Advanced Thermodynamics for Hydrogen Applications

Exercise: EoS

Task 1 Enthalpy Balance

In a process of specialty chemistry of a chemical substance heated under pressure.

For this purpose, the volume flow 𝑉 = 50 𝑙/𝑠 is heated to the temperature 𝑇2 = 250°𝐶
at a temperature 𝑇1 = 20°𝐶 in a heat exchanger; the density is
𝑘𝐽
𝜌 = 1020 𝑘𝑔/𝑚³ = 𝑐𝑜𝑛𝑠𝑡. The mean specific heat capacity is 𝑐𝑚 = 4.10 𝑘𝑔⋅𝐾. At the inlet

cross-section into the heat exchanger the pressure is measured 𝑃1 = 50 𝑏𝑎𝑟, at the
outlet cross-section the pressure is 𝑃2 = 49 𝑏𝑎𝑟. The entry velocity and exit velocity
are the same. The inlet and outlet cross-sections are at the same height. For the heat
source, a constant average temperature of 𝑇𝐻𝑆 = 573.15 𝐾, for the liquid to be heated,
an average temperature of 𝑇𝐿𝑖 = 408.15 𝐾 can be assumed.

a) What is the mass flow 𝑚̇ of the liquid?

𝑚3 𝑘𝑔 𝑘𝑔
𝑚̇ = 𝑉̇ ⋅ 𝜌 → 𝑚̇ = 0.05 ⋅ 1020 3 = 51
𝑠 𝑚 𝑠

b) Which heat flow follows from the energy balance for an open system that is
supplied to the liquid?

1
𝑄̇12 + 𝑃12 = 𝑚̇ ⋅ [(𝑢2 + 𝑃2 ⋅ 𝑣2 ) − (𝑢1 + 𝑃1 ⋅ 𝑣1 ) + ⋅ (𝑐22 − 𝑐12 ) + 𝑔(𝑧2 − 𝑧1 )]
2

𝑃12 = 0 ; 𝑐2 = 𝑐1 ; 𝑧2 = 𝑧1

𝑃2 𝑃1
𝑄̇12 = 𝑚̇ ⋅ (𝑢2 − 𝑢1 + 𝑃2 ⋅ 𝑣2 − 𝑃1 ⋅ 𝑣1 ) = 𝑚̇ ⋅ (𝑢2 − 𝑢1 + − )=
𝜌1 𝜌1

1
= 𝑚̇ ⋅ (𝑐𝑚 ⋅ (𝑇2 − 𝑇1 ) + ⋅ (𝑃2 − 𝑃1 )) =
𝜌1

𝑘𝑔 𝑘𝐽 1 𝑃𝑎 𝐽
Prof.
= 51Dr.-Ing. Johannes
⋅ (4.1 Völkl − 20°𝐶) +
⋅ (250°𝐶 ⋅ (49 − 50) ⋅ 105 ⋅ 10−3 ) = 48088 𝑘𝑊
𝑠 for Simulation
Professor 𝑘𝑔 ⋅ 𝐾 in Chemical Engineering𝑘𝑔 𝑏𝑎𝑟 𝑘𝐽 - 1 -
1020 3
𝑚
 c) Calculate the entropy current changes for the heat source (𝑆2̇ − 𝑆1̇ )𝐻𝑆 and the

liquid (𝑆2̇ − 𝑆1̇ )𝐿𝑖 ! Is the entire process reversible or irreversible?

𝑄̇12,𝑟𝑒𝑣 = 𝑄̇12 + 𝑃12 → 𝑄̇12,𝑟𝑒𝑣 = 𝑄̇12

𝜕𝑄̇𝑟𝑒𝑣
𝜕𝑄̇𝑟𝑒𝑣 = 𝑇𝑑𝑆 → 𝑑𝑆 =
𝑇
𝑄̇12 48088 𝑘𝑊 𝑘𝑊
(𝑆2 − 𝑆1 )𝐻𝑆 = − =− = −83.9
𝑇𝐻𝑆 573.15 𝐾 𝐾
𝑄̇12 48088 𝑘𝑊 𝑘𝑊
(𝑆2 − 𝑆1 )𝐿𝑖 = = = 117.82
𝑇𝐿𝑖 408.15 𝐾 𝐾
𝑘𝑊 𝑘𝑊 𝑘𝑊
→ (𝑆2 − 𝑆1 )𝑔𝑒𝑠 = Δ𝑆𝐻𝑆 + Δ𝑆𝐿𝑖 = −83.9 + 117.82 = 33.92 > 0 → 𝑖𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑒𝑙
𝐾 𝐾 𝐾

Task 2 Natural Gas consumption

A natural gas consumption of 47.6 m³ was read from a gas meter. During consumption,
the natural gas was under an average overpressure of 𝑃𝑂 = 20 𝑚𝑏𝑎𝑟 with a barometer
reading of 𝑃𝑈 = 961 𝑚𝑏𝑎𝑟 and a temperature of 𝑇 = 9°𝐶. The consumer pays 0.3 euros
𝑘𝑔
for 1 m³ of gas. Given : 𝑀𝐸𝑟𝑑𝑔𝑎𝑠 = 16.03 𝑘𝑚𝑜𝑙

a) How much does 1 kg of natural gas cost?

