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Thermodynamic Properties of Dimethyl Carbonate

Article  in  Journal of Physical and Chemical Reference Data · December 2011

DOI: 10.1063/1.3664084

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 Thermodynamic Properties of Dimethyl Carbonate*

Yong Zhou ( ) and Jiangtao Wu ( )a)

MOE Key Laboratory of Thermo-Fluid Science and Engineering, Xi’an Jiaotong University, Xi’an Shaanxi 710049, People’s 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)

A thermodynamic property formulation for dimethyl carbonate has been developed

with the use of available experimental thermodynamic property data. The equation
of state was developed with multiproperty fitting methods involving pressure-density-
temperature (pqT), heat capacity, vapor pressure, and saturated-liquid density data. The
equation of state conforms to the Maxwell criterion for two-phase liquid-vapor equilib-
rium states, and is valid for temperatures from the triple-point temperature
(277.06 6 0.63) K to 600 K, for pressures up to 60 MPa, and for densities up to 12.12
mol dm3. The extrapolation behavior of the equation of state at low and high tempera-
tures and pressures is reasonable. The uncertainties (k ¼ 2, indicating a 95% confidence
level) of the equation of state in density are 0.05% for saturated-liquid states below
350 K, rising to 0.1% in the single phase between 278 K and 400 K at pressures up to
60 MPa. Due to the lack of reliable data outside this region, the estimated uncertainties
increase to 0.5% to 1% in the vapor and critical regions. The uncertainties in vapor pres-
sure are 0.6% from 310 K to 400 K, and increase to 1% at higher temperatures and to 2%
at lower temperatures due to a lack of experimental data. The uncertainty in isobaric heat
capacity and speed of sound in the liquid phase at saturation or atmospheric pressure is
0.5% from 280 K to 335 K. The uncertainties are higher for all properties in the critical
region. Detailed comparisons between experimental and calculated data, and an analysis
of the equation, have been performed. V C 2011 American Institute of Physics.

[doi:10.1063/1.3664084]

Key words: dimethyl carbonate; equation of state; thermodynamic properties.

CONTENTS List of Tables

1. Fundamental constants and characteristic

Nomenclature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 properties of dimethyl carbonate . . . . . . . . . . . . . . 3
2. Experimental data for dimethyl carbonate . . . . . . 3
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Coefficients and exponents of the ideal-gas
2. Critical and Triple-Point Parameters of isobaric heat capacity equation . . . . . . . . . . . . . . . 5
Dimethyl Carbonate. . . . . . . . . . . . . . . . . . . . . . . . . 2 4. Coefficients and exponents of the residual
3. Experimental Data . . . . . . . . . . . . . . . . . . . . . . . . . . 3 Helmholtz energy equation. . . . . . . . . . . . . . . . . . . 6
4. Equation of State . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.1. The formulation of the equation of state . . . 5
List of Figures
4.2. Comparisons with experimental data . . . . . . 6
4.3. The extrapolation behavior of the equation
1. Comparisons of vapor pressures pr calculated
of state. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
with the equation of state to experimental
5. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 data. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
6. Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . 10 2. Comparisons of saturated-liquid densities q0
7. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 calculated with the equation of state to
experimental data . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3. Comparisons of densities q calculated with the
equation of state to experimental data . . . . . . . . 7
4. Calculations of (Z–1)=q along isotherms
a)
Author to whom correspondence should be addressed; electronic mail: versus density q . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
[email protected]; Fax: 86-29-82668789. 5. Comparisons of atmospheric pressure isobaric
*
Contribution in part of the National Institute of Standards and Technology,
not subject to copyright in the U.S. heat capacities cp calculated with the equation
C 2011 American Institute of Physics.
V of state to experimental data . . . . . . . . . . . . . . . . 7

0047-2689/2011/40(4)/043106/11/$47.00 043106-1 J. Phys. Chem. Ref. Data, Vol. 40, No. 4, 2011

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043106-2 ZHOU, WU, AND LEMMON

