Thermodynamic

2021-1

NEDHER SÁNCHEZ RAMÍREZ

Ideal and Real Gases

1
Y.A. Çengel, and M.A. Boles, Thermodynamics, An Engineering Approach, 8th ed. New York, USA: McGraw-Hill Education, 2015.
Session 5: Apply the ideal gas model for thermodynamic
analysis using the equation of state and estimating
properties such as internal energy and enthalpy.
 ¿What is a phase?

The term phase refers to a quantity of matter that is homogeneous throughout in

both chemical composition and physical structure.

Homogeneity in physical structure means A system can contain one or more

that the matter is all solid, or all liquid, or phases.
all vapor (or equivalently all gas).

¿What is a pure substance?

 ¿What is a pure substance?

A pure substance is one that is uniform and invariable in chemical composition. A

pure substance can exist in more than one phase, but its chemical composition must
be the same in each phase.

Single chemical element or compound Homogenous mixture of chemical

elements or compounds
¿ What is a pure substance?

?
?
 Pure substance in this course

Water, refrigerants… Ideal and real gases

This week. Next week.
As long as there is no condensation, air and natural gas are
considered pure substances.
 Opening thoughts…
Have you ever…

These are examples of gases !

Gases

https://www.youtube.com/watch?v=xDF8VSRgapI
 Gases

http://www.100ciaquimica.net/temas/tema5/punto6.htm M.J. Moran, H.N. Shapiro, D.D. Boettner, M.B. Bailey, Fundamentals of Engineering Thermodynamics, 10th ed. New Jersey, USA: John Wiley & Sons, 2014.
What this imply?
Ideal Gases

In this region the so-called ideal gases

have some characteristics, allowing
them to be described by a simple model
based on macroscopic properties.

https://proyectodescartes.org/iCartesiLibri/materiales_didacticos/Fisica_III/indexb.html
STATE POSTULATE FOR A PURE SUBSTANCE:

• Given Prop. 1 and Prop. 2 which are intensive and

independent:

Prop.3 = f (Prop.1 + Prop.2)

What is the implication of this in the use of the properties table?

 What tools do we need to understand these cycles?

Pure substance: Water, refrigerants… Pure substance: Ideal gas

Tables: Like those that are tabulated for some pure substances in the book appendices.
Week 2

1. Calculation of properties Models: As the ideal gas equation, or other relationships or approximations that allow
calculating properties of liquids, solids or gases that are not tabulated. Weeks 3-4

First Law of Thermodynamics: Energy Balance

2. Law of Thermodynamics
Second Law of Thermodynamics: Entropy Balance
 Properties of Ideal Gases
You can predict the behavior of gases based on the
following properties:

Pressure
Volume
Amount (moles)
Temperature
Lets review each of these briefly…
 Volume
Volume is the three-dimensional space inside the
container holding the gas. The SI unit for volume is
the cubic meter, m3. A more common and convenient
unit is the liter, L.
 Amount (kg-moles)
We can convert measured mass (in kg) to the number
of moles, n, using……

Molar mass!
 Temperature
Temperature is the measurement of how fast the particles are moving.
 Temperature
• Always use absolute temperature (Kelvin) when
working with gases.

K
0 273 373

ºC
-273 0 100
 How do they all relate?

Now that we understand the factors that affect the

behavior of gases, we will study how those factors interact.
 Boyle’s Law _ P vs V

https://smithsonianlibraries.tumblr.com/post/148462022830/boyles-lesser-known-law-the-pressure-of-the-wig

P1V1 =P2V2 = C

Volume vs. 1/Pressure

V
https://cdn.pixabay.com/photo/2018/08/03/07/00/thermometer-3581190_960_720.jpg
Boyle’s Law _ P vs V

https://smithsonianlibraries.tumblr.com/post/148462022830/boyles-lesser-known-law-the-pressure-of-the-wig

https://imgur.com/oapLBD7
 Charles’ Law
This lesson introduces Charles’ Law, which describes the
relationship between volume and temperature of gases. https://xn--cumpleaosdefamosos-t0b.com/persona/jacques-charles/fotos/jacques-charles-fotos-ampliamente-sublimes-de

