Documente Academic
Documente Profesional
Documente Cultură
Yong Zhou (
) and Jiangtao Wu (
)a)
MOE Key Laboratory of Thermo-Fluid Science and Engineering, Xian Jiaotong University, Xian Shaanxi 710049, Peoples Republic of China
Eric W. Lemmon
Thermophysical Properties Division, National Institute of Standards and Technology, 325 Broadway, Boulder, Colorado 80305, USA
(Received 2 November 2009; accepted 25 October 2011; published online 30 December 2011)
List of Tables
CONTENTS
1.
Nomenclature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.
Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.
2.
3.
4.
3.
Experimental Data . . . . . . . . . . . . . . . . . . . . . . . . . .
4.
5
5
6
5.
Equation of State . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1. The formulation of the equation of state . . .
4.2. Comparisons with experimental data . . . . . .
4.3. The extrapolation behavior of the equation
of state. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
8
10
6.
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . .
10
7.
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
10
1.
2.
4.
a)
0047-2689/2011/40(4)/043106/11/$47.00
3
3
5
6
List of Figures
3.
5.
043106-1
7
7
7
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.6.105.191 On: Tue, 30 Dec 2014 17:39:38
043106-2
6.
7.
8.
9.
10.
11.
12.
13.
14.
cp
cv
cr
d, l, t, b, f, e, g
e
f
h
i
ks
kT
M
N
n
p
R
s
T
v
w
Z
Greek Letters
D
av
c
d
/
q
s
x
deviation
volume expansivity
Gruneisen parameter
reduced density
dimensionless Helmholtz energy
specific density
inverse reduced temperature
acentric factor
Superscripts
8
8
o
r
0
00
ideal-gas
residual
saturated-liquid state
saturated-vapor state
8
8
9
9
Subscripts
0
c
calc
exp
l
nbp
tp
v
r
reference-state property
critical
calculated
experimental
liquid property
normal-boiling-point property
triple-point property
vapor property
saturation property
9
10
1. Introduction
Dimethyl carbonate (DMC, C3H6O3, CAS 616-38-6) is a
nonirritating and nontoxic chemical. In recent years, researchers have found that dimethyl carbonate can be used as a fuel
additive, because it helps to reduce the vapor pressure of fuels,
which in turn reduces the emissions to the atmosphere by
evaporation.1 Carbon monoxide and smoke decrease as the
carbonate addition increases; additionally, NOx emissions do
not increase as the amount of dimethyl carbonate increases.2
Dimethyl carbonate is a strong contender to help the refining
industry meet the Clean Air Act3 because dimethyl carbonate
has about three times the oxygen content per volume as
methyl tert-butyl ether. Dimethyl carbonate blends well with
octane; it does not separate in a water stream like some alcohols, has low toxicity, and is quickly biodegradable.4
Thermodynamic properties of this fluid are very important
for simulating, designing, and optimizing the use of dimethyl
carbonate in various systems. This work presents an equation
of state for dimethyl carbonate based on an extensive collection of experimental data. The fundamental constants and
characteristic properties used in this work are summarized in
Table 1. Detailed comparisons between experimental and
calculated data have been performed. The extrapolation
behavior of the equation of state at low and high temperatures and pressures is shown to be reasonable.
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.6.105.191 On: Tue, 30 Dec 2014 17:39:38
Quantity
Value
043106-3
3. Experimental Data
A literature search was performed for the thermodynamic
properties of dimethyl carbonate, including sources obtained
from the THERMODATA ENGINE10 database developed by the
Thermodynamics Research Center (TRC) of NIST, and the
results are listed in Table 2 with the temperatures converted
to ITS-90. Data sets with only one to three data points are labeled as other data sets in the plots, except those that were
important to the development of the equation of state.
Although many researchers have studied the thermodynamic
properties of dimethyl carbonate, the experimental data are
few and scattered. Even worse, their uncertainties are high
compared to those of reference fluids and some refrigerants.
A literature survey found that there are 81 articles containing
experimental pqT data, but, unfortunately, there are only
four articles1114 containing a significant amount of experimental data, and the other articles contain only experimental
values near atmospheric pressure. Many of these were made
only to verify the purity of the sample; therefore, there are
many duplicated experimental data points, and some deviate
substantially from other data.
There are only five articles5,6,1517 containing experimental vapor-pressure data over a wide range. Similar to the pqT
data, many documents report only the normal boiling point
to test the purity of the sample. The experimental ranges of
the five articles mostly overlap, and the experimental data
sets deviate significantly from each other.