6. Comparisons of saturation heat capacities cr Superscripts

calculated with the equation of state to
experimental data . . . . . . . . . . . . . . . . . . . . . . . . . . 8 o¼ ideal-gas
7. Isochoric heat capacity cv versus temperature r¼ residual
8 0
T diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ¼ saturated-liquid state
00
8. Isobaric heat capacity cp versus temperature T ¼ saturated-vapor state
diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
9. Speed of sound w versus temperature T
diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 Subscripts
10. Density behavior along isobars from very low
0¼ reference-state property
to high temperatures of the equation of state
c¼ critical
for dimethyl carbonate . . . . . . . . . . . . . . . . . . . . . 9
calc ¼ calculated
11. Density behavior along isobars of the equation
9 exp ¼ experimental
of state for dimethyl carbonate . . . . . . . . . . . . . .
l¼ liquid property
12. Isothermal behavior of the equation of state at
nbp ¼ normal-boiling-point property
extreme conditions of temperature T, pressure
tp ¼ triple-point property
p, and density q . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
v¼ vapor property
13. Characteristic (ideal) curves of the equation of
r¼ saturation property
state as a function of reduced temperature
T=Tc and reduced pressure p=pc . . . . . . . . . . . . . 9
14. Gruneisen parameter c versus density q
diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 1. Introduction
Dimethyl carbonate (DMC, C3H6O3, CAS 616-38-6) is a
nonirritating and nontoxic chemical. In recent years, research-
Nomenclature ers have found that dimethyl carbonate can be used as a fuel
cp ¼ specific isobaric heat capacity additive, because it helps to reduce the vapor pressure of fuels,
cv ¼ specific isochoric heat capacity which in turn reduces the emissions to the atmosphere by
cr ¼ specific saturation heat capacity evaporation.1 Carbon monoxide and smoke decrease as the
d, l, t, b, f, e, g ¼ exponents carbonate addition increases; additionally, NOx emissions do
e¼ specific internal energy not increase as the amount of dimethyl carbonate increases.2
f¼ specific Helmholtz energy Dimethyl carbonate is a strong contender to help the refining
h¼ specific enthalpy industry meet the Clean Air Act3 because dimethyl carbonate
i¼ serial number has about three times the oxygen content per volume as
ks ¼ isentropic expansion coefficient methyl tert-butyl ether. Dimethyl carbonate blends well with
kT ¼ isothermal expansion coefficient octane; it does not separate in a water stream like some alco-
M¼ molar mass hols, has low toxicity, and is quickly biodegradable.4
N¼ number of data points Thermodynamic properties of this fluid are very important
n¼ coefficients for simulating, designing, and optimizing the use of dimethyl
p¼ pressure carbonate in various systems. This work presents an equation
R¼ molar gas constant of state for dimethyl carbonate based on an extensive collec-
s¼ specific entropy tion of experimental data. The fundamental constants and
T¼ temperature characteristic properties used in this work are summarized in
v¼ specific volume Table 1. Detailed comparisons between experimental and
w¼ sound speed calculated data have been performed. The extrapolation
Z¼ compressibility factor behavior of the equation of state at low and high tempera-
tures and pressures is shown to be reasonable.

Greek Letters 2. Critical and Triple-Point Parameters of

Dimethyl Carbonate
D¼ deviation
av ¼ volume expansivity The critical parameters are among the most important fun-
c¼ Gruneisen parameter damental properties for a fluid, and are a prerequisite for the
d¼ reduced density development of an equation of state, because they are often
/¼ dimensionless Helmholtz energy used as the reducing parameters for the independent proper-
q¼ specific density ties. The difficulty of determination of the critical parameters
s¼ inverse reduced temperature can cause considerable differences among reported values.
x¼ acentric factor In this work, the critical temperature obtained by Steele

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 EQUATION OF STATE FOR DIMETHYL CARBONATE 043106-3

TABLE 1. Fundamental constants and characteristic properties of dimethyl equation of state. Ding8 and Biltz et al.9 also measured the
carbonate triple-point temperature and reported values of (278.2 6 1) K
and (267.554 6 0.54) K, respectively.
Symbol Quantity Value

R Molar gas constant 8.314 472 J mol1 K1 3. Experimental Data

M Molar mass 90.0779 g mol1
Tc Critical temperature 557 K A literature search was performed for the thermodynamic
pc Critical pressure 4908.8 kPa properties of dimethyl carbonate, including sources obtained
qc Critical density 4.0 mol dm3 from the THERMODATA ENGINE10 database developed by the
Ttp Triple-point temperature 277.06 K Thermodynamics Research Center (TRC) of NIST, and the
ptp Triple-point pressure 2.2 kPa results are listed in Table 2 with the temperatures converted
qtpv Vapor density at the triple point 9.68104 mol dm3 to ITS-90. Data sets with only one to three data points are la-
qtpl Liquid density at the triple point 12.111 mol dm3
beled as “other data sets” in the plots, except those that were
Tnbp Normal-boiling-point temperature 363.256 K
important to the development of the equation of state.
qnbpv Vapor density at the normal boiling point 0.035 mol dm3
qnbpl Liquid density at the normal boiling point 10.813 mol dm3
Although many researchers have studied the thermodynamic
x Acentric factor 0.346 properties of dimethyl carbonate, the experimental data are
T0 Reference temperature for 298.15 K few and scattered. Even worse, their uncertainties are high
ideal-gas properties compared to those of reference fluids and some refrigerants.
p0 Reference pressure for 1 kPa A literature survey found that there are 81 articles containing
ideal-gas properties experimental pqT data, but, unfortunately, there are only
ho0 Reference ideal-gas enthalpy at T0 26 712.371 J mol1 four articles11–14 containing a significant amount of experi-
so0 Reference ideal-gas entropy at T0 and p0 109.66 202 J mol1 K1
mental 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
et al.5,6 was used as the reducing temperature in the equation many duplicated experimental data points, and some deviate
of state; this value is (557 6 2) K. As it is difficult to accu- substantially from other data.
rately determine the critical density because of the infinite There are only five articles5,6,15–17 containing experimen-
compressibility at the critical point and the difficulty of tal vapor-pressure data over a wide range. Similar to the pqT
reaching thermodynamic equilibrium, the critical density data, many documents report only the normal boiling point
was obtained while fitting the equation of state. The value is to test the purity of the sample. The experimental ranges of
(4.0 6 0.1) mol dm3. The critical pressure was determined the five articles mostly overlap, and the experimental data
once the final equation of state was obtained. This value is a sets deviate significantly from each other.
simple calculation of the pressure at the critical temperature A good equation of state should be able to represent well
and density. The value is (4908.8 6 50) kPa. the properties related to energy (such as heat capacity and
The triple-point temperature measured by Wachter et al.7 sound speed). For dimethyl carbonate, there are nine publica-
is (277.06 6 0.63) K. The triple-point pressure and density tions (77 data points) with isobaric heat capacity values in
were calculated here from the final equation of state, and are the liquid phase, with high deviations among the reported ex-
given in Table 1 along with other calculated values from the perimental values.8,18–25

