Engineering Thermodynamics:

Properties of Pure Substances

Lecture notes by Dr. Abdalla Al-Amiri

Department of Mechanical Engineering
Modified by Dr. Eyas Mahmoud
Department of Chemical and Petroleum Engineering
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display
 Outline
• 2−1 Pure Substances
• 2−2 Phases of a Pure Substance
• 2−3 Phase Change processes of a Pure Substance
• 2−4 Property Diagrams for Phase Change Processes
• 2−5 Property Tables
• 2-6 The Ideal gas Equation of State
• 2−7 Compressibility Factor
• 2-9 Specific Heats
• 2-10&11 Internal Energy and Enthalpy Formulation For
Ideal Gases and Condensed Phases (Solid and Liquids)
2
 Pure Substances

A pure substance does not change chemical composition but can change phase.

Is the working fluid a two-phase substance?

H2O
R-134a

An “ideal” gas?
Air

3
 Phases of a Pure Substance

Water Air

vapor vapor

liquid liquid
Not pure: different condensation
Pure H2O temperatures for different
components

4
 Phase Change Processes of Pure
Substances

Terminology

• Compressed liquid -- not about to evaporate

• Saturated liquid -- about to evaporate
• Saturated liquid-vapor mixture --two phase
• Saturated Vapor -- about to condense
• Superheated Vapor -- not about to condense

5
 Heating Water- Phases
Compressed Saturated Saturated Liquid-Vapor
Liquid Liquid Mixture

Liquid Liquid Liquid/Vapor 6

 Heating Water- Phases

Saturated Vapor Superheated Vapor

Vapor Vapor
7
T-v Diagram for Heating Water

Isobaric process

8
 Saturation

• At a given pressure, a substance changes phase at a fixed

temperature, called the saturation temperature.

• At a given temperature, the pressure at which a substance

changes phase is called the saturation pressure.

• T and P are dependant during the phase change, i.e., Tsat

= f(Psat)
9
 Latent Heat

• Latent heat is the amount of energy absorbed or released during

phase change

• Latent heat of fusion: melting/freezing. Equals 333.7 kJ/kg for 1 atm

H2O

• Latent heat of vaporization: boiling/condensation. Equals 2257.1 kJ/kg

for 1 atm H2O

10
 Property Diagrams for Phase Change
Processes
A point beyond which T  Tcr, a
T-v diagram liquid-vapor transition is no
longer possible at constant
pressure. If T  Tcr , the
substance cannot be liquefied, no
matter how great the pressure.

11
 Scenarios for Phase Change
Processes
• Compressed liquid or subcooled liquid:
- If heat is added, the temperature will rise but there will be no phase change.
- “Not about to vaporize”
- Example: liquid water at 20oC/1 atm.

• Saturated liquid:
- If heat is added, the temperature does not change but some of the liquid
vaporizes.
- Example: liquid water at 100oC/1 atm.
• Saturated liquid/vapor mixture:
- As heat is added, liquid turns to vapor. QH
- Example: vapor water at 100oC/l atm.

• Saturated vapor:
- If heat is removed, the temperature does not change, but some of
the vapor condenses.
- Example: vapor water at 100oC/1 atm.
• Superheated vapor:
- If heat is added, the temperature will rise but there will be no phase change.
- Example: vapor vapor at 120oC/1 atm. 12
Phase-Change: P-T Diagram

13
 P-T Diagram: Isothermal Process

Superheated G AS @ g
Vapor
g

T
14
 P-T Diagram: Isothermal Process

W eight
d

Superheated
Vapor G AS
g
State d

T LIQ U ID
15
 P-T Diagram: Isothermal Process

P
Compressed
Liquid
a
d

Superheated
Vapor
W eight
g

LIQ UID
GAS @ a
T 16
 P-T Diagram: Isobaric Process

G as @ b
Superheated
Vapor

T Q 17
 P-T Diagram: Isobaric Process

f b

Superheated
GAS
Vapor
STATE f

LIQ U ID

T Q 18
 P-T Diagram: Isobaric Process

P
Subcooled
Liquid
f b
a

Superheated
Vapor

GAS
LIQ U ID

T Q 19
 P-V Diagram: Substance that
Contracts on Freezing

For water, the triple point is at 273.16 K (32.018 F) and 0.6113 kPa (0.0887 psia) 20
P-V Diagram: Substance that
Expands on Freezing

21
 Using T-v Diagrams

T
1. Draw saturation lines
Sat.
Liquid 2. Note given information on state properties
line Sat. Vapor
line T
P
v
U
H

22
 Using T-v Diagrams

T P

P
const.

T const.

v v

3. Draw constant pressure or constant temperature lines

23
 Using T-v Diagrams

T P

critical point
critical point

P
const.

T sat.
P sat.