A good equation of state should be able to represent well
the properties related to energy (such as heat capacity and
sound speed). For dimethyl carbonate, there are nine publications (77 data points) with isobaric heat capacity values in
the liquid phase, with high deviations among the reported experimental values.8,1825
Author (year)
Number
of dataa
Temperature
range
(K)
Vapor pressure, pr
Harris (1961)33
Jiang and Zhang (1987)15
Negadi et al. (1993)32
Comelli and Francesconi (1994)35
Steele et al. (1997)5,6
Rodriguez et al. (2002)16
Zhang et al. (2003)36
Shi et al. (2005)37
Fukano et al. (2006)38
Li et al. (2008)39
Kozlova et al. (2008)17
6
38
9
4
18 (10)
131
4
5
5
4
16
278328
288371
283373
298333
311397
326411
361363
337428
337361
293373
274304
Pressure
range
(MPa)
AAD
(%)
Bias
(%)
0.0020.028
0.0040.127
0.0030.137
0.0070.035
0.0130.27
0.0270.384
0.101
0.0410.566
0.040.093
0.010.14
0.0020.01
1.208
0.626
0.581
1.098
0.042
0.718
3.436
0.564
0.060
18.862
2.879
1.208
0.445
0.581
1.098
0.032
0.638
3.436
0.449
0.037
17.254
2.879
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.6.105.191 On: Tue, 30 Dec 2014 17:39:38
043106-4
Author (year)
Saturated-liquid density, q0
Steele et al. (1997)5
Pardo et al. (1999)18
Lopez et al. (2000)40
Comunas et al. (2001)12
Lugo et al. (2001)11
Pardo et al. (2001)20
Rodriguez et al. (2001)41
Pardo et al. (2002)21
Bi et al. (2003)42
Romano et al. (2003)43
Pereiro et al. (2004)44
Rivas et al. (2004)45
Tojo et al. (2004)46
Troncoso et al. (2004)13
Yang et al. (2004)47
Pardo et al. (2005)22
Rodriguez et al. (2006)48
Iglesias-Otero et al. (2007)49
Rivas and Iglesias (2007)50
Rivas and Iglesias (2008)51
Mosteiro et al. (2009)52
Saturated-vapor density, q00
Steele et al. (1997)5
Steele et al. (1997)6
Number
of dataa
Temperature
range
(K)
5
4 (1)
6
8
9 (2)
4
4
4
21
5
5
7 (1)
6
10
7
4
4
7
5
5
5
4
5
Pressure
range
(MPa)
AAD
(%)
Bias
(%)
308393
278308
278323
283353
278353
288308
293313
288308
282383
288313
293313
288328
293318
283328
293343
288308
293313
293323
288328
288328
288308
0.027
0.017
0.017
0.029
0.033
0.019
0.018
0.014
0.047
0.012
0.014
0.008
0.019
0.027
0.016
0.019
0.012
0.016
0.007
0.017
0.021
0.023
0.009
0.017
0.029
0.032
0.019
0.015
0.014
0.047
0.012
0.014
0.007
0.017
0.023
0.016
0.019
0.012
0.016
0.006
0.003
0.021
540557
540557
5.023
5.472
1.487
2.643
0.016
0.033
0.023
0.031
1.486
0.007
0.094
0.015
0.032
0.021
0.031
1.486
0.006
0.088
0.109
0.147
0.127
0.260
0.100
0.054
0.087
0.220
1.653
1.553
0.123
0.041
0.029
0.029
0.541
0.029
0.243
3.882
1.803
0.123
0.015
0.006
0.006
0.490
0.006
0.243
3.882
1.803
pqT
Comunas et al. (2001)12
Lugo et al. (2001)11
Troncoso et al. (2004)13
Ma and Li (2005)53
Shi et al. (2005)37
Wisniak et al. (2008)54
Meng et al. (2009)14
90 (90)
72 (72)
80 (80)
7
5
5
45
283353
278353
283328
293343
337428
293313
283353
Sound speed, w
Rodriguez et al. (2001)41
Pardo et al. (2002)21
Pereiro et al. (2004)44
Mosteiro et al. (2009)52
4
4 (2)
5
5
293313
288308
293313
288308
13 (9)
300540
3
4
3 (2)
3
40
3
3
10
8
288308
288308
288308
288308
281320
288308
288308
288333
288323
560
125
540
0.101
0.101
0.101
0.119.6
Sat. liquid
Sat. liquid
Sat. liquid
Sat. liquid
0.101
0.101
0.101
0.101
0.101
0.101
0.101
0.101
0.101
a
Numbers listed in parentheses are the number of data points used in the fit, although the statistics given in the table
include all data.
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.6.105.191 On: Tue, 30 Dec 2014 17:39:38
4. Equation of State
043106-5
f T; q f T; q f T; q;
(1)
noi
toi
0
1
2
3
4
5
6
9.284 21
1.485 25
0.822 585
16.245 3
1.159 25
4.991 646 2
0.170 944 9
21
1340
1672
7395
-
o 2
4
X
cop
exptoi =T
o
o ti
n0
ni
2 ;
R
T
expto =T 1
i1
f o T; q ho T RT Tso T; q:
(2)
T
T0
cop dT ho0 RT T
T
cop R
q
o
dT R ln o s0 ;
T
q0
T0
(3)
where R 8.314 472 J mol1 K1 is the molar gas constant,28 and qo0 , ho0 , and so0 are properties at the reference
state (T0, p0). In this equation, cop is the ideal-gas heat
capacity as a function of temperature T.
