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Department of Chemical Engineering, Ben Gurion University of the Negev, POB 653, 84105 Beer Sheva, Israel
Departamento de Ciencias Agrarias, Universidade dos Acores, Terra-Cha, 9700 Angra do Herosmo, Portugal
Departamento de Qumica e Bioqumica, Faculdade de Ciencias da Universidade de Lisboa, 1749-016 Lisbon, Portugal
b
Received 12 September 2004; received in revised form 16 November 2004; accepted 17 November 2004
Abstract
It was found that transport properties of gases (viscosity , thermal conductivity , and diffusion coefficients D) in the form of the quantity:
D
C = T
are temperature independent in the 7002000 K temperature interval. Although the exponent seems to be independent inside the
group for all the monoatomic vapours it seems to change between different groups ( = 1.909 0.015 for alkali metal vapours Li, Na, K,
Rb and Cs; = 1.72 0.05 for noble gases He, Ne, Ar, Kr, and Xe). In this approach, transport properties of gases are correlated using only
different values of C. This fact was extended to the properties of the binary mixtures of monoatomic and diatomic molecules in the alkali
metal vapours, to obtain the mutual diffusion coefficients D12 (T, p) and the self-diffusion coefficients of diatomic molecules, D22 (T).
2004 Elsevier B.V. All rights reserved.
Keywords: Alkali metal vapours; Dimerization; Noble gases; Viscosity; Thermal conductivity; Diffusion coefficients
1. Introduction
Considering the technological importance of gases at high
temperatures, as a part of the project developed under the
auspices of the Subcommittee on Transport Properties of
the Commission of Thermodynamics of IUPAC, the transport properties of the alkali metal vapours were investigated
by Nieto de Castro group in Lisbon [15]. These properties
included viscosities, , thermal conductivities, , and selfdiffusion coefficients, D, of the lithium, sodium, potassium,
rubidium and cesium monoatomic vapours in the 7002000 K
temperature range. In Fialho thesis and in the series of papers
[16], transport properties of the alkali metal vapours were
derived from the kinetic theory of gases [79] and compared
(T ) =
1
5
(mkT )1/2 (2,2)
16
(T )
1/2
75 k3 T
1
(T ) =
(2,2)
64
m
(T )
(1)
(2)
216
1/2
3 k3 T 3
1
D(T ) =
(1,1)
8p
m
(T )
(T ) =
4m
(T )
15k
(4)
1/2
D
(kmT 3 )
=
(1,1) (T )
10p
(5)
At constant pressure p, diffusion coefficients are often empirically correlated by the two-parameter C, equation [11]
D(T ) = CT
(6)
of correlation (i.e. D
is proportional to T ) then it is expected
that the plot of ln (D/) against ln T will be linear. This is
actually observed for all alkali metals; for example, the behaviour of lithium vapours is illustrated in Fig. 1. Values of
(T), (T) and D(T) in calculations of the D/ quotients
Table 1
The coefficients of Eq. (7)
1013 C
1013 C
Li
Na
K
Rb
Cs
1.909
1.883
1.910
1.922
1.919
0.735
1.517
1.203
1.478
1.638
0.735
1.265
1.217
1.627
1.763
1.909
0.015
He
Ne
Ar
Kr
Xe
1.735
1.642
1.742
1.773
1.699
10.914
3.084
1.139
1.074
1.718
12.294
1.792
1.348
1.593
1.496
1.72
0.05
N2
1.690
7.342
D
T
T (K)
1013
Li
Na
Rb
Cs
700
800
