Thermodynamics: Answers 3 Thermodynamic Properties of Pure Substances

3 Thermodynamic Properties of Pure Substances

3.1 Phases of matter
3.1a The three phases that matter can have are: the solid phase, the liquid phase and the gas phase.

3.1b The six phase transitions that can occur are:

1) From solid to liquid called melting.
2) From solid to gas called sublimation.
3) From liquid to solid called freezing.
4) From liquid to gas called vaporization.
5) From gas to solid called desublimation.
6) From gas to liquid called condensation.

3.1c If a substance starts to boil the pressure and temperature are fixed, they are at their saturation
point. This is that at a given pressure, the temperature at which a pure substance changes phases
is called the saturation temperature, Tsat . Likewise, at a given temperature,the pressure at which a
substance changes phases is called the saturation pressure, Psat . For example for water at a pressure
of 101.325 kPa, Tsat = 99.97 ◦ C. Conversely, at a temperature of 99.97 ◦ C, Psat =101.325 kPa. For
practically all substances tables that list the saturation pressure against the temperature (or the
saturation temperature against the pressure) are available.

3.1d The area in which substances exist in two phases is called the co-existential area or simply the
two phase area or the mixture phase.

3.1e A substance that exists in two phases is called a mixture.

3.1f The temperature of the liquid is equal to the temperature of the gas in the mixture, Tl = Tv ,
also the pressure of the liquid is equal to the pressure of the gas, Pl = Pv

3.1g The pressure and temperature of a mixture in an open system do not change if heat is added to
the mixture. The heat added is used to vaporize the liquid in the mixture. However, if all the liquid
finally is vaporized the temperature of the vapor will rise (this is the superheated vapor phase).

3.1h In general the amount of heat absorbed or released during a phase-change process is called the
latent heat. The energy (heat) necessary to vaporize the liquid is called the latent heat of vaporization.
The amount of energy absorbed during melting is called the latent heat fusion.

3.1i The energy necessary to vaporize a liquid and the energy necessary to condense the vapor are
equal. In other words the energy used for vaporization is equal to the energy that is released during
condensation.

3.2 T v-diagram
3.2a See figure 3.2.1.

3.2b Critical point → top of the dome curve where the line of saturated liquid (kooklijn) and the
line of saturated vapor (damplijn) though each other.

3.2c Saturated liquid → on the left part of the dome curve (only the line!), this is the saturated
liquid line (kooklijn).

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Thermodynamics: Answers 3 Thermodynamic Properties of Pure Substances

Figure 3.2.1: The T − v diagram with the vapor dome and the different regions.

3.2d Saturated vapor → on the right part of the dome curve (only the line!), this is the saturated
vapor line (damplijn).

3.2e Compressed liquid → in the area left of the saturated liquid line, thus left of the dome.

3.2f Saturated mixture → in the area below the dome.

3.2g Superheated vapor → in the area right of the saturated vapor line, thus right of the dome.

3.3 Incompressible liquid

3.3a An incompressible liquid is a substance of which the volume hardly changes when the pressure
or temperature changes. That is it can not be compressed when pressure is applied to it, water is an
example. The most important property is: v=constant → dv = 0. This means no change in volume.

3.3b β = v1 ∂T
∂v


P
= 0 as dv = 0.
1 ∂v


κ = − v ∂P T = 0 as dv = 0.

3.4 Mixtures
3.4a T v - diagram. Lines of constant
quality

3.4b vlv = vv − vl .

3.5 Quality of a mixture

3.5a The total mass is the mass of the liquid plus the mass of the vapor, m = ml + mv .

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Thermodynamics: Answers 3 Thermodynamic Properties of Pure Substances

3.5b The quality is defined as,

M ass of vapor mv
x = M ass f raction of vapor = =
T otal mass of mixture m
M ass of liquid ml
1 − x = M ass f raction of liquid = = .
T otal mass of mixture m

3.5c No, outside the mixture region x is not defined and has no meaning.

3.5d the quality can have values between zero and one, 0 ≤ x ≤ 1.

3.5e For saturated liquid the quality is x = 0.

3.5f For saturated vapor the quality is x = 1.

3.5g Temperature and pressure do not change, they are coupled and constant during vaporization or
condensation. Volume, internal energy, enthalpy and entropy do change. In a vaporization (conden-
sation) process the volume, internal energy, enthalpy and entropy increase (decrease).
The quality of a mixtures also changes, during vaporization it increases during condensation it de-
creases.

3.5h See figure at exercise 3.4 a (the dotted red lines, they go down from the critical point).

