Thermal Conductivity Equation For Carbon

A Reference Multiparameter Thermal Conductivity Equation for Carbon
Dioxide with an Optimized Functional Form

G. Scalabrin,a P. Marchi, and F. Finezzo
Dipartimento di Fisica Tecnica, Universit di Padova, via Venezia 1, I-35131 Padova, Italy
R. Span
Thermodynamik und Energietechnik (ThEt), Universitt Paderborn, D-33098 Paderborn, Germany
Received 8 May 2006; accepted 9 May 2006; published online 16 October 2006
A new thermal conductivity equation = T , in a multiparameter format was developed for carbon dioxide through the application of an optimization technique of the
functional form. The proposed equation is valid for temperatures from the triple point
Tt = 216.592 K; Pt = 0.51795 MPa to 1000 K and pressures up to 200 MPa. The calculation of density, which is an independent variable of the equation, from the experimental
T , P conditions is performed with a high accuracy equation of state for the fluid. The
thermal conductivity equation shows an average absolute deviation of 1.19% on the
selected 1407 primary data points. Its performances are slightly better than those of the
corresponding conventional model by Vesovic et al. J. Phys. Chem. Ref. Data 19, 763
1990 available from the literature; moreover the new equation is simpler to use in
particular for the near-critical region. Tables of generated values of carbon dioxide thermal conductivity are provided for check of the code implementations and for quick
evaluations. 2006 American Institute of Physics. DOI: 10.1063/1.2213631
Key words: carbon dioxide; CO2; multiparameter equations; thermal conductivity; transport properties correlation techniques.
CONTENTS
1.
2.
3.
4.
5.
6.
7.
Nomenclature. . . . . . . . . . . . . . . . . . . . . . . . . . . .
Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Experimental Data. . . . . . . . . . . . . . . . . . . . . . . . .
Procedure for Heuristically Developing the
New Equation for Thermal Conductivity. . . . . . .
4.1. Fitting a Multiparameter Empirical
Equation. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2. Bank of Terms. . . . . . . . . . . . . . . . . . . . . . . .
4.3. Screening of Data and Fitting Procedure...
The New Thermal Conductivity Equation for
Carbon Dioxide. . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1. Recommended Equation of State. . . . . . . . .
5.2. The Multiparameter Equation. . . . . . . . . . . .
5.3. Validation of the New Thermal
Conductivity Equation. . . . . . . . . . . . . . . . .
5.4. Behavior of the Thermal Conductivity
Surface. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.5. Discussion on the Validity Limits. . . . . . . .
Comparison with the Conventional Equation. . .
Tabulations of the Thermal Conductivity
Equation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
8.
9.
1550
1550
1551
1.
1551
2.
1551
1554
1555
3.
4.
1556
1556
1556
List of Tables
5.
6.
1559
7.
1560
1561
1563
8.
1567
Author to whom correspondence should be addressed; electronic mail:

gscala@unipd.it
2006 American Institute of Physics.
0047-2689/2006/354/1549/27/$40.00
1549
Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1568
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1574
9.
Summary of the available thermal conductivity

data sets for CO2. . . . . . . . . . . . . . . . . . . . . . . . . .
Substance-specific parameters for the target
fluid CO2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Parameters of Eq. 7. . . . . . . . . . . . . . . . . . . . . .
Parameters of the critical term, Eqs. 5 and
6. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Validity limits of Eq. 7. . . . . . . . . . . . . . . . . . . .
Deviations of the new thermal conductivity
equation, Eq. 7, with respect to primary,
secondary, and overall data in liquid, vapor,
and supercritical regions. Data are within the
Eq. 7 validity limits.. . . . . . . . . . . . . . . . . . . . . .
equation, Eq. 7, with respect to primary and
secondary data in vapor with temperatures
lower than the CO2 triple point. . . . . . . . . . . . . .
equation, Eq. 7, with respect to primary and
secondary data in vapor with temperatures
higher than the Eq. 7 validity limits. . . . . . . . .
Comparison of the performances of the new
thermal conductivity equation, Eq. 7, and of
1552
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1556
1556
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1557
1559
1560
J. Phys. Chem. Ref. Data, Vol. 35, No. 4, 2006
1550
10.
11.
SCALABRIN ET AL.
the Vesovic et al.16 conventional equation.
Data are within the conventional equation
validity limits. . . . . . . . . . . . . . . . . . . . . . . . . . . . 1564
Thermal conductivity of carbon dioxide along
the saturation line. The saturation pressures
and the densities are calculated by the EoS of
Span and Wagner1. . . . . . . . . . . . . . . . . . . . . . . . . 1568
Thermal conductivity of carbon dioxide in the
single phase regions. The densities are
calculated by the EoS of Span and Wagner1. . . . 1569
List of Figures
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
Distribution of the experimental points

selected as primary data.. . . . . . . . . . . . . . . . . . . .
Distribution of the primary data around the
critical temperature.. . . . . . . . . . . . . . . . . . . . . . . .
Deviations between Eq. 7 and the points in
the primary data sets.. . . . . . . . . . . . . . . . . . . . . .
Deviations between Eq. 7 and the primary
data around the critical temperature.. . . . . . . . . .
Deviations between Eq. 7 and the primary
experimental points in the low-density region...
Deviations of Eq. 7 with respect to all the
experimental points in the primary data sets
and with respect to the conventional equation16
as a function of pressure for several intervals
of temperature.. . . . . . . . . . . . . . . . . . . . . . . . . . .
Representation of Eq. 7 on a , plane for
some isotherms and isobars.. . . . . . . . . . . . . . . . .
Representation of Eq. 7 on a , plane in
the near-critical region.. . . . . . . . . . . . . . . . . . . . .
Deviations between the conventional
equation16 and the points in the primary data
sets.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Deviations between the conventional
equation16 and the primary data around the
critical temperature.. . . . . . . . . . . . . . . . . . . . . . . .
Representation of the conventional equation on
a , plane in the near-critical region.. . . . . . . .
1554
Description
NPT
P
R
T
u%
Number of data
Pressure
Gas constant
Thermodynamic temperature
Ascribed uncertainty
Greek
1554
1560
Subscripts
1561
c
ce
calc
exp
i, j,k,l
r
t
1561
Function
Sum of squares
Error deviation
Thermal conductivity
Thermal conductivity reducing
parameter
Mass density
At the critical point

Critical enhancement
Calculated
Experimental
Indexes
Reduced
At the triple point
1562
1563
1563
1566
1567
1567
1. Nomenclature
Symbol
Description
a
AAD
Bias
g,h,n
i
M
MAD
n
N
NA
Array of individual coefficients

Average absolute deviation
Bias
Adjustable parameters
Index
Molar mass
Maximum average deviation
Array of individual coefficients
Number of primary data
Avogadro number
Symbol
2. Introduction
Carbon dioxide is a fluid with a wide scientific and technological interest. In particular, its industrial applications are
becoming more and more important for instance as refrigerant fluid with low environmental impact, as supercritical solvent in extraction processes, and as enhancement agent for
reservoir oil recovery.
The scientific importance of carbon dioxide is also related
to the easiness for the experimenter to reach critical states,
because the CO2 critical temperature is not far from ambient
temperature; in fact its critical point is located at
Tc = 304.1282 K and Pc = 7.3773 MPa, as reported by Span
and Wagner.1 This substance is then regarded as test fluid for
the application of theories of critical phenomena. Also the
triple point Tt = 216.592 K, Pt = 0.51795 MPa, from Span
and Wagner1 can be quite easily reached and in particular it
is characterized by a pressure value greater than the atmospheric one. Moreover, carbon dioxide is important as a
working fluid for calibration purposes.
Therefore the knowledge of thermodynamic and thermophysical properties of CO2 with the highest possible precision is a crucial need. A high accuracy fundamental equation
of state EoS is available for CO2,1 from which all the thermodynamic properties can be calculated. The present work
is instead addressed to the modeling of the thermal conductivity.
Several approaches for the representation of transport
properties are published in the literature; a brief summary is
THERMAL CONDUCTIVITY EQUATION FOR CARBON DIOXIDE

given in other works.2,3 Among different techniques, the
method usually adopted for dedicated equations development
is based on the residual concept: it considers each transport
property function as composed of three parts, that are the
zero-density term, the excess term, and the critical enhancement term.4 Empirical or theoretically founded equations are
given for each term. In spite of the theoretical base of part of
the model, the technique is however correlative and the development of the equation for the considered fluid requires
experimental data of the transport property in the whole interest range. In the following the equations in this format will
be referred to as conventional.
The general form of the obtained thermal conductivity
equation is = T , , where the independent variables are
the temperature T and the density . Since the controlled
variables for the experimentation and for the technical applications are the temperature T and the pressure P, an accurate
EoS is needed for the calculation of the corresponding density value. This is a necessary condition for all the transport
property equations covering the whole fluid surface, unless
implicit functional forms are used.5
Some totally correlative techniques, alternative to the conventional procedure, were also developed.2,3,614 The technique for optimizing the functional form of multiparameter
EoSs, set up by Setzmann and Wagner,15 has proved to be a
powerful function approximator capable of drawing a transport property equation directly from the available experimental data. The method was previously used with successful
results for the modeling of viscosity2,12,13 and of thermal
conductivity.3,14 The present work deals with the application
of this modeling technique to the representation of the thermal conductivity of carbon dioxide.
The thermal conductivity equation developed by Vesovic
et al.16 in the conventional format and published in 1990 has
been assumed here for comparison.
critical indicates that both temperature and pressure are

higher than the respective critical values; zero density stands
for vapor conditions extrapolated to the limit of zero density.
The number of points NPT and the independent variables
ranges of each data set are also reported. Where necessary,
temperatures were converted to the International Temperature Scale of 1990 ITS-90.77
Table 1 reports also the result of the screening procedure
described in Sec. 4.3, i.e., the final classification of the data
sources as primary I or secondary II. The estimated uncertainties used to determine the weighting factors for the
primary data are given in the last column of the table.
The distribution of these primary data in the T , P plane is
shown in Fig. 1 and a magnification for the region around the
critical temperature is given in Fig. 2.
As it is evident from Table 1 and Figs. 1 and 2, the lowdensity vapor region and the near-critical region are thoroughly investigated, whereas the thermal conductivity in the
liquid region and in the vapor region at higher temperatures
and intermediate pressures is not as well documented.
4. Procedure for Heuristically Developing

the New Equation for Thermal
Conductivity
4.1. Fitting a Multiparameter Empirical Equation
The thermal conductivity surface of a fluid can be described through an empirical multiparameter equation in the
form = T , , n, where n represents the array of the individual coefficients to be fitted. The optimum set of values for
the equation coefficients n is obtained by minimizing an objective function calculated as a weighted sum of squares
N
=
n
2
i=1
3. Experimental Data
Due to its scientific and technological interest, the carbon
dioxide thermal conductivity was extensively studied in the
last 70 years, so data sets from several researchers are found
in the literature. However, in the last 20 years only few
sources of precise data17,18 were published and were used
also in the development of the Vesovic et al.16 equation,
whereas more recent data1921 are found to be rather inaccurate. The available data were measured with several experimental techniques, in some cases not completely well established, and the data sets have very different uncertainty
levels.
The data sources in chronological order, grouped according to the described states liquid, vapor, supercritical, are
reported in Table 1. All over the present work, liquid refers to
a thermodynamic condition with temperature lower than the
critical temperature and pressure higher than the saturation
pressure; vapor is characterized by pressure lower than the
saturation pressure or, at temperatures above the critical temperature, by pressure lower than the critical pressure; super-
1551
100 exp calcn

