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It is custom to approximate solid and liquid thermodynamic properties as being a function of temperature only, since they are virtually incompressible, and Pdv boundary work
may be neglected. Furthermore, in classical literature, for isothermal compression processes, a general improvement and correction for liquid enthalpy approximation is
given by adding the pressure correction, vdP, to the corresponding saturation value. It
is shown that such correction given for isothermal processes is generally valid for isentropic processes only. Analysis of water real properties, over the saturation temperature
range and a wide pressure range up to 100 MPa, shows that the recommended corrections are only beneficial for higher pressures at smaller temperatures (below 200 C),
insignificant for smaller pressures at most of the temperatures, about the same but opposite sign (thus unnecessary) for intermediate temperatures and pressures, and more
erroneous (thus counterproductive and misleading) for higher temperatures and pressures, than the corresponding saturation values without any correction. The misconception in the literature is a result of the erroneous assumption, that due to incompressibility
for liquids in general, the internal energy is less dependent on pressure than
enthalpy. DOI: 10.1115/1.2175090
Keywords: enthalpy, water, thermodynamic properties, thermodynamic analysis,
isothermal, isentropic
Introduction
Since solids and liquids are virtually but not exactly incompressible, then the compression work, Pdv, could be neglected and
thus many properties virtually will not be a function of pressure
but temperature only, such as specific internal energy, u, etc. Furthermore, any process is also at the same time an isochoric,
constant-volume process. Namely, the isobaric, constant-pressure
process will be a simultaneously constant-volume process for an
incompressible substance, so that specific heat at constant pressure, c p, and constant volume, cv, are the same, or approximately
the same for virtually incompressible real solids and liquids, particularly when compared to vapors and gases, i.e.:
u uT usatT and c p cv cT
4
Furthermore, for isothermal processes dT = 0 and du 0, then
dh vdP, and finally, for finite pressure difference change from
saturated pressure, Psat, corresponding to the given temperature,
T, the specific enthalpy with correction, hcorrT , P at that temperature, T, and any pressure, P, will be 1,2:
5a
Even the specific enthalpy for a liquid from here on word specific will be assumed and omitted for brevity, can be approximated to be independent from pressure and conveniently taken to
be equal to the corresponding saturated liquid value at the given
temperature:
hP,T hT hsatT
thus,
5b
where, hsatT and vsatT are liquid saturation enthalpy and liquid
saturation specific volume at given temperature, T, respectively. It
is stated in many references, including 1,2, that the above equations 5a and 5b are recommended as the correction for isothermal, liquid enthalpy dependence on pressure, and that it is more
accurate than a simple, approximation without correction, hsat Eq.
2.
It is the objective of this paper to point out the erroneous general recommendations in the literature. The correction Eq. 5, as
recommended in many references, is only useful for higher pressures at smaller temperatures, but is actually more erroneous thus
counterproductive and misleading for higher temperatures and
pressures, and is about the same but opposite sign, thus not necessary for intermediate temperatures, than the simple approximation Eq. 2 without any correction. Corresponding analysis using real water data 3 and physical justification are presented
below.