3.6 Use of tables: water

The values for the tables are found in tables with the properties of water, like tables A-4, A-5, A-6,
and A-7 from the book of Cengel and Boles. Note that tables A-4 and A-5 contain the same infor-
mation, however, A-4 is sorted on temperature and A-5 on pressure. Also note, different books can
have slightly different values. In the answer the required values come from table 10, 11 and 12 from
the book of Schmidt. Given values are underlined.

T (◦ C) P (kPa) v (m3 /kg) Phase description

50 12.344 4.16 mixture
120.24 200 0.8859 saturated vapor
250 400 0.5951 superheated vapor
110 600 0.001052 compressed liquid

T (◦ C) P (kPa) h (kJ/kg) x Phase description

120.24 200 2045.99 0.7 mixture
140 361.19 1800 0.56 mixture
177.70 950 753.10 0.0 saturated liquid
80 500 334.93 - compressed liquid
350 800 3161.4 - superheated vapor

Explanation to the tables: The required values come from table 10, 11 and 12 from the book of
Schmidt. Note that tables 10 and 11 contain the same information: 10 is sorted on temperature and
11 on pressure.

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Thermodynamics: Answers 3 Thermodynamic Properties of Pure Substances

Table 1: see also figure 3.6.1.

First row: Given is the temperature of T = 50 ◦ C. Look in table 10. It is seen that the specific
volume of the saturated liquid phase is vf = 0.001012 m3 /kg and the specific volume of the saturated
vapour phase is vg = 12.026 m3 /kg. The given specific volume of v = 4.16 m3 /kg is between these
values, so we are in the mixture phase. The pressure is therefore the saturation pressure at 50 ◦ C:
Psat@50◦ C = 12.344 kPa.
Second row: Given is saturated vapour at P = 200 kPa. So, the point is on the vapour line. In
table 11 the temperature belonging to this saturation pressure can be found: Tsat@200kP a = 120.24 ◦ C.
The volume is the volume of saturated vapour: vg = 0.8859 m3 /kg.
Third row: Temperature and pressure are given. The first thing that we need to find is at which
temperature water boils for the given pressure. Table 11 gives Tsat@400kP a = 143.61 ◦ C. The given
temperature is higher, so the water already has boiled and we now have a superheated vapour. The
volume is found in table 12 at T = 250 ◦ C (interpolate).
Fourth row: As in 3, we look in table 11: Tsat@600kP a = 158.83. This is higher than the given
temperature of T = 110 ◦ C. The water is therefore a compressed liquid. Since volume is independent
of of pressure, we take the volume at T = 110 ◦ C in table 10.

Figure 3.6.1: T -v diagram for the first table

(not to scale) Figure 3.6.2: T -v diagram for the second table
(not to scale)

Table 2: see also figure 3.6.2.

First row: Given is x = 0.7. x is the vapour fraction (x = numberof partsvapour
totalparts , not defined outside
the mixture region), so we have a mixture of liquid and vapour. Therefore, T = Tsat@200kP a =
120.24 ◦ C (table 11). h follows from h = hf +x(hg −hf ) with hf = 504.71 kJ/kg and hg = 2706.3 kJ/kg
⇒ h = 2045.8 kJ/kg.
Second row: Given is T = 140 ◦ C. From table 10 it follows that hf = 589.16 kJ/kg and hg =
2733.5 kJ/kg. The given h is between these values, so it is a mixture. Therefore, from table 10,
h−h
p = Psat@140◦ C = 361.19 kPa. x is then determined as x = hg −hff = 0.56.
Third row: x = 0.0, so there is no vapour, only liquid. So, it is a saturated liquid (outside
the mixture region x does not have a value). From table 11: T = Tsat@950kP a = 177.70 ◦ C and
h = hf = 752.74 kJ/kg.
Fourth row: At P = 500 kPa, the saturation temperature is 151.83 ◦ C (table 11). The given
temperature of 80 ◦ C is lower, so we have a compressed liquid. Using dh = vdP , we find h =
hf @80◦ C + v(P − Psat@80◦ C = 335.02 + 0.001029(500 − 47.416) = 335.49 kJ/kg. We are not in the
mixture region, so x is not defined.
Fifth row: At P = 800 kPa, hg = 2768.3 kJ/kg (table 11). The given value for h is higher, so it
is a superheated vapour. In table 12 at P = 800 kPa= 0.8 Mpa and h = 3161.4 kJ/kg, we find that
T = 350 ◦ C. Since we are not in the mixture region, x is not defined.

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Thermodynamics: Answers 3 Thermodynamic Properties of Pure Substances

3.7 Use of tables, refrigerant 134a

The values for the tables are found in tables with the properties of refrigerant 134a, 11, 12 and 13.
Note, different books can have slightly different values.

