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REFERENCES 339
314 Appendix A
/. Alkanes
methane CH4 111.6 190.55 4.599 99.2 0.0 0.011
ethane C2H6 184.6 305.33 4.871 148.3 0.0 0.099
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/. Alkanes
1.925E+1 5.213E-2 1.197E-5 -1.132E-8 16.0436 methane
5.409E+0 1.781E-1 -6.938E-5 8.713E-9 30.069 ethane
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K K MPa cm'-mol"cm'-mol"1
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debydebyee
4. Alkyl Cyclopentanes
cyclopentane C5H10 322.4 511.7 4.51 260. 0.0 0.196
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methylcyclopentane C H
6 12 345.0 532.7 3.78 319. 0.0 0.231
ethylcyclopentane C7H14 376.6 569.5 3.40 375. 0.271
rc-propylcyclopentane C 8 H 1 6 404.1 603. 3.0 425. 0.335
5. Alkyl Cyclohexanes
cyclohexane C H
6 12 353.8 553.5 4.07 308. 0.3 0.212
methylcyclohexane C 7 H |4 374.1 572.2 3.47 368. 0.0 0.236
ethylcyclohexane C H
8 16 404.9 609. 3.0 450. 0.0 0.243
ra-propylcyclohexane C 9 H |8 429.9 639.0 2.80 0.258
6. Alkyl Cycloalkenes
cyclopentene C5Hg 317.4 506.0 0.9 0.196
cyclohexene C H
6 10 356.1 560.5 4.34 0.6 0.210
7. Acetylenes
acetylene C2H2 188.4 308.3 6.14 112.7 0.0 0.190
methylacetylene C3H4 249.9 402.4 5.63 164. 0.7 0.215
1-pentyne C5H8 313.3 493.5 4.05 278. 0.9 0.164
8. Alkyl Benzenes
benzene C
6H6 353.2 562.06 4.895 259. 0.0 0.212
toluene C7H8 383.8 591.75 4.108 316. 0.4 0.263
ethylbenzene C
8 HI 0 409.3 617.16 3.609 374. 0.4 0.302
o-xylene ^-8^10 417.6 630.3 3.732 369. 0.5 0.310
m-xylene *--8^10 412.3 617.0 3.541 376. 0.3 0.325
p-xylene C
8H10 411.5 616.2 3.511 379. 0.1 0.320
cumene C9H]2 177.1 425.6 3.21 0.326
mesitylene C9H12 228.4 637.3 3.127 275 0.1 0.399
9. Alkyl Halides
methyl bromide CH3Br 276.6 464.0 6.61 1.8
methyl chloride CH3C1 249.1 416.3 6.70 138.9 1.9 0.153
methyl fluoride CH3F 194.7 315.0 5.6 113.2 1.8 0.187
ethyl bromide C2H5Br 311.5 503.9 6.23 215. 2.0 0.229
ethyl chloride C2H5C1 285.5 460.4 5.27 199. 2.0 0.191
ethyl fluoride C2H5F 235.5 375.3 5.02 169. 2.0 0.215
propyl chloride C3H7C1 320.4 503.0 4.58 254. 2.0 0.235
1-chlorobutane C4H9C1 351.6 542.0 3.68 312. 2.0 0.218
Appendix A 317
4. AlkyI Cyclopentanes
-5.362E+1 5.426E-1 -3.031E-4 6.485E-8 70.134 cyclopentane
-5.011E+1 6.381E-1 -3.642E-4 8.014E-8 84.161 methylcyclopentane
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10. Refrigerants
Rll CCI3F 296.4 471.15 4.403 245.7 0.4 0.189
R12 CCI2F2 243.0 384.95 4.129 215.9 0.5 0.204
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// . Refrigerants
3.209E+1 2.162E-1 -2.334E-4 8.869E-8 137.368 Rll
2.352E+1 2.263E-1 -2.335E-4 8.586E-8 120.914 R12
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pc r/c Dipm
Compound Name Formula CO
13. Monatomics
argon AT 87.3 150.8 4.87 74.9 0.0 0.001
helium He 3.19 3.31 0.114 72.9 0.0 -0.473
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CpA C
P,2 Molecular Compound Name
Jmol"'K"' Jmol-'K"2 Jmol-'K"3 Jmol-'K 4 Weight
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13. Monatomics