Table 1 Compressed liquid water property data at 260 C 3 and different enthalpy corrections
P
MPa
v
m3 / kg
u
kJ/kg
h
kJ/kg
s
kJ/ kg K
Cv
kJ/ kg K
Cp
kJ/ kg K
csound
m/s
JT
K/MPa
hu
kJ/kg
hv
kJ/kg
hP
kJ/kg
hcorr
kJ/kg
h or
CpdP
kJ/kg
4.69sat
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
0.001276
0.001276
0.001265
0.001256
0.001247
0.001239
0.001231
0.001224
0.001217
0.001211
0.001204
0.001199
0.001193
0.001187
0.001182
0.001177
0.001172
0.001167
0.001163
0.001158
0.001154
1129.0
1128.5
1121.6
1115.1
1109.0
1103.2
1097.8
1092.5
1087.6
1082.8
1078.2
1073.8
1069.6
1065.5
1061.6
1057.7
1054.0
1050.5
1047.0
1043.6
1040.3
1135.0
1134.9
1134.3
1134.0
1134.0
1134.2
1134.7
1135.4
1136.3
1137.3
1138.4
1139.7
1141.1
1142.7
1144.3
1146.0
1147.8
1149.7
1151.6
1153.7
1155.8
2.8849
2.8841
2.8710
2.8586
2.8469
2.8357
2.8250
2.8148
2.8050
2.7955
2.7864
2.7775
2.7690
2.7607
2.7526
2.7447
2.7371
2.7297
2.7224
2.7153
2.7084
3.1301
3.1299
3.1257
3.1220
3.1187
3.1158
3.1131
3.1107
3.1084
3.1063
3.1043
3.1024
3.1006
3.0989
3.0973
3.0957
3.0943
3.0928
3.0914
3.0901
3.0888
4.9856
4.9804
4.9019
4.8336
4.7733
4.7195
4.6711
4.6272
4.5871
4.5502
4.5162
4.4847
4.4553
4.4279
4.4022
4.3781
4.3553
4.3338
4.3134
4.2940
4.2756
1105.3
1107.2
1135.8
1162.6
1187.8
1211.7
1234.3
1256.0
1276.7
1296.6
1315.8
1334.3
1352.2
1369.5
1386.3
1402.6
1418.5
1433.9
1449.0
1463.7
1478.1
0.03472
0.03373
0.01884
0.00582
0.00
0.50
7.40
13.90
20.00
25.80
31.20
36.50
41.40
46.20
50.80
55.20
59.40
63.50
67.40
71.30
75.00
78.50
82.00
85.40
88.70
0.00
0.00
0.00
0.39
6.74
13.05
19.31
25.52
31.70
37.84
43.94
50.01
56.05
62.05
68.03
73.98
79.91
85.80
91.68
97.53
103.35
109.15
114.93
0.00
0.39
6.77
13.15
19.53
25.91
32.30
38.68
45.06
51.44
57.82
64.20
70.58
76.96
83.34
89.72
96.10
102.48
108.86
115.24
121.62
0.00
0.05
0.70
1.00
1.00
0.75
0.26
0.42
1.28
2.30
3.46
4.76
6.17
7.70
9.32
11.03
12.83
14.71
16.67
18.69
20.77
0.00568
0.01595
0.02519
0.03355
0.04117
0.04816
0.05458
0.06051
0.06601
0.07113
0.07590
0.08037
0.08456
0.08850
0.09220
0.09570
0.09901
0.08
0.20
0.35
0.53
0.74
0.98
1.24
1.52
1.82
2.12
2.45
2.80
3.15
3.52
3.90
4.29
4.69
5.09
5.51
hsat-h
kJ/kg
hcorr-h
kJ/kg
0.00
0.10
0.70
1.00
1.00
0.80
0.30
0.00
0.49
7.47
14.15
20.53
26.71
32.60
38.28
43.76
49.14
54.42
59.50
64.48
69.26
74.04
78.72
83.30
87.78
92.26
96.54
100.82
0.40
1.30
2.30
3.40
4.70
6.10
7.70
9.30
11.00
12.80
14.70
16.60
18.70
20.80
Table 2 Compressed liquid water property data at different temperatures and pressures 3
T=4C
T = 20 C
P
MPa
v
m3 / kg
u
kJ/kg
h
kJ/kg
v
m3 / kg
Sat
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
0.001000
0.000998
0.000995
0.000993
0.000990
0.000988
0.000986
0.000984
0.000981
0.000979
0.000977
0.000975