T (◦ ) P (kPa) v (m3 /kg) Phase description

-8 500 0.0007571 compressed liquid
30 771.61 0.022 mixture
2.46 320 0.063604 saturated vapor
100 600 0.47900 superheated

T (◦ ) P (kPa) u (kJ/kg) Phase description

20 572.07 95 mixture
-12 185.37 35.78 saturated liquid
87 400 300 superheated vapor
6 600 59.68 compressed liquid

3.8 Boiling of water

3.8a The temperature at which the water starts to boil is dependent on the pressure inside the
cylinder. The pressure inside the cylinder is a combination of the outside pressure (Patm ) and the
pressure of the piston (Ppiston = F/A = (M · g)/A, with A the surface and M the mass of the piston).
Pcylinder = Patm +M ·g)/A = (20·9.8)/100·10−4 )+100·103 = 19600+100000 = 119600Pa = 119.6 kPa.
The pressure inside the cylinder is 119.6 kPa. In tabel A-5 the saturation temperature of this pressure
can be found. It is seen that at 100 kPa that water boils at Tsat@100kP a = 99.632 degree Celsius and
at 125 kPa the water boils at Tsat@125kP a = 105.99 degree Celsius. By interpolation the temperature
at a pressure of 119.4 kPa can be found. This temperature is [email protected] a = 104.7 degree Celsius.

3.8b If you go up in the mountains the outside pressure (Patm ) will decrease. Therefore the pressure
inside the cylinder will decrease. At a lower pressure the water starts to boil at a lower temperature.

3.8c If the pressure outside the cylinder decrease to 95 kPa the pressure inside the cylinder will also
decrease with 5 kPa and becomes 114.6 kPa. The water will boil then at [email protected] a = 103.4 degree
Celsius.

3.9 Vessel with 2 kg refrigerant 134a

Given: Refrigerant 134a, m=2 kg, in a vessel at P =900 kPa and T =80◦ C.
From table 12 or 13 follows that at a pressure of 900 kPa the saturation temperature of refrigerent 134a
is 35.53◦ C. The temperature in the vessel is 80◦ C, therefore the refrigerant in the vessel is superheated
vapor.
Table 13, P =900 kPa and T =80◦ C → v=0.02861 m3 /kg and u=288.87 kJ/kg.
The total volume of the vessel is V = mv = 2 · 0.02863 = 0.05726 m3 and the total internal energy is
U = mu = 2 · 288.87 = 577.74 kJ.

3.10 Vessel with refrigerant 134a

Given: Refrigerant 134a, m=10 kg, in a vessel, V =0.5m3 , at T =-20◦ C.

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Thermodynamics: Answers 3 Thermodynamic Properties of Pure Substances

3.10a The density of the refrigerent inside the vessel is ρ = m/V = 10/0.5 = 20 kg/m3 . The specific
volume is v = 1/ρ = 1/20 = 0.05 m3 /kg. This is a mixture as 10 kg of the fluid takes less space than
0.5m3 and 10 kg of gas takes more space than 0.5m3 . This can be seen from tabel 11 → vl < v < vv
with vl = 0.000736 m3 /kg and vv = 0.1464 m3 /kg. Therefore the pressure is the saturation pressure
P = Psat@−20◦ C = 132.99 kPa (tabel 11).

3.10b The total internal energy U can be determined by U = mu = m(ul + x(uv − ul )). The mixture
fraction x follows from the volumes as x = vv−vl
v −vl
0.05−0.000736
= 0.1464−0.000736 = 0.338. The values for ul and uv
follow from table 11 → ul = 24.17 kJ/kg and uv = 215.84 kJ/kg. U = mu = m(ul + x(uv − ul )) =
10(24.17 + 0.338(215.84 − 24.17)) = 889.5 kJ.

3.10c The mixture fraction is defined as x = mv /m → mv = xm = 3.38 kg and ml = m − mv =

6.62 kg → Vl = vl ml = 0.00487 m3 .

3.11 Water mixture of liquid and vapor

We have 0.1m3 of liquid water and 0.9m3 of water vapor in equilibrium at P = 800 kPa. The substance
is in the mixture phase! Heat is added at a constant pressure till the temperature is 350◦ C.

3.11a See figure 3.11.1.

Figure 3.11.1: P-v and T-v diagrams

3.11b Initially the substance is in the mixture phase. In this phase the temperature is coupled to
the pressure. It can be found in table 5 → T = Tsat@800kP a = 170.44◦ C.

3.11c Table 11 gives for the mixture phase at 800 kPa → vl = 0.001115 m3 /kg and vv = 0.2404 m3 /kg.
Vlw 0.1
Liquid water → Vlw = 0.1m3 → Mlw = = = 89.7 kg.
vl 0.001115
Vwv 0.9
Water vapor → Vwv = 0.9m3 → Mwv = = = 3.7 kg.
vv 0.2404
Mtotal = Mlw + Mwv = 89.7 + 3.7 = 93.4 kg.
Mwv 3.7
The mixture fraction x = Mtotal = 93.4 = 0.04 → initially only 4% of the mixture is water vapor and
96% of the mixture is liquid water.

