1.5
1. 9
2.3
2.9
3.7

Potassiulll

Strontium

Sodium

Iodid e

Ch loride

Nitrate

73.30
72. I I
70.98
69.90
68.86
67.89
66 .96
66 .09
65.26
64.49
63 . 78
63.1 1
62.50
61.93
61.43
60.97
60.S6
60.21

0.34
0.31
0.28
0.26
0.24
0.23
0.23
0.23
0.24
0.26
0.28
0.31
0.34
0.38
0.43
0.48
0.54
0.61

77.13
75.66
74.13
72 .52
70.85
69.12

0 .1 2
0.09
0.06
0.05
0.04
0.03

78.57
77.53
76.46
75.36
74.25
73. 14
72.06
71.00
69.99
69.04
68.15
67.35
66.64
66.04
65.56
65.22
65.03
65.00

0.52
0.45
0.39
0.35
0.32
0.31
0.32
0.34
0.37
0.42
0.49
0.57
0.67
0.78
0 .91
I. I
1.2
1.4

Sodium
Chloride
75.51 0.34
75.65 0.27
75.67 0.22
705.6 1 0.18
75.47 0.14
75.29 0.12
75.09 0.11
74.87 0.12
74.68 0.13
74.52 0 . 16
74.43 0.19
74.41 0.24
74.50 0.30
74.710.37
75.06 0.45
705 .58 0.55
76.29 0 .65

relative humidity at 5-degree intervals . Eac h calculated

value of relative humidity was assigned an un certainty equal
to three times th e standard deviation of the predicted value.
As might be expected , th e calc ulated re lative humidities and
th e corresponding un certainties d iffered for each of the three
weightings. For the saturated so lutions chosen for presentation in this paper, it was noted with so me sati sfac tion that all
relative humidities calcul ated from th e three differentl y
weighted fits agreed with each oth er to within th e assigned
uncertainty for eac h.
A we ighting inversely proporti ona l to the square of th e
estimated total un certainty for eac h da tum was jud ged to be
inappropriate . Although it is common to assign we ights proportional to th e inverse of s igma squared such an approach is
usuall y based on a s igma whic h is stati sti call y dete rmin ed.
Thi s is not th e case he re. The method used to obta in the
estimated total un certa inty is give n in th e Appe ndi x. It was
felt tha t th e use of th e square of th e estima ted un ce rtainty
would have placed a n un acceptabl y high va lue on the author's estim ate of th e errors co ntributing to th e total unce rtainty. So me investi ga tors did not provide suffi c ie nt inforrn ati on in th e ir publi cations to make poss ible co mpl e te ly objective es timates of the ir errors. [n those cases, th e estimated
total un ce rta inty included componen ts based on the au thor's
s ubj ec tive judgme nts .
A we ighting of unit y was like wise unsati s fac tory s ince it
would in no way take into accou nt th e innate diffe re nce in
un certainty du e to me th od, temperature a nd rela ti ve humidity
ran ge, nor wo uld it place a ny re liance on th e a uth or's jud gme nt of th e quality of th e research. A we ighting proporti onal
to th e inverse of th e estima ted un certaint y a ppea red to be a
reasonable co mpromi se betwee n the othe r ex tremes and all
data prese nted in this publi cation were processed us ing th at
we ighting me th od .
Whe re th e data for a partic ular saturated salt solution
incl ud ed a numbe r of in ves ti gation s , three times th e standa rd
deviati ons of the co mputed values were acce pted as the
estimated un certaint y. Whe re th e data were based onl y on
one or two inves ti ga ti ons it is evide nt that self co nsiste nt
data, th ough quite in accu rate, co uld give small estimated
sta ndard de viations of the computed values . It is al so evid e nt
th at such standard deviation s a re not a valid estimate of
unce rta inty. Und er those c ircumsta nces where th e res ults
from fittin g th e polynomial equation to th e original data for
any saturated salt solution gave values for three times the
standa rd de viation of th e predic ted value that we re less th an
th e estimated total un certainty of the original data , it was the
estimated total un certainty of the original data whic h was
used as the final estimate of un certainty for th e calc ulated
" best" value of relative humidity.
The data presented in table 2 are given at 5C intervals
over the temperature range of the original data with ex trapolations beyond these ranges never exceedin g 2.5
All
calculated values of relative humidity are give n to 0.01
percent relative humidity. This does not in an y way impl y a n
accuracy of 0.01 percent. The designated es timated un ce rtainties still give the bes t predi ction of accuracy . It was fe lt
that to fail to give the relative humiditi es to .01 pe rce nt would
be discarding information , imprecise as it mi ght be . Since th e
estimated uncertainties are given, we see no proble m with
presenting the values of relative humidit y with fi gures far
beyond their estimated un certainties .
The uncertainties presented do not includ e un ce rtainti es in
the vapor pressure equation [22] or e nhancement equations

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93

TABLE

3.