0.000973
0.000971
0.000969
0.000967
0.000965
0.000963
0.000961
0.000959
0.000958
16.81
16.81
16.79
16.77
16.74
16.70
16.65
16.59
16.53
16.46
16.38
16.30
16.21
16.12
16.01
15.91
15.80
15.68
15.56
15.44
15.31
16.81
21.80
26.75
31.66
36.55
41.40
46.23
51.02
55.79
60.53
65.24
69.93
74.59
79.23
83.84
88.43
93.00
97.55
102.07
106.58
111.06
0.001002
0.001000
0.000997
0.000995
0.000993
0.000991
0.000989
0.000987
0.000985
0.000982
0.000980
0.000978
0.000977
0.000975
0.000973
0.000971
0.000969
0.000967
0.000965
0.000964
0.000962
T = 200 C
u
kJ/ kg
83.912
83.609
83.308
83.007
82.708
82.409
82.112
81.815
81.520
81.225
80.931
80.637
80.345
80.053
79.762
79.471
79.182
78.893
78.604
78.317
78.031
T = 50 C
v
m3 / kg
u
kJ/kg
h
kJ/kg
v
m3 / kg
u
kJ/ kg
Sat
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
0.001157
0.001153
0.001148
0.001144
0.001139
0.001135
0.00113
0.001126
0.001122
0.001119
0.001115
0.001111
0.001108
0.001104
0.001101
0.001098
0.001095
0.001091
0.001088
0.001086
0.001083
850.47
847.91
844.31
840.84
837.49
834.24
831.10
828.06
825.10
822.23
819.45
816.73
814.09
811.51
809.00
806.56
804.17
801.83
799.55
797.32
795.14
852.27
853.68
855.80
857.99
860.27
862.61
865.02
867.48
870.00
872.57
875.19
877.85
880.55
883.29
886.07
888.89
891.73
894.61
897.51
900.44
903.40
0.001252
0.00125
0.001241
0.001233
0.001225
0.001218
0.001211
0.001205
0.001199
0.001193
0.001187
0.001182
0.001176
0.001171
0.001167
0.001162
0.001157
0.001153
0.001149
0.001145
0.001141
1080.8
1079.5
1073.4
1067.6
1062.2
1057.0
1052.0
1047.3
1042.7
1038.4
1034.2
1030.1
1026.2
1022.5
1018.8
1015.3
1011.8
1008.5
1005.3
1002.1
999.06
T = 150 C
h
kJ/ kg
v
m3 / kg
u
kJ/ kg
h
kJ/ kg
v
m3 / kg
u
kJ/kg
h
kJ/kg
v
m3 / kg
u
kJ/kg
h
kJ/kg
83.914
88.607
93.281
97.934
102.57
107.18
111.77
116.34
120.90
125.44
129.95
134.45
138.94
143.40
147.85
152.29
156.70
161.10
165.49
169.86
174.22
0.001012
0.001010
0.001008
0.001006
0.001004
0.001001
0.000999
0.000997
0.000995
0.000993
0.000991
0.000989
0.000988
0.000986
0.000984
0.000982
0.000980
0.000978
0.000977
0.000975
0.000973
209.33
208.59
207.86
207.15
206.44
205.75
205.07
204.40
203.75
203.10
202.46
201.84
201.22
200.61
200.01
199.42
198.84
198.26
197.70
197.14
196.59
209.34
213.64
217.94
222.23
226.51
230.79
235.05
239.31
243.56
247.80
252.03
256.26
260.47
264.68
268.88
273.07
277.26
281.44
285.61
289.77
293.92
0.001044
0.001041
0.001039
0.001036
0.001034
0.001031
0.001029
0.001027
0.001025
0.001022
0.001020
0.001018
0.001016
0.001014
0.001012
0.001010
0.001008
0.001006
0.001004
0.001002
0.001000
419.06
417.64
416.23
414.85
413.50
412.17
410.87
409.60
408.35
407.13
405.93
404.76
403.61
402.47
401.36
400.27
399.20
398.14
397.11
396.09
395.09
419.17