900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
0.735
0.736
0.737
0.736
0.736
0.735
0.734
0.734
0.734
0.734
0.735
0.736
0.737
0.738
1.294
1.285
1.277
1.270
1.264
1.260
1.257
1.255
1.255
1.254
1.255
1.257
1.259
1.262
1.221
1.219
1.217
1.215
1.214
1.212
1.212
1.212
1.213
1.214
1.217
1.219
1.222
1.225
1.621
1.620
1.621
1.619
1.620
1.620
1.620
1.623
1.626
1.629
1.632
1.637
1.642
1.646
average
0.735
0.001
1.265
0.013
1.217
0.004
1.627
0.009
Table 3
Temperature dependence of the quotient
D
T
T (K)
1013
He
Ne
Ar
Kr
Xe
N2
1.758
1.760
1.758
1.757
1.758
1.757
1.758
1.760
1.762
1.765
1.768
1.771
1.775
1.780
700
800
900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
1.214
1.215
1.221
1.224
1.230
1.235
1.236
1.234
1.232
1.231
1.232
1.235
1.237
1.236
0.188
0.186
0.185
0.182
0.181
0.180
0.179
0.178
0.177
0.176
0.175
0.175
0.174
0.174
0.134
0.132
0.134
0.134
0.134
0.134
0.135
0.135
0.135
0.135
0.136
0.136
0.136
0.137
0.155
0.155
0.156
0.157
0.158
0.158
0.159
0.160
0.160
0.161
0.162
0.162
0.163
0.164
0.152
0.153
0.150
0.149
0.149
0.150
0.149
0.149
0.149
0.149
0.149
0.149
0.149
0.149
0.614
0.611
0.607
0.604
0.601
0.600
0.598
0.597
0.596
0.596
0.596
0.596
0.597
0.597
1.763
0.008
average
1.229
0.008
0.179
0.005
0.135
0.001
0.158
0.003
0.150
0.001
0.601
0.006
were taken from [3]. If the accuracy of experimental and theoretical data is compared [110], it is clear from Table 1 that
the applied correlation (7) is only one-adjustable parameter
equation, because the - parameter is practically the same
for all alkali metal vapours (the average value for Li, Na, K,
Rb and Cs vapours is: = 1.909 0.015)
(T )D(T )
=C
(T )T
217
(7)
prevents verification of this hypothesis. In the case of the noble gases, the average value of -parameter, = 1.72 0.05,
shows greater variation than was observed for the alkali metals, mainly as a result of a low value of the -parameter for the
neon gas (Table 1). This fact that can possibly be attributed
to a less accurate knowledge of the transport properties of
neon gas. On the contrary, the constancy of the C-parameter
is even better obeyed by the noble gases than by the alkali
metal vapours.
For molecular gases (O2 , N2 , Cl2 , . . .), the quotient D/
can only be evaluated for nitrogen (lack of diffusion coefficients for other gases [11]). The - parameter of N2 is not
far from those observed for the noble gases (Table 1), but
because it should be compared with the - values of other
molecular gases, nitrogen is treated separately and only the
and C parameters are reported (Tables 1 and 3).
y2 p
(1 y)p0
(8)
Table 4
The coefficients of Eq. (10)
Li
Na
K
Rb
T (K)
A (J K1 mol1 )
103 B (J K2 mol1 )
106 C (J K3 mol1 )
H (kJ mol1 )
12002000
8001300
8001900
7001200
5.180802
7.711819
3.939518
6.502770
10.175629
5.631470
1.732501
6.845959
3.736591
1.652149
1.804059
4.091932
7.290692
3.416005
5.349325
3.527915
107.80
71.38
53.80
48.57
218
Fig. 2. The ratios fD (T, p) of sodium vapours as a function of temperature and pressure. B: 1 kPa; C: 5 kPa; D: 10 kPa; E: 50 kPa; F: 80 kPa; G: 100 kPa; H:
200 kPa; I: 400 kPa; J: 800 kPa and K: saturated pressure (liquidvapour system).