2.080E+1 39.948 argon
2.080E+1 3.017 helium
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1. Alkanes
methane CH4 5.77884 397.847 -61.890 91 127
ethane C2H6 5.94631 662.404 -16.387 136 200
propane C3Hg 6.95075 1467.362 71.564 310 370
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4. Alkyl Cyclopentana
cyclopentane C H
5 10 6.02877 1133.199 -40.735 288 325
methylcyclopentane C H
6 12 5.99178 1188.320 -46.843 288 345
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10. Refrigerants
Rll CC13F 6.01505 1043.600 -36.566 243 335
R12 CC12F2
R22 CHC1F2 6.096617 821.095 -31.640 210 240
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R32 CH2F2
R123 C2HC12F3
R124 C2HC1F4
R125 C2HF5
R134a C2H2F4 6.17338 874.648 -37.217 210 260
R141b C2H3CI2F 6.00691 1049.840 -42.820 250 330
R142b C2H3CIF2
R143a C2 H3F 3
R152a C2 H4F 2
// . 1-Alkanots
methanol CH 40 7.24693 1605.615 -31.317 274 336
ethanol C2H60 7.24222 1595.811 -46.702 292 365
1-propanol C3HgO 6.87065 1438.587 -74.598 330 377
1-butanol C4 H]0O 6.76666 1460.309 -83.939 296 390
1-pentanol C 5 H 12 0 6.31559 1292.273 -111.313 347 420
1-hexanol C 6 H 14 0 6.20107 1305.984 -119.249 325 430
1-heptanol C 7 H, 6 0 6.10824 1323.566 -126.909 336 449
1-octanol C 8 H180 6.80512 1752.302 -99.080 327 386
1-nonanol C9H20O 5.83497 1297.059 -147.711 364 486
1-decanol C|0H22O 5.76028 1315.019 -154.022 378 504
1-undecanol C„H 24 0
1 -dodecanol C |2 H 26 0 5.70652 1388.338 -163.157 400 538
12. Alkyl Acetates
methyl acetate C3H602 6.25449 1189.608 -50.035 260 351
ethyl acetate C 4 H80 2 6.20229 1232.542 -56.563 271 373
Appendix A 325
13. Monatomics
argon Ar 6.99579 448.390 -3.130 72 84
helium He
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Compound Name Y
0.739
acetone 0.652
ethylene oxide 0.565
hydrogen chloride 0.565
Thermophysical Properties of Fluids Downloaded from www.worldscientific.com
Alcohols
methanol 0.652
ethanol 0.213
n-propanol -0.052
/-propanol 0.052
AlkyI Halldes
methyl chloride 0.304
methyl fluoride 0.739
Refrigerants
Rll 0.015
R12 0.021
R22 0.164
R32 0.704
R123
R124 -0.001
R125 -0.001
R134a 0.180
R141b 0.073
R142b
R143a
R152a 0.483
Appendix A ill
Alcohol mixtures
methanol acetone 334.18 -108.17 0.1
335.64 -102.17 328
benzene 815.39 77.43 0.1
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Water mixtures
water acetonitrile1 1098.8 -516.04 0.104 0.1 333
rt-butanol 316.11 273.05 0.208 0.1 298
ethyl acetate1 1343.3 -751.71 0.063 0.1 333
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Components SnIR au P T
1 2 K K MPa K
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Alcohol mixtures
ethanol ethyl acetate 151.47 162.03 0.300 0.1 343
methanol rc-heptane' 565.80 345.19 0.200 0.1 303
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1 2 K K K
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Alcohol mixtures
methanol acetone -96.90 359.10 328-337
benzene -56.05 988.60 308
-38.37 902.56 318
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r <7 <?'