u%
exp
1
i
where N is the total number of primary experimental data

and u% is the estimated uncertainty of the point; the subscripts exp and calc stand for experimental and calculated
values, respectively.
In Eq. 1 the data are weighted using their estimated experimental uncertainties u%, so the contribution to the objective function resulting from the points with a larger experimental error is lower than for the more precise
measurements. For the way the uncertainties were estimated
see Sec. 4.3.
The algorithm developed by Setzmann and Wagner15 is the
base of the optimization technique used for the present study.
Given a bank of terms, i.e., a set of simple mathematical
expressions whose summation is suitable to represent the
desired functional dependence, the algorithm determines the
functional form which yields the best representation of the
selected experimental data with the lowest number of terms.
Since the Setzmann and Wagner algorithm is limited to
equations linear in the coefficients n, for the present problem
the flexibility of the technique was increased by coupling
also a nonlinear regression method. In this way the restricJ. Phys. Chem. Ref. Data, Vol. 35, No. 4, 2006
1552
SCALABRIN ET AL.
TABLE 1. Summary of the available thermal conductivity data sets for CO2
Ref.
First author
Phasea
NPT
T range
K
P range
MPa
Meas. methodb
Class
Uncert.
%
CC
HW, S
CC
CC
CC
PP
CC
HW, S
CC
HW, S
CC
HW
HW
I
HW, S
HW, S
CC, PP
I
II
II
II
II
I
I
II
I
II
I
II
I
II
I
II
II
5.0
2.0
5.0
5.0
5.0
5.0
5.0
HW, S
HW, S
HW, S
HW, S
CC
HW, S
HW, S
HW, S
HW, S
HW, S
HW, S
CC
CC
HW, S
CC
HW, S
HW, S
CC
CC
CC
CC
HW, S
HW, S
CC
CC
CC
CC
PP
HW, S
CC
HW, S
HW, S
HW, S
HW, S
II
II
I
II
II
II
II
II
II
I
II
II
II
II
II
II
II
I
II
I
II
II
II
II
II
II
II
I, II
II
II
II
II
II
II
1.0
1.0
5.0
1.0
2.0
Liquid
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
23
37
Sellschopp
Koch
Borovik
Keyes
Guildner
Michels
Le Neindre
Shingarev
Le Neindre
Tarzimanov
Le Neindre
Paul
Salmanov
Becker
Tarzimanov
Koch
Amirkhanov
l
l
l
l
l
l
l
l
l
l
l
l
l
l
l
sl
sl
Total
22
18
9
1
4
14
13
17
6
4
11
5
19
19
12
8
90
285304
283303
283303
274
277299
298303
295304
231303
296304
299
298
298
222282
298
297304
283303
293303
5.79.0
5.19.1
5.19.1
5.8
4.57.7
6.4134.4
10.7104.1
5.820.3
21.181.1
10.181.0
10.0110.0
6.630.7
2.09.0
6.640.1
9.0196.0
*
*
272
Vapor
38
39
40
41
22
42
43
44
23
45
46
24
25
47
48
49
50
51
52
53
54
55
56
57
58
59
26
27
60
28
61
62
63
29
Weber
Trautz
Dickins
Kannuluik
Sellschopp
Archer
Sherratt
Eucken
Koch
Johnston
Kannuluik
Borovik
Keyes
Stops
Kannuluik
Stolyarov
Franck
Keyes
Keyes
Lenoir
Rothman
Thomas
Salceanu
Guildner
Vines
Geier
Guildner
Michels
Westenberg
Le Neindre
Mukhopadhyay
Barua
Christensen
Shingarev
zd
zd
zd
zd
v
zd
zd
zd
v
zd
v
v
v
zd
v
v
zd
zd
v
v
v
zd
zd
v
v
v
v
v
zd
v
v
zd
zd
v
1
1
1
1
18
11
10
6
32
14
26
7
14
6
9
12
7
5
9
12
29
4
1
4
4
12
12
104
3
11
7
5
3
2
273
273
285
273
285314
285592
339566
195598
283313
186379
197375
293313
274298
5771308
275
280475
197598
274631
274423
314340
6311047
314337
303
304305
5431173
2731373
277347
298348
300500
294309
258473
273473
308388
299307
0.16.7
0.17.1
0.00.1
5.17.1
0.16.1
0.00.1
0.13.0
0.16.1
0.16.8
0.1
0.27.3
0.1
0.1
0.25.8
0.17.4
0.15.7
0.1
1.0
1553
TABLE 1. Summary of the available thermal conductivity data sets for CO2Continued
Ref.
First author
Phasea
NPT
64
30
65
66
67
31
32
68
33
69
70
71
35
36
72
73
74
17
18
19
20
21
23
van Dael
Le Neindre
Rosenbaum
Gupta
Murthy
Tarzimanov
Le Neindre
Haarman
Paul
Shashkov
Bakulin
Bakulin
Becker
Tarzimanov
Clifford
Snel
Scott
Johns
Millat
Chen
Dohrn
Heinemann
Koch
Total
v
v
v
v
v
v
v
zd
v
zd
v
v
v
v
v
v
v
v
v
v
v
v
sv
1
112
8
98
2
8
37
8
12
9
28
10
28
12
22
133
42
14
91
19
7
3
9
1116
T range
K
P range
MPa
297
327961
336434
3731348
305308
299581
298951
328468
298313
315403
225316
4001300
298308
290654
301304
298323
301350
381474
305426
304316
300420
323420
279303
0.1
0.17.1
3.37.1
0.00.1
0.2
0.16.5
0.1
0.76.9
0.12.0
0.1
3.17.4
0.16.1
0.65.9
0.05.5
0.36.8
1.87.2
0.46.7
1.47.4
0.1
0.1
*
Meas. methodb
Class
Uncert.
%
HW, S
CC
CC
HW, S
PP
HW, S
CC
HW, S
HW
HW
HW, S
HW, S
I
HW, S
HW, T
HW, S
HW, T
HW, T
HW, T
TM
HW, T
HW, T
HW, S
II
I, II
II
II
II
II
II
II
II
II
I
I
II
II
I
I
I
I
I
II
II
II
II
5.0
5.0
5.0
0.5
1.5
0.5
0.5
0.5
CC
HW, S
CC
HW, S
CC
CC
CC
PP
CC
HW, S
CC
CC
PP
PP
HW, S
CC
PP
HW
I
HW, S
HW, T
HW, T
TM
II
II
II
II
II
II
II
I
I
II
I
II
II
II
II
I
II
II
II
I
I
I
II
2.0
5.0
5.0
5.0
5.0
0.5
0.5
Supercritical region
22
23
24
49
53
57
26
27
28
29
30
65
75
67
31
32
76
33
35
36
74
17
19
Sellschopp
Koch
Borovik
Stolyarov
Lenoir
Guildner
Guildner
Michels
Le Neindre
Shingarev
Le Neindre
Rosenbaum
Murthy
Murthy
Tarzimanov
Le Neindre
Murthy
Paul
Becker
Tarzimanov
Scott
Johns
Chen
Total
sc
sc
sc
sc
sc
sc
sc
sc
sc
sc
sc
sc
sc
sc
sc
sc
sc
sc
sc
sc
sc
sc
sc
10
4
2
23
20
18
1
136
7
4
407
42
53
1
53
146
65
4
170
70
50
33
47
304323
308313
313
326473
314340
305348
304
304348
305306
310326
304961
336434
305310
308
379678
327951
305310
313
304308
305678
315348
381473
304316
7.59.1
8.19.1
8.19.1
10.130.4
8.020.8
7.530.4
7.9
7.4209.7
13.168.8
19.920.0
7.6127.8
10.069.0
7.58.3
8.3
10.1101.3
10.0120.0
7.58.3
9.127.6
7.448.8
9.8196.0
7.424.6
7.430.6
7.413.1
1366
Overall
Overall
2754
Phase: l = liquid phase; sl= saturated liquid; v = vapor phase; sv= saturated vapor; zd= zero density; sc= supercritical region.
Measurement method: CC= concentric cylinder; HW= hot wire; HW, S = hot wire steady-state; HW, T = hot wire transient; I = interferometry; PP= parallel
plate; TM= thermoelectric module.
1554
SCALABRIN ET AL.
FIG. 1. Distribution of the experimental points selected as primary data.
tions imposed by the linear method was overcome. The details of the fitting procedure are described at Sec 4.3.
4.2. Bank of Terms
A bank of terms including a total of 285 terms was used
for the optimization of the functional form. According to this
choice, the most general form of the thermal conductivity
equation can be written as
12 10
12 10
,a
= nijTri/2rj + e5r nklTrk/2rl
rTr, r,n
2
i=0 j=0
k=0 l=0
+ ncr,ceTr, r,a
with j 0 when i = 0, and l 0 when k = 0.
The reduced variables in Eq. 2 are defined as

Tr = T/Tc ,
r = /c ,
r = /c .
For temperature and density the corresponding critical values are used as reducing parameters, but the same is not
possible for thermal conductivity because this property becomes infinite at the critical point,78 so a critical thermal
conductivity cannot be measured. A parameter derived from
the dimensional analysis is therefore adopted, as it was done
in former cases such as by Laesecke et al.:5
FIG. 2. Distribution of the primary

data around the critical temperature.

TABLE 2. Substance-specific parameters for the target fluid CO2
Reference
M kg mol1
Tc K
Pc MPa
c kg m3
c mW m1 K1
c =
0.044098
304.1282
7.3773
467.6
4.81384
R5/6 P2/3
c
1/2 1/3
T1/6
c M NA
1
1
1
1
For carbon dioxide the values of the parameters involved in

the former variable definitions are reported in Table 2 to-
r exp
=
r,ceTr, r,a
gether with the literature reference.