Table 5
The mutual diffusion coefficients of the lithium vapours
T (K)
5 kPa
10 kPa
30 kPa
80 kPa
100 kPa
200 kPa
400 kPa
600 kPa
800 kPa
1150
1175
1200
1225
1250
1275
1300
1325
1350
1375
1400
1425
1450
1475
1500
1525
1550
1575
1600
1625
1650
1675
1700
1725
1750
1775
1800
1825
1850
1875
1900
1925
1950
1975
2000
2.292
2.388
2.486
2.586
2.687
2.791
2.896
3.004
3.113
3.224
3.337
3.452
3.568
3.687
3.807
3.929
4.054
4.180
4.307
4.437
4.568
4.702
4.837
4.974
5.113
5.254
5.396
5.540
5.687
5.835
5.984
6.136
6.290
6.445
6.602
1.805
2.003
2.200
2.395
2.587
2.773
2.955
3.130
3.301
3.468
3.631
3.791
3.947
4.101
4.254
4.407
4.558
4.707
4.860
5.011
5.160
5.313
5.465
5.621
5.775
5.931
6.090
6.246
6.407
6.567
2.034
2.232
2.432
2.631
2.829
3.021
3.209
3.393
3.574
3.750
3.924
4.092
4.260
4.425
4.587
4.749
4.911
5.071
5.232
5.391
5.550
5.711
5.875
6.037
6.198
6.362
6.526
2.394
2.593
2.796
3.000
3.204
3.406
3.606
3.805
4.001
4.194
4.384
4.574
4.759
4.944
5.125
5.305
5.484
5.662
5.839
6.018
6.194
6.371
2.769
2.967
3.170
3.374
3.582
3.791
4.001
4.208
4.417
4.624
4.831
5.035
5.237
5.437
5.638
5.836
6.034
2.821
3.018
3.197
3.422
3.630
3.839
4.050
4.260
4.470
4.682
4.889
5.099
5.303
5.508
5.714
5.916
3.146
3.337
3.537
3.738
3.946
4.155
4.370
4.583
4.799
5.015
5.231
5.449
3.645
3.836
4.033
4.238
4.442
4.654
4.867
3.947
4.137
4.333
4.534
4.326
219
Table 6
The mutual diffusion coefficients of the sodium vapours
T (K)
825
850
875
900
925
950
975
1000
1025
1050
1075
1100
1125
1150
1175
1200
1225
1250
1275
1300
1325
1350
1375
1400
1425
1450
1475
1500
5 kPa
10 kPa
50 kPa
80 kPa
100 kPa
200 kPa
400 kPa
800 kPa
1000 kPa
0.433
0.504
0.573
0.639
0.700
0.758
0.813
0.866
0.918
0.968
1.018
1.068
1.118
1.168
1.220
1.270
1.323
1.375
1.429
1.483
1.538
1.594
1.651
1.709
1.768
1.827
1.888
1.949
0.435
0.507
0.581
0.654
0.726
0.796
0.864
0.929
0.992
1.053
1.113
1.172
1.231
1.288
1.347
1.404
1.462
1.521
1.579
1.639
1.699
1.759
1.821
1.882
1.945
0.476
0.547
0.620
0.695
0.769
0.842
0.913
0.983
1.050
1.116
1.181
1.244
1.307
1.369
1.431
1.493
1.555
1.617
1.679
1.741
1.804
1.868
1.933
0.637
0.708
0.782
0.858
0.935
1.013
1.090
1.168
1.244
1.320
1.396
1.470
1.544
1.617
1.691
1.763
1.836
0.695
0.766
0.839
0.916
0.993
1.072
1.151
1.230
1.308
1.387
1.465
1.543
1.621
1.697
1.774
0.725
0.796
0.869
0.945
1.023
1.102
1.181
1.261
1.341
1.421
1.500
1.580
1.658
1.736
1.024
1.101
1.180
1.260
1.342
1.424
1.507
1.590
0.957
1.026
1.098
1.173
1.250
1.330
1.411
1.106
1.175
1.245
1.204
ln K(T ) = E
H
A
B
C 2
+ ln T + T +
T
RT
R
R
2R
(9)
Fig. 3. The mutual diffusion coefficients D12 (T, p) of potassium vapours as a function of temperature and pressure. B: 1 kPa; C: 5 kPa; D: 10 kPa; E: 50 kPa;
F: 100 kPa; G: 200 kPa; H: 400 kPa; I: 800 kPa; J: 1000 kPa and K: 1500 kPa.