TABLE 2. Experimental data for dimethyl carbonate

Temperature Pressure
Number range range AAD Bias
Author (year) of dataa (K) (MPa) (%) (%)

Vapor pressure, pr
Harris (1961)33 6 278–328 0.002–0.028 1.208 1.208
Jiang and Zhang (1987)15 38 288–371 0.004–0.127 0.626 0.445
Negadi et al. (1993)32 9 283–373 0.003–0.137 0.581 0.581
Comelli and Francesconi (1994)35 4 298–333 0.007–0.035 1.098 1.098
Steele et al. (1997)5,6 18 (10) 311–397 0.013–0.27 0.042 0.032
Rodriguez et al. (2002)16 131 326–411 0.027–0.384 0.718 0.638
Zhang et al. (2003)36 4 361–363 0.101 3.436 3.436
Shi et al. (2005)37 5 337–428 0.041–0.566 0.564 0.449
Fukano et al. (2006)38 5 337–361 0.04–0.093 0.060 0.037
Li et al. (2008)39 4 293–373 0.01–0.14 18.862 17.254
Kozlova et al. (2008)17 16 274–304 0.002–0.01 2.879 2.879

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043106-4 ZHOU, WU, AND LEMMON

TABLE 2. Experimental data for dimethyl carbonate—Continued

Temperature Pressure
Number range range AAD Bias
Author (year) of dataa (K) (MPa) (%) (%)

Saturated-liquid density, q0
Steele et al. (1997)5 5 308–393 0.027 0.023
Pardo et al. (1999)18 4 (1) 278–308 0.017 0.009
Lopez et al. (2000)40 6 278–323 0.017 0.017
Comunas et al. (2001)12 8 283–353 0.029 0.029
Lugo et al. (2001)11 9 (2) 278–353 0.033 0.032
Pardo et al. (2001)20 4 288–308 0.019 0.019
Rodriguez et al. (2001)41 4 293–313 0.018 0.015
Pardo et al. (2002)21 4 288–308 0.014 0.014
Bi et al. (2003)42 21 282–383 0.047 0.047
Romano et al. (2003)43 5 288–313 0.012 0.012
Pereiro et al. (2004)44 5 293–313 0.014 0.014
Rivas et al. (2004)45 7 (1) 288–328 0.008 0.007
Tojo et al. (2004)46 6 293–318 0.019 0.017
Troncoso et al. (2004)13 10 283–328 0.027 0.023
Yang et al. (2004)47 7 293–343 0.016 0.016
Pardo et al. (2005)22 4 288–308 0.019 0.019
Rodriguez et al. (2006)48 4 293–313 0.012 0.012
Iglesias-Otero et al. (2007)49 7 293–323 0.016 0.016
Rivas and Iglesias (2007)50 5 288–328 0.007 0.006
Rivas and Iglesias (2008)51 5 288–328 0.017 0.003
Mosteiro et al. (2009)52 5 288–308 0.021 0.021

Saturated-vapor density, q00

Steele et al. (1997)5 4 540–557 5.023 1.487
Steele et al. (1997)6 5 540–557 5.472 2.643

pqT
Comunas et al. (2001)12 90 (90) 283–353 5–60 0.016 0.015
Lugo et al. (2001)11 72 (72) 278–353 1–25 0.033 0.032
Troncoso et al. (2004)13 80 (80) 283–328 5–40 0.023 0.021
Ma and Li (2005)53 7 293–343 0.101 0.031 0.031
Shi et al. (2005)37 5 337–428 0.101 1.486 1.486
Wisniak et al. (2008)54 5 293–313 0.101 0.007 0.006
Meng et al. (2009)14 45 283–353 0.1–19.6 0.094 0.088

Sound speed, w
Rodriguez et al. (2001)41 4 293–313 Sat. liquid 0.109 0.100
Pardo et al. (2002)21 4 (2) 288–308 Sat. liquid 0.147 0.054
Pereiro et al. (2004)44 5 293–313 Sat. liquid 0.127 0.087
Mosteiro et al. (2009)52 5 288–308 Sat. liquid 0.260 0.220

Saturation heat capacity, cr

Steele et al. (1997)5,6 13 (9) 300–540 1.653 1.553

Isobaric heat capacity, cp

Pardo et al. (1999)18 3 288–308 0.101 0.123 0.123
Regueiro (1999)19 4 288–308 0.101 0.041 0.015
Pardo et al. (2001)20 3 (2) 288–308 0.101 0.029 0.006
Pardo et al. (2002)21 3 288–308 0.101 0.029 0.006
Ding (2004)8 40 281–320 0.101 0.541 0.490
Pardo et al. (2005)22 3 288–308 0.101 0.029 0.006
Valencia et al. (2005)23 3 288–308 0.101 0.243 0.243
Comelli et al. (2006)24 10 288–333 0.101 3.882 3.882
Comelli et al. (2010)25 8 288–323 0.101 1.803 1.803

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.