Further parameters are the molar gas constant R
= 8.314472 J mol1 K1 as given by Mohr and Taylor,79 and
the Avogadros number NA = 6.0221353 1023 mol1 as
given by Becker et al.80
Excluding the term r,ce, the present bank of terms, Eq.
2, is similar to that successfully set up for the development
of equations for thermodynamic properties81,82 and for
viscosity2,12,13 of pure fluids. Some preliminary tests have
shown that it is suitable to represent the background thermal
conductivity of a pure fluid. The representation of the thermal conductivity enhancement in the near-critical region relies on the critical term r,ce reading:
ra1
a2Tr 12 a3r 12
a1
1
1
+ a4r 121/2a5
Tr
2 a6
= Tr = 1 a10 arccosh1 + a111 Tr2a12.
+ a7r 2a8
in which it is
6
The functional form in Eq. 5 was empirically obtained

with a trial-and-error procedure on generated data of different fluids; it is sufficiently flexible to follow the trends of the
data, as it was also shown by the results obtained for the
fluids R134a3 and R152a.14 The parameters a and the multiplying coefficient nc are regressed on data of the target fluid
during the fitting procedure.
As required by the thermal conductivity behavior, the
functional form given by Eqs. 5 and 6 diverges to infinity
at the critical point, it is identically null at zero-density conditions, and its numerical value decreases moving away from
the critical point with a rate depending on the a parameters.
The purpose of the function is to allow the r,ce term to
assume, along isotherms at temperatures higher than the
critical one, a maximum value at densities different from the
critical one, following the trend shown by the experimental
data. The function makes Eq. 5 nonsymmetric with respect to critical density.
The coefficients a4 and a5, similarly to the corresponding
parameters of the nonanalytical terms for the EoS
development,82 should be fitted to density data of both saturated vapor and saturated liquid in the vicinity of the critical
point. In this work these coefficients were fitted in such a
way using density values at the saturation condition generated by the Span and Wagner EoS;1 the obtained coefficients
were then rounded to proper values with only two decimal
digits.
It was chosen to include in the bank of terms a single but
1555
a9
very flexible critical enhancement term instead of several

simpler terms with different values of the parameters; the
choice is justified by the need for avoiding unreasonable interactions among the terms when more than one of them
would be selected for the equation during the fitting procedure. The obtained results show that one single term with the
form of Eq. 5 is sufficient to satisfactorily represent the
critical enhancement part of the thermal conductivity.
4.3. Screening of Data and Fitting Procedure
The experimental data sets available from the literature
cannot be used as a whole in the fitting procedure because of
their different uncertainty levels and the possible presence of
systematic errors. They then have to undergo a screening
procedure with the goal of identifying the more precise data
sources to include in the final regression; these experimental
points are called primary data. The rejected sources compose
the secondary data, that are used only for comparison.
The adopted modeling technique, being heuristic, can be
used for this purpose. The screening and the fitting are performed at the same time through a series of steps according
to the exposed procedure. The statistical indexes defined in
Eq. 9 are used to evaluate the deviations of the data sets
from the correlation.
The first choice of primary data was done considering the
same data sets used in the development of the conventional
equation of Vesovic et al.16 i.e., the data of Johns et al.,17
Millat et al.,18 Michels et al.,27 Le Neindre et al.,28,30,32
Dickins,40 Johnston and Grilly,45 Franck,50 Keyes,51 Lenoir
and Comings,53 Clifford et al.,72 Snel et al.,73 and Scott et
1556
SCALABRIN ET AL.
TABLE 3. Parameters of Eq. 7
gi
hi
ni
gi
hi
1
2
3
4
5
6
0.0
0.0
1.5
0.0
1.0
1.5
1.0
5.0
1.0
1.0
2.0
0.0
7.69857587
0.159885811
1.56918621
6.73400790
16.3890156
3.69415242
7
8
9
10
1.5
1.5
3.5
5.5
5.0
9.0
0.0
0.0
nc
TABLE 5. Validity limits of Eq. 7
22.3205514
66.1420950
0.171779133
0.00433043347
0.775547504
al.74. The same values of experimental uncertainty adopted

by Vesovic et al. were assumed for weighting the data in the
objective function, Eq. 1. All the points of each of these
data sets were included as primary data, supposing that, apart
from evident outliers, all the data from the same source had
been obtained with a rather homogeneous accuracy. It should
be noted that no significant experimental source has been
published after the development of the conventional equation; in fact the most recent data sets1921 either present a
limited number of points or show a low accuracy level with
respect to the other sets. Therefore, the analysis of the data
sources done by Vesovic et al.16 can be exploited here as
well.
A first correlation was regressed with the optimization algorithm based on these data, considering only those falling
outside the near-critical region. In this first step the critical
term r,ce was excluded from the bank of terms.
The deviations of the experimental data from the obtained
preliminary equation were calculated. It was evidenced that
the data of Franck50 have a lower accuracy compared to the
other sources and this set was then moved to secondary data.
Moreover, the three data sets of Le Neindre et al.28,30,32 in the
vapor phase showed inconsistencies and systematic shifting
with respect to the other data sets. From the three data sets of
Le Neindre et al. in the vapor phase, it was decided to consider as primary data only the points of Le Neindre et al.30
that cover the sparsely investigated regions, i.e., for temperatures greater than 450 K.
After a new regression on the modified set of primary data
it was found that some secondary data sets in regions with
few primary experimental data show deviations from the
equation with an acceptable level. These are the data in the
liquid region from Sellschopp22 and from Salmanov and
Tarzimanov,34 the vapor phase data from Bakulin et al.,70,71
and the data from Tarzimanov and Arslanov36 for the liquid
and supercritical regions. These data sets were included in
TABLE 4. Parameters of the critical term, Eqs. 5 and 6
i
ai
ai
1
2
3
4
5
6
3.0
6.70697
0.94604
0.30
0.30
0.39751
7
8
9
10
11
12
0.33791
0.77963
0.79857
0.90
0.02
0.20
T K
P MPa
216.591000
200
the set of the primary sources assuming an uncertainty of 5%

and a new equation was obtained using the optimization algorithm.
After the foregoing steps, the primary data inside the nearcritical region were also considered and the critical term r,ce
with tentative a coefficients was added to the last equation
obtained in the previous part. A nonlinear regression method
was used to fit only the coefficients n and a. It was found that
the vapor phase data from Michels et al.27 indicated as near
the coexistence line in the original paper, have a lower quality compared to the other ones from the same source and
these data were consequently excluded from the set of primary data. A new nonlinear regression was then done.
At this point the term r,ce with the last obtained coefficients n and a, was included again in the bank of terms and
a few cycles, consisting of the Setzmann and Wagner
algorithm15 followed by the nonlinear regression, were performed, each time updating the a coefficients of r,ce in the
bank of terms. The cycles were stopped when convergence
was reached, i.e., when the equation coefficients remained
substantially constant.
In Table 1 the primary data sets are indicated by the symbol I, while the secondary ones are labeled as II. For the
primary data the uncertainties used in the evaluation of the
objective function, Eq. 1, are reported in the last column of
the table.
5. The New Thermal Conductivity