Comparison of Relative Humidity Values of Selected Saturated Salt Solutions for Various CornpilatiollS
-

Relative Humidit y, %

a
Hydroxid e
LithiulII Ch lorid e

Potass iul1l

PotassiU lll Acetat e

Magn esiulll Chl orid e

Sodium Iod id e
Potass ium Carbo ll ate

Magnesium Nitrate

20 C

10 C

Saturat ed Sal t

12.34
11. 29
23.38
33.47
41.83
43 . 14
57.36

b
14
21
34
47
57

34.7

13
13
24
34
42
47
57

47.0

Sodium Bromide

a
9 .32
11.31
23.11
33.07
39.65
43.1 6
54.38
59. 14

b
12
22
33
44
55

33.1

9
12
23
33
39
44
55

44.0

f
15
20

33
42

Sodiu lll Chloride

Ammonium Chlorid e
Pot ass ium Bromid e
Ar ll tllOniulll Sulfat e
Potassiu lll Chl orid e
Pot ass iulll Nitrate
Potassi um Sulfate

72. 11
75.67

83.75
82 .06
86.77
95.96
98. 18

72

76

76.9

76

86.0
82
88
95
98

87.4
95.1
98.2

82
88
95
98

a Valu es from thi s work.

b Values from references 24 and 25 whi ch are ide nti ca l.

c Values frolll referell ce 26.
d Values from reference 27 .
e Va lues frolll refe re nce 28.

f Va lues frolll reference 29.

69 .90
75.47
79.23
81.67
81.34
85 11
1 94.62
.
9 7. 59

a
7.38
11. 28
2 1. 6 1
32.44
36.15
43.17
5 1.40

12
22
33
43
52

31.7

7
12
22
33
36
43
52

43 .0

a
6.26
11. 2 1

32

6
11

31.60
32.88

32

48.42

49

11

31.3

32
33

32

49

58

Cobalt Chloride
Potass iulll I odide

40C

30 C

76

75.8

70
76

76
79.2

84.0
81
86
93
97

86.3
94.2
97 .1

81
86
93
97

81
86
96.5

79.2
84
8 1.0

6 1. 83
67 .89
75.09
77.90
80.27
80.63
83 .62
92.31
97.00

61.9
75

75.1
82.0

80
85
91
96

84.5
92.5
96.6

56.6

55.48
68
75

84
RO
91
96

75
79.5

I'Ll
84

96.5

74.68

75

79.43
79.91
82.32
89.03
96.4 1

79
82
88
96

74.4

75

75

79
82
88
96

81.1
83

79.5
81.1

80.0
82.8
89.4
96. 1

96.5

[23] used . Th e "es ults prese nted are therefore for the exact
valu es of references [22] and [23]. The enhancement fac tor
for a satura ted salt solution in air is not known precisely .
Analys is of th e fa ctors involved indicate that at one a tm osphere press ure or less , the difference between the enhancement fa c tor over a saturated salt solution and over pure water
is negligible . That is not the case at high pressures. The data
presented are therefore considered valid near or below one
atmosphere total pressure. If saturation vapor pressure values
other than those given by Wexler [22] are used , the relative
humidities should be multiplied by the ratio of th ese saturation vapor pressures to those of Wexler.
Many compilations of non-critically e valuated data on th e
equilibrium humidity of saturated salt solutions ex is t [2438]. Table 3 is a comparison of values from thi s work and
corresponding values tak e n from five of these othe r compilations at four te mpe ratures . Of th e li sted compilations, o nl y
this work (column a) and Hic kman's work (co lumn d) give the
so urces of the data. Hic km a n's values (in column d) we re
directl y co pied from hi s c ited refe re nces without modifi cation. None of the compilations oth e r th an ou rs (column a)
gives es timates of un ce rtaint y. The re fore, one would logica ll y
co nclud e that th e authors of those compilation s cons ide r th eir
valu es to be un certain onl y in th e las t fi g ure prese nted. It is
also likel y that some of th e values in one co mpilatio n came
from the same sources as th e values in oth e r co mpilations such a relationship a ppea rs to exis t between column b a nd
column d.
If we assume an un certaint y of 1/2 of th e las t di git in th e
values give n in th ese oth e r co mpilations, and if we add that
un ce rta int y to th e es tim ated un certaint y for th e co rres pondin g
values in column a , we find that th e valu es in co lumn a (the
res ults of this work) agree with the values in at least o ne of the
other co mpilations to within this composite un certainty at all
points, exce pt fo r:
Potassium carbonat e at 10 C
Sodium bromid e at 20 C
Ammonium c hloride at 30 C
Potassium bromid e at 10 C, 20C, and 30 C
Potassium chloride at 10 C, and 20 C

It should be noted that this comparison of compilations is

over a limited temperature range and for onl y 17 of the 28 salt
solutions eval uated and collated in this pape r.