3.11d At T = 350◦ C en P = 800 kPa the substance is in the superheated vapor phase. The
final volume can be found using table 6. At T = 350◦ C en P = 800 kPa the specific volume is
v = 0.3544 m3 /kg → Vf inal = Mtotal × v = 93.4 × 0.3544 = 33.1 m3 .
At the point all liquid water has turned into water vapor the volume is Vtotal@sat = Mtotal ×vv@800kP a =
93.4 × 0.2404 = 22.45 m3 .

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Thermodynamics: Answers 3 Thermodynamic Properties of Pure Substances

3.12 Vaporization of water at constant pressure

Given is a piston-cylinder device that contains 50 liters of water at T = 25◦ C and 300 kPa. At constant
pressure heat is added to the water until the entire liquid is vaporized.

3.12a Heat is added, the temperature of the water rises, but the water stays liquid until it reaches
the temperature at which it starts to boil at a pressure of 300 kPa (point on the saturated liquid line).
From there on the water starts to evaporate and the temperature stays constant until the entire liquid
is vaporized (point on the saturated vapor line).

3.12b The end point is on the saturated vapor line, therefore the final temperature is the temperature
at which the water boils at 300 kPa, → T = Tsat@300kP a = 133.55◦ C.

3.12c The mass of the water is the total volume, V in m3 divided by the specific volume of the water
at a temperature of T = 25◦ C, vf @25C .
V = 50 liters = 50 · 10−3 = 0.050 m3 and vf @25C = 0.001003 m3 /kg (table 4).

V 0.050 [m3 ]
Mass → m = = = 49.85 kg.
vf @25C 0.001003 [m3 /kg]

3.12d The total enthalpy change is:

∆H = Hend − Hbegin = m · hend − m · hbegin = m · (hend − hbegin ) = m · ∆h.

hbegin = hf @25C = 104.83 kJ/kg (table 4) and hend = hg@300kP a = 2724.9 kJ/kg (table 5).

∆H = m·∆h = m·(hend −hbegin ) = 49.85·(2724.9−104.83) = 49.85·2620.07 = 130610 kJ = 130.6 MJ.

3.13 Work done by heating 1

Given is a piston-cylinder device that contains 200 liters of saturated liquid refrigerant 134a at 800 kPa.
At a constant pressure of 800 kPa heat is added until the refrigerant reaches a temperature of T = 50◦ C.

3.13a The process starts at the saturated liquid line at 800 kPa. By adding heat the liquid starts to
vaporize and the volume increases. The temperature however stays constant till the entire liquid is
vaporized (the added heat/energy is used to break the water bindings instead of heating the liquid).
The temperatrue is teh saturation temperature at 800 kPa which is: Tsat@800kP a = 31.31◦ C (table 12).
Only when all the liquid is vaporized the temperature starts to increase and also the volume increases
while the pressure stays constant at 800 kPa. When the temperature T2 = 50◦ C the process ends. At
that point the refrigerant is superheated.

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Thermodynamics: Answers 3 Thermodynamic Properties of Pure Substances

3.13b The specific work follows from the differential equation for the volume work δw = P dv, when
the pressure P is constant this is evaluated as:
ˆ v2
Specific work in kJ/kg → w = P dv = P (v2 − v1 ).
v1

For the total work in kJ this expression has to be multiplied by the mass: W = m · w.

3.13c v1 = vf @800kP a = 0.0008458 m3 /kg (table 12) and v2 = v@50C@800kP a = 0.028547 m3 /kg (ta-
ble 13).

Specific work in kJ/kg → w = P (v2 − v1 ) = 800(0.028547 − 0.0008458) = 800 · 0.0277 = 22.16 kJ/kg.

To determine the total work the mass of the liquid should be known. The mass of the liquid is the
total volume, V in m3 divided by the specific volume of the liquid at the saturation liquid line at
800 kPa.
V = 200 liters = 200 · 10−3 = 0.200 m3 and vf @800kP a = 0.0008458 m3 /kg (table 12).
V 0.200 [m3 ]
Mass refrigerant → m = = = 236.57 kg.
vf @800kP a 0.0008458 [m3 /kg]
Total work in kJ → W = m · w = 236.57 · 22.16 = 5242.4 kJ = 5.24 MJ.
The gas performs 5.24 MJ of total work on the environment (gas expands, volume gets larger).