Equation for Carbon Dioxide
5.1. Recommended Equation of State
As usual, the independent variables of the proposed thermal conductivity equation are temperature and density,
whereas the variables that can be controlled in the experimentation and in the technical applications are temperature
and pressure. Therefore an EoS is needed to convert the variables from T , P into T , . The very accurate equation
from Span and Wagner1 was assumed in the present work
and it was used to calculate the density of each experimental
point, given T and P, and to transform the thermal diffusivity
measurements of Becker and Grigull35 into thermal conductivity values. The same EoS1 should be used when calculating values from the new thermal conductivity equation as a
function of temperature and pressure.
5.2. The Multiparameter Equation
Once the final choice of primary data sets had been done,
the new thermal conductivity equation in the form
= T , was obtained at the end of the fitting procedure
described in Sec. 4.3:
1557
TABLE 6. Deviations of the new thermal conductivity equation, Eq. 7, with respect to primary, secondary, and overall data in liquid, vapor, and supercritical
regions. Data are within the Eq. 7 validity limits.
Ref.
First author
Phase
NPT
T range
K
P range
MPa
Meas. method
AAD
%
Bias
%
MAD
%
Class
CC
PP
CC
CC
CC
HW
HW, S
1.30
1.38
0.91
0.39
0.52
1.54
0.80
0.68
0.32
0.91
0.08
0.29
1.47
0.23
4.30
3.12
1.80
1.04
0.91
2.12
1.71
I
I
I
I
I
I
I
1.11
0.20
1.11
2.65
1.91
2.41
3.47
1.06
1.83
1.98
6.50
8.60
1.09
2.63
1.91
2.41
1.26
0.99
1.83
1.21
4.78
6.72
3.48
6.41
1.91
3.36
11.28
1.77
3.75
5.75
32.38
46.36
II
II
II
II
II
II
II
II
II
II
4.06
2.42
0.23
0.65
1.59
1.27
1.33
2.85
1.68
0.69
0.83
0.92
0.65
0.40
0.50
0.23
0.65
0.97
1.24
0.57
2.64
1.45
0.12
0.81
0.81
0.50
0.03
0.18
0.23
1.82
4.24
3.83
4.75
6.26
7.46
1.46
2.77
2.03
1.60
0.90
3.37
I
I
I
I
I
I
I
I
I
I
I
I
I
1.17
0.33
1.56
3.25
1.59
7.01
7.12
1.75
6.75
5.91
1.83
10.26
7.66
3.05
2.06
4.64
6.27
2.43
1.56
3.25
1.59
7.01
7.12
1.48
6.75
5.91
1.76
10.26
7.66
1.75
2.06
2.61
6.27
1.44
1.56
3.25
1.59
14.18
11.13
4.48
9.38
34.75
4.70
41.98
20.20
8.48
3.60
13.04
8.55
7.14
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
Liquid phase
22
27
28
30
32
34
36
Sellschopp
Michels
Le Neindre
Le Neindre
Le Neindre
Salmanov
Tarzimanov
l
l
l
l
l
l
l
Primary
23
24
25
26
29
31
33
35
23
37
Koch
Borovik
Keyes
Guildner
Shingarev
Tarzimanov
Paul
Becker
Koch
Amirkhanov
22
14
13
6
10
19
11
285304
298303
295304
296304
298
222282
297304
5.79.0
6.4134.4
10.7104.1
21.181.1
10.0110.0
2.09.0
29.4196.0
95
l
l
l
l
l
l
l
l
sl
sl
Total
18
9
1
4
17
4
5
19
8
90
283303
283303
274
277299
231303
299
298
298
283303
293303
5.19.1
5.19.1
5.8
4.57.7
5.820.3
10.181.0
6.630.7
6.640.1
*
*
HW, S
CC
CC
CC
HW, S
HW, S
HW
I
HW, S
CC, PP
270
Vapor phase
40
45
51
53
27
30
70
71
72
73
74
17
18
Dickins
Johnston
Keyes
Lenoir
Michels
Le Neindre
Bakulin
Bakulin
Clifford
Snel
Scott
Johns
Millat
zd
zd
zd
v
v
v
v
v
v
v
v
v
v
Primary
38
39
41
22
42
43
44
23
46
24
25
47
48
49
50
52
Weber
Trautz
Kannuluik
Sellschopp
Archer
Sherratt
Eucken
Koch
Kannuluik
Borovik
Keyes
Stops
Kannuluik
Stolyarov
Franck
Keyes
1
12
5
12
71
70
28
7
22
133
42
14
91
285
216379
274631
314340
298348
456961
225316
4001000
301304
298323
301350
381474
305426
0.16.8
0.17.4
0.17.1
0.12.0
0.1
0.65.9
0.05.5
0.36.8
1.87.2
0.46.7
HW, S
HW, S
CC
CC
PP
CC
HW, S
HW, S
HW, T
HW, S
HW, T
HW, T
HW, T
508
zd
zd
zd
v
zd
zd
zd
v
v
v
v
zd
v
v
zd
v
1
1
1
18
11
10
5
32
15
7
14
4
9
12
6
9
273
273
273
285314
285592
339566
273598
283313
275375
293313
274298
577912
275
280475
276598
274423
0.16.7
0.17.1
0.00.1
5.17.1
0.16.1
0.00.1
0.13.0
0.16.1
HW, S
HW, S
HW, S
CC
HW, S
HW, S
HW, S
HW, S
HW, S
CC
CC
HW, S
CC
HW, S
HW, S
CC
1558
SCALABRIN ET AL.
regions. Data are within the Eq. 7 validity limits.Continued
Ref.
First author
Phase
NPT
T range
K
P range
MPa
54
55
56
57
58
59
26
27
60
28
61
62
63
29
64
30
65
66
67
31
32
68
33
69
35
36
19
20
21
23
Rothman
Thomas
Salceanu
Guildner
Vines
Geier
Guildner
Michels
Westenberg
Le Neindre
Mukhopadhyay
Barua
Christensen
Shingarev
van Dael
Le Neindre
Rosenbaum
Gupta
Murthy
Tarzimanov
Le Neindre
Haarman
Paul
Shashkov
Becker
Tarzimanov
Chen
Dohrn
Heinemann
Koch
v
zd
zd
v
v
v
v
v
zd
v
v
zd
zd
v
v
v
v
v
v
v
v
zd
v
zd
v
v
v
v
v
sv
23
4
1
4
2
8
12
33
3
11
7
5
3
2
1
42
8
63
2
8
37
8
12
9
27
12
19
7
3
9
631961
314337
303
304305
543823
273973
277347
298303
300500
294309
258473
273473
308388
299307
297
327406
336434
373973
305308
299581
298951
328468
298313
315403
298308
290654
304316
300420
323420
279303
0.1
0.27.3
0.1
0.1
0.25.8
6.47.2
0.15.7
0.1
1.0
0.1
0.17.1
3.37.1
0.00.1
0.2
0.16.5
0.1
0.76.9
4.17.4
0.16.1
1.47.4
0.1
0.1
Total
Meas. method
AAD
%
Bias
%
MAD
%
Class
CC
HW, S
HW, S
CC
CC
CC
CC
PP
HW, S
CC
HW, S
HW, S
HW, S
HW, S
HW, S
CC
CC
HW, S
PP
HW, S
CC
HW, S
HW
HW
I
HW, S
TM, S
HW, T
HW, T
HW, S
3.82
1.33
6.01
1.33
1.95
1.71
1.99
14.40
1.57
0.68
1.90
2.61
1.53
2.04
1.05
2.33
1.07
4.26
0.59
2.16
2.54
0.48
1.80
1.21
5.97
4.15
20.74
4.18
4.40
24.11
2.46
1.33
6.01
0.90
1.95
0.08
0.89
13.94
1.57
0.10
0.82
2.10
1.53
2.04
1.05
2.10
1.03
4.26
0.37
2.16
1.69
0.48
0.39
0.87
5.83
3.37
15.10
4.18
4.40
23.29
7.52
1.49
6.01
2.38
2.32
2.34
5.78
59.17
2.03
1.45
4.79
4.95
1.72
2.58
1.05
5.02
2.72
8.72
0.96
3.92
5.02
0.62
6.46
3.05
15.69
10.53
38.24
5.47
5.38
95.99
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
3.30
0.62
1.22
0.77
1.21
1.03
1.87
1.15
0.76
0.82
0.72
0.48
0.25
0.93
0.69
0.10
4.37
1.89
6.41
3.90
4.68
6.30
4.65
I
I
I
I
I
I
I
1.21
0.25
14.04
40.41
27.38
7.71
4.65
12.16
3.55
9.82
2.83
16.96
0.91
2.25
13.99
10.07
40.41
27.38
1.89
4.64
11.01
3.55
9.82
0.13
12.95
0.91
2.06
10.72
30.07
102.35
31.77
20.26
9.06
51.60
3.55
19.02
13.24
42.27
0.91
5.05
42.27
II
II
II
II
II
II
II
II
II
II
II
II
II
1048
27
28
30
32
36
74
17
Michels
Le Neindre
Le Neindre
Le Neindre
Tarzimanov
Scott
Johns
sc
sc
sc
sc
sc
sc
sc
Primary
22
23
24
49
53
57
26
29
65
75
67
31
76
Sellschopp
Koch
Borovik
Stolyarov
Lenoir
Guildner
Guildner
Shingarev
Rosenbaum
Murthy
Murthy
Tarzimanov
Murthy
94
7
405
145
70
50
33
304348
305306
304961
327951
305678
315348
381473
7.4209.7
13.168.8
7.6127.8
10.0120.0
9.8196.0
7.424.6
7.430.6
PP
CC
CC
CC
HW, S
HW, T
HW, T
804
sc
sc
sc
sc
sc
sc
sc
sc
sc
sc
sc
sc
sc
10
4
2
23
20
18
1
4
42
53
1
53
65
304323
308313
313
326473
314340
305348
304
310326
336434
305310
308
379678
305310
7.59.1
8.19.1
8.19.1
10.130.4
8.020.8
7.530.4
7.9
19.920.0
10.069.0
7.58.3
8.3
10.1101.3
7.58.3
CC
HW, S
CC
HW, S
CC
CC
CC
HW, S
CC
PP
PP
HW, S
PP
1559
regions. Data are within the Eq. 7 validity limits.Continued
Ref.
First author
Phase
NPT
T range
K
P range
MPa
Meas. method
AAD
%
Bias
%
MAD
%
Class
33
35
19
Paul
Becker
Chen
sc
sc
sc
4
170
47
313
304308
304316
9.127.6
7.448.8
7.413.1
HW
I
TM
0.78
9.49
27.04
0.29
1.39
25.26
1.69
54.76
74.05
II
II
II
5.15
1.67
Total
1321
Overall
Primary
1407
1.19
0.25
Total
2639
4.31
0.35
rTr, r =
From the error deviation the following statistical quantities are evaluated: the average absolute deviation AAD,
the bias Bias, and the maximum absolute deviation MAD.
These are calculated according to:
10
niTrgirhi
+e
5r2
i=1
niTrg rh + ncr,ceTr, r
i=4
i
7
The coefficients of this equation are reported in Table 3. In
Eq. 7 the term r,ceTr , r is given by Eqs. 5 and 6 with
the parameters from Table 4. In Table 5 the validity limits of
the proposed equation are reported. The extrapolation of the
equation far outside these validity limits, particularly at low
temperatures and at high pressures, should be avoided because it may result in rather unreliable calculated values.
As shown in Fig. 1 the primary data do not regularly fill
all the extension of the stated validity range, however a regular contour was assumed for it. This assumption will be discussed further on in Sec. 5.5.
NPT
AAD% =
NPT
Bias% =
i=1,NPT
Table 6 presents the deviations of the equation from the

available experimental data inside the validity limits indicated in Table 5. Some of the primary data sets in vapor
phase contain experimental points at temperatures outside
the validity limits, but they were chosen to include also these
points in the regression in order to improve the extrapolation
capability of the obtained equation. Also data belonging to
secondary sources can be found outside the range. Comparisons of the equation with data outside its validity limits are
reported in Table 7 for temperatures lower than the triple
point and in Table 8 for higher temperatures.
The representation of the deviations of the new thermal
A detailed comparison of the new thermal conductivity

equation with both primary and secondary data is reported in
this section.
Through all the present work the error deviation was
calculated as:
exp calc
exp
100
i
NPT i=1
MAD% = 100 Max i.
5.3. Validation of the New Thermal Conductivity

Equation
100
i
NPT i=1
TABLE 7. Deviations of the new thermal conductivity equation, Eq. 7, with respect to primary and secondary data in vapor with temperatures lower than the
CO2 triple point
Ref.
First author
Phase
NPT
T range
K
P range
MPa
Meas. method
AAD
%
Bias
%
MAD
%
Class
45
Johnston
zd
186201
HW,S
2.75
2.75
3.34
2.75
2.75
5.46
4.18
1.97
5.86
3.36
1.97
5.86
8.67
1.97
II
II
II
3.93
1.60
Primary
44
46
50
Eucken
Kannuluik
Franck
Total
2
zd
v
v
1
11
1
15
195
197
197
0.00.1
0.0
HW,S
HW,S
HW,S
1560
SCALABRIN ET AL.
TABLE 8. Deviations of the new thermal conductivity equation, Eq. 7, with respect to primary and secondary data in vapor with temperatures higher than the
Eq. 7 validity limits
Ref.
First author
Phase
NPT
T range
K
P range
MPa
Meas. method
AAD
%
Bias
%
MAD
%
Class
71
Bakulin
11001300
0.1
HW,S
1.63
0.27
2.03
1.63
0.27
2.61
5.72
2.64
3.67
1.25
2.61
5.72
2.64
3.67
0.39
4.64
5.72
3.16
8.50
4.28
II
II
II
II
II
1.78
0.33
Primary
47
58
54
59
66
Stops
Vines
Rothman
Geier
Gupta
Total
3
zd
v
v
v
v
2
2
2
4
35
12031308
10331173
10421045
10731373
10731348
0.1
0.1
0.1
0.00.1
48
conductivity equation with respect to all primary data is

shown in Fig. 3 and a magnification of the same plot for the
near-critical region is given in Fig. 4.
Deviations from primary data in the low-density region,
here defined by P 0.12 MPa, are presented in detail in Fig.
5. Furthermore, the deviations of Eq. 7 with respect to the
experimental points of the primary data sets are shown in
Fig. 6 as a function of pressure for several intervals of temperature. The dashed-dotted lines represent the deviation of
data calculated by the conventional equation of Vesovic et
al.16 from the new equation; for each figure the comparison
temperature for the two equations was taken at the mean
value of the indicated range.
The tables and figures discussed above show the satisfactory performance of the new thermal conductivity equation
for CO2. The observed deviations of primary data from the
equation correspond to the claimed experimental uncertainties in each of the three regions. The significant values of
bias are probably due to systematic shifting among different
primary data sets.
Larger deviations of the data from the equation are located
HW,S
CC
CC
CC
HW,S
in the region at high temperatures and for the points at pressures higher than 100 MPa, where less accurate data sets are
available. Also the data for the low-density region show a
strong scattering and some inconsistencies, but the equation
results in a good balance between them.
The equation can safely be used for low-density vapor at
temperatures outside the validity limits, even if at lower temperatures the deviations of the equation from the few available data are larger.
Table 6 shows that several experimental data sets, belonging to secondary sources, are affected by high systematic
errors, particularly in vapor and supercritical regions.
5.4. Behavior of the Thermal Conductivity Surface
The obtained thermal conductivity equation is plotted on a
, plane for some isotherms and isobars in Fig. 7. In the
same plot there is also a magnification for the liquid and
supercritical regions at high pressures. The representation of
the surface is regular, confirming the reliability of the new
equation. The steep trends of the vapor and liquid lines at
FIG. 3. Deviations between Eq. 7 and

the points in the primary data sets.
1561

the primary data around the critical
temperature.
saturated conditions are due to the divergence toward infinity

of the thermal conductivity when approaching the critical
point. The effect of the critical term contribution can also be
noted in the plots of an isotherm and an isobar at temperature
or pressure near the respective critical values.
A more detailed representation for the near-critical region
is shown in Fig. 8, where some of the experimental data from
Michels et al.27 are plotted for comparison reporting for each
isotherm the points at approximately the same temperature.
The good representation of the experimental data confirms
the capability of the critical enhancement term, Eqs. 5 and
6, in representing the near-critical behavior of thermal conductivity.
5.5. Discussion on the Validity Limits