V V1 V2
= =C
T
T1 T2
https://en.wikipedia.org/wiki/Charles%27s_law
 Avogadro’s Law
• Equal volumes of gases contain equal numbers of moles at
constant temp & pressure true for any ideal gas.
ahombrosdegigantescienciaytecnologia.wordpress.com/2015/08/09/leyes-constantes-y-numeros-el-gigante-avogadro/

https://b2b.partcommunity.com/community/knowledge/es/detail/4049/Ley+de+Avogadro

=C

n
 Gay-Lussac’s_ Amontons Law

The P and absolute T (K)

of a gas are directly
related at constant mass &
volume.

P P1 P2 = C
=
T1 T2
T
 Recall
Boyle’s Law Charles’ Law Avogadro’s Law

V  1/P V  T (Kelvin) Vn

Constant T, n Constant P, n Constant T, P

So V  1/P X n X T
 Ideal Gas Law
• To turn a proportionality into an equation, insert a constant:

PV = n𝑅ഥ T ഥ ” is the universal gas constant. V volume i.e. m3.

Where “𝑹

-How many variables do we have here?

-How many are intensive?
-How many are extensive?
n or N = m/M (mass/molar mass)

Pv = (𝑅ഥ /M)T, v specific volume i.e. m /kg;

3 ഥ /M ”= Rg =R=gas constant
“𝑹

STATE EQUATION!
 Ideal Gas Law
• Alternatively :

PV = n𝑅ഥ T, V... volume i.e. m3

Pῡ = 𝑅ഥ T, ῡ... molar volume i.e. m /mol = V/n

3

“STATE EQUATION”
http://gaslawsperiod6.yolasite.com/
 Ideal Gas Law
• The units of R depend on the units used for P, T, and V

𝑅𝑈
Example:
1.3´. A perfect gas undergoes isothermal compression, which reduces its volume
by 3.00 dm3. The final pressure and volume of the gas are 4.0 bar and 1.0 dm3,
respectively. Calculate the original pressure of the gas in (a) bar, (b) Torr.
Boyle
a) Boyle’s law:
Remember that
1 atm is equal to: 𝑃1 𝑉1 = 𝑃2 𝑉2
101.325 kPa (kilopascal)
𝑃1 × 3.0 + 1.0 = 4.0 × 1.0 PV= cte

1.01325 bar
𝑃1 = 1.0 𝑏𝑎𝑟
760 mm Hg
760 torr b) Converting bar to torr:
14.7 psi
760 𝑡𝑜𝑟𝑟
𝑃1 = 1.0 𝑏𝑎𝑟 × = 750.06 𝑡𝑜𝑟𝑟
1.01325 𝑏𝑎𝑟
Example:
2.3´. Carbon dioxide (CO2) is compressed in a piston-cylinder assembly from 𝑝1 =
0.7bar, 𝑇1 = 280K to 𝑝2 = 10bar. The initial volume is 0.400 m3. The process is
described by 𝑝V1.3 = constant. Assuming ideal gas determine V2 (m3).

Process: 𝑝1 𝑉11.3 = 𝑝2 𝑉21.3

0.7 × 0.4001.3 = 10 × 𝑉21.3

0.7 × 0.4001.3
𝑉21.3
10 bar
= = 0.0213
𝑝V1.3 = constant 10
𝑉2 = 0.0517 m3
 p (kPa) k= Cp/Cv k =∞
k=1
p=cte
v=cte
k=0
T=cte
pVk=cte

v 3
(m /mol)
EXAMPLE 3.3´´
A piston/cylinder arrangement, shown below, contains air at 250 kPa and 300°C. The 50-kg
piston has a diameter of 0.1 m and initially pushes against the stops. The atmosphere is at 100
kPa and 20°C. The cylinder now slowly cools as heat is transferred to the ambient surroundings.
a. At what temperature does the piston begin to move down? [K]
b. How far has the piston dropped when the temperature reaches ambient? [m]
c. Show the process in a P [kPa]–V [L] and a T [K]–V [L] diagram.

