Beruflich Dokumente
Kultur Dokumente
1348 to 1353
#2005 The Japan Institute of Metals
1.
Introduction
Molecular effusion
d
L
H
D
Fig. 1
Vapor Pressure Measurements for Metal Chloride Systems by the Knudsen Eusion Method
turbo molecular pump and a rotary pump, and the temperature of the sample was controlled by an electric furnace.
Weight loss of the sample was continuously recorded by the
data system.
3.3 Analysis method
The vapor pressure of pure chlorides can be obtained
directly using eq. (1). In the case of KClNaCl system, it was
assumed that the mixed condensed and vapor phases exhibit
the same behavior with ideal solution and ideal gas,
respectively, since they have similar molecule structures
and vapor pressure values. Therefore, the composition and
molecular weight of the vapor could be estimated by eqs. (2)
and (3):
v
c
0
NKCl
NKCl
PKCl
v
0
c
NNaCl
NNaCl
PNaCl
Mv
3.1 Samples
KCl (Wako Pure Chem. Ltd., mass fraction 99.5%), NaCl
(Wako Pure Chem. Ltd., mass fraction 99.5%) and CaCl2
(Wako Pure Chem. Ltd., mass fraction 99.5%) were used as
reference compounds to test the apparatus. Dierent mixtures
of these were used to measure the vapor pressures of a KCl
NaClCaCl2 system. All samples were in powdered state.
3.2 Apparatus and procedure
The schematic diagram of the apparatus is shown in Fig. 2.
A cylindrical cell made of pure platinum with equal height
and diameter (D H 10 mm) was used. The cell consists
of two parts, i.e., upper and lower pans. The upper pan has an
orice and its diameter d is 0.07, 0.13, 0.20, or 0.30 mm. The
sample powder was charged and compressed in a thin layer
on the bottom of the lower pan. Then, the lips of the two pans
were press-sealed and the cell was hung with the hook of the
balance by a platinum wire, which was set at the center of the
reaction tube. The balance gives an accuracy of 0.01 mg. A
high vacuum condition ( 102 Pa) was maintained by a
1
11
4
5
10
9
3
Fig. 2
5.Thermal couple
6. Electric furnace
7. Turbo molecular pump
8. Rotary pump
9. Temperature controller
10. Data system
11. Reaction tube
c
0
c
0
MKCl NKCl
PKCl
MNaCl NNaCl
PNaCl
3
0
0
c
c
NKCl
PKCl
NNaCl
PNaCl
c
c
v
v
where NKCl
, NNaCl
, NKCl
, NNaCl
are the mole fractions of KCl
and NaCl in condensed and vapor phases, respectively, and
0
0
PKCl
, PNaCl
are the vapor pressures of pure KCl and NaCl,
respectively. Mv is the molecular mass of the vapor; MKCl ,
MNaCl are the molecular mass of KCl and NaCl, respectively.
After the experiment, the total vapor pressure of the sample
was obtained by using its weight loss at a controlled
temperature and combining eqs. (1) and (3).
For KClCaCl2 , NaClCaCl2 , and KClNaClCaCl2
systems, after the experiment, the compositions of K and
Na were analyzed by ICP (inductively coupled plasma),
based on which the weight loss of KCl and NaCl were
calculated. Then, their partial vapor pressures and activities
in the system could be obtained by using eq. (1). However in
the case of CaCl2 , the weight loss of CaCl2 could not be
detected because of its extremely low vapor pressure (0.05
0.18 Pa) at the experimental temperature (10731103 K) and
the ICP analysis error. Therefore, it is very dicult to obtain
the partial vapor pressure and activity of CaCl2 in the present
study.
1. Balance
2. High vacuum room
3. Water cooling
4. Knudsen cell
1349
1350
Ziij
Zijj
Na
Na
Ca
Ca
7
6
5
ln (p/Pa)
4
3
2
1
by Kubaschewski 19)
this study
-1
-2
0.8
1.1
1.2
1.2
1.3
1000 (K/T)
Fig. 3
5
4
ln (p/Pa)
2
1
0
-1
by I.Barin20)
-2
0.9
this study
-3
-4
0.9
1.1
1000 (K/T)
Fig. 4
Gibbs energy change of the pair change for the pair-exchange reactions.