The validity limits of the new thermal conductivity equation are stated in Sec. 5.2. It is evident from Fig. 1 that the
primary data do not uniformly fill a single regular range,
both in temperature and in pressure. For the validity range an
irregular contour should be selected for sake of precision. In
fact one can see for instance a total lack of data for liquid at
T 295 K and P 10 MPa, a scarcity of data for vapor at
T 400 K, and 0.1 P 1 MPa, and quite a few points for
the region at T 700 K or P 100 MPa. But, looking at the
plot reporting sections of the new equation Fig. 7, it appears that the trends of the new equation, even in the zones
where experimental points are not available, are regular and

the primary experimental points in the
low-density region.
1562
SCALABRIN ET AL.
FIG. 6. Deviations of Eq. 7 with respect to all the experimental points in

the primary data sets and with respect
to the conventional equation16 as a
function of pressure for several intervals of temperature.
agree with the expected behavior. This indicates that the

equation could also be used in these zones, but taking into
account that there the equation accuracy cannot be verified
for lack of experimental data.
Moreover, it should be remembered that in the liquid
phase, particularly at high pressures, the effect of a pressure
variation on density is quite small see also Fig. 7. Therefore, since the equation variables are T and , a strong extrapolation in pressure may correspond to a small extrapolation of the thermal conductivity equation. On the other hand,
in the vapor and supercritical regions at high temperatures,

the dependence of thermal conductivity on pressure is quite
regular and smooth, allowing a reliable behavior of both interpolation and extrapolation. For these reasons the validity
range in the T , P plane is taken with a rectangular shape see
Table 5.
However, for the region at temperatures higher than 500 K
only experimental sources with lower experimental quality
are available from the literature and consequently at those
conditions the uncertainty of the equation also increases.
1563
FIG. 7. Representation of Eq. 7 on a

, plane for some isotherms and
isobars.
6. Comparison with the Conventional

Equation
The conventional equation from Vesovic et al.16 was used
for comparison. In that work the density and the involved
thermodynamic properties were calculated by the analytic
equation of state from Ely et al.,83 except for the critical
region where the scaled fundamental equation developed by
Albright et al.84 was used. Therefore the Vesovic et al.16
equation here was coherently applied using the same equations of state from Ely et al.83 and Albright et al.84 for the
calculation of the thermodynamic properties required by that
conventional equation.
A comparison with the proposed equation is made within

the validity limits of the conventional equation, which are
somewhat more restricted then the ones of the new equation.
The results of the comparison are shown in Table 9.
With respect to primary data the two equations are substantially equivalent in the liquid region; in the vapor phase
the AAD values are comparable, but the new equation shows
quite a lower value for the bias; in the supercritical region
the proposed equation has better values for both AAD and
bias.
A graphic comparison between the two equations and with
respect to experimental data is reported in Fig. 6. Further-
FIG. 8. Representation of Eq. 7 on a

, plane in the near-critical region.
1564
SCALABRIN ET AL.
TABLE 9. Comparison of the performances of the new thermal conductivity equation, Eq. 7, and of the Vesovic et al.16 conventional equation. Data are within
the conventional equation validity limits
Eq. 7
Ref.
First author
Phase
NPT
AAD
%
Bias
%
Vesovic et al.16
MAD
%
AAD
%
Bias
%
MAD
%
Class
Eq. 7
4.30
3.12
1.80
1.04
0.91
2.12
1.13
1.55
0.94
1.03
0.35
0.70
1.51
0.69
0.97
0.27
0.99
0.03
0.19
1.51
0.69
4.74
2.24
2.06
0.95
1.30
2.42
1.59
I
I
I
I
I
I
I
1.15
0.21
1.58
3.08
2.60
1.77
3.18
0.99
1.30
1.76
6.33
9.51
1.58
3.08
2.60
1.77
1.45
0.98
1.30
0.57
5.65
7.91
3.23
6.15
2.60
2.65
10.30
2.21
2.44
5.46
31.73
45.64
II
II
II
II
II
II
II
II
II
II
4.47
3.06
0.52
0.26
1.72
0.87
0.81
2.72
1.24
2.04
0.17
1.15
1.04
0.60
0.65
0.52
0.14
0.08
0.66
0.31
2.55
0.65
2.04
0.11
1.15
1.04
0.59
0.54
0.52
0.47
3.50
2.98
2.36
5.98
5.26
3.21
0.77
2.43
2.50
0.90
4.19
I
I
I
I
I
I
I
I
I
I
I
I
I
1.16
0.87
1.77
3.46
1.80
8.92
8.28
1.33
7.80
7.06
1.37
11.71
6.61
4.53
2.26
3.80
1.77
3.46
1.80
8.92
8.28
0.31
7.80
7.06
1.12
11.71
6.61
3.67
2.26
1.72
1.77
3.46
1.80
16.67
12.38
3.52
10.63
37.01
3.46
44.36
17.69
9.40
3.82
12.01
II
II
II
II
II
II
II
II
II
II
II
II
II
II
Liquid phase
22
27
28
30
32
34
36
Sellschopp
Michels
Le Neindre
Le Neindre
Le Neindre
Salmanov
Tarzimanov
l
l
l
l
l
l
l
Primary
23
24
25
26
29
31
33
35
23
37
Koch
Borovik
Keyes
Guildner
Shingarev
Tarzimanov
Paul
Becker
Koch
Amirkhanov
l
l
l
l
l
l
l
l
sl
sl
Total
22
13
12
6
9
19
6
1.30
1.39
0.93
0.39
0.49
1.54
0.66
0.68
0.26
0.93
0.08
0.41
1.47
0.66
87
1.13
0.24
18
9
1
4
17
4
5
19
8
90
1.11
2.65
1.91
2.41
3.47
1.06
1.83
1.98
6.50
8.60
1.09
2.63
1.91
2.41
1.26
0.99
1.83
1.21
4.78
6.72
262
4.16
2.49
3.48
6.41
1.91
3.36
11.28
1.77
3.75
5.75
32.38
46.36
Vapor phase
40
45
51
53
27
30
70
71
72
73
74
17
18
Dickins
Johnston
Keyes
Lenoir
Michels
Le Neindre
Bakulin
Bakulin
Clifford
Snel
Scott
Johns
Millat
zd
zd
zd
v
v
v
v
v
v
v
v
v
v
Primary
38
39
41
22
42
43
44
23
46
24
25
47
48
49
Weber
Trautz
Kannuluik
Sellschopp
Archer
Sherratt
Eucken
Koch
Kannuluik
Borovik
Keyes
Stops
Kannuluik
Stolyarov
zd
zd
zd
v
zd
zd
zd
v
v
v
v
zd
v
v
1
12
5
12
71
70
28
7
22
133
42
14
91
0.23
0.65
1.59
1.27
1.33
2.85
1.68
0.69
0.83
0.92
0.65
0.40
0.50
0.23
0.65
0.97
1.24
0.57
2.64
1.45
0.12
0.81
0.81
0.50
0.03
0.18
508
1.17
0.33
1
1
1
18
11
10
5
32
15
7
14
4
9
12
1.56
3.25
1.59
7.01
7.12
1.75
6.75
5.91
1.83
10.26
7.66
3.05
2.06
4.64
1.56
3.25
1.59
7.01
7.12
1.48
6.75
5.91
1.76
10.26
7.66
1.75
2.06
2.61
0.23
1.82
4.24
3.83
4.75
6.26
7.46
1.46
2.77
2.03
1.60
0.90
3.37
1.56
3.25
1.59
14.18
11.13
4.48
9.38
34.75
4.70
41.98
20.20
8.48
3.60
13.04
1565
the conventional equation validity limitsContinued
Eq. 7
Vesovic et al.16
Ref.
First author
Phase
NPT
AAD
%
Bias
%
MAD
%
AAD
%
Bias
%
MAD
%
Class
Eq. 7
50
52
54
55
56
57
58
59
26
27
60
28
61
62
63
29
64
30
65
66
67
31
32
68
33
69
35
36
19
20
21
23
Franck
Keyes
Rothman
Thomas
Salceanu
Guildner
Vines
Geier
Guildner
Michels
Westenberg
Le Neindre
Mukhopadhyay
Barua
Christensen
Shingarev
Van Dael
Le Neindre
Rosenbaum
Gupta
Murthy
Tarzimanov
Le Neindre
Haarman
Paul
Shashkov
Becker
Tarzimanov
Chen
Dohrn
Heinemann
Koch
zd
v
v
zd
zd
v
v
v
v
v
zd
v
v
zd
zd
v
v
v
v
v
v
v
v
zd
v
zd
v
v
v
v
v
sv
6
9
23
4
1
4
2
8
12
33
3
11
7
5
3
2
1
42
8
63
2
8
37
8
12
9
27
12
19
7
3
9
6.27
2.43
3.82
1.33
6.01
1.33
1.95
1.71
1.99
14.40
1.57
0.68
1.90
2.61
1.53
2.04
1.05
2.33
1.07
4.26
0.59
2.16
2.54
0.48
1.80
1.21
5.97
4.15
20.74
4.18
4.40
24.11
6.27
1.44
2.46
1.33
6.01
0.90
1.95
0.08
0.89
13.94
1.57
0.10
0.82
2.10
1.53
2.04
1.05
2.10
1.03
4.26
0.37
2.16
1.69
0.48
0.39
0.87
5.83
3.37
15.10
4.18
4.40
23.29
8.55
7.14
7.52
1.49
6.01
2.38
2.32
2.34
5.78
59.17
2.03
1.45
4.79
4.95
1.72
2.58
1.05
5.02
2.72
8.72
0.96
3.92
5.02
0.62
6.46
3.05
15.69
10.53
38.24
5.47
5.38
95.99
7.25
2.01
4.16
2.16
6.55
1.94
0.81
2.44
2.04
13.93
2.65
1.57
2.52
3.70
2.54
2.09
1.41
3.09
1.76
6.12
0.57
3.58
3.00
1.80
1.81
2.00
6.91
3.01
20.20
3.38
3.33
25.75
7.25
0.49
4.13
2.16
6.55
1.57
0.55
1.65
2.04
13.52
2.65
1.36
1.68
3.26
2.54
2.09
1.41
3.00
1.76
6.12
0.06
3.58
3.00
1.80
0.48
2.00
6.91
1.79
14.49
3.38
3.33
25.75
9.51
4.97
8.28
2.33
6.55
2.76
1.36
6.11
3.77
58.39
3.52
4.20
5.95
6.17
3.16
2.60
1.41
6.51
3.53
9.67
0.63
5.39
6.51
2.05
6.37
3.74
16.44
6.50
38.13
4.11
4.02
87.38
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
II
1048
3.30
0.62
3.59
1.48
1.23
0.74
1.46
1.20
1.10
2.43
0.56
0.47
0.58
1.14
0.77
0.06
1.73
0.40
8.81
2.12
6.84
4.19
3.39
10.82
4.85
I
I
I
I
I
I
I
1.39
0.57
14.55
37.77
24.85
7.34
5.25
13.25
4.33
9.76
3.22
11.38
37.77
24.85
1.66
5.25
12.77
4.33
9.76
0.76
31.13
97.88
28.02
19.43
10.29
55.55
4.33
18.72
12.15
II
II
II
II
II
II
II
II
II
Total
27
28
30
32
36
74
17
Michels
Le Neindre
Le Neindre
Le Neindre
Tarzimanov
Scott
Johns
sc
sc
sc
sc
sc
sc
sc
Primary
22
23
24
49
53
57
26
29
65
Sellschopp
Koch
Borovik
Stolyarov
Lenoir
Guildner
Guildner
Shingarev
Rosenbaum
sc
sc
sc
sc
sc
sc
sc
sc
sc
89
7
367
134
33
50
33
1.28
0.77
1.22
1.02
1.45
1.15
0.76
0.87
0.72
0.60
0.34
1.06
0.69
0.10
713
1.17
0.38
10
4
2
23
20
18
1
4
42
14.04
40.41
27.38
7.71
4.65
12.16
3.55
9.82
2.83
10.07
40.41
27.38
1.89
4.64
11.01
3.55
9.82
0.13
4.37
1.89
6.41
3.90
4.41
6.30
4.65
30.07
102.35
31.77
20.26
9.06
51.60
3.55
19.02
13.24
1566
SCALABRIN ET AL.
the conventional equation validity limitsContinued
Eq. 7
Vesovic et al.16
Ref.
First author
Phase
NPT
AAD
%
Bias
%
MAD
%
AAD
%
Bias
%
MAD
%
Class
Eq. 7
75
67
31
76
33
35
19
Murthy
Murthy
Tarzimanov
Murthy
Paul
Becker
Chen
sc
sc
sc
sc
sc
sc
sc
53
1
48
65
4
170
47
16.96
0.91
2.35
13.99
0.78
9.49
27.04
12.95
0.91
2.15
10.72
0.29
1.39
25.26
42.27
0.91
5.05
42.27
1.69
54.76
74.05
19.22
2.07
3.20
16.05
0.70
6.16
27.87
17.49
2.07
3.20
14.64
0.70
1.76
25.96
43.01
2.07
5.25
43.01
1.46
44.47
70.70
II
II
II
II
II
II
II
1225
5.43
1.76
5.39
2.50
Total
Overall
Primary
1308
1.17
0.38
1.28
0.63
Total
2535
4.41
0.34
4.55
0.28
more, the deviations of the conventional equation from the