𝑔 𝑘𝑔
𝑀 𝑎𝑖𝑟 = 28.97 = 28.97
𝑚𝑜𝑙 𝑘𝑚𝑜𝑙
With the initial conditions (STATE 1) we can calculate
mass of air inside the cylinder:

𝑃𝑉 250 × 𝜋 × 0.052 × 0.25

𝑚𝑎𝑖𝑟 = = = 𝟐. 𝟗𝟖𝟓 × 𝟏𝟎−𝟑 𝐤𝐠
𝑅𝑇 8.314
28.97 × 300 + 273
 The body free diagram for the piston is:
A force balance on the piston shows that (FN is the force on the stops):
Patm A mg FN

𝑃𝐺 𝐴 = 𝑃0 𝐴 + 𝑚𝑔 + FN PGA

𝑃0 𝐴+𝑚𝑔
The piston just moves down (STATE 2) when FN is zero and the gas pressure is equal to
𝐴
𝑚𝑔
𝑃𝐺 = 𝑃0 +
𝐴
50×9.81
𝑃𝐺 = 𝑷𝟐 = 100000 + = 𝟏𝟔𝟐𝟒𝟓𝟐. 𝟐𝟓 𝐏𝐚 = 𝟏𝟔𝟐. 𝟒𝟓 𝐤𝐏𝐚
𝜋×0.052

a) The temperature at that moment is:

𝑃2 𝑉 162.45 × 𝜋 × 0.052 × 0.25

𝑻𝟐 = = = 𝟑𝟕𝟐. 𝟑𝟒 𝐊 = 𝟗𝟗. 𝟑𝟒 °𝐂
𝑚𝑅 8.314
2.985 × 10−3 × 28.97
b) When the temperature is equal to ambient (20°C) (STATE 3), the volume is: [Remember P
remain constant…P2 = P3]
2.985 × 10 −3 × 8.314 × 20 + 273
𝑚𝑅𝑇3 28.97
𝑉3 = = = 𝟏. 𝟓𝟒𝟓 × 𝟏𝟎−𝟑 𝐦𝟑
𝑃3 162.45

The height of the piston is:

𝑉 1.545 × 10−3
ℎ= = = 𝟎. 𝟏𝟗𝟕 𝐦 = 𝟏𝟗. 𝟕 𝐜𝐦
𝐴 𝜋 × 0.052

c) P-V and T-V diagrams:

P (kPa) T (K)

250 1 573 1

372.34 2
3 3
162.45 2
293

1.545 1.963 V (L) 1.545 1.963 V (L)

EXAMPLE 3.3
A cylinder has a thick piston initially held by a pin, as shown below. The cylinder contains carbon
dioxide at 200 kPa and ambient temperature of 290 K. The metal piston has a density of 8000 kg/m3
and the atmospheric pressure is 101 kPa. The pin is now removed, allowing the piston to move, and
after a while the gas returns to ambient temperature. Is the piston against the stops?

