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1.
Introduction
2.
Background
89
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
5.
Discussion
90
TABL E
I.
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
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
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.
J()()
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
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.
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
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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
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
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
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
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
95
7.
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(Paper 81Al-924)
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