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 EQUATION OF STATE FOR DIMETHYL CARBONATE 043106-5

4. Equation of State TABLE 3. Coefficients and exponents of the ideal-gas isobaric heat capacity
equation
4.1. The formulation of the equation of state
i noi toi
The equation of state is formulated with the Helmholtz
energy as the fundamental property, with independent varia- 0 9.284 21 -
bles of temperature and density. The Helmholtz energy is di- 1 1.485 25 21
2 0.822 585 1340
vided into two parts. One part describes the ideal gas at the
3 16.245 3 1672
given temperature and density, and the other part describes
4 1.159 25 7395
the residual properties of the fluid. This type of equation has 5 4.991 646 2 -
the advantage that all thermodynamic properties can be 6 0.170 944 9 -
derived simply from the equation of state; more information
can be found in the books of Span26 and Jacobsen et al.27
The Helmholtz energy is represented as enthalpy and entropy of the saturated liquid to zero at the
o r normal boiling point. The ideal-gas isobaric heat capacity
f ðT; qÞ ¼ f ðT; qÞ þ f ðT; qÞ; (1) formula is
where the superscript o denotes the ideal-gas Helmholtz X  o 2
cop 4
o ti expðtoi =TÞ
energy and the superscript r denotes the residual Helmholtz o
¼ n0 þ ni  2 ; (6)
energy. The ideal-gas Helmholtz energy is given by R i¼1
T expðto =TÞ  1 i

f o ðT; qÞ ¼ ho ðT Þ  RT  Tso ðT; qÞ: (2) where the coefficients noi and exponents toi are given in
Table 3. These coefficients and exponents were obtained
The ideal-gas enthalpy ho is a function only of temperature simultaneously with the parameters of the reduced Helm-
T, and the ideal-gas entropy so is a function of temperature T holtz energy during fitting. The functional form in Eq. (6) is
and density q. This equation can be expressed as a function superior to a polynomial form in that the extrapolation
of the ideal-gas isobaric heat capacity behavior at high temperatures is consistent with physical
ð T  models. A more convenient form of the dimensionless
ideal-gas Helmholtz energy, derived from the integration of
f o ðT; qÞ ¼ cop dT þ ho0  RT  T
T0 Eq. (5) and the application of the reference state, is
ð T   
cop  R q o 
 dT  R ln o þ s0 ; (3) /o ðs; dÞ ¼ ln d þ no0  1 ln s þ no5 þ no6 s
T0 T q0   o 
X4
ti s
where R ¼ 8.314 472 J mol1 K1 is the molar gas con- þ noi ln 1  exp ; (7)
i¼1
Tc
stant,28 and qo0 , ho0 , and so0 are properties at the reference
state (T0, p0). In this equation, cop is the ideal-gas heat where the values of the coefficients noi and exponents toi are
capacity as a function of temperature T. the same as those in Eq. (6) and are given in Table 3.
The equation of state used in this work is explicit in the The coefficients and exponents of the residual Helmholtz
dimensionless Helmholtz energy energy were determined from experimental data, and many
constraints were added to the fit to ensure good extrapolation
f ðT; qÞ f o ðT; qÞ f r ðT; qÞ behavior of the equation of state. These constraints have
/ðs; dÞ ¼ ¼ þ
RT RT RT been explained elsewhere by Span and Wagner,29 Lemmon
o r
¼ / ðs; dÞ þ / ðs; dÞ; (4) and Jacobsen,30 and Lemmon et al.31 In this work, the fitting
methods by Lemmon and Jacobsen30 and Lemmon et al.31
where the dimensionless ideal-gas Helmholtz energy, were employed to fit the equation of state. The equation for
derived from Eq. (3), is given by, the residual Helmholtz energy obtained in this work is
ðs ðs
o h o s so ds0 s cop 1 cop X
6 X
12 
/ ðs; dÞ ¼ 0  0  1 þ ln  2
ds þ ds; /r ðs; dÞ ¼ ni ddi sti þ ni ddi sti exp dli
RTc R d0 s R s0 s R s0 s
i¼1 i¼7
(5) X
18

þ ni ddi sti exp gi ðd  ei Þ2 bi ðs  fi Þ2 ;
with inverse reduced temperature s ¼ Tc =T and reduced den- i¼13
sity d ¼ q=qc . (8)
As shown in the above formulation, the dimensionless
ideal-gas Helmholtz energy can be derived from the ideal- where the coefficients and exponents obtained in this work
gas isobaric heat capacity if the reference state is given. In are given in Table 4. The equation of state is valid from the
this work, the reference state is defined by setting the triple-point temperature to 600 K, for pressures up to

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043106-6 ZHOU, WU, AND LEMMON