primary experimental points are plotted in Figs. 9 and 10,
which correspond to Figs. 3 and 4 for the new equation. The
behavior of the conventional equation in the near-critical region is shown in Fig. 11 and it can be compared with that of
the proposed equation plotted in Fig. 8.
However, apart from limited differences in the performances also depending on the selection of the primary data
sets, the behaviors of the two equations with respect to data
can be regarded as equivalent. Nevertheless, another element
of comparison has to be stressed: from the users point of
view, the conventional equation is quite heavy to implement
into computer software. In fact the critical enhancement term
of the conventional thermal conductivity equation is extremely complicated: its calculation also requires the viscos-
ity value, the solution of cubic and quartic equations in complex variables, the solution of linear systems with complex
coefficients and variables, and the handling of equations with
complex parameters. Furthermore, different thermodynamic
properties, like density, isobaric and isochoric heat capacities, and isothermal compressibility, are required and they
have to be calculated from the EoS. The scaled EoS84 itself is
very difficult to handle because it implies the solution of a
number of implicit equations.
Consequently, apart from calculation speed and numerical
stability, in order to overcome these difficulties a user not
particularly experienced in numerical methods and in scaled
fundamental equations of state could decide to use the simplified equation for the critical enhancement16 and the Ely et
al.83 EoS or the Span and Wagner1 EoS all over the T , P
FIG. 9. Deviations between the conventional equation16 and the points in

the primary data sets.
1567
FIG. 10. Deviations between the conventional equation16 and the primary
data around the critical temperature.
plane, as it was done for instance by Lemmon et al.85 The

effect of these simplifications on the accuracy of such an
implemented model is not exactly known, even if it can be
roughly guessed. In fact Vesovic et al.16 stated that the use of
the simplified equation for the critical enhancement, although maintaining the scaled EoS of Albright et al.84 for the
critical region, raises the standard deviation of the Michels et
al.27 data from 1.5% to 2.7%.
On the contrary, the computer implementation of the thermal conductivity model proposed in the present work is absolutely plain: it is composed of few explicit equations involving basic mathematics and the only required
thermodynamic quantity, i.e., density, can be easily calculated all over the T , P plane from an accurate EoS.1
7. Tabulations of the Thermal Conductivity

Equation
Tabulations of thermal conductivity values of carbon dioxide generated from Eq. 7 are reported in Tables 10 and 11
for the saturation line and the single phase regions,
respectively. The density values and the saturation
properties are obtained from the EoS of Span and
FIG. 11. Representation of the conventional equation on a , plane in the

near-critical region.
1568
SCALABRIN ET AL.
TABLE 10. Thermal conductivity of carbon dioxide along the saturation line. The saturation pressures and the densities are calculated by the EoS of Span and
Wagner1
Saturated liquid
Saturated vapor
Temperature
K
Pressure
MPa
Density
kg m3
Therm. cond.
mW m1 K1
Density
kg m3
Therm. cond.
mW m1 K1
218.0
220.0
222.0
224.0
226.0
228.0
230.0
232.0
234.0
236.0
238.0
240.0
242.0
244.0
246.0
248.0
250.0
252.0
254.0
256.0
258.0
260.0
262.0
264.0
266.0
268.0
270.0
272.0
274.0
276.0
278.0
280.0
282.0
284.0
286.0
288.0
290.0
292.0
294.0
296.0
298.0
300.0
302.0
304.0
0.55042
0.59913
0.65101
0.70621
0.76484
0.82703
0.89291
0.96262
1.0363
1.1141
1.1961
1.2825
1.3734
1.4690
1.5693
1.6746
1.7850
1.9007
2.0217
2.1483
2.2806
2.4188
2.5630
2.7134
2.8701
3.0334
3.2033
3.3802
3.5642
3.7555
3.9542
4.1607
4.3752
4.5978
4.8289
5.0688
5.3177
5.5761
5.8443
6.1227
6.4121
6.7131
7.0268
7.3555
1173.40
1166.14
1158.81
1151.40
1143.92
1136.34
1128.68
1120.93
1113.08
1105.12
1097.05
1088.87
1080.56
1072.13
1063.56
1054.84
1045.97
1036.93
1027.72
1018.32
1008.71
998.89
988.83
978.51
967.92
957.04
945.83
934.26
922.30
909.90
897.02
883.58
869.52
854.74
839.12
822.50
804.67
785.33
764.09
740.28
712.77
679.24
633.69
530.30
181.09
178.26
175.46
172.69
169.94
167.21
164.51
161.83
159.18
156.54
153.93
151.33
148.76
146.20
143.65
141.13
138.61
136.11
133.62
131.14
128.68
126.21
123.76
121.31
118.87
116.43
113.99
111.55
109.11
106.68
104.24
101.80
99.359
96.920
94.487
92.066
89.673
87.334
85.100
83.074
81.485
80.957
83.968
140.30
14.584
15.817
17.131
18.530
20.016
21.595
23.271
25.050
26.936
28.935
31.052
33.295
35.670
38.184
40.845
43.662
46.644
49.801
53.144
56.685
60.438
64.417
68.640
73.124
77.891
82.965
88.374
94.148
100.32
106.95
114.07
121.74
130.05
139.09
148.98
159.87
171.96
185.55
201.06
219.14
240.90
268.58
308.15
406.42
10.837
11.007
11.180
11.357
11.537
11.721
11.910
12.104
12.303
12.509
12.721
12.942
13.173
13.414
13.669
13.939
14.227
14.542
14.845
15.162
15.501
15.865
16.255
16.676
17.132
17.627
18.168
18.762
19.417
20.143
20.952
21.861
22.888
24.059
25.409
26.985
28.855
31.123
33.962
37.680
42.908
51.240
68.705
217.95
Wagner.1 These tables can also provide useful reference

values in the validation of a computer code for the
calculation procedure.
8. Conclusions
A completely correlative modeling method was adopted
for the development of a new thermal conductivity equation
for carbon dioxide, for which a former conventional