3.14 Work done by heating 2

3.14a Given is a mass of 5 kg of saturated water at P1 = 200 kPa that is heated at constant pressure
to a temperature of T2 = 300◦ C.
´
The work done by the steam can be calculated as W = P dV , which is, since the pressure is
kept constant, equal to W = P (V2 − V1 ). From table 11, we find that the specific volume is
v1 = vf @200kP a = 0.001061 m3 /kg. The volume is then V1 = mv1 = 5 · 0.001061 = 0.005305 m3 . The
final specific volume can be determined from the tables for superheated water using P2 = P1 = 200 kPa
and T2 = 300◦ C: v2 = 1.3162 m3 /kg. This results in a final volume of V2 = mv2 = 5·1.3162 = 6.581 m3 .
Filling in the equation for the work then gives:
ˆ
W = P dV = P (V2 − V1 ) = 200 · (6.581 − 0.005305) = 1315.13 kJ

What is happening in this situation? The water is saturated at the saturated liquid line at 200 kPa.
Adding extra heat does not result in a rise of temperature, but in the evaporation of the water. During
evaporation the volume increases as molecules enter the gas phase, where they are further from each
other. When all water has evaporated the temperature does rise when more heat is added. The volume
also further increases. Hence, the volume increases all the time, while the temperature is constant
during evaporation.

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Thermodynamics: Answers 3 Thermodynamic Properties of Pure Substances

3.15 Perfect gas

3.15a A perfect gas (or ideal gas) is an imaginary substance that obeys the relation P v = RT . The
ideal gas-relation closely approximates the P − v − T behavior of real gases at low densities. At low
pressures and high temperatures, the density of a gas decreases, and the gas behaves as an ideal gas
under these conditions.
In the range of practical interest, many familiar gases such as air, nitrogen, oxygen, hydrogen, helium,
argon, neon, krypton, and even heavier gases such as carbon dioxide can be treated as ideal gases
with negligible error. Dense gases such as water vapor in steam power plants and refrigerant vapor
in refrigerators, however, should not be treated as ideal gases. Instead, the property tables should be
used for these substances.

3.15b The ideal-gas equation of state, or simply the ideal-gas relation (the relation between P −v−T )
can be written in different forms. With pressure P , temperature T , the gas constant R and the specific
volume v its form is: P v = RT .
If the volume is the total volume V = mv, with m the total mass, instead of the specific volume v
this changes to: P V = mRT .
Instead of the gas constant R, which is different for every gas (see table 2 in the book) also the
universal gas constant, Ru = 8.31 kJ/(kmol K) (the same for every gas) can be used. In this case the
ideal-gas relation changes to: P V = N Ru T , with N the number of molecules in mol.
The relation between R and Ru is: R = RMu with M the molar mass (also called the molecular weight,
see table 1 in the book).

RT
3.15c The ideal-gas relation with the specific volume is used, P v = RT which gives v = P or
P = RT
v .

1 ∂v
β = v ∂T P = v1 PR = PRv = T1 .
κ = − v1 ∂P
∂v
= − v1 (−1) RT = RT 1 1


T P2 v P2 = P .

3.16 A balloon
3.16a Given: A balloon with diameter D and pressure P . What is the relation for the mole number?
To determine the mole number the ideal gas law with the universal gas constant in it has to be used
P V = nRu T → n = TPRVu . In this case the volume is the total volume, V = 4/3π(1/2D)2 (and not the
specific volume).

3.16b The total mass depends on the mole number and the molar mass, M , of the gas inside the
balloon, m = nM .

3.16c The mole number is independent of the gas in the balloon, Ru is the universal gas constant
2 3
·4/3·π(1/2·6) 2
which is the same for every gas, Ru = 8.314 J/(molK) → n = P (4/3π(1/2D)
T Ru
)
= 200·108.314·293 =
9.285 · 103 mol = 9.285 kmol.
For helium the molar mass is Mhelium = 4.003 kg/mol → mhelium = nMhelium = 9.285 · 4.003 =
37.16 kg.

3.16d The mole number is the same for every gas, therefore also in the case of nitrogen it is 9.285 kmol.
For nitrogen the molar mass is Mnitrogen = 28.013 kg/kmol → mnitrogen = nMnitrogen = 9.285 ·
28.013 = 260.10 kg.

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Thermodynamics: Answers 3 Thermodynamic Properties of Pure Substances

3.17 An automobile tire

3.17a Given: A tire, pressure P1 , temperature T1 and volume V1 . It is assumed that the tire is rigid
and therefore the volume is constant.
Find the relation for the pressure rise ∆P when the
 temperature
 rises to T2 .
P1 P2 T2
Ideal gas law P V = mRT → T1 = T2 → P2 = P1 T1 as the volume and the mass are constant.
 
∆P = P2 − P1 = P1 TT21 − P1 = P1 ( TT21 − 1). In which R is the specific gas constant for air,
Rair = 287 J/kgK (table A-1). Also P V = nRu T can be used but the first one is preferred in this
case as in b) the amount of air has to be calculated that has to be bled off to restore the pressure.