TABLE 4. Coefficients and exponents of the residual Helmholtz energy

equation

i ni ti di li gi bi fi ei

1 0.000 526 831 87 1 5 - - - - -

2 1.353 396 0.227 1 - - - - -
3 2.649 283 1.05 1 - - - - -
4 0.278 541 2 1.06 2 - - - - -
5 0.174 255 4 0.5 3 - - - - -
6 0.031 606 252 0.78 4 - - - - -
7 0.399 866 1.3 1 1 - - - -
8 1.178 144 1.347 2 1 - - - -
9 0.023 528 1 0.706 7 1 - - - -
10 1.015 2 1 2 - - - -
11 0.788 043 6 2.5 2 2 - - - -
12 0.126 96 4.262 3 2 - - - -
13 1.219 8 1 1 - 0.9667 1.240 1.2827 0.6734
14 0.488 3 2.124 1 - 1.5154 0.821 0.4317 0.9239
15 0.003 329 3 0.4 2 - 1.0591 15.45 1.1217 0.8636
16 0.003 538 7 3.5 2 - 1.6642 2.210 1.1871 1.0507
17 0.511 72 0.5 3 - 12.4856 437.0 1.1243 0.8482
18 0.168 82 2.7 3 - 0.9662 0.743 0.4203 0.7522 FIG. 1. Comparisons of vapor pressures pr calculated with the equation of
state to experimental data.

60 MPa, and for densities up to 12.12 mol dm3. Equations

for calculating pressure, enthalpy, entropy, heat capacity, with values calculated by the equation of state are presented
and sound speed can be found in Lemmon et al.31 in Fig. 1. As shown in this figure, most of the deviations are
within 1%. The equation represents the data by Steele
et al.5,6 generally within 0.2%. There are many normal boil-
4.2. Comparisons with experimental data
ing temperatures reported; the equation represents most of
The percentage deviation between the experimental data them within 0.6%. At low temperature, the data by Kozlova
and the values calculated from the equation for any property, et al.17 and Jiang and Zhang15 show positive deviations,
X, is defined as whereas the data by Negadi et al.32 and Harris33 show nega-
  tive deviations. Additionally, there are no data reported
Xexp  Xcalc above 430 K.
DX ¼ 100 : (9)
Xexp The equation of state represents experimental saturated-
liquid density data to within their uncertainty, which is gen-
With this definition, the average absolute deviation (AAD) is erally within 0.04%, as shown in Fig. 2. However, these data
defined as were measured over a very limited temperature range (from
278 K to 393 K). As the saturated-vapor density data are
N
1 X exp very few, comparisons of experimental data with values cal-
AAD ¼ jDXi j; (10) culated from the equation of state are not shown in the form
Nexp i¼1
of a diagram. The only available data by Steele et al.5,6 are
close to the critical point.
where Nexp is the number of experimental data points. The
In the liquid region, deviations between the experimental
Bias is defined as
pqT data and the values calculated from the equation of state
N are within 0.05% to 0.1% between 278 K and 400 K, except
1 X exp
for the data by Meng et al.14 that were obtained with a
Bias ¼ ðDXi Þ: (11)
Nexp i¼1 vibrating-wire instrument; these deviations are within 0.2%.
Figure 3 shows comparisons of experimental pqT data sets
The AAD and Bias between the experimental data and the with values calculated from the equation of state as a func-
values calculated from the equation of state are listed in the tion of pressure. There are no pqT data in the vapor phase.
last two columns of Table 2. We used various constraints to ensure that the properties in
Deviations between experimental data and values calcu- the vapor region are represented as well as possible without
lated with the equation of state are shown in plots, beginning data. Figure 4, in which the y-intercept (zero density) repre-
with the vapor pressure in Fig. 1. There are considerable sents the second virial coefficient at a given temperature, and
deviations among the vapor-pressure data sets of dimethyl the third virial coefficient is the slope of each line at zero
carbonate, and comparisons of experimental vapor pressures density, shows that the behavior of the second, third, and

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 EQUATION OF STATE FOR DIMETHYL CARBONATE 043106-7

FIG. 4. Calculations of (Z–1)=q along isotherms versus density q. The inter-

secting 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 Comparisons of experimental isobaric heat-capacity data
equation of state to experimental data.
with values calculated from the equation of state are pre-
sented in Fig. 5. Deviations between the experimental iso-
fourth virial coefficients, as well as the shape of the equation baric heat-capacity data and the values calculated from the
of state, are reasonable. These virial coefficients define the equation of state are within 1%, except for the data by
behavior in the vapor phase. Comelli et al.,24,25 who reported two data sets that differ sub-
stantially. One has large positive deviations and the other
negative deviations. Figure 6 shows comparisons of experi-
mental saturation heat-capacity data with values calculated
from the equation of state; the deviations are within 0.5%
below 460 K, and there is a downward trend as the data
approach the critical point. The sound speed data are very

FIG. 3. Comparisons of densities q calculated with the equation of state to FIG. 5. Comparisons of atmospheric pressure isobaric heat capacities cp cal-
experimental data. culated with the equation of state to experimental data.

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043106-8 ZHOU, WU, AND LEMMON

FIG. 6. Comparisons of saturation heat capacities cr calculated with the FIG. 8. Isobaric heat capacity cp versus temperature T diagram. Isobars are
equation of state to experimental data. shown at pressures of (0, 0.1, 0.2, 0.5, 1, 2, pc, 10, 20, 50, 100, 200, 500, and
1000) MPa.

limited, and are located only on the saturated-liquid line.