6.

Appendix

In all cases, the mos t fundam e ntal meas ure me nts presented we re used to calc ulate the actual relative humidit y
obtained by ea ch inves tigator for eac h datum. No atte mpt was
made to evaluate purity of water or solute o r its e ffect in any
investigation.
As a first s tep, 'Ill temperatures we re conve rted from the
temperature scale in whic h the data we re prese nted into
IPTS-68 temperature equivale nts. Where the temperature
scales were not given, a judgment was made as to the most
likely temperature scale used, based on the date of the
researc h.
Likewise, where vapor pressures based on vapor pressure
equations or tables were given, these were converted to new

vapor pressures based on the Wexle r formulation. In the case

of reported relative humidities based on de w-point meas ureme nts, the dew-point te mperature was reco nstru c ted from a
knowledge of the vapor pressure equation used. From th e
reported control temperature and the recons tru cted dew-poi nt
temperature a new relative humidity was calculated us ing th e
Wexler and Gree nspan equations for vapor press ures and
enhancements factors , respectively.
Whe re the isopiestic method was used with sulfuric acid as
the isopiestic solution, the values of Shankman [39] for
sulfuric acid activity were used to determine th e relative
humidity of the saturated salt solution. This was don e (1) for
co nsis te nc y, because many of the researchers had done likewise; (2) because Shankman described his ex pe rim en tal work
in suffi cien t detail to e nable us'to judge its quality and to
es tim a te the un ce rtainty in his work ; and (3) his values
appeared to be th e most acc urate ava ilable.
In dete rminin g es timates of total un ce rtaint y for eac h
datum, th e un cert a int y was ta ke n as the square root of th e
sum s of individual un certainti es (in te rm s of relative humidity) squared as desc ribed by Ku [40]. Individual un certainties
involved in th e individual meas ure me nt s we re obta ined from
th e inves ti gators' own es tima tes whe re th ese see med reaso nable . Whe re th e in ves ti gator did not present a reaso nable
es timate of un ce rta int y for a partic ula r parame te r, thi s a utho r
made his own es timate of th e un cert ain ty of that parame te r
based on his judgme nt of th e in vestiga tor's work a nd hi s
es tima te of th e s ta te of th e art at th e time of th e investi ga ti on.
The relative humidit y un ce rta inty assoc ia ted with each of th e
parame te r un certainties was obtained by calc ulatin g the re lative humidity with and without the un certaint y add ed to th e
re lated parame te r, th e diffe re nce be ing th e relative humidity
un ce rtainty [or th at parti c ular param e ter.
In so me cases the indi vidual param ete r un ce rtainti es are
not ind e pe nd e nt in the ir effec t on th e relative humidit y
un ce rtainty. A case in point is th e relative vapor press ure
meas ure me nt method. In this tec hnique, the individual te mpe rature and pressure meas ure me nt un certainti es are of no
great co nsequ e nce, it is the estimates of th e te mperature
diffe re nce and th e pressure difference in the two press ure
meas ure me nt s that are significant. In addition , an es timate of
th e degree of equilibrium achieved is of significance . In th ese
types of s ituations, estimates of the differences were used in
lie u of es timates of th e individual measureme nts.
In th e case of the relative humidity sensor calibration
technique, an es timate of the calibration uncertainty as well
as te mpe rature un certainty were used. In the isopiestic
tec hnqiue, the relevant uncertainties are the te mperature
difference, the concentration determination, the un certainty
in equilibrium and the uncertainty in the refere nce solution
data.
Composite uncertainties for each datum based on the
square root of the sum of the individual param ete r un certainties squared were thus obtained.
As stated earlier, these estimates of uncertainties are the
result of subjective judgments as well as objective es timates .
For the great preponderance of data prese nted in this paper,
these judgments have a minor effect on th e relative humidity
values as well as the total uncertainty, as was shown by the
small difference obtained for the three differe nt methods of
weighting.

95

7.

References

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