gAB/Cl (J/mol)
NaClKCl
NaClCaCl2
KClCaCl2
H 298.15 K
(J/mol)
S 298.15 K
(J/mol K)
Cp
(J/mol K)
NaCl17
298.15 to 1500
1500 to 2000
394956:0
390090:1
76.0761
84.5055
77:7638 0:0075312T
66.9440
KCl17
298.15 to 2500
421824:9
86.5225
73.5966
660 to 2500
606887:4
117.2971
92.0480
CaCl2 18
Vapor Pressure Measurements for Metal Chloride Systems by the Knudsen Eusion Method
4
by Kubaschewski 19)
ln (p/Pa)
this study
0
c
0
c
NKCl
PNaCl
NNaCl
Pt PKCl
0
0.7
0.75
0.8
0.85
1000 (K/T)
Fig. 5
30
1003K
Vapor pressures of the KCl-NaCl
system (p/Pa)
1351
25
993K
20
983K
15
973K
10
963K
5
0
0
0.2
0.4
0.6
0.8
1.0
Fig. 6
handling diculty caused by the strong deliquescent property of CaCl2 , despite its preparation in a glove box lled
with Ar. However, the results reveal that this apparatus is
suitable for measuring the saturated vapor pressures of
substances at high temperatures.
4.2 Measurement for the KClNaClCaCl2 system
4.2.1 KClNaCl
Samples of KCl:NaCl = 0.2:0.8, 0.5:0.5, and 0.8:0.2 (in
molar fractions) were prepared, and the measurements were
Table 4
The experimental and calculated data on partial vapor pressure and activity of KCl in the KClCaCl2 system.
Caculation
data
Experimental results
Sample compositon,
mole fraction
0.25KCl+0.75CaCl2
0.50KCl+0.50CaCl2
0.75KCl+0.25CaCl2
Temperature
(T/K)
Partial vapor
pressure of
KCl (p/Pa)
Activity of
KCl
Activity of
KCl
1073
13.07
0.14
0.05
1103
16.98
0.11
1123
43.06
0.19
0.06
1073
25.45
0.27
0.23
1103
37.98
0.24
1123
83.61
0.37
0.24
0.61
1073
62.10
0.67
1103
113.71
0.71
1123
138.70
0.61
0.62
1352
1.0
0.9
0.9
0.8
Calculation result
0.6
0.7
Activity of NaCl
0.7
Activity of KCl
Experimental data
0.8
Experimental data
0.5
0.4
0.3
Calculation result
0.6
0.5
0.4
0.3
0.2
0.2
0.1
0.1
0
0
0.2
0.4
0.6
0.8
1.0
Fig. 7
Table 5
0.2
0.4
0.6
0.8
1.0
Fig. 8
The experimental and calculated data on partial vapor pressure and activity of NaCl in a NaClCaCl2 system.
Caculation
data
Experimental results
Sample compositon,
mole fraction
0.25NaCl+0.75CaCl2
0.50NaCl+0.50CaCl2
0.75NaCl+0.25CaCl2
Temperature
(T/K)
Partial vapor
pressure of
NaCl (p/Pa)
Activity of
NaCl
Activity of
NaCl
0.12
1073
7.32
0.11
1103
20.01
0.18
1123
28.53
0.18
0.12
1073
24.45
0.36
0.34
1103
55.24
0.48
1123
66.22
0.42
0.35
1073
45.01
0.66
0.67
1103
81.15
0.71
1123
109.76
0.70
0.67
Table 6 The experimental and calculated data on partial vapor pressures and activities of KCl and NaCl in the KClNaClCaCl2 system.
Caculation
data
Experimental result
Sample composition,
mole fraction
Temperature
(T/K)
Partial vapor
pressure (p/Pa)
KCl
0.50CaCl2 +0.25NaCl+0.25KCl
0.50KCl+0.25CaCl2 +0.25NaCl
0.50NaCl+0.25CaCl2 +0.25KCl
NaCl
Activity
KCl
Activity
NaCl
KCl
NaCl
0.20
1073
12.92
13.12
0.14
0.19
0.10
1103
31.10
19.41
0.09
0.13
1123
34.62
27.75
0.15
0.18
0.10
0.20
0.25
1073
41.44
18.57
0.44
0.27
0.35
1103
64.75
17.55
0.40
0.15
1123
87.93
41.42
0.39
0.26
0.36
0.25
0.47
1073
9.35
33.47
0.10
0.49
0.16
1103
20.52
51.39
0.13
0.45
1123
37.08
60.89
0.16
0.39
0.16
0.47
4.2.4 KClNaClCaCl2
Table 6 shows the measured data of partial vapor pressures
and activities of KCl and NaCl in the KClNaClCaCl2
system, along with the calculated results obtained using
Factsage 5.2. Figure 9 shows the comparison between the
experimental and calculated data on the activities of KCl and
NaCl in a 0.25CaCl2 NaClKCl system at 1073 K. As
Vapor Pressure Measurements for Metal Chloride Systems by the Knudsen Eusion Method
1353
0.75
0.6
REFERENCES
Activity
0.45
NaCl
KCl
0.3
0.15
0
0
0.15
0.3
0.45
NaCl
0.6
0.75
KCl
Mole fraction
5.
Conclusion