Comparisons of experimental data with values calculated versus temperature (Figs. 10 and 11), pressure versus density
from the equation of state are not shown in the form of a dia- (Fig. 12), characteristic (ideal) curves26,30,31 (Fig. 13), and
gram. The equation represents most of these data within Gruneisen value versus density (Fig. 14).
0.15%. Figure 7 shows the isochoric heat capacity versus temper-
ature. There is an upward trend around the critical point, and
the value of the isochoric heat capacity rises to a local
4.3. The extrapolation behavior of the
maximum at the critical point. Because we did not use a
equation of state
nonanalytic form for the equation of state, the calculated
An equation of state should have reasonable extrapolation heat capacity at the critical point is not correct. Figure 8 is a
behavior, and plots of constant property lines on various diagram for the isobaric heat capacity versus temperature.
thermodynamic coordinates are useful in assessing the Both figures (Figs. 7 and 8) indicate that the behavior of the
behavior of an equation of state. The equation developed in equation of state is appropriate within the valid range, and
this work was used to plot isochoric heat capacity (Fig. 7), that the extrapolation behavior is reasonable at lower and
isobaric heat capacity (Fig. 8), sound speed (Fig. 9), density

FIG. 7. Isochoric heat capacity cv versus temperature T diagram. Isobars are FIG. 9. Speed of sound w versus temperature T diagram. Isobars are shown
shown at pressures of (0, 0.1, 0.2, 0.5, 1, 2, pc, 10, 20, 50, 100, 200, 500, and at pressures of (0, 0.1, 0.2, 0.5, 1, 2, pc, 10, 20, 50, 100, 200, 500, and 1000)
1000) MPa. MPa.

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 EQUATION OF STATE FOR DIMETHYL CARBONATE 043106-9

FIG. 10. Density behavior along isobars from very low to high temperatures FIG. 12. Isothermal behavior of the equation of state at extreme conditions
of the equation of state for dimethyl carbonate. Isobars are shown at pres- of temperature T, pressure p, and density q. Isotherms are shown at tempera-
sures of (0, 0.1, 0.2, 0.5, 1, 2, pc, 10, 20, 50, 100, 200, 500, and 1000) MPa. tures of (Ttp, Tc, 103, 104, 105, 106, 107, 108, and 109) K.

higher temperatures and pressures. In addition, Figs. 7 and 8 Figures 10 and 11 show the density behavior along isobars
show that there is a reasonable upward trend in the liquid of the equation of state. Figure 10 shows that the liquid iso-
region at low temperatures below the triple-point tempera- bars are straight on a logarithmic scale down to very low
ture,31 as expected. Figure 9 shows sound speed versus tem- temperature. The rectilinear diameter, which is shown in
perature along the saturation lines and along isobars. The Fig. 11, has near zero curvature, as it should, up to the criti-
figure shows that the saturation line for the liquid is a smooth cal point. The constraint used in the fit to obtain this effect
arc when displayed on a logarithmic scale, and that the helps ensure that vapor densities are more reliable.30 As
extrapolation behavior to high temperatures and pressures is shown in Fig. 11, the isobars near the critical point are nearly
reasonable. As with the isochoric heat capacity, the true flat, as is typical with all fluids. Further analysis shows that
nonanalytic behavior of the speed of sound at the critical the slope of the critical isobar is positive everywhere.30
point cannot be calculated with the equation of state pre- Figure 12 indicates that the extrapolation behavior to
sented here. extremely high temperatures, pressures, and densities is rea-
sonable. As explained by Lemmon and Jacobsen,30 the
smooth behavior comes from the term with ti ¼ 1 and di ¼ 5
(the first term of the residual Helmholtz energy).

FIG. 11. Density behavior along isobars of the equation of state for dimethyl
carbonate. The straight line intersecting the critical point is the rectilinear di-
ameter. Isobars are shown at pressures of (0, 0.1, 0.2, 0.5, 1, 2, pc, 10, 20, FIG. 13. Characteristic (ideal) curves of the equation of state as a function of
50, 100, 200, 500, and 1000) MPa. reduced temperature T=Tc and reduced pressure p=pc.

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043106-10 ZHOU, WU, AND LEMMON

ter, shown in Fig. 14, indicates that other properties and the
equation of state are more likely to be correct because of the
sensitive nature of this property.34
Overall, these plots indicate that the equation of state
behavior is accurate within the valid range, and that the
extrapolation behavior is reasonable at higher and lower tem-
peratures and at higher pressures.