3.17b The mass of the air that must be beld of to restore the pressure to its original pressure P1 at
temperature T2 must be determined. You should not determine the change in volume as the volume
is not defined properly, it depends on the conditions as pressure and temperature.
The original mass is m1 = PRT 1 V1
1
, the new mass after bleeding of the air is m2 = PRT
1 V1
2
. The mass that
 
P1 V1 P1 V1 P 1 V1 1 1
must be bled of is ∆m = m1 − m2 = RT1 − RT2 = R T1 − T2 .

3.17c Given: P1 = 210 kPa gauge pressure, T1 = 25◦ C = 298 K, V1 = 0.025 m3 , T2 = 50◦ C = 323 K
and Patm = 100 kPa. Calculate the pressure rise. Note P1−absolute = 210 + 100 = 310 kPa.
∆P = P2 − P1 = P1 ( TT21 − 1) = 310( 323
298 − 1) = 26 kPa.

 
P1 V1 1 1 310·103 ·0.025 1 1
3.17d The mass that must be bled off is ∆m = R T1 − T2 = 287 ( 298 − 323 ) = 7.01 ·
10−3 kg = 7 gram.

3.18 Two tanks with air

Tank 1 Tank 2 Situation 3

P1 T1 V1 P2 T2 P3 T3 V3 m3
m1 V2 m2
T3 T3

3.18a Use the ideal gas law with the total volume and the mass in it because these numbers are given
P V = mRT → V2 = m2PRT 2
2
.

3.18b Ideal gas law P V = mRT → m1 = PRT1 V1

1
.
m3 RT3
The new pressure P3 will be P3 = V3 . The mass and the volume are extensive value and can be
added therefore the new mass m3 = m1 + m2 and the new volume V3 = V1 + V2 .
P3 = (m1V+m 2 )RT3
1 +V2
.

3.18c Given is P1 = 500 kPa, T1 = 25 ◦ C = 298 K, V1 = 1 m3 , P2 = 200 kPa, T2 = 35◦ C = 308 K,

m2 = 5 kg and T3 = 20 ◦ C = 293 K. R is the specific gas constant for air which can be found in table
2 → R = 287 J/kgK.
V2 = m2PRT
2
2
= 5·287·308
200·103
= 2.21 m3 .

P 1 V1 500·103 ·1
3.18d m1 = RT1 = 287·298 = 5.846 kg.
(m1 +m2 )RT3
P3 = V1 +V2 = (5.846+5)·287·293
1+2.2 = 284128 Pa = 284.1 kPa.

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Thermodynamics: Answers 3 Thermodynamic Properties of Pure Substances

3.19 Enthalpy change of nitrogen

Asked is to calculate the change in enthalpy of nitrogen (∆h) if it is heated from 600 K to 1000 K
´ T2
using three different values for cp . The enthalpy change is given by dh = cp dT → ∆h = T 1 dh =
´ T2
T 1 cp (T )dT .

3.19a The empirical relation for cp can be found in table 2 and is cp = a + bT + cT 2 + dT 3 with
T in Kelvin and cp in kJ/kmolK. For nitrogen the constants are a = 28.9, b = −0.1571 · 10−2 , c =
0.8081 ´· 10−5 and d = −2.873
´ T2 · 10−9 .
T2
∆h = T 1 cp (T )dT = T 1 (a + bT + cT 2 + dT 3 )dT = [aT + 12 bT 2 + 13 cT 3 + 14 dT 4 ]TT 21 = a(T2 − T1 ) +
1 2 2 1 3 3 1 4 4
2 b(T2 − T1 ) + 3 c(T2 − T1 ) + 4 d(T2 − T1 ).
Filling in T1 = 600 K and T2 = 1000 K and the values for a, b, c and d gives ∆h = 12544 kJ/kmol.
12544
The molar weight of nitrogen is Mnitrogen = 28.013 kg/kmol → ∆h = 28.013 = 447.79 kJ/kg.

3.19b The average value for cp is cp−avr = 12 (cp (T = 600) + cp (T = 1000)) = 21 (1.075 + 1.167) =
1.21 kJ/kgK (the values of Cp follow from tabel 2.
´ T2 ´ T2
∆h = T 1 cp (T )dT = T 1 cp−avr dT = [cp−avr T ]TT 21 = cp−avr (T2 −T1 ). Fill in the numbers and it follows
that ∆h = 448.46 kl/kg.

3.19c The value of Cp at room temperature is cp−room = 1.0403 klJ/kgK (Table 2, 25 degree Celsius).
´ T2 ´ T2
∆h = T 1 cp (T )dT = T 1 cp−room dT = [cp−room T ]TT 21 = cp−avr (T2 − T1 ). Fill in the numbers and it
follows that ∆h = 416.12 kl/kg.