The first thing is to see if there is expansion once the pin is

𝑃0
removed. We need to calculate the external pressure:

𝑚𝑔 𝜌𝑉𝑝𝑖𝑠𝑡𝑜𝑛 𝑔
𝑃𝑒𝑥𝑡 = 𝑃0 + = 𝑃0 +
𝐴 𝐴
 𝑚𝑔 𝜌𝑉𝑝𝑖𝑠𝑡𝑜𝑛 𝑔
𝑃𝑒𝑥𝑡 = 𝑃0 + = 𝑃0 +
𝐴 𝐴

8000 × 𝜋 ∗ 0.052 ∗ 0.1 × 9.81

𝑃𝑒𝑥𝑡 = 101000 + = 108848 Pa = 108.848 kPa
𝜋 ∗ 0.052

In the state 1 we can calculate de CO2 mass:

𝑃𝑉 200 × 𝜋 ∗ 0.052 ∗ 0.1

𝑚𝐶𝑂2 = = = 2.867 × 10−3 kg
𝑅𝑇 8.314
44.01 × 290
 To check if the final state is at the stops or not, we have to estimate the pressure when the
CO2 occupies all the available volume and verify that the pressure at that point is larger
than 𝑃𝑒𝑥𝑡= 108.848 kPa:

Assuming the piston is at the stops (“state 2”), the pressure is:

8.314
𝑚𝑅𝑇2 2.867×10−3 ×44.01×290 𝑇2= 𝑇1
𝑃2 = = =133.32 kPa
𝑉2 𝜋∗0.052∗×0.15 𝑉2

As the pressure is larger than 108.848 kPa, the piston must be at the stops
EXAMPLE 4.3
A 1-m3 rigid tank with air at 1 MPa and 400 K is connected to an air line as shown below. The
valve is opened and air flows into the tank until the pressure reaches 5 MPa, at which point the
valve is closed and the temperature inside is 450 K. a. What is the mass [kg] of air in the tank
before and after the process? b. The tank eventually cools to room temperature, 300 K. What is
the pressure inside the tank then [kPa]?
The air before opening the valve is (state 1):

𝑃𝑉 1000 × 1
𝑚= = = 8.711 kg
𝑅𝑇 8.314 × 400
28.97
The air after opening the valve and letting the air from the line enters(state 2):

𝑃𝑉 𝟓𝟎𝟎𝟎 × 1
𝑚= = = 38.72 kg
𝑅𝑇 8.314 × 𝟒𝟓𝟎
28.97

After cooling to 300 k(state 3):

8.314
𝑚𝑅𝑇 38.72 × 28.97 × 𝟑𝟎𝟎
𝑃= = = 3333.64 kPa
𝑉 1
EXAMPLE 5.3
A 1-m3 rigid tank has nitrogen at 100 kPa, 300 K and connected by a valve to another tank of 0.5
m3 with nitrogen at 250 kPa, 400 K. The valve is opened, and the two tanks come to a uniform
state at 325 K. What is the final pressure?
Nitrogen mass in tank A:

𝑃𝑉 100 × 1
𝑚= = = 1.123 kg
𝑅𝑇 8.314 × 300
28.01
Nitrogen mass in tank B:

𝑃𝑉 250 × 0.5
𝑚= = = 1.053 kg
𝑅𝑇 8.314
28.01 × 400

When the valve is opened, the final pressure is:

8.314
𝑚 𝑇 𝑅𝑇 1.123 + 1.053 × × 325
𝑃= = 28.01 = 139.94 kPa
𝑉 1 + 0.5
Session 5: Apply the ideal gas model for thermodynamic
analysis using the equation of state and estimating
properties such as internal energy and enthalpy.
u,h for Ideal Gas?

Is there another way?

M.J. Moran, H.N. Shapiro, D.D. Boettner, M.B. Bailey, Fundamentals of Engineering Thermodynamics, 10th ed. New Jersey, USA: John Wiley & Sons, 2014.
INTERNAL ENERGY, ENTHALPY, AND SPECIFIC HEATS OF IDEAL GASES

demonstrated that for I.G.

:

Y.A. Çengel, and M.A. Boles, Thermodynamics, An Engineering Approach, 8th ed. New York, USA: McGraw-Hill Education, 2015.
INTERNAL ENERGY, ENTHALPY, AND SPECIFIC HEATS OF IDEAL GASES

demonstrated that for I.G.