422.85
426.62
430.39
434.17
437.95
441.74
445.54
449.33
453.14
456.94
460.75
464.56
468.37
472.19
476.00
479.82
483.64
487.46
491.29
495.11
0.001091
0.001088
0.001084
0.001081
0.001078
0.001075
0.001072
0.001069
0.001066
0.001064
0.001061
0.001058
0.001056
0.001053
0.001051
0.001048
0.001046
0.001043
0.001041
0.001039
0.001036
631.66
629.55
627.27
625.05
622.89
620.78
618.73
616.72
614.77
612.85
610.98
609.15
607.36
605.61
603.89
602.21
600.56
598.95
597.36
595.81
594.29
632.18
634.98
638.11
641.27
644.45
647.66
650.89
654.14
657.42
660.71
664.02
667.35
670.69
674.05
677.43
680.81
684.21
687.63
691.05
694.48
697.93
T = 250 C
P
MPa
T = 100 C
T = 300 C
h
kJ/ kg
1085.8
1085.7
1085.8
1086.1
1086.7
1087.4
1088.4
1089.4
1090.7
1092.0
1093.5
1095.1
1096.8
1098.6
1100.5
1102.4
1104.4
1106.5
1108.7
1110.9
1113.1
v
m3 / kg
u
kJ/ kg
T = 350 C
h
kJ/ kg
0.001404
1332.9
1345.0
Psat = 8.5879 MPa
0.001398
1329.4
1343.3
0.001378
1317.6
1338.3
0.001361
1307.1
1334.4
0.001346
1297.6
1331.3
0.001332
1288.9
1328.9
0.001320
1280.8
1327.0
0.001308
1273.3
1325.6
0.001298
1266.2
1324.6
0.001288
1259.6
1324.0
0.001279
1253.3
1323.6
0.001270
1247.3
1323.5
0.001262
1241.6
1323.6
0.001254
1236.1
1323.9
0.001247
1230.9
1324.4
0.001240
1225.9
1325.1
0.001233
1221.1
1325.9
0.001227
1216.4
1326.8
0.001221
1212.0
1327.9
0.001215
1207.6
1329.1
v
m3 / kg
0.00174
u
kJ/kg
h
kJ/kg
1642.1
1670.9
Psat = 16.529 MPa
0.001665
0.001599
0.001553
0.001517
0.001488
0.001464
0.001443
0.001424
0.001407
0.001391
0.001377
0.001364
0.001353
0.001341
0.001331
0.001321
0.001312
1612.7
1583.9
1562.2
1544.5
1529.3
1515.9
1503.9
1493.1
1483.1
1473.8
1465.2
1457.1
1449.5
1442.3
1435.5
1429.0
1422.8
1646.0
1623.9
1608.8
1597.6
1588.8
1581.8
1576.1
1571.4
1567.5
1564.3
1561.6
1559.5
1557.7
1556.3
1555.3
1554.5
1554.0
Table 3 Compressed liquid water enthalpies, h, their approximation differences, hsat h Eq. 2, and hcorr h Eq. 5, and related percentages Note: More erroneous approximations are indicated in bold.
TC
P
MPa
4C
h kJ/kg
hsat h
hcorr h
kJ/kg
kJ/kg
%
%
Sat.
20 C
h kJ/kg
hsat h
hcorr h
kJ/kg
kJ/kg
%
%
16.81
0
0%
50 C
h kJ/kg
hsat h
hcorr h
kJ/kg
kJ/kg
%
%
83.91
0
0%
0
0%
100 C
h kJ/kg
hsat h
hcorr h
kJ/kg
kJ/kg
%
%
209.34
0
0%
0
0%
150 C
h kJ/kg
hsat h
hcorr h
kJ/kg
kJ/kg
%
%
419.17
0
0%
0
0%
200 C
h kJ/kg
hsat h
hcorr h
kJ/kg
kJ/kg
%
%
632.18
0
0%
0
0%
250 C
h kJ/kg
hsat h
hcorr h
kJ/kg
kJ/kg
%
%
852.27
0
0%
0
0%
300 C
h kJ/kg
hsat h
hcorr h
kJ/kg
kJ/kg
%
%
1085.80
0
0%
0
0%
0
0%
350 C
h kJ/kg
hsat h
hcorr h
kJ/kg
kJ/kg
%
%
1345.00
0
0%
0
0%
1670.90
0
0%
0
0%
21.80
0.02
4.98
0.1%
22.9%
88.61
0.31
4.69
0.4%
5.3%
213.64
0.75
4.30
0.4%
2.0%
422.85
1.43
3.68
0.3%
0.9%
634.98
2.13
2.80
0.3%
0.4%
853.68
2.57
