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Fluid Phase Equilibria 227 (2005) 215223

The correlation of transport properties of alkali metal vapours


and noble gases
Alexander Apelblata, , Paulo S. Fialhob , Carlos A. Nieto de Castroc
a

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

with the limited and not always consistent experimental data


[6,10].
Theoretical predictions of thermophysical parameters are
important considering the experimental difficulties associated with highly reactive gases at elevated temperatures. The
reported results were evaluated by solving the Boltzmann
equation in the ChapmanEnskog approximation, using the
appropriate intermolecular potentials and taking into account
the monomerdimer equilibrium in the gas phase [16]. The
viscosities, thermal conductivities and self-diffusion coefficients of the monoatomic alkali metal vapours are expressible in terms of the temperature dependent collision integrals
(l,s) (T )

(T ) =

Corresponding author. Tel.: +972 8 6461487; fax: +972 8 6472916.


E-mail addresses: apelblat@bgu.ac.il (A. Apelblat),
paulo.fialho@angra.uac.pt (P.S. Fialho), cacastro@fc.ul.pt
(C.A. Nieto de Castro).
0378-3812/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2004.11.015

1
5
(mkT )1/2 (2,2)

16

(T )


1/2
75 k3 T
1
(T ) =
(2,2)

64
m

(T )

(1)

(2)

216

A. Apelblat et al. / Fluid Phase Equilibria 227 (2005) 215223

Fig. 1. Representation of transport properties of monoatomic lithium vapours as a function of temperature.


1/2
3 k3 T 3
1
D(T ) =
(1,1)

8p
m
(T )

(1) and (2) (T) and (T) are interrelated by


(3)

where p is the pressure, k the Boltzmann constant, m the


(l,s) (T ) are the weighted average colmolecular mass, and
lision integrals which have contributions from the singlet and
(l,s) (T ),
triplet interactions (for the corresponding singlet,
1
(l,s) (T ), interaction collision integrals see
and the triplet,
3
Fialho et al. [5]). The logarithms of the weighted average
collision integrals were fitted to polynomials of temperature
in order to calculate (T), (T) and D(T) and to compare them
with the available experimental data. The applied model potentials of the singlet and triplet type permitted to select the
most consistent and precise sets of viscosities and thermal
conductivities for the alkali metal vapours [5].
In spite of an evident advantage in applying rigorous
molecular models, theoretical procedures are rather complex,
and therefore there is also a benefit to correlate physical properties with the help of simple, empirical equations. Such phenomenological approach is discussed in this work by treating
not only transport properties of the alkali metal vapours (Li,
Na, K, Rb, and Cs) but also those of the noble gases (He, Ne,
Ar, Kr, and Xe) and that of nitrogen.

(T ) =

4m
(T )
15k

(4)

it follows that the quotient


collision integral

In order to simplify presentation of results, viscosities,


(T), thermal conductivities, (T), and diffusion coefficients,
D(T), will be considered as dimensionless quantities, i.e. they
are treated as the quantity/[quantity unit]. In numerical calculations the units used by Fialho et al. [3] were applied,
viscosities are expressed in Pa s, thermal conductivities in
mW m1 K1 and diffusion coefficients in m2 s1 .
It is worthwhile to mention that experimental diffusion
coefficients are less documented in the literature than the
corresponding viscosities or thermal conductivities (see for
example, the Vargaftik et al. tabulation [11]). Since from Eqs.

depends only on the diffusion

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)

If the monoatomic alkali metal vapours follow the same type

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)

2. Temperature dependence of the D/ quotient

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

A. Apelblat et al. / Fluid Phase Equilibria 227 (2005) 215223


Table 2
Temperature dependence of the quotient

D
T

for the alkali metal vapours

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

for the noble gases and nitrogen

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)

Thus, it follows from Eq. (7) that transport properties in the


gaseous phase are correlated with the aid of only one, the C parameter (C has dimensions, and in the SI units is expressed
in K1 s), considering that is the same for all alkali metal
vapours.
Comparison between Eqs. (3) and (7) show that the dif (1,1) (T ) should be proportional to
fusion collision integral
T 3/2 . How accurately the correlation (7) fits the Fialho et
al. data [3] is illustrated in Table 2. As can be observed, the
constancy of the C-values in the 7002000 K temperature interval is remarkable, and is evidently good enough for the
purpose of engineering calculations.
It is worthwhile to note that the application of correlation
(7) to other gases is also successful. Similar calculations were
performed with the noble gases (He, Ne, Ar, Kr and Xe) and
nitrogen, using the available (T), (T) and D(T) values from
the Vargaftik et al. tabulation [11] and they are reported in
Table 1. Probably, Eq. (7) is valid also for other gases, but
lack of the self-diffusion coefficients at elevated temperatures

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).