220
Table 7
The mutual diffusion coefficients of the potassium vapours
T (K)
700
725
750
775
800
825
850
875
900
925
950
975
1000
1025
1050
1075
1100
1125
1150
1175
1200
1225
1250
1275
1300
1325
1350
1375
1400
1425
1450
1475
1500
5 kPa
10 kPa
50 kPa
100 kPa
200 kPa
400 kPa
800 kPa
1000 kPa
1500 kPa
0.221
0.248
0.274
0.298
0.322
0.345
0.368
0.391
0.414
0.437
0.461
0.485
0.509
0.535
0.560
0.586
0.613
0.640
0.667
0.696
0.724
0.754
0.784
0.814
0.845
0.877
0.909
0.942
0.975
1.009
1.043
1.079
1.114
0.277
0.307
0.336
0.364
0.391
0.418
0.445
0.471
0.498
0.525
0.551
0.578
0.606
0.634
0.662
0.691
0.720
0.750
0.780
0.811
0.842
0.870
0.907
0.940
0.973
1.007
1.042
1.064
1.113
0.306
0.337
0.368
0.398
0.427
0.456
0.484
0.513
0.541
0.569
0.598
0.627
0.656
0.685
0.715
0.746
0.776
0.807
0.839
0.871
0.904
0.937
0.971
1.005
1.040
1.076
1.111
0.377
0.412
0.445
0.479
0.513
0.547
0.580
0.613
0.646
0.679
0.713
0.746
0.780
0.814
0.848
0.882
0.917
0.953
0.988
1.020
1.061
1.098
0.433
0.468
0.503
0.538
0.574
0.609
0.644
0.680
0.716
0.751
0.787
0.823
0.859
0.896
0.932
0.968
1.006
1.043
1.081
0.486
0.522
0.558
0.595
0.632
0.669
0.706
0.744
0.782
0.820
0.858
0.897
0.935
0.974
1.013
1.052
0.575
0.611
0.650
0.687
0.725
0.764
0.804
0.843
0.883
0.924
0.964
1.006
0.701
0.739
0.778
0.818
0.858
0.899
0.940
0.757
0.796
0.836
0.876
0.917
0.837
0.877
can be defined for the gas mixtures under consideration. In the absence of any information about the interaction monomerdimer (D12 ) and dimerdimer (D22 ),
the binary diffusion coefficient can be approximated by
Fig. 4. The apparent self-diffusion coefficients D22 (T, p) of rubidium vapours as a function of temperature and pressure. B: 1 kPa; C: 5 kPa; D: 10 kPa; E:
50 kPa; F: 100 kPa; G: 200 kPa; H: 400 kPa; I: 800 kPa; J: 1000 kPa and K: 1500 kPa.
221
Table 8
The mutual diffusion coefficients of the rubidium vapours
T (K)
700
725
750
775
800
825
850
875
900
925
950
975
1000
1025
1050
1075
1100
1125
1150
1175
1200
1225
1250
1275
1300
1325
1350
1375
1400
1425
1450
1475
1500
5 kPa
10 kPa
50 kPa
100 kPa
200 kPa
400 kPa
800 kPa
1000 kPa
1500 kPa
0.146
0.160
0.173
0.187
0.200
0.213
0.226
0.240
0.253
0.267
0.281
0.296
0.311
0.326
0.342
0.358
0.374
0.390
0.408
0.425
0.442
0.461
0.479
0.498
0.517
0.537
0.557
0.577
0.598
0.619
0.640
0.662
0.684
0.151
0.168
0.184
0.200
0.215
0.230
0.245
0.261
0.276
0.291
0.307
0.322
0.338
0.355
0.371
0.388
0.406
0.423
0.441
0.459
0.478
0.497
0.516
0.536
0.556
0.576
0.597
0.618
0.639
0.662
0.684
0.169
0.187
0.203
0.220
0.237
0.253
0.269
0.285
0.302
0.318
0.335
0.352
0.368
0.386
0.403
0.421
0.439
0.458
0.476
0.496
0.515
0.534
0.554
0.575
0.596
0.617
0.639
0.661
0.683
0.195
0.214
0.233
0.252
0.271
0.291
0.309
0.329
0.348
0.367
0.386
0.405
0.425
0.444
0.464
0.484
0.504
0.525
0.546
0.567
0.588
0.610
0.632
0.654
0.677
0.228
0.248
0.268
0.288
0.308
0.328
0.348
0.369
0.389
0.409
0.430
0.451
0.472
0.493
0.514
0.535
0.557
0.579
0.601
0.624
0.646
0.670
0.261
0.281
0.302
0.322
0.343
0.365
0.386
0.408
0.429
0.451
0.473
0.495
0.518
0.540
0.563
0.586
0.609
0.633
0.657
0.314
0.335
0.356
0.378
0.400
0.422
0.445
0.468
0.491
0.514
0.537
0.561
0.585
0.609
0.634
0.368
0.390
0.411
0.434
0.457
0.480
0.503
0.527
0.551
0.576
0.601
0.402
0.423
0.446
0.468
0.492
0.515
0.539
0.564
0.589
0.450
0.472
0.494
0.518
0.542
0.565
[2,8]
1
y(T, p)
1 y(T, p)
=
+
D12 (T, p)
D11 (T )
D22 (T )
(10)
and they satisfy the inequality D22 (T) < D12 (T, p) < D11 (T).