𝑅
𝑃 ⋅ 𝑉 = 𝑚 ⋅ 𝑅𝑖 ⋅ 𝑇; 𝑅𝑖 =
𝑀

5 𝑃𝑎 3 𝑘𝑔
𝑃 ⋅ 𝑉 𝑃 ⋅ 𝑉 ⋅ 𝑀𝐸𝑟𝑑𝑔𝑎𝑠 (0.961 + 0.02)𝑏𝑎𝑟 ⋅ 10 𝑏𝑎𝑟 ⋅ 47.6 𝑚 ⋅ 16.03 𝑘𝑚𝑜𝑙
𝑚𝑁𝑎𝑡 𝐺𝑎𝑠 = = = = 32 𝑘𝑔
𝑅𝑖 ⋅ 𝑇 𝑅⋅𝑇 𝑘𝐽 𝐽
8.314 ⋅ (9 + 273.15)𝐾 ⋅ 1000
𝑘𝑚𝑜𝑙 ⋅ 𝐾 𝑘𝐽

𝑃𝑟𝑒𝑖𝑠 𝐸𝑢𝑟𝑜
𝑃𝑟𝑖𝑐𝑒 = 𝑉 ⋅ = 47.6 𝑚3 ⋅ 0.3 3 = 14.28 𝐸𝑢𝑟𝑜
𝑉 𝑚

14.28 𝐸𝑢𝑟𝑜 𝐸𝑢𝑟𝑜

↳ = 0.44625
32 𝑘𝑔 𝑘𝑔

Prof. Dr.-Ing. Johannes Völkl

Professor for Simulation in Chemical Engineering -2-
 b) By how many euros does the price per kg of natural gas increase if the specified
volume is delivered under an overpressure 𝑃𝑂 = 16 𝑚𝑏𝑎𝑟 at the same
barometer reading and a temperature 𝑇 = 34°𝐶?

𝑃𝑎 𝑘𝑔
(0.961 + 0.016)𝑏𝑎𝑟 ⋅ 105 ⋅ 47.6 𝑚3 ⋅ 16.03
𝑚𝑁𝑎𝑡 𝐺𝑎𝑠 = 𝑏𝑎𝑟 𝑘𝑚𝑜𝑙 = 29.19 𝑘𝑔
𝑘𝐽 𝐽
8.314 ⋅ (34 + 273.15)𝐾 ⋅ 1000
𝑘𝑚𝑜𝑙 ⋅ 𝐾 𝑘𝐽

𝐸𝑢𝑟𝑜 𝐸𝑢𝑟𝑜
↳ 0.48916 → 0.0429 𝑚𝑒ℎ𝑟
𝑘𝑔 𝑘𝑔

Task 3

A combustion gas with the constant mass 𝑚1 = 𝑚2 = 𝑚 = 0.01258 𝑘𝑔, of which the
specific gas constant is not known, is located in the cylinder of a large diesel engine at
𝑃1 = 83.021 𝑏𝑎𝑟, 𝑇1 = 2137.52°𝐶, 𝑉1 = 0.0011 𝑚3. The combustion gas can be
approximately assumed to be an ideal gas. The gas is reversibly and isentropically
expanded, whereby its temperature decreases to 𝑇2 = 841.45°𝐶 and the volume
increases to 𝑉2 = 0.0121 𝑚³. Given: 𝜅 = 1.3217

a) Calculate the special gas constant 𝑅𝑖 !

𝑃𝑎
𝑃⋅𝑉 83.021 𝑏𝑎𝑟 ⋅ 105 ⋅ 0.0011 𝑚3 𝐽
𝑃 ⋅ 𝑉 = 𝑚 ⋅ 𝑅𝑖 ⋅ 𝑇 → 𝑅𝑖 = = 𝑏𝑎𝑟 = 301.14
𝑚 ⋅ 𝑇 0.01258 𝑘𝑔 ⋅ (2137.52 + 273.15)𝐾 𝑘𝑔 ⋅ 𝐾

b) Calculate the average specific isochoric or isobaric heat capacity 𝑐𝑣𝑚 , 𝑐𝑃𝑚 !