3.19d The answers from c is much different form the answer from a and b. A is probably the most
exact answer as here the temperature dependence of Cp is taken into account. It seems that taking
the average Cp value is not bad at all. The answer of b is close to the answer of a. Taking the Cp at
room temperature gives a large error in the answer, this cp is far away from the right one.

3.20 Heat transfer and work at constant enthalpy

3.20a For an ideal gas the enthalpy is only a function of the temperature h = h(T ) 6= h(P ) → dh =
cp dT . If the enthalpy is constant dh = 0.
dh = cp dT = 0 → dT = 0 → T1 = T2 .

P1 v1 P2 v2
3.20b Ideal gas law P v = RT → T1 = T2 → P1 v1 = P2 v2 .

3.20c Also the internal energy of an ideal gas is only a function of temperature u = u(T ) 6= u(P ) →
du = cv dT . From a it follows that dT is zero and therefore du = cv dT = 0.
du = δq + δw = 0 → δq = −δw → q = −w → Q = −W .

´V2 ´V2 V2

V2

3.20d The specific work is, δw = P dv → w = V 1 P dv = V 1 RT v dv = RT [ln v]V1 = RT ln V1 =
     
P1 v1 ln VV21 . The total work is W = mw = mP1 v1 ln VV12 = P1 V1 ln VV12 .

 
3.20e W = P1 V1 ln VV21 = 1 · 105 · 1 · ln 2 = 69315 J = 69.3 kJ. The work is positive because it is an
expansion process. Work is done by the system on the surroundings.
Q = −W → Q = −69.315 J = -69.3 kJ.

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Thermodynamics: Answers 3 Thermodynamic Properties of Pure Substances

3.21 Air in a turbine

The change in specific enthalpy (kJ/kg) of air through a turbine is computed in five different ways.
´ T2
To calculate the specific heat use dh = cp dT → ∆h = T 1 cp dT . For a constant cp (method 1, 2 and
3) this results in ∆h = cp (T2 − T1 ).
1. Assumed is a constant specific heat at the inlet temperature (table 4s).
The inlet temperature is 1500◦ C = 1773 K. The specific heat at this temperature is 1.1466 kJ/kgK.
For constant cp at the outlet temperature → ∆h = cp (T2 − T1 ) = 1.1337(773 − 1773) =
−1133.7 kJ/kg.

2. Assumed is a constant specific heat at the outlet temperature (table 4s).

The outlet temperature is 500◦ C = 773 K. The specific heat at this temperature is 1.0411 kJ/kgK.
For constant cp at the outlet temperature → ∆h = cp (T2 − T1 ) = 1.0411(773 − 1773) =
−1041.1 kJ/kg.

3. Assumed is a constant specific heat at the mean temperature (table 4s).

The mean temperature is 1000◦ C = 1273 K. The specific heat at this temperature is 1.0935 kJ/kgK.
For constant cp at the mean temperature → ∆h = cp (T2 − T1 ) = 1.0935(773 − 1773) =
−1093.5 kJ/kg.

4. A variable specific heat dependent on temperature is used by integrating the polynomial function
in table 3s. Table 2 gives cp = a + bT + cT 2 + dT 3 with T in Kelvin and Cp in kJ/kmolK. For
air the´constants are a´= 28.11, b = 0.1967 · 10−2 , c = 0.4802 · 10−5 and d = −1.966 · 10−9 .
T2 T2
∆h = T 1 cp (T )dT = T 1 (a + bT + cT 2 + dT 3 )dT = [aT + 12 bT 2 + 13 cT 3 + 14 dT 4 ]TT 21 = a(T2 −
T1 ) + 12 b(T22 − T12 ) + 13 c(T23 − T13 ) + 14 d(T24 − T14 ).
Filling in T1 = 1500◦ C = 1773 K and T2 = 500◦ C = 773 K and the values for a, b, c and d gives
∆h = −34114.6 kJ/kmol. The molar weight of air is Mair = 28.97 kg/kmol → ∆h = −34114.6 28.97 =
−1177.58 kJ/kg.

5. The h values tabulated in table 17 are used.

1500◦ C → h1500 = 1971.3 kJ/kg.
500◦ C → h500 = 793.56 kJ/kg.
∆h = h500 − h1500 = −1177.74 kJ/kg.
By comparing the results for methods 1, 2, 3 and 4 with those of method 5 it can be concluded that
results of method 4 and 5 are equal. Method 4 takes into account the variable specific heat. Therefore
it can be concluded that also the table takes the variable specific heat into account. The first three
methods use a constant specific heat and it can be seen that the result is less accurate.