1.41
0.3%
0.2%
1085.70
0.10
1.38
0.0%
0.1%
Vapor
Psat=
8.5879 MPa
10
26.75
0.07
9.93
0.3%
37.1%
93.28
0.65
9.37
0.7%
10.0%
217.94
1.51
8.60
0.7%
3.9%
426.62
2.88
7.45
0.7%
1.7%
638.11
4.46
5.93
0.7%
0.9%
855.80
6.24
3.53
0.7%
0.4%
1085.80
0.00
7.54
0.0%
0.7%
1343.30
1.70
3.68
0.1%
0.3%
15
31.66
0.15
14.85
0.5%
46.9%
97.93
1.00
14.02
1.0%
14.3%
222.23
2.28
12.89
1.0%
5.8%
430.39
4.33
11.22
1.0%
2.6%
641.27
6.75
9.09
1.1%
1.4%
857.99
9.83
5.72
1.1%
0.7%
1086.10
13.50
0.30
0.0%
1.2%
1338.30
6.70
15.70
0.5%
1.2%
20
36.55
0.27
19.74
0.7%
54.0%
102.57
1.38
18.66
1.3%
18.2%
226.51
3.06
17.17
1.4%
7.6%
434.17
5.76
15.00
1.3%
3.5%
644.45
9.02
12.27
1.4%
1.9%
860.27
13.33
8.00
1.5%
0.9%
1086.70
19.16
0.90
1.8%
0.1%
1334.40
10.60
26.62
0.8%
2.0%
1646.00
24.90
30.94
1.5%
1.9%
30
46.23
0.59
29.41
1.3%
63.6%
111.77
2.20
27.86
2.0%
24.9%
235.05
4.64
25.71
2.0%
10.9%
441.74
8.63
22.57
2.0%
5.1%
650.89
13.49
18.71
2.1%
2.9%
865.02
20.15
12.75
2.3%
1.5%
1088.40
29.97
2.60
2.8%
0.2%
1328.90
16.10
46.17
1.2%
3.5%
1608.80
62.10
85.54
3.9%
5.3%
40
55.79
1.03
38.98
1.8%
69.9%
120.90
3.08
36.99
2.6%
30.6%
243.56
6.25
34.22
2.6%
14.0%
449.33
11.47
30.16
2.6%
6.7%
657.42
17.86
25.24
2.7%
3.8%
870.00
26.73
17.73
3.1%
2.0%
1090.70
40.19
4.90
3.7%
0.4%
1325.60
19.40
63.51
1.5%
4.8%
1588.80
82.10
122.94
5.2%
7.7%
50
65.24
1.58
48.43
2.4%
74.2%
129.95
4.05
46.04
3.1%
35.4%
252.03
7.90
42.69
3.1%
16.9%
456.94
14.30
37.77
3.1%
8.3%
664.02
22.17
31.84
3.3%
4.8%
875.19
33.11
22.92
3.8%
2.6%
1093.50
49.91
7.70
4.6%
0.7%
1324.00
21.00
79.15
1.6%
6.0%
1576.10
94.80
153.04
6.0%
9.7%
60
74.59
2.23
57.78
3.0%
77.5%
138.94
5.08
55.03
3.7%
39.6%
260.47
9.58
51.13
3.7%
19.6%
464.56
17.11
45.39
3.7%
9.8%
670.69
26.40
38.51
3.9%
5.7%
880.55
39.31
28.28
4.5%
3.2%
1096.80
59.12
11.00
5.4%
1.0%
1323.50
21.50
93.69
1.6%
7.1%
1567.50
103.40
179.04
6.6%
11.4%
80
93.00
3.82
76.19
4.1%
81.9%
156.70
7.36
72.79
4.7%
46.4%
277.26
13.04
67.92
4.7%
24.5%
479.82
22.72
60.65
4.7%
12.6%
684.21
34.69
52.03
5.1%
7.6%
891.73
51.26
39.46
5.7%
4.4%
1104.40
76.56
18.60
6.9%
1.7%
1325.10
19.90
120.18
1.5%
9.1%
1557.70
113.20
223.64
7.3%
14.4%
100
111.06
5.76
94.25
5.2%
84.9%
174.22
9.87
90.31
5.7%
51.8%
293.92
16.62
84.58
5.7%
28.8%
495.11
28.30
75.94
5.7%
15.3%
697.93
42.78
65.75
6.1%
9.4%
903.40
62.72
51.13
6.9%
5.7%
1113.10
92.89
27.30
8.3%
2.5%
1329.10
15.90
144.26
1.2%
10.9%
1554.00
116.90
262.14
7.5%
16.9%
Vapor
Psat=
6.529 MPa
Analysis
hP =
N1
P dv
i=1sat
N1
v dP
i=1sat
1
Pi + Pi+1 vi+1 vi
2
1
vi + vi+1 Pi+1 Pi hcorr
2
pressure increase due to a strong decrease of internal energy, making the recommended positive correction, hcorr, to be erroneous
and thus counterproductive and misleading, see Tables 2 and 3.