equation16 was available. The technique is based on the optimization method for the functional form of multiparameter
equations of state, set up by Setzmann and Wagner15, and it
is combined with a nonlinear method. Such a function approximator was applied to the available thermal conductivity
data of the target fluid. An analytical expression able to ac-
1569
TABLE 11. Thermal conductivity of carbon dioxide in the single phase regions. The densities are calculated by the EoS of Span and Wagner1
Temperature
225 K
250 K
275 K
Pressure
MPa
Density
kg m3
Therm. cond.
mW m1 K1
Density
kg m3
Therm. cond.
mW m1 K1
Density
kg m3
Therm. cond.
mW m1 K1
0.01
0.05
0.10
0.15
0.20
0.25
0.30
0.40
0.50
0.60
0.80
1.00
1.50
2.00
2.50
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
15.00
20.00
25.00
30.00
40.00
50.00
60.00
70.00
80.00
100.00
150.00
200.00
0.23555
1.1837
2.3828
3.5977
4.8292
6.0779
7.3445
9.9347
12.607
15.369
1147.83
1148.32
1149.53
1150.73
1151.92
1153.10
1155.43
1157.72
1159.97
1162.17
1164.35
1166.48
1168.59
1178.64
1188.00
1196.78
1205.06
1220.33
1234.21
1246.96
1258.77
1269.80
1289.91
1332.10
1366.64
11.037
11.057
11.081
11.107
11.132
11.159
11.185
11.240
11.298
11.359
171.37
171.56
172.03
172.50
172.97
173.43
174.35
175.26
176.16
177.05
177.93
178.80
179.66
183.84
187.84
191.68
195.39
202.44
209.10
215.44
221.51
227.35
238.44
263.68
286.50
0.21191
1.0634
2.1363
3.2191
4.3120
5.4153
6.5292
8.7902
11.097
13.454
18.326
23.435
37.509
1046.88
1048.97
1051.02
1055.01
1058.86
1062.59
1066.20
1069.70
1073.11
1076.42
1091.77
1105.47
1117.90
1129.30
1149.68
1167.59
1183.63
1198.21
1211.60
1235.57
1284.39
1323.31
12.849
12.870
12.896
12.922
12.949
12.976
13.003
13.060
13.118
13.179
13.308
13.450
13.898
138.88
139.51
140.12
141.33
142.51
143.66
144.79
145.89
146.97
148.04
153.08
157.77
162.17
166.34
174.11
181.31
188.05
194.43
200.50
211.94
237.60
260.52
0.19260
0.96552
1.9374
2.9157
3.9006
4.8921
5.8905
7.9081
9.9545
12.031
16.278
20.660
32.288
45.090
59.448
76.011
919.56
928.78
937.12
944.77
951.86
958.48
964.71
991.45
1013.23
1031.80
1048.09
1075.88
1099.22
1119.48
1137.45
1153.65
1182.06
1238.14
1281.64
14.727
14.748
14.776
14.803
14.831
14.859
14.888
14.946
15.006
15.067
15.194
15.330
15.718
16.204
16.845
17.744
108.61
110.58
112.41
114.13
115.75
117.30
118.78
125.43
131.21
136.42
141.21
149.87
157.65
164.82
171.51
177.82
189.56
215.51
238.44
Temperature
Pressure
MPa
0.01
0.05
0.10
0.15
0.20
0.25
0.30
0.40
0.50
0.60
0.80
1.00
1.50
2.00
2.50
300 K
Density
kg m3
0.17652
0.88434
1.7730
2.6661
3.5636
4.4657
5.3723
7.1994
9.0456
10.911
14.703
18.579
28.674
39.420
50.936
325 K
Therm. cond.
mW m1 K1
16.659
16.681
16.708
16.736
16.764
16.793
16.821
16.879
16.937
16.997
17.120
17.248
17.599
18.006
18.492
Density
kg m3
0.16293
0.81585
1.6348
2.4568
3.2819
4.1101
4.9416
6.6141
8.2996
9.9985
13.437
16.932
25.930
35.333
45.186
350 K
Therm. cond.
mW m1 K1
18.637
18.657
18.683
18.710
18.736
18.762
18.788
18.841
18.895
18.949
19.060
19.173
19.474
19.806
20.180
Density
kg m3
0.15128
0.75726
1.5167
2.2784
3.0423
3.8085
4.5770
6.1207
7.6736
9.2360
12.389
15.581
23.739
32.165
40.878
Therm. cond.
mW m1 K1
20.652
20.671
20.695
20.719
20.743
20.767
20.791
20.839
20.887
20.936
21.034
21.133
21.390
21.663
21.957
1570
SCALABRIN ET AL.
TABLE 11. Thermal conductivity of carbon dioxide in the single phase regions. The densities are calculated by the EoS of Span and Wagner1Continued
Temperature
Pressure
MPa
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
15.00
20.00
25.00
30.00
40.00
50.00
60.00
70.00
80.00
100.00
150.00
200.00
300 K
Therm. cond.
mW m1 K1
Density
kg m3
63.376
91.965
128.40
182.31
706.06
753.17
780.97
801.62
865.82
905.57
935.42
959.70
998.35
1028.94
1054.48
1076.54
1096.02
1129.45
1193.37
1241.61
Temperature
325 K
19.083
20.759
23.635
29.773
80.915
84.071
87.110
89.783
99.977
107.58
113.93
119.50
129.19
137.61
145.20
152.17
158.69
170.68
196.80
219.64
Density
kg m3
Therm. cond.
mW m1 K1
55.544
78.043
103.53
133.08
168.48
212.90
272.52
358.04
683.09
773.46
825.55
862.99
917.21
957.10
989.03
1015.81
1038.99
1077.91
1150.09
1203.16
375 K
350 K
20.607
21.677
23.156
25.240
28.230
32.660
39.616
50.703
76.055
86.518
94.397
100.92
111.72
120.76
128.72
135.94
142.62
154.79
180.96
203.64
Density
kg m3
Therm. cond.
mW m1 K1
49.901
68.976
89.619
112.12
136.82
164.16
194.63
228.80
449.20
614.18
702.22
758.98
833.72
884.76
923.92
955.90
983.05
1027.73
1108.35
1166.27
400 K
22.279
23.031
23.971
25.155
26.637
28.474
30.719
33.433
53.133
67.117
77.030
84.813
96.943
106.63
114.95
122.38
129.17
141.45
167.54
189.98
425 K
Pressure
MPa
Density
kg m3
Therm. cond.
mW m1 K1
Density
kg m3
Therm. cond.
mW m1 K1
Density
kg m3
Therm. cond.
mW m1 K1
0.01
0.05
0.10
0.15
0.20
0.25
0.30
0.40
0.50
0.60
0.80
1.00
1.50
2.00
2.50
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
15.00
20.00
25.00
30.00
40.00
50.00
60.00
0.14118
0.70656
1.4147
2.1245
2.8360
3.5490
4.2638
5.6982
7.1393
8.5871
11.503
14.447
21.931
29.601
37.464
45.530
62.313
80.038
98.799
118.70
139.84
162.33
186.24
326.31
471.78
580.03
654.38
750.62
813.55
860.29
22.697
22.716
22.739
22.761
22.784
22.807
22.830
22.876
22.921
22.967
23.059
23.151
23.385
23.628
23.882
24.151
24.750
25.452
26.281
27.260
28.403
29.717
31.209
41.505
53.688
63.216
71.388
84.561
94.860
103.50
0.13235
0.66224
1.3257
1.9903
2.6562
3.3233
3.9916
5.3318
6.6770
8.0271
10.742
13.477
20.405
27.464
34.658
41.992
57.094
72.804
89.155
106.18
123.90
142.35
161.53
267.42
380.50
481.55
561.50
672.08
745.45
799.32
24.764
24.782
24.805
24.828
24.850
24.873
24.895
24.940
24.985
25.030
25.120
25.210
25.435
25.664
25.900
26.144
26.667
27.253
27.916
28.668
29.515
30.460
31.504
38.172
47.071
55.418
62.411
74.852
85.295
94.104
0.12456
0.62317
1.2472
1.8722
2.4981
3.1249
3.7526
5.0107
6.2725
7.5380
10.080
12.637
19.094
25.647
32.296
39.043
52.838
67.044
81.670
96.725
112.21
128.13
144.47
231.75
323.66
411.09
487.13
602.30
682.49
742.12
26.845
26.863
26.886
26.909
26.931
26.954
26.976
27.021
27.066
27.111
27.200
27.289
27.510
27.732
27.957
28.187
28.666
29.183
29.748
30.368
31.049
31.792
32.596
37.495
43.948
51.129
57.354
68.022
77.812
86.494
1571
Temperature
Pressure
MPa
70.00
80.00
100.00
150.00
200.00
375 K
Therm. cond.
mW m1 K1
Density
kg m3
897.61
928.79
979.26
1068.23
1130.90
Temperature
400 K
111.09
117.98
130.29
156.18
178.33
Density
kg m3
Therm. cond.
mW m1 K1
841.76
876.80
932.81
1029.80
1097.04
450 K
425 K
101.79
108.71
120.98
146.58
168.38
Density
kg m3
Therm. cond.
mW m1 K1
789.03
827.56
888.67
993.12
1064.66
475 K
94.161
101.05
113.23
138.47
159.89
500 K
Pressure
MPa
Density
kg m3
Therm. cond.
mW m1 K1
Density
kg m3
Therm. cond.
mW m1 K1
Density
kg m3
Therm. cond.
mW m1 K1
0.01
0.05
0.10
0.15
0.20
0.25
0.30
0.40
0.50
0.60
0.80
1.00
1.50
2.00
2.50
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
15.00
20.00
25.00
30.00
40.00
50.00
60.00
70.00
80.00
100.00
150.00
200.00
0.11764
0.58847
1.1776
1.7674
2.3580
2.9491
3.5410
4.7268
5.9154
7.1067
9.4975
11.899
17.952
24.075
30.268
36.531
49.270
62.295
75.605
89.200
103.07
117.22
131.63
207.01
285.14
361.01
430.25
542.98
626.20
689.59
739.96
781.42
847.00
958.22
1033.74
28.933
28.951
28.974
28.997
29.019
29.042
29.065
29.110
29.155
29.199
29.288
29.377
29.596
29.814
30.032
30.251
30.701
31.172
31.671
32.206
32.779
33.392
34.044
37.872
42.726
48.580
54.318
63.700
72.295
80.461
87.936
94.736
106.78
131.62
152.63
0.11144
0.55743
1.1154
1.6738
2.2328
2.7923
3.3523
4.4739
5.5975
6.7232
8.9808
11.247
16.947
22.699
28.502
34.357
46.218
58.281
70.542
82.996
95.637
108.46
121.45
188.44
256.99
324.00
386.66
493.67
576.97
642.26
694.91
738.59
807.90
925.10
1004.26
31.020
31.039
31.062
31.084
31.107
31.130
31.153
31.198
31.243
31.288
31.377
31.466
31.684
31.899
32.112
32.325
32.754
33.193
33.648
34.123
34.622
35.145
35.694
38.806
42.595
47.269
52.366
61.103
68.544
75.881
82.946
89.547
101.38
125.82
146.43
0.10587
0.52951
1.0594
1.5897
2.1204
2.6514
3.1829
4.2470
5.3126
6.3798
8.5189
10.664
16.054
21.482
26.948
32.451
43.566
54.826
66.223
77.753
89.410
101.19
113.07
173.76
235.24
295.46
352.51
452.94
534.42
600.13
654.00
699.16
771.37
893.75
976.16
33.101
33.119
33.143
33.166
33.189
33.212
33.235
33.280
33.325
33.371
33.460
33.548
33.766
33.980
34.191
34.400
34.815
35.231
35.654
36.087
36.533
36.994
37.470
40.077
43.127
46.866
51.231
59.505
66.195
72.623
79.083
85.351
96.884
120.91
141.12
Temperature
Pressure
MPa
0.01
0.05
0.10
0.15
0.20
525 K
Density
kg m3
0.10083
0.50426
1.0088
1.5137
2.0188
550 K
Therm. cond.
mW m1 K1
35.169
35.187
35.211
35.234
35.257
Density
kg m3
0.096243
0.48130
0.96283
1.4446
1.9265
575 K
Therm. cond.
mW m1 K1
37.218
37.237
37.260
37.284
37.307
Density
kg m3
0.092058
0.46035
0.92087
1.3816
1.8424
Therm. cond.
mW m1 K1
39.243
39.262
39.286
39.309
39.333
1572
SCALABRIN ET AL.
Temperature
Pressure
MPa
0.25
0.30
0.40
0.50
0.60
0.80
1.00
1.50
2.00
2.50
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
15.00
20.00
25.00
30.00