3.22 Oxygen in a rigid tank

3.22a From the ideal gas law it follows that the pressure rises as the temperature rises while the
volume is constant (which is the case as the tank is rigid). The tank is insulated therefore no heat
transfer can take place through the walls of the tank. The heat has to come from the fan. The power
to drive the fan is converted into heat and heats the oxygen.

3.22b Oxygen can be assumed to be an ideal gas under these circumstances. In the case of an ideal
gas the´ internal energy change can be calculated using the specific heat of oxygen → du = cv dT →
T2
∆u = T 1 cv dT = cv (T2 − T1 ). The specific heat of oxygen at the mean temperature can be found in
table 7.
The temperature T2 follows from the ideal gas law → T2 = PP2 T1 1 .
The mass of the oxygen also follows from the ideal gas law P V = mRT → m = PRT 1V
1
.
Finally the change in internal energy in kJ is → ∆U = m∆u = RT1 cv (T2 − T1 ) = RT1 cv ( PP2 T1 1 − T1 ) =
P1 V P1 V
P1 V cv P2
R ( P1 − 1).

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Thermodynamics: Answers 3 Thermodynamic Properties of Pure Substances

3.22c Given V = 0.3 m3 , P1 = 100 kPa, P2 = 150 kPa and T1 = 27◦ C = 300 K.
T2 = PP2 T1 1 = 450 K = 177◦ C. The mean temperature is 375 K = 102◦ C and in table 7 it is found
that cv = 0.6742 kJ/kgK at 100 degree Celsius. The specific gas constant for oxygen is 0.260 kJ/kgK
(table 2) → ∆U = P1R V cv P2
( P1 − 1) = 38.9 kJ.

3.23 Two closed rigid system in thermal equilibrium

3.23a In thermal equilibrium the temperature at both sides should be equal Ta 2 = Tb 2 = T2 .
The total internal energy of the whole system does not change as no heat or power is added to the
system. Only the internal energy is distrubuted different over both parts of the system (this is because
the system goes from an non-equilibrium to an equilibrium state)
→ U1 = Ua1 + Ub1 = Ua2 + Ub2 = U2

3.23b Na and Nb do not change during the process in which the system goes to thermal equilibrium
from state 1 to state 2 as the mass cannot pass the wall. But the temperature and the internal energy
(which is a function of temperature) will change.
3 5 3 5
Ua2 = Ru Na T2 and Ub2 = Ru Nb T2 → U2 = Ua2 + Ub2 = Ru T2 ( Na + Nb ). (3.23.1)
2 2 2 2

3.23c Ru = 8.314 J/molK

Ua1 = 23 Ru Na Ta1 = 23 · 8.314 · 2 · 250 = 6235.5 J.
Ub1 = 25 Ru Nb Tb1 = 52 · 8.314 · 3 · 350 = 21824.3 J.
U1 = Ua 1 + Ub 1 = 28059.8 J.
U2 = Ru T2 ( 32 Na + 25 Nb ) = U1 → T2 = R ( 3 NU1+ 5 N = 321.4 K.
u 2 a 2 b)

3.23d Ua2 = 32 Ru Na T2 = 32 · 8.314 · 2 · 321.4 = 8017 J.

Ub2 = 52 Ru Nb T2 = 52 · 8.314 · 3 · 321.4 = 20041 J.

3.24 Two closed movable systems in equilibrium

3.24a In this case in equilibrium an additional condition has to be fulfilled. Besides the temperatures
also the pressures at both sides of the wall should be equal therfore → P2a = P2b = P2 and Ta2 =
Tb2 = T2 .

3.24b For the equilibrium temperature is does not matter if the wall can move or not, the heat transfer
is not influenced by the movement of the wall. As in problem 3.23 the equilibrium temperature is
321.4 K. The internal energies of the subsystems are also the same as in problem 3.23 as the internal
energy of an ideal gas is a function of the temperature only. As the equilibrium temperature is still
T2 = 321.4 K the internal energies are still Ua2 = 8017 J and Ub2 = 20041 J.

3.24c In the case of state 2 the state equations become:

P2 Na Ru Na T2 P2 Nb Ru Nb T2
= Ru → Va2 = and = Ru → Vb2 = . (3.24.1)
T2 Va2 P2 T2 Vb2 P2

3.24d It follows that VNa2a = VNb2b → VVab22 = N

Nb
a
= 32 .
Vt = Va2 + Vb2 = 80 liter.
Together this gives: Va2 + 32 Va2 = 80 → Va2 = 1+3/2 80
= 32 liter. Vb2 = 80 − 32 = 48 liter.

Ru T2 Na 8.314·321.4·2
3.24e The equilibrium pressure is P2 = Va2 = 32·10−3
= 167006 Pa = 167 kPa.

33