The hu correction is not included in Eq. 5 even though its
magnitude may be, and sometimes is, larger than the included
hcorr hP correction. Therefore, the recommended enthalpy
correction for isothermal compression in the literature is appropriate for the isentropic processes see additional justification below, but not appropriate for isothermal processes, although it
may sometimes be beneficial, due to an erroneous assumption that
internal energy is not, and enthalpy is, dependent on pressure. It is
quite the opposite in Table 1, see how the corresponding values
u and h change with pressure at constant temperature of 260 C.
The above physical justifications could be confirmed using the
corresponding differential property correlations obtained using the
Maxwells relations 1:
10
From Eq. 9 it is evident that change in internal energy for the
isothermal process is zero du = 0 only for ideal incompressible
fluids dv = 0, but for real liquids dv 0 the bracketed term
with dv in Eq. 9 is not zero since real liquids are not exactly
incompressible.
Equation 10 confirms that pressure correction vdP is always
appropriate for isentropic processes dh = Tds + vdP = vdP for s
= const, but not for isothermal processes as given in many referMAY 2006, Vol. 128 / 425
of the erroneous assumption that, due to incompressibility for liquids in general, the internal energy is less dependent on pressure
than enthalpy. The literature recommendations may be erroneous
and thus counterproductive and misleading, as is the case for liquid water at higher temperatures and pressures. For intermediate
pressures and temperatures, the enthalpy corrections recommended in the literature are unnecessary, since the errors are about
the same in magnitude but opposite in sign as if the corresponding saturated enthalpy values without any corrections were used.
The isothermal corrections are only beneficial for very high pressures at smaller temperatures below 200 C for liquid water.
In summary, the recommended pressure corrections in the classical reference textbooks for isothermal, liquid enthalpy approximation are not appropriate and often insignificant, unnecessary or
more erroneous than the simple approximation using the corresponding saturated values. Furthermore, it is shown here that the
recommended pressure correction for isothermal processes are
actually valid in general for enthalpy correction for isentropic
processes.
Nomenclature
11
Since the Joule-Thomson coefficient is defined as JT = T / Ph,
then Eq. 11 could be expressed as:
hT = hP,T hsatTT = hu + hv + hP
=
C PJTdP
Psat
N1
i=1sat
1
C PJT,i + C PJT,i+1 Pi+1 Pi
2
12
Note that real data values for both, the JT and CP are available
3, and for the isothermal enthalpy correction, h, Eq. 12 was
used instead of Eqs. 68, see Table 1.
Compressed liquid water enthalpies h, different corrections,
their approximation differences hsat h, and hcorr h and the corresponding error percentages, with regard to the saturation value,
are presented in Table 3, without any correction Eq. 2 and the
correction recommended in the literature hcorr hP, Eq. 5,
for a wide range of temperatures and pressures. The corrections,
as recommended in 1,2 Eq. 5, are only beneficial for higher
pressures at smaller temperatures, insignificant for smaller pressures at most of the temperatures, about the same but opposite
sign thus unnecessary for intermediate temperatures and pressures, and more erroneous thus counterproductive and misleading for higher temperatures and pressures, than the simple approximation without any correction Eq. 2, as seen from Tables
1 and 3.
Subscripts
s50 isentropic compression from saturated to
50 MPa
sat for saturated liquid
T50 isothermal compression from saturated to
50 MPa
References
Conclusion