The self-diffusion coefficients D11 (T) are defined for the
hypothetical gas at T, which consists of only monoatomic
molecules and similarly, D22 (T) is defined for the hypothetical gas at T, which consists of only diatomic molecules (actually the products pD(T) and not the self-diffusion coefficients
are independent of pressure p, see Eq. (3)). The mutual diffusion coefficients are function of T and p because the mole
fractions of monomers and dimers depend on temperature
and pressure.
Let us introduce
C(T, p) =
(T, p)D11 (T )
(T, p)T
(11)
(12)
222
Table 9
The self-diffusion coefficients of the alkali metal vapours
T (K)
700
750
800
850
900
950
1000
1050
1100
1150
1200
1250
1300
1350
1400
1450
1500
1550
1600
1650
1700
1750
1800
1850
1900
1950
2000
0.093
0.112
0.135
0.161
0.191
0.225
0.264
0.307
0.356
0.411
0.472
0.541
0.616
0.700
0.792
0.893
1.004
1.125
Na
104 D11
2.292
2.486
2.687
2.896
3.113
3.337
3.568
3.807
4.054
4.307
4.568
4.837
5.113
5.396
5.687
5.984
6.290
6.602
104 D22
0.045
0.056
0.069
0.084
0.102
0.121
0.144
0.169
0.198
0.230
0.265
0.305
0.348
0.396
K
104 D11
104 D22
104 D11
104 D22
104 D11
0.676
0.752
0.831
0.914
1.002
1.093
1.188
1.287
1.390
1.498
1.609
1.723
1.842
1.965
0.028
0.036
0.044
0.055
0.066
0.079
0.094
0.111
0.130
0.152
0.175
0.201
0.230
0.261
0.295
0.332
0.373
0.263
0.299
0.337
0.378
0.421
0.467
0.514
0.564
0.617
0.671
0.728
0.787
0.849
0.912
0.978
1.046
1.117
0.018
0.023
0.029
0.036
0.044
0.053
0.064
0.076
0.089
0.104
0.120
0.139
0.159
0.181
0.206
0.233
0.262
0.160
0.182
0.205
0.230
0.257
0.285
0.314
0.344
0.377
0.410
0.445
0.481
0.519
0.558
0.599
0.641
0.685
Rb
(13)
D11 (T) and the mutual diffusion coefficients D12 (T, p). In
the case of D22 (T) this happens only at high temperatures
(T > 1500 K), when at lower temperatures it is observed that
D22 (Li) < D22 (Na) < D22 (Rb) < D22 (K) (Table 9). At this moment, there is no plausible explanation for this fact. Probably,
at low temperatures (i.e. also at low pressures), the knowledge about the monomer dimer equilibrium, in the case
of the lithium and sodium vapours, is not enough accurate
to give correct estimation of D22 (T) coefficients by the applied method. In fact, some suggestion about the possibility
of tetramer or higher order n-mer formation was reported
previously [12] and this can justify such departures, as the
self-diffusion coefficients of the dimers would be overestimated.
4. Conclusion
New and simple relations where found for the transport properties of gases (viscosity , thermal conducitivity , and diffusion coeffients D) in the form of the quo)D(T )
tient C = (T
(T )T , temperature independent between 700
and 2000 K, with the parameter characterising a group (alkali metal monoatomic vapours or noble gases). In this approach, transport properties of gases are correlated only by
different values of C. This fact was extended to the prop-
thermal conductivity
viscosity
(l,s) (T ) collision integrals, Eqs. (1), (2), (3) and (5)
Acknowledgment
One of us (AA) would like to thank the Department of
Chemistry and Biochemistry of the University of Lisbon for
the kind hospitality offered during his stay there on sabbatical
leave in 1995 when this work was initiated.
223
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