5. Conclusions
The equation of state for dimethyl carbonate, valid from
the triple-point temperature (277.06 6 0.63) K to 600 K with
pressures up to 60 MPa, was fitted with the Helmholtz
energy as the fundamental property, and temperature and
density as the independent variables. The equation is based
on experimental pqT data, heat capacities, sound speeds,
vapor pressures, and saturated-liquid densities. The uncer-
tainties (k ¼ 2, indicating a level of confidence of 95%) of
FIG. 14. Gruneisen parameter c versus density q diagram. Isotherms are the equation of state in density are 0.05% for saturated-liquid
shown at temperatures of (Ttp, 300, 350, 400, 450, 500, Tc, 600, 700, 800,
900, 1000, 1200, 1400, 1600, 1800, and 2000) K.
states below 350 K, rising to 0.1% in the single phase
between 278 K and 400 K at pressures up to 60 MPa. Due to
the lack of reliable data outside this region, the estimated
Figure 13 shows the characteristic (ideal) curves of the uncertainties increase to 0.5% to 1% in the vapor and critical
equation of state as a function of reduced temperature T=Tc regions. The uncertainties in vapor pressure are 0.6% from
and reduced pressure p=pc. Figure 13 is used to assess the 310 K to 400 K, and increase to 1% at higher temperatures
behavior of the equation in regions without available experi- and to 2% at lower temperatures due to a lack of experimen-
mental data.26,30,31 The characteristic curves include the tal data. The uncertainty in isobaric heat capacity and speed
Boyle curve, the Joule-Thomson inversion curve, the Joule of sound in the liquid phase at saturation or atmospheric
inversion curve, and the ideal curve. The Boyle curve is pressure is 0.5% from 280 K to 335 K. The uncertainties are
given by higher for all properties in the critical region. The extrapola-
  tion behavior of the equation of state at low and high temper-
@Z atures and pressures is reasonable.
¼ 0: (12)
@v T Vapor pressures and saturated-liquid densities above
400 K should be further measured to decrease the uncertainty
The Joule-Thomson inversion curve is given by in new equations, along with density measurements in the
  vapor phase. Additionally, there is a need for further meas-
@Z urements of caloric properties, including heat capacity and
¼ 0: (13)
@T p sound speed.

The Joule inversion curve is given by

6. Acknowledgments
 
@Z We thank Mostafa Salehi from NIST for his assistance in
¼ 0: (14)
@T v the literature search. Yong Zhou and Jiangtao Wu acknowl-
edge support from the Foundation for the Author of National
The ideal curve is given by Excellent Doctoral Dissertation (Grant 200540) and Fok
p Ying Tung Education Foundation (Project Number 111060).
Z ¼ 1: (15)
qRT
7. References
The Gruneisen parameter c, which cannot be measured 1
directly, is given by Y. Katrib, G. Deiber, P. Mirabel, S. L. Calve, C. George, A. Mellouki, and
G. L. Bras, J. Atmos. Chem. 43, 151 (2002).
  2
F. K. Wang, J. T. Wu, and Z. G. Liu, Fluid Phase Equilib. 220, 123
@p av ks av kT (2004).
c¼v ¼ ¼ : (16) 3
Clean Air Act Amendments of 1990, Pub. L. 101-549, 104 Stat. 2399,
@e v cp q cv q
1990-11-15 (1990).
4
M. A. Pacheco and C. L. Marshall, Energy Fuels 11, 2 (1997).
The Gruneisen parameter is a combination of different prop- 5
W. V. Steele, R. D. Chirico, S. E. Knipmeyer, and A. Nguyen, J. Chem.
erties, and the reasonable behavior of the Gruneisen parame- Eng. Data 42, 1008 (1997).

J. Phys. Chem. Ref. Data, Vol. 40, No. 4, 2011

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 EQUATION OF STATE FOR DIMETHYL CARBONATE 043106-11