The equation of state used in this work is explicit in the
dimensionless Helmholtz energy
/s; d
f T; q f o T; q f r T; q
RT
RT
RT
o
r
/ s; d / s; d;
(4)
cop
1
ds
2
s
R
s0
/o s; d ln d no0 1 ln s no5 no6 s
o
4
X
ti s
;
noi ln 1 exp
Tc
i1
/r s; d
6
X
ni ddi sti
i1
(5)
with inverse reduced temperature s Tc =T and reduced density d q=qc .
As shown in the above formulation, the dimensionless
ideal-gas Helmholtz energy can be derived from the idealgas isobaric heat capacity if the reference state is given. In
this work, the reference state is defined by setting the
(7)
where the values of the coefficients noi and exponents toi are
the same as those in Eq. (6) and are given in Table 3.
The coefficients and exponents of the residual Helmholtz
energy were determined from experimental data, and many
constraints were added to the fit to ensure good extrapolation
behavior of the equation of state. These constraints have
been explained elsewhere by Span and Wagner,29 Lemmon
and Jacobsen,30 and Lemmon et al.31 In this work, the fitting
methods by Lemmon and Jacobsen30 and Lemmon et al.31
were employed to fit the equation of state. The equation for
the residual Helmholtz energy obtained in this work is
cop
ds;
s0 s
(6)
18
X
12
X
ni ddi sti exp dli
i7
ni ddi sti exp gi d ei 2 bi s fi 2 ;
i13
(8)
where the coefficients and exponents obtained in this work
are given in Table 4. The equation of state is valid from the
triple-point temperature to 600 K, for pressures up to
J. Phys. Chem. Ref. Data, Vol. 40, No. 4, 2011
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.6.105.191 On: Tue, 30 Dec 2014 17:39:38
043106-6
ni
ti
1
0.227
1.05
1.06
0.5
0.78
1.3
1.347
0.706
2
2.5
4.262
1
2.124
0.4
3.5
0.5
2.7
gi
di li
5
1
1
2
3
4
1
2
7
1
2
3
1
1
2
2
3
3
bi
1
1
1
2
2
2
- 0.9667
1.240
- 1.5154
0.821
- 1.0591 15.45
- 1.6642
2.210
- 12.4856 437.0
- 0.9662
0.743
fi
ei
1.2827
0.4317
1.1217
1.1871
1.1243
0.4203
0.6734
0.9239
0.8636
1.0507
0.8482
0.7522
Xexp Xcalc
:
Xexp
(9)
AAD
exp
1 X
jDXi j;
Nexp i1
(10)
Bias
exp
1 X
DXi :
Nexp i1
(11)
The AAD and Bias between the experimental data and the
values calculated from the equation of state are listed in the
last two columns of Table 2.
Deviations between experimental data and values calculated with the equation of state are shown in plots, beginning
with the vapor pressure in Fig. 1. There are considerable
deviations among the vapor-pressure data sets of dimethyl
carbonate, and comparisons of experimental vapor pressures
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.6.105.191 On: Tue, 30 Dec 2014 17:39:38
043106-7
FIG. 4. Calculations of (Z1)=q along isotherms versus density q. The intersecting curve is the saturation line. Isotherms are shown at temperatures
from 250 to 1000 K with an interval of 25 K.
FIG. 2. Comparisons of saturated-liquid densities q0 calculated with the
equation of state to experimental data.
FIG. 5. Comparisons of atmospheric pressure isobaric heat capacities cp calculated with the equation of state to experimental data.
J. Phys. Chem. Ref. Data, Vol. 40, No. 4, 2011
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.6.105.191 On: Tue, 30 Dec 2014 17:39:38
043106-8
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.6.105.191 On: Tue, 30 Dec 2014 17:39:38
043106-9
FIG. 10. Density behavior along isobars from very low to high temperatures
of the equation of state for dimethyl carbonate. Isobars are shown at pressures of (0, 0.1, 0.2, 0.5, 1, 2, pc, 10, 20, 50, 100, 200, 500, and 1000) MPa.
FIG. 11. Density behavior along isobars of the equation of state for dimethyl
carbonate. The straight line intersecting the critical point is the rectilinear diameter. Isobars are shown at pressures of (0, 0.1, 0.2, 0.5, 1, 2, pc, 10, 20,
50, 100, 200, 500, and 1000) MPa.
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.6.105.191 On: Tue, 30 Dec 2014 17:39:38
043106-10
5. Conclusions
(12)
@Z
@T
0:
(13)
@Z
@T
6. Acknowledgments
0:
(14)
p
1:
qRT
(15)
@p
av ks av kT
@e v cp q
cv q
(16)
The Gruneisen parameter is a combination of different properties, and the reasonable behavior of the Gruneisen parame-
7. References
1
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.6.105.191 On: Tue, 30 Dec 2014 17:39:38
043106-11
29
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
129.6.105.191 On: Tue, 30 Dec 2014 17:39:38