:

Y.A. Çengel, and M.A. Boles, Thermodynamics, An Engineering Approach, 8th ed. New York, USA: McGraw-Hill Education, 2015.
INTERNAL ENERGY, ENTHALPY, AND SPECIFIC HEATS OF
IDEAL GASES

Note that the du and dh relations given previously

are not restricted to any kind of process. They are
valid for all processes.
HOW TO EVALUATE INTERNAL ENERGY AND ENTHALPYOF IDEAL GASES?

• Using expression for Cp(T) and integrating

• Tabulated data and calculating ∆h.

∆h= h2(T2)-h1(T1)

• Cp(T) average and and integrating

∆h=
∆h= Cpavg ∆T

• C(T) constant and and integrating:

∆h = cp ∆T →h = cpT
 In the same way…..

Y.A. Çengel, and M.A. Boles, Thermodynamics, An Engineering Approach, 8th ed. New York, USA: McGraw-Hill Education, 2015.
Example:
8.1. Determine the enthalpy change h of nitrogen, in kJ/kg, as it is heated from 400 to 800 K, using
(a) the empirical specific heat equation as a function of temperature (Table A–21), (b) the cp value at
the average temperature (Table A–20), and (c) the cp value at room temperature (Table A–20). d)
Using the table A-23.

a) Cp as function of temperature – Table A-21

∆ℎҧ = න 𝑐𝑝 𝑑𝑇

800

∆ℎҧ = න 𝑅ҧ 𝛼 + 𝛽𝑇 + 𝛾𝑇 2 + 𝛿𝑇 3 + 𝜀𝑇 4 𝑑𝑇
400

800
𝑇2 𝑇3 𝑇4 𝑇5
∆ℎҧ = 𝑅ҧ 𝛼𝑇 + 𝛽 +𝛾 +𝛿 +𝜀
2 3 4 5 400

M.J. Moran, H.N. Shapiro, D.D. Boettner, M.B. Bailey, Fundamentals of Engineering Thermodynamics, 10th ed. New Jersey, USA: John Wiley & Sons, 2014.
 −3
8002 − 4002 −6
8003 − 4003 −9
8004 − 4004
3.675 800 − 400 − 1.208 × 10 + 2.324 × 10 − 0.632 × 10
2 3 4
∆ℎ ҧ = 𝑅 ҧ
8005 − 4005
−0.226 × 10−12
5

kJ 8.314 𝐤𝐉 kJ
∆𝒉ത = 𝑅ҧ 1452.11 … … . ∆𝒉 = × 1452.11 = 𝟒𝟑𝟏. 𝟏𝟕
k𝑚𝑜𝑙 28 kg 𝐤𝐠

b) Cp at an average temperature = 600K

∆ℎ = න 𝑐𝑝 𝑑𝑇 = 𝑐𝑝,𝑎𝑣𝑔 ∆𝑇

𝐤𝐉
∆ℎ = 1.075 × 400 = 𝟒𝟑𝟎
𝐤𝐠
c) Cp at room temperature = 300K

∆ℎ = න 𝑐𝑝 𝑑𝑇 = 𝑐𝑝 ∆𝑇

𝐤𝐉
∆ℎ = 1.039 × 400 = 𝟒𝟏𝟓. 𝟔
𝐤𝐠

d) Ideal gas enthalpy

∆𝒉ത = 𝒉ത 2 − 𝒉ഥ𝟏
kJ
∆𝒉ത = 23714 − 11640 = 12074
kmol
kJ 1 kmol
∆ℎ = 12074 ×
kmol 28 kg
𝐤𝐉
∆ℎ = 𝟒𝟑𝟏. 𝟐𝟏
M.J. Moran, H.N. Shapiro, D.D. Boettner, M.B. Bailey, Fundamentals of Engineering Thermodynamics, 10th ed. New Jersey, USA: John Wiley & Sons, 2014. 𝐤𝐠