6 29
W. V. Steele, R. D. Chirico, S. E. Knipmeyer, A. Nguyen, and N. K. R. Span and W. Wagner, Int. J. Thermophys. 18, 1445 (1997).
30
Smith, J. Chem. Eng. Data 42, 1037 (1997). E. W. Lemmon and R. T. Jacobsen, J. Phys. Chem. Ref. Data 34, 69
7
P. Wachter, H. G. Schweiger, F. Wudy, and H. J. Gores, J. Chem. Thermo- (2005).
31
dyn. 40, 1542 (2008). E. W. Lemmon, M. O. McLinden, and W. Wagner, J. Chem. Eng. Data 54,
8
M. S. Ding, J. Chem. Eng. Data 49, 276 (2004). 3141 (2009).
9 32
W. Biltz, W. Fischer, and E. Wunnenberg, Z. Phys. Chem. Abt. A 151, 13 L. Negadi, A. Blondel, I. Mokbel, A. Ait-Kaci, and J. Jose, Int. Data Ser.,
(1930). Sel. Data Mixtures, Ser. A 21, 169 (1993).
10 33
M. Frenkel, R. D. Chirico, V. Diky, C. D. Muzny, A. F. Kazakov, J. W. H. G. Harris, Ph.D. thesis, University of California, 1961.
34
Magee, I. M. Abdulagatov, and J. W. Kang, NIST ThermoData Engine, E. W. Lemmon, V. D. Arp, and D. O. Ortiz-Vega, “The Gruneisen param-
NIST Standard Reference Database 103b, Version 5.0 (National Institute eter and fluid state equations” (unpublished).
35
of Standards and Technology, Standard Reference Data Program: F. Comelli and R. Francesconi, J. Chem. Eng. Data 39, 560 (1994).
36
Gaithersburg, MD, 2010). L. Q. Zhang, J. G. Chen, and J. H. Ding, Speciality Petrochemicals 20, 42
11
L. Lugo, M. J. P. Comunas, E. R. Lopez, and J. Fernandez, Fluid Phase (2003).
37
Equilib. 186, 235 (2001). Y. H. Shi, H. L. Liu, K. Wang, W. D. Xiao, and Y. Hu, Fluid Phase Equi-
12
M. J. P. Comunas, A. Baylaucq, C. Boned, and J. Fernandez, Int. J. Ther- lib. 234, 1 (2005).
38
mophys. 22, 749 (2001). M. Fukano, H. Matsuda, K. Kurihara, and K. Ochi, J. Chem. Eng. Data 51,
13
J. Troncoso, D. Bessieres, C. A. Cerdeirina, E. Carballo, and L. Romani, 1458 (2006).
39
J. Chem. Eng. Data 49, 923 (2004). H. L. Li, R. J. Zhu, Y. L. Tan, H. F. Xu, and Z. L. Dong, J. Chem. Eng.
14
X. Y. Meng, P. J. Zheng, J. T. Wu, and Z. G. Liu, J. Eng. Thermophys. 30, Data 53, 2095 (2008).
40
26 (2009). E. R. Lopez, L. Lugo, M. J. P. Comunas, J. Garcia, and J. Fernandez,
15
B. Y. Jiang and J. H. Zhang, J. Tianjin Univ. 20, 53 (1987). J. Chem. Thermodyn. 32, 743 (2000).
16 41
A. Rodriguez, J. Canosa, A. Dominguez, and J. Tojo, Fluid Phase Equilib. A. Rodriguez, J. Canosa, and J. Tojo, J. Chem. Eng. Data 46, 1476
198, 95 (2002). (2001).
17 42
S. A. Kozlova, V. N. E. Yanenko, M. Georgieva, S. P. Verevkin, Y. Chernyak, S. S. Bi, J. T. Wu, Z. G. Liu, and X. Y. Meng, J. Xi’an Jiaotong Univ. 37,
B. Schaffner, and A. Borner, J. Chem. Thermodyn. 40, 1136 (2008). 903 (2003).
18 43
J. M. Pardo, C. A. Tovar, C. A. Cerdeirina, E. Carballo, and L. Romania, E. Romano, J. L. Trenzado, E. Gonzalez, J. S. Matos, L. Segade, and
J. Chem. Thermodyn. 31, 787 (1999). E. Jimenez, Fluid Phase Equilib. 211, 219 (2003).
19 44
J. M. P. Regueiro, Ph.D. thesis, Universidad de Vigo, 1999. A. B. Pereiro, A. Rodriguez, J. Canosa, and J. Tojo, J. Chem. Eng. Data
20
J. M. Pardo, C. A. Tovar, C. A. Cerdeirina, E. Carballo, and L. Romani, 49, 1392 (2004).
45
Fluid Phase Equilib. 179, 151 (2001). M. A. Rivas, S. M. Pereira, N. Banerji, and T. P. Iglesias, J. Chem. Ther-
21
J. M. Pardo, D. Gonzalez-Salgado, C. A. Tovar, C. A. Cerdeirina, modyn. 36, 183 (2004).
46
E. Carballo, and L. Romani, Can. J. Chem. 80, 370 (2002). J. Tojo, J. Canosa, A. Rodriguez, J. Ortega, and R. Diepp, J. Chem. Eng.
22
J. M. Pardo, C. A. Tovar, J. Troncoso, E. Carballo, and L. Romani, Ther- Data 49, 86 (2004).
47
mochim. Acta 433, 128 (2005). C. S. Yang, W. Xu, and P. S. Ma, J. Chem. Eng. Data 49, 1802
23
J. L. Valencia, J. Troncoso, J. Peleteiro, E. Carballo, and L. Romani, Fluid (2004).
48
Phase Equilib. 232, 207 (2005). A. Rodriguez, A. B. Pereiro, J. Canosa, and J. Tojo, J. Chem. Thermodyn.
24
F. Comelli, R. Francesconi, A. Bigi, and K. Rubini, J. Chem. Eng. Data 38, 505 (2006).
49
51, 665 (2006). M. A. Iglesias-Otero, J. Troncoso, E. Carballo, and L. Romani, J. Solution
25
F. Comelli, A. Bigi, D. Vitalini, and K. Rubini, J. Chem. Eng. Data 55, 205 Chem. 36, 1219 (2007).
50
(2010). M. A. Rivas and T. P. Iglesias, J. Chem. Thermodyn. 39, 1546 (2007).
26 51
R. Span, Multiparameter Equations of State: An Accurate Source of Ther- M. A. Rivas and T. P. Iglesias, J. Chem. Thermodyn. 40, 1120 (2008).
52
modynamic Property Data (Springer, New York, 2000). L. Mosteiro, A. B. Mariano, L. M. Casas, M. M. Pineiro, and J. L. Legido,
27
R. T. Jacobsen, S. G. Penoncello, and E. W. Lemmon, in Equations of J. Chem. Eng. Data 54, 1056 (2009).
53
State for Fluids and Fluid Mixtures, edited by J. V. Sengers, R. F. Kayser, P. S. Ma and N. N. Li, J. Tianjin Univ. 38, 577 (2005).
54
and C. J. Peters (Elsevier, Amsterdam, 2000), Vol. V, p. 35. J. Wisniak, G. Cortez, R. D. Peralta, R. Infante, L. E. Elizalde,
28
P. J. Mohr, B. N. Taylor, and D. B. Newell, J. Phys. Chem. Ref. Data 37, T. A. Amaro, O. Garcı́a, and H. Soto, J. Chem. Thermodyn. 40, 1671
1187 (2008). (2008).

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