Alcohols
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Aromatic hydrocarbons
benzene 3.19 2.40 2.40
toluene 3.92 2.97 2.97
ethylbenzene 4.60 3.51 3.51
o,m-,p-xylene 4.66 3.54 3.54
Alkanes
ethane 1.80 1.70 1.70
propane 2.48 2.24 2.24
«-butane 3.15 2.78 2.78
rc-pentane 3.82 3.31 3.31
rc-hexane 4.50 3.86 3.86
rc-heptane 5.17 4.40 4.40
n-octane 5.85 4.94 4.94
H-decane 7.20 6.02 6.02
Other compounds
acetone 2.57 2.34 2.34
acetonitrile 1.87 1.72 1.72
2-butanone 3.25 2.88 2.88
carbon tetrachloride 3.33 2.82 2.82
chloroform 2.70 2.34 2.34
cyclohexane 3.97 3.01 3.01
cyclopentane 3.30 2.47 2.47
ethyl acetate 3.48 3.12 3.12
methyl acetate 2.80 2.58 2.58
methylcyclohexane 4.64 3.55 3.55
methylcyclopentane 3.97 3.01 3.01
water 0.92 1.40 1.00
Note: parameter q' = q, in all cases except water and alcohols
336 Appendix A
nm K nm
A Alkanes 7. 1-Alkanols
methane 0.3758 148.6 methanol 0.3626 481.8
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1. Alkanes
H-hexane1 280 - ■390 294.9 -5.873 11.047 -7.384 2.211
rt-heptane1 290 -■350 389.0 -6.265 12.022 -8.411 2.655
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/. Alkanes
n-hexane 290 -330 120.7 3.110 -3.329 1.219
rc-heptane' 190 -370 122.8 1.730 -0.730
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REFERENCES
configurational, residual and excess properties of pure fluids and mixtures. We also
review the thermodynamic relations required in the calculation of the fugacity of a
component in a mixture.
and may therefore be expressed as the sum of a molecular part and a configurational
part. We therefore have for a property X
where A™0' is called the molecular property and A"' is the configurational property.
The relation, given in Chapter 2, between the molecular properties and the perfect-
gas properties can easily be derived. The partition function for a perfect gas, QV&, is
obtained by setting the potential energy 1l to zero. The configuration integral,
Eq.( 1.31), then reduces to VN. Consequently, the molecular partition function and the
perfect-gas partition function are related simply by
and
342 Appendix B
It follows from Eq.(B.4) that the perfect-gas part of a thermodynamic property may
be expressed in terms of the molecular contribution plus terms in N and V. For
example, the Helmholtz free energy of the perfect gas, obtained from Eq.(1.18) with
Q = £?pg> maY be written
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A™ = -kBT\nQ™ = -kBT\nQmo^NkBT\nV
(B.5)
= Amo1 - NkBT \nV
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S pg = kBT(d\nQPZ/dT)v + kB In (2pg
= Smol + M B ln K
The form of Eqs.(B.7) is as expected as these properties of the perfect gas are
independent of volume.
A residual property Xres is defined as the difference between the actual value of
a thermodynamic property X and the value XP& that would prevail in a hypothetical
perfect gas at either the same values of T and Vm or at the same values of T and P.
The residual property therefore gives a measure of the effects of intermolecular
forces in the system. Rather than writing X as the sum of configurational and
molecular parts, one can instead write X as the sum of perfect-gas and residual terms:
This separation is often useful because quite different techniques apply to the
prediction of these different kinds of property.