1 1 𝐽 𝐽
𝑐𝑉𝑚 = ⋅ 𝑅𝑖 = ⋅ 301.14 = 936.08
𝜅−1 1.3217 − 1 𝑘𝑔 ⋅ 𝐾 𝑘𝑔 ⋅ 𝐾

𝐽 𝐽 𝐽
𝑐𝑃𝑚 = 𝑐𝑉𝑚 + 𝑅𝑖 = 936.08 + 301.14 = 1237.22
𝑘𝑔 ⋅ 𝐾 𝑘𝑔 ⋅ 𝐾 𝑘𝑔 ⋅ 𝐾

Prof. Dr.-Ing. Johannes Völkl

Professor for Simulation in Chemical Engineering -3-
Task 4

In a gas cylinder with 𝑉 = 50 𝑙 there is 𝑚 = 12 𝑘𝑔 oxygen at 𝑇 = 20°𝐶.

𝐽 𝑉 𝑚3
Given: 𝑃𝐾𝑟𝑖𝑡 = 50.5 𝑏𝑎𝑟, 𝑇𝐾𝑟𝑖𝑡 = 154.0 𝐾, 𝑅𝑂2 = 259.84 𝑘𝑔⋅𝐾 , 𝑣 = 𝑚 = 0.004167 𝑘𝑔 .

Determine the pressure in the gas:

a) With ideal gas law

𝐽
𝑇 ⋅ 𝑅𝑂2 293.15 𝐾 ⋅ 259.84 𝑘𝑔 ⋅ 𝐾
𝑃 ⋅ 𝑉 = 𝑇 ⋅ 𝑅𝑖 → 𝑃 = = = 182.8 𝑏𝑎𝑟
𝑣 𝑚3
0.004167
𝑘𝑔

b) With van der Waals Equation

2
𝐽
27 (𝑅𝑖 ⋅ 𝑇𝑐 )2 27 (259.84 ⋅ 154 𝐾) 𝑃𝑎 ⋅ 𝑚6
𝑘𝑔 ⋅ 𝐾
𝑎= ⋅ = ⋅ = 133.7664
64 𝑃𝑐 64 50.5 ⋅ 105 𝑃𝑎 𝑘𝑔2
2
𝐽 𝐽
𝑅𝑖 𝑇𝑐 259.84 (259.84 ⋅ 154 𝐾) 𝑚3
𝑘𝑔 ⋅ 𝐾 𝑘𝑔 ⋅ 𝐾 −4
𝑏= ⋅ = ⋅ = 9.905 ⋅ 10
8 𝑃𝑐 864 50.5 ⋅ 105 𝑃𝑎 𝑘𝑔

𝐽 𝑃𝑎 ⋅ 𝑚6
𝑅𝑖 ⋅ 𝑇 𝑎 259.84
⋅ 293.15 𝐾 133.7664
𝑘𝑔 ⋅ 𝐾 𝑘𝑔2
𝑃= − 2= − = 162.8 𝑏𝑎𝑟
𝑣−𝑏 𝑣 𝑚3 −4 𝑚3 𝑚 3 2
0.004167 − 9.905 ⋅ 10 (0.004167 )
𝑘𝑔 𝑘𝑔 𝑘𝑔

Prof. Dr.-Ing. Johannes Völkl

Professor for Simulation in Chemical Engineering -4-
c) With Redlich-Kwong-Equation

5 𝐽 2 5
259.84 ⋅ (154 𝐾)2
𝑅𝑖2⋅ 𝑇𝑐2 𝑘𝑔 ⋅ 𝐾 𝑃𝑎 ⋅ 𝑚6
𝑎 = 0.42748 ⋅ = 0.42748 ⋅ = 1682.05
𝑃𝑐 50.5 ⋅ 105 𝑃𝑎 𝑘𝑔2

𝐽
𝑅𝑖 ⋅ 𝑇𝑐 259.84 ⋅ 154 𝐾 𝑚3
𝑘𝑔 ⋅ 𝐾 −4
𝑏 = 0.08664 ⋅ = 0.08664 ⋅ = 6.865 ⋅ 10
𝑃𝑐 50.5 ⋅ 105 𝑃𝑎 𝑘𝑔

𝐽
𝑅𝑖 ⋅ 𝑇 𝑎 259.84 ⋅ 293.15 𝐾
𝑘𝑔 ⋅ 𝐾
𝑃= − = −
𝑣 − 𝑏 𝑣 ⋅ (𝑣 + 𝑏) ⋅ 𝑇 0.5 𝑚3 𝑚3
0.004167 − 6.865 ⋅ 10−4
𝑘𝑔 𝑘𝑔

𝑃𝑎 ⋅ 𝑚6
1682.05
𝑘𝑔2
− = 170.28 𝑏𝑎𝑟
𝑚3 𝑚3 𝑚3
0.004167 ⋅ (0.004167 + 6.865 ⋅ 10−4 ) ⋅ (293.15 𝐾)0.5
𝑘𝑔 𝑘𝑔 𝑘𝑔

Prof. Dr.-Ing. Johannes Völkl

Professor for Simulation in Chemical Engineering -5-