3. Diffusion coefcients of the alkali metal vapours


It is generally accepted that vapours of the alkali metals are
mixtures of monoatomic (monomer) and diatomic (dimer)
molecules. The mole fractions of monomer molecules, y,
and the dimer molecules, 1 y, are available from the massaction equation:
K(T ) =

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

A. Apelblat et al. / Fluid Phase Equilibria 227 (2005) 215223

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)

104 D12 (T, p) (m2 s1 )


1 kPa

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

A. Apelblat et al. / Fluid Phase Equilibria 227 (2005) 215223

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

104 D12 (T, p) (m2 s1 )


1 kPa

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

where K(T) is the dissociation constant of dimer molecules,


p the pressure, and p0 the reference pressure (p0 = 0.1 MPa).
Temperature dependence, which is consistent with the Vargaftik et al. composition of the alkali metal vapour mixtures
[11] is expressed by [2,5]:

ln K(T ) = E

H
A
B
C 2
+ ln T + T +
T
RT
R
R
2R

(9)

and the coefficients of this equation are presented in


Table 4.
The effect of the monomer dimer equilibrium at different T and p on viscosity and thermal conductivity was
considered in the Fialho thesis [2] and in other papers [4,6]
by determining the (T, p) and (T, p) surfaces in the case
of Li, Na, K and Rb vapours. However, the corresponding D(T, p) surfaces were not determined and therefore

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

A. Apelblat et al. / Fluid Phase Equilibria 227 (2005) 215223

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

104 D12 (T, p) (m2 s1 )


1 kPa

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

they will discussed here in the context of the correlation


(7).
Two self-diffusion coefficients, D11 (T, monomer), D22 (T,
dimer) and the mutual diffusion coefficient, D12 (T, p)

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.

A. Apelblat et al. / Fluid Phase Equilibria 227 (2005) 215223

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

104 D12 (T, p) (m2 s1 )


1 kPa

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)

This quantity is similar to that in Eq. (7) but in this case


the quantity C(T, p) is not constant and depends on T and p.
The ratios fD (T, p) = C(T, p)/C (C is the value taken from Eq.
(7) for monoatomic vapours) were calculated for the alkali

metals and a typical plot is presented in Fig. 2 for the sodium


vapours.
As can be seen in Fig. 2, all fD (T, p) curves tend to unity
when temperature increases, i.e. to the limit of monoatomic
gas where fD = 1 (the saturated pressure is evidently excluded). On the other hand, the isobaric fD curves differ more
and more from the monoatomic curve, fD = 1, as pressure increases. This can be expected from Eq. (8), because the mole
fraction of dimers (diatomic molecules) in the mixture increases as pressure increases. Since the mutual diffusion coefficients D12 (T, p) are unknown, they were replaced in C(T,
p) (Eq. (11)) by the self-diffusion coefficients D11 (T). If it
is assumed that the same form of correlation can be applied
to both diffusion coefficients, then D12 (T, p) can be approximated by
D12 (T, p) = fD (T, p)D11 (T )

(12)

and fD (T, p) can be treated as the correction factor. Without


experimental evidence, it is difficult to estimate the accuracy
of this approximation, but it is a simplest one.
In Tables 58 are presented determined in such way (Eqs.
(7), (11) and (12)) the mutual diffusion coefficients D12 (T,

222

A. Apelblat et al. / Fluid Phase Equilibria 227 (2005) 215223

Table 9
The self-diffusion coefficients of the alkali metal vapours
T (K)

104 D22 (T) and 104 D11 (T) (m2 s1 )


Li
104 D22

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

p) for the lithium, sodium, potassium and rubidium vapours.


A typical behaviour of D12 (T, p) as a function of T and p is
illustrated in the case of potassium vapours in Fig. 3. As expected, at given T, the mutual diffusion coefficients decrease
as pressure increases.
Since fD (T, p) is a function of pressure and Eq. (12) gives
only approximate values of D12 (T, p), the self-diffusion coefficients of dimers D22 (T), as calculated from Eqs. (10) and
(12), also depend on p
D22 (T, p) =

D11 (T )fD (T, p)[1 y(T, p)]


1 fD (T, p)y(T, p)

Rb

(13)

However, with increasing pressure, D22 (T, p) tends to limit


the value of D22 (T). For example, as can be observed in the
case of rubidium vapours (Fig. 4), the limiting curve is easily
recognized. Estimated in such way the self-diffusion coefficients of dimers D22 (T) for alkali metal vapours are reported
in Table 9. They are presented together with the self-diffusion
coefficients of monomers, D11 (T), calculated previously by
Fialho et al. [2,3].
As pointed out above, diffusion coefficients satisfy
D22 (T) < D12 (T, p) < D11 (T) and this inequality is observed for all alkali metal vapours. On the other
hand, it is expected between the alkali metals that:
Dij (Rb) < Dij (K) < Dij (Na) < Dij (Li), i, j = 1,2. However these
inequalities take place only for the self-diffusion coefficients

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-

A. Apelblat et al. / Fluid Phase Equilibria 227 (2005) 215223

erties 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).
List of symbols
A, B, C, E constants, Eq. (9)
C
constant, Eqs. (6) and (7)
C(T, p) defined in Eq. (11)
D11 (T) self-diffusion coefficient of monoatomic vapours
D12 (T, p) mutual diffusion coefficient
D22 (T) self-diffusion coefficient of diatomic vapours
fD (T, p) the ratio C(T,P)
C
H
standard molar enthalpy of dissociation reaction,
Eq. (9)
k
Boltzmann constant
K(T)
dissociation constant, Eqs. (8) and (9)
m
molecular mass
p
pressure
R
gas constant
T
temperature
y
mole fraction of monoatomic molecules in the gas
phase, Eq. (8)
Greek letters

constant, Eqs. (6), (7) and (11)

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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