40.00
50.00
60.00
70.00
80.00
100.00
150.00
200.00
525 K
Pressure
MPa
0.01
0.05
0.10
0.15
0.20
0.25
0.30
0.40
0.50
0.60
0.80
1.00
1.50
2.00
2.50
3.00
4.00
5.00
6.00
7.00
Therm. cond.
mW m1 K1
Density
kg m3
2.5242
3.0299
4.0423
5.0558
6.0704
8.1032
10.141
15.254
20.396
25.565
30.761
41.233
51.807
62.477
73.239
84.085
95.010
106.01
161.74
217.77
272.64
325.03
419.10
497.78
562.86
617.13
663.12
737.38
864.10
949.42
Temperature
550 K
35.280
35.303
35.349
35.395
35.440
35.530
35.619
35.838
36.051
36.260
36.467
36.872
37.273
37.674
38.077
38.486
38.902
39.325
41.567
44.083
47.109
50.771
58.492
64.819
70.490
76.251
82.058
93.148
116.74
136.59
Density
kg m3
Therm. cond.
mW m1 K1
2.4087
2.8911
3.8566
4.8229
5.7901
7.7271
9.6675
14.533
19.419
24.326
29.252
39.160
49.140
59.186
69.294
79.458
89.672
99.930
151.63
203.30
253.87
302.37
390.67
466.18
529.96
584.01
630.31
705.86
836.09
923.96
600 K
575 K
37.331
37.354
37.400
37.446
37.492
37.582
37.672
37.891
38.105
38.314
38.519
38.919
39.310
39.695
40.078
40.460
40.843
41.228
43.201
45.322
47.806
50.857
57.898
64.059
69.236
74.332
79.594
90.089
113.20
132.71
Density
kg m3
Therm. cond.
mW m1 K1
2.3034
2.7646
3.6874
4.6108
5.5349
7.3850
9.2375
13.880
18.536
23.208
27.893
37.302
46.761
56.264
65.807
75.385
84.993
94.626
142.97
191.06
238.08
283.31
366.46
438.78
500.89
554.27
600.50
676.71
809.65
899.74
650 K
39.357
39.380
39.427
39.473
39.519
39.610
39.701
39.921
40.136
40.346
40.550
40.948
41.332
41.707
42.076
42.439
42.799
43.156
44.931
46.757
48.827
51.368
57.663
63.684
68.610
73.175
77.882
87.649
110.19
129.40
700 K
Density
kg m3
Therm. cond.
mW m1 K1
Density
kg m3
Therm. cond.
mW m1 K1
Density
kg m3
Therm. cond.
mW m1 K1
0.088221
0.44115
0.88242
1.3238
1.7653
2.2069
2.6487
3.5325
4.4168
5.3015
7.0723
8.8449
13.284
17.733
22.193
26.661
35.625
44.621
53.645
62.694
41.239
41.258
41.282
41.306
41.330
41.354
41.377
41.424
41.471
41.518
41.610
41.701
41.923
42.140
42.350
42.555
42.952
43.333
43.702
44.061
0.081434
0.40719
0.81444
1.2217
1.6291
2.0365
2.4439
3.2590
4.0743
4.8897
6.5212
8.1535
12.237
16.325
20.417
24.513
32.712
40.921
49.136
57.354
45.126
45.145
45.170
45.194
45.218
45.243
45.267
45.315
45.363
45.410
45.504
45.597
45.824
46.044
46.258
46.466
46.867
47.248
47.614
47.965
0.075616
0.37809
0.75619
1.1343
1.5124
1.8906
2.2687
3.0250
3.7814
4.5378
6.0507
7.5638
11.347
15.130
18.914
22.697
30.262
37.823
45.377
52.922
48.848
48.868
48.893
48.917
48.942
48.967
48.992
49.041
49.089
49.138
49.234
49.329
49.561
49.786
50.005
50.218
50.627
51.015
51.386
51.739
1573
Temperature
Pressure
MPa
8.00
9.00
10.00
15.00
20.00
25.00
30.00
40.00
50.00
60.00
70.00
80.00
100.00
150.00
200.00
600 K
Therm. cond.
mW m1 K1
Density
kg m3
71.762
80.846
89.941
135.43
180.50
224.54
266.99
345.60
414.84
475.12
527.55
573.40
649.77
784.69
876.69
Temperature
650 K
44.412
44.756
45.094
46.724
48.327
50.079
52.207
57.753
63.575
68.409
72.619
76.826
85.783
107.64
126.56
Density
kg m3
Therm. cond.
mW m1 K1
65.573
73.789
81.999
122.86
163.12
202.40
240.36
311.36
375.06
431.61
481.74
526.29
601.91
738.93
833.86
750 K
700 K
48.304
48.631
48.948
50.403
51.717
53.040
54.571
58.779
63.974
68.763
72.714
76.255
83.612
103.69
122.08
Density
kg m3
Therm. cond.
mW m1 K1
60.457
67.979
75.486
112.72
149.27
184.90
219.39
284.29
343.27
396.36
444.05
486.96
560.93
698.17
795.00
800 K
52.078
52.402
52.713
54.098
55.268
56.348
57.511
60.692
65.096
69.723
73.715
77.045
83.204
101.07
118.86
850 K
Pressure
MPa
Density
kg m3
Therm. cond.
mW m1 K1
Density
kg m3
Therm. cond.
mW m1 K1
Density
kg m3
Therm. cond.
mW m1 K1
0.01
0.05
0.10
0.15
0.20
0.25
0.30
0.40
0.50
0.60
0.80
1.00
1.50
2.00
2.50
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
15.00
20.00
25.00
30.00
40.00
50.00
60.00
70.00
80.00
100.00
150.00
200.00
0.070575
0.35287
0.70572
1.0586
1.4114
1.7642
2.1170
2.8226
3.5281
4.2335
5.6442
7.0546
10.579
14.102
17.622
21.140
28.168
35.184
42.185
49.171
56.139
63.089
70.019
104.32
137.90
170.61
202.31
262.24
317.20
367.18
412.53
453.73
525.63
661.81
759.66
52.383
52.404
52.429
52.454
52.480
52.505
52.530
52.580
52.630
52.680
52.778
52.875
53.112
53.343
53.568
53.787
54.207
54.606
54.987
55.349
55.695
56.026
56.341
57.725
58.845
59.808
60.760
63.221
66.852
71.137
75.179
78.567
84.116
99.605
116.63
0.066164
0.33081
0.66158
0.99233
1.3230
1.6537
1.9844
2.6456
3.3067
3.9676
5.2892
6.6102
9.9104
13.207
16.500
19.789
26.355
32.904
39.435
45.945
52.435
58.904
65.349
97.199
128.34
158.65
188.05
243.83
295.34
342.56
385.75
425.28
494.96
629.28
727.46
55.720
55.741
55.767
55.793
55.819
55.845
55.870
55.921
55.972
56.023
56.123
56.222
56.466
56.703
56.934
57.159
57.593
58.006
58.400
58.775
59.134
59.477
59.804
61.232
62.367
63.299
64.149
66.147
69.124
72.966
76.946
80.467
85.909
99.219
115.23
0.062271
0.31134
0.62264
0.93390
1.2451
1.5563
1.8674
2.4896
3.1116
3.7334
4.9765
6.2190
9.3220
12.421
15.515
18.604
24.769
30.913
37.036
43.138
49.217
55.272
61.304
91.077
120.15
148.45
175.92
228.18
276.69
321.46
362.68
400.64
468.08
600.07
698.04
58.858
58.879
58.906
58.932
58.958
58.985
59.011
59.063
59.115
59.167
59.269
59.371
59.621
59.864
60.102
60.334
60.782
61.211
61.620
62.011
62.386
62.745
63.088
64.591
65.785
66.745
67.573
69.309
71.788
75.171
78.978
82.590
88.231
99.823
114.57
1574
SCALABRIN ET AL.
Temperature
900 K
950 K
1000 K
Pressure
MPa
Density
kg m3
Therm. cond.
mW m1 K1
Density
kg m3
Therm. cond.
mW m1 K1
Density
kg m3
Therm. cond.
mW m1 K1
0.01
0.05
0.10
0.15
0.20
0.25
0.30
0.40
0.50
0.60
0.80
1.00
1.50
2.00
2.50
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
15.00
20.00
25.00
30.00
40.00
50.00
60.00
70.00
80.00
100.00
150.00
200.00
0.058812
0.29404
0.58803
0.88198
1.1759
1.4697
1.7635
2.3510
2.9383
3.5254
4.6989
5.8718
8.8004
11.724
14.643
17.556
23.367
29.156
34.924
40.668
46.389
52.086
57.759
85.740
113.04
139.62
165.44
214.66
260.55
303.13
342.55
379.04
444.32
573.72
671.10
61.808
61.829
61.856
61.883
61.910
61.937
61.964
62.017
62.070
62.123
62.228
62.332
62.588
62.838
63.082
63.322
63.785
64.229
64.655
65.064
65.457
65.834
66.195
67.793
69.075
70.105
70.965
72.594
74.726
77.697
81.261
84.883
90.845
101.31
114.60
0.055716
0.27856
0.55707
0.83553
1.1139
1.3923
1.6706
2.2271
2.7833
3.3394
4.4509
5.5615
8.3345
11.102
13.865
16.622
22.119
27.595
33.047
38.477
43.883
49.265
54.623
81.037
106.80
131.89
156.26
202.83
246.41
287.02
324.80
359.93
423.15
549.85
646.36
64.594
64.616
64.644
64.671
64.699
64.726
64.753
64.808
64.862
64.916
65.023
65.129
65.391
65.648
65.899
66.146
66.625
67.086
67.529
67.956
68.368
68.764
69.146
70.847
72.236
73.362
74.292
75.926
77.846
80.482
83.780
87.336
93.612
103.55
115.30
0.052930
0.26463
0.52921
0.79373
1.0582
1.3226
1.5870
2.1156
2.6439
3.1721
4.2278
5.2826
7.9159
10.544
13.166
15.783
21.001
26.196
31.368
36.517
41.644
46.746
51.825
76.856
101.27
125.04
148.15
192.37
233.89
272.73
309.01
342.88
404.15
528.11
623.57
67.258
67.280
67.308
67.336
67.364
67.392
67.420
67.475
67.530
67.585
67.695
67.804
68.072
68.335
68.593
68.847
69.341
69.818
70.279
70.724
71.155
71.571
71.973
73.784
75.287
76.523
77.548
79.265
81.081
83.465
86.508
89.946
96.464
106.39
116.65
curately represent the critical enhancement of thermal conductivity was set up and included in the equation.
The new multiparameter thermal conductivity equation
presents an AAD value of 1.19% for the selected 1407 primary data. The performance comparison with the conventional equation on the same data base shows that the two
models have similar behaviors, with a slight advantage for
the present one. However, the new equation is easier to use
and to implement into computer software; moreover it is
based on the most recent and precise equation of state for
carbon dioxide.
The functional form optimization procedure by Setzmann
and Wagner is then a useful tool for the development of
thermal conductivity equations for pure fluids since it is capable of representing the thermal conductivity surface within
the uncertainty of the experimental data all over the T , P
plane.
In order to check and improve the accuracy of the equation, additional experimental data for the thermal conductivity of carbon dioxide would be mainly needed for the liquid
phase at T 295 K, for the vapor phase at T 400 K and
0.1 P 1 MPa, and for the regions at high temperatures
and high pressures.
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45

Thermal Conductivity Equation For Carbon

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Thermal Conductivity Equation For Carbon

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A Reference Multiparameter Thermal Conductivity Equation for Carbon

Dioxide with an Optimized Functional Form

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Summary of the available thermal conductivity

J. Phys. Chem. Ref. Data, Vol. 35, No. 4, 2006

Distribution of the experimental points

At the critical point

Array of individual coefficients

J. Phys. Chem. Ref. Data, Vol. 35, No. 4, 2006