T const.

v v

vf; uf; hf vg; ug; hg vf; uf; hf vg; ug; hg

4. Note saturation temperature or saturation pressure, sat. liquid and sat. vap. states
24
 Using T-v Diagrams

T P
P>

P
const.

T sat. P sat. T>

T const.

v v

vf; uf; hf vg; ug; hg vf; uf; hf vg; ug; hg

5. Add lines showing higher or lower temperature or pressure

Property Tables

Enthalpy – A Combination Property

H = U + PV
or
h = u + Pv

26
 Using Property Tables
Saturated Liquid and saturated vapor water Tables A-4 and A-5

Example:
A rigid tank contains 50 kg of
saturated liquid water at 90oC.
Determine the pressure in the tank
and the volume of the tank.

(Answers: 70.14 kPa, 0.0518 m)

27
 Dependence of Tsat and Psat

.Boiling Temp Atmospheric Elevation

)o C ( Pressure (kPa) )m(
100.0 101.33 0
96.3 89.50 1000
83.0 54.05 5000
66.2 26.50 10,000

Tsat (oC) Substance

100 H 20
@ Patm 26- R-134a
196- N2
28
 Quality- practical application to
finding properties

v – vf u – uf
h – hf
x = = =
hg – hf
vg – vf ug – uf

v = vf + x vfg , (vfg = vg – vf)

Same procedure applies in finding specific internal energy or enthalpy values.

29
 Quality- An Alternative Approach
Since Quality is a mass fraction of the vapor content in mixture, we define
P or T
x = mg / m
Sat. vapor
vg
Since mtotal = mliquid + mvapor ,
Sat. liquid
or m = m f + mg vf

Also, V = Vf + Vg

& V = mv •

or mv = mf vf + mg vg, vf vf<v<vg vg v
mv = (m-mg) vf + mgvg

v = (1-x) vf + xvg = vf + x vfg 30

 Quality: Example Problem

Example:
Determine the specific volume of 2 kg of water at 100oC with a quality of 70%,
i.e., moisture content of 30%? Also, obtain mass fraction of the vapor?

Ans.

From Table (A-4): vf=0.0010435 m3/kg & vg=1.673 m3/kg

v = vf + x.vfg = 0.0010435 + 0.7(1.673 -0.0010435)

v = 1.7141 m3/kg

Since, x = mg/m then mg = 0.7x2 = 1.4 kg

31
 Fixing the State

Is P > Psat. or T < Tsat. ?

Yes: Sub-cooled liquid (vf @T; uf @T; hf @T)

No: Liquid-vapor mix. or Super-heated vapor

P = Psat. T = Tsat.
Liquid-vapor mixture
Quality calculation required

Is P < Psat. or T > Tsat. ?

Super-heated vapor
(super-heated vapor tables)

32
 Using Superheated Vapor Table
Table (A-6)
In the region to the right of the saturated
vapor line, a substance exists as
superheated vapor.

Example:
Determine the temperature of water at a
state of P = 0.5 MPa and h = 2890
kJ/kg.

(Answers: 216.4 oC)

33
 Compressed Liquid

- In the absence of compressed liquid tables, a general rule of thumb for properties v &
u is to treat compressed liquid as saturated liquid at the given temperature:

y = yf @T

i.e., v = vf @T & u = uf @T

- For ‘h’ values in the compressed region:

h = hf @T + vf (P - Psat)

34
 Compressed Liquid: Example Problem

Determine the specific enthalpy of liquid water at 25oC and 300 kPa?

Ans. The state is compressed liquid as Psat@25C = 3.169 kPa

However, the pressure of 300 kPa is below the minimum pressure (0.5 MPa) listed in Table (A-7):

So we will use the approximation!

v = vf @T = 0.001003 m3/kg

h = hf @T + vf (P - Psat)
= 104.89 + 0.001003(300 – 3.169) = 105.19 kJ/kg
35
 Reference State and Reference Values

• Values of u and h are arbitrary since we are only interested in changes of these properties.

• For water, the reference state is u = 0 for saturated liquid @ 0.01°C.

• For R-134a and many other substances, the reference state is h = 0 for the saturated
liquid at -40 °C.

36
 Basics of Interpolation

Assuming a linear variation in the examined property over a relatively short range.

(Table A-13E) Superheated R-134a

Temp. Sp. Volume Enthalpy
T (oF) v (ft3/lbm) h (Btu/lbm)
80 0.5408 113.47
93 v=? h=?
100 0.5751 118.39

37
 Steam Table: Example Problem

Complete the following steam table. Locate each point on a PV diagram.