Although the variables T and Vm are natural in statistical mechanics based on
the canonical ensemble, practical considerations usually dictate the use of T and P. It
Appendix B 343
the hypothetical perfect gas with the given values of (T, Vm) differs from that with
the given values of (T, P). In fact, when residual properties are quoted it is almost
always with the choice of temperature and pressure as the independent variables and
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that convention has been followed throughout this book. Consequently, the residual
properties given in Tables 4.4 (for the virial equation of state), 5.1 (for the Lee-
Kesler corresponding states model) and 6.1 and 6.5-6.7 (for other equations of state)
all refer to residual properties at specified T and P even though T and pn=\IVm
appear in the expressions.
Given that most thermodynamic models are explicit functions of T and Vm (or
of T and pn but that distinction is not important here) it is easiest to derive directly
from the model expressions for a residual property at T and Vm, JFes(T, Vm), and
then incorporate an additional term to obtain the residual property at T and P,
JPes(T, P). The connection between A™(r, Vm) and X**(T, P) is established as
follows. We have that
where
The relation between XPS(T, Vm) and X?HT,P) is given by the identities
The integrals that appears in these equations are easy to evaluate in terms of the
equation of state of the perfect gas (a Maxwell equation is sometimes needed to
obtain the partial derivative in terms of the equation of state). As an example,
consider the molar Helmholtz free energy for which (8Am/8Vm)T = -P and hence
where
is the compression factor. The key relations between the two kinds of residual
property are summarised in Table B1.
where X pg is the molar perfect-gas property for the pure component i and Amix-
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^mS ' s m e so " ca ll e< i 'deal mixing term equal to the change in X^ on mixing the
components at constant temperature and pressure. It is sometimes convenient to
consider a different quantity, the excess molar property X^_, defined by
Here, X^ is the value of the molar property for an ideal mixture and ^f*is the actual
(rather than perfect-gas) value of the molar property for the pure component i at the
specified temperature and pressure. This excess property is then the difference
between the actual value of the property for the mixture and that which would prevail
in an ideal mixture at the same temperature and pressure. The ideal mixing terms
may all be derived from the change in molar Helmholtz free energy on mixing the
perfect gases at constant temperature and volume.1 Starting from Eq.(2.25), it is
easy to show that
All other ideal mixing terms follow from this expression and the results are given in
Table B2. Since Amix[/Pg = 0, Amix^Pg is most closely related to the change in molar
entropy on mixing:
The ideal mixing term for molar entropy is derived below in Example B. 1.
' Since there is no change in pressure when perfect gases are mixed at constant temperature
and volume, there is no distinction between that situation and mixing at constant tempera-
ture and pressure.
346 Appendix B
m -/?£*, In*,
i
rf* ^rinjc,
Figure B.l
and, in a perfect gas, (PIT) dVm = -Rd\r\ P, the change in entropy on mixing the
perfect gases is given by
Appendix B 347
The residual molar Gibbs free energy is itself given by the identity
dP (B.21)
In order to convert this relation into one that can be evaluated readily from an
equation of state that gives P as a function of T and Vm, we change the variable of
integration from P to the total (not molar) volume V, making use of the relation
V{dPldV)Tn = - n{dPldn)TV, and, after some working, we obtain:
348 Appendix B
and this is the relation used directly to obtain expressions for the mixture fugacity in
terms of an equations of state. Since G^es = H™s - TS™S, the mixture fugacity
coefficient may also be obtained from the residual enthalpy and residual entropy:
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and this equation may be used to obtain cpt in terms of an equation of state.
The fugacity coefficient may also be obtained in another way by noting that
property X, molar property Xm and partial molar property Xi are related by
Since /ujes is identical with the partial molar residual Gibbs free energy, it follows
from (B.20) and (B.26) that RT\xv(pi is the partial molar analogue of RT]n(pmix and
hence that
This relation was used in Section 5.4 together with expressions for the partial
derivatives of rn</>mjx with respect to rand P obtained by operating on Eq.(B.25).
Appendix B 349
and
where * denotes a property of the pure liquid. Subtracting these two equations we
obtain