Phase x h, kJ/kg u, kJ/kg v, m3/kg P, kPa T,oC #

1300 160 1
1.0 150 2
1000 200 3

4000 200 4

38
 The Ideal Gas Equation of State
• Equation of State: Property relation that involves other properties of a substance at equilibrium
states. Ideal (imaginary) Gas Equation is the simplest among other equation of states

• History Background:
- Boyle (1662): P α 1/v = for constant temperature (P1v1=P2v2)
- Charles (1802): for const pressure = v/T=const.
or combined: Pv = RT at low pressures
- Ideal gas is an imaginary substance that could be resembled by gases at low densities (low P
& high T)

Ru Universal gas constant (kJ/kg.K)

• Gas Constant R = =
M Molar mass (molecular weight)
Ru = 8.314 kJ/(kmol.K) = 1.986 Btu/(lbmol.R)
M = mass of one mol of the gas (Table A-1) = m / N
39
 Property Diagrams for Ideal Gases

P>

T P

P const.

T>

T const.

v v
Charles Boyle
for const pressure = v/T=const. P α 1/v = for constant temperature
40
 Drawing Process Paths
Special processes:

- Constant Pressure (Isobaric) moves along lines of constant

pressure
Moves along lines of constant
- Constant Volume (Isochoric)
specific volume (if mass constant)

- Constant Temperature (Isothermal) Moves along lines of constant

temperature

- Polytropic (PV n = C) As pressure increases, volume

decreases (non-linear relationship)

P1 v 1 P 2 v2
- Ideal Gas
P v = RT , R = =
T1 T2 41
 Drawing Process Path (cont.)

Using other information:

“ Pressure increases to three times its present …..”

“ Volume decreases to ¼ its present value …..”
“ Heat losses cause temperature to decrease ….”

Read the problem statement and relate to the property diagram !

42
 Water Vapor and Ideal Gas

Q. Is water vapor an Ideal gas?

Percentage of error involved in assuming steam to

be an ideal gas, and the region where steam can
be treated as an ideal gas with less than 1 percent
error.

43
 Compressibility Factor

The deviation from the ideal-gas behavior can

be corrected by compressibility factor Z.

P  actual
Z 
RT ideal

 Z represents the volume ratio or compressibility.

 Z < 1 or Z > 1 for real gases.

44
 Principle of corresponding states

• The compressibility factor Z is approximately the same for all gases at the same reduced temperature
and reduced pressure.

Z = Z(PR,TR) for all gases

PR = P/Pcr & TR = T/Tcr

where,
PR and TR are reduced values.
Pcr and Tcr are critical properties (Table A-1).

45
 Reduced Properties

• This works great if you are given a gas with known P &T and asked to find the v.

• However, if you were given P and v and asked to find T (or T and v and asked to find
P), you need to use:

pseudo-reduced specific volume, which is defined as:

vactual
vR = not vcr !
RTcr / Pcr

• Ideal gas approximation (Z=1), if (see Fig. A-30):

 PR < 10 and TR > 2
 PR << 1

46
 Ideal Gas Example

Calculate the specific volume of nitrogen at

(a) 300 K and 8.0 MPa (b) 200 K and 20.0 MPa.

Tcr = 126.2 K and Pcr = 3.39 MPa for nitrogen (Table A-1)

Part (a):
TR = T/Tcr = 300 K / 126.2 K =2.38
PR = P/Pcr = 8.0 MPa / 3.39 MPa = 2.36

Since, TR > 2 and PR < 10, we can use ideal gas equation of state.

kJ
(0.2968 )(300 K ) 3
ZRT kg .K m kPa m3
v   0.01113
P 8,000 kPa kJ kg
47
 Ideal Gas Example

Part (b):
TR = T/Tcr = 200 K / 126.2 K =1.58
PR = P/Pcr = 20.0 MPa / 3.39 MPa = 5.90

From Figure (A-30)b: Z=0.91

kJ
(0.91)(0.2968 )( 200 K ) 3
ZRT kg.K m kPa m3
v   0.002701
P 20,000 kPa kJ kg

48
 Specific Heats
Definition:

The amount of energy required to raise the temperature of a unit mass of a substance by one
degree.

5 kJ

m  1 kg
T  1o C
Specific heat  5 kJ / kg.o C

49
 Internal Energy & Enthalpy Formulation
Using Specific Heats

 u   h 
Cp   
Cv   
 T  v  T  p

Cv & Cp are properties

J/kg.K OR Btu/lbm.R
du = Cv dT dh = Cp dT
Constant volume process Constant pressure process

50
 Specific Heat of Ideal Gases

For real gases, specific heats vary with pressure but for most practical purposes a suitable average value may be
used.

h = u + Pv = u + RT dh = du + RdT

Cp = Cv + R (kJ/kg.K)

Cp = Cv + Ru (kJ/kmol.K)

Introducing another ideal gas property called specific heat ratio:

k = Cp / Cv > 1

In general, k is about 1.4, 1.6 and 1.3 for diatomic gases (CO, N2, O2), monatomic gases (Ar, He) and triatomic
gases (CO2, SO2), respectively.
51
Special Cases for a Polytropic Process (PVn = C)

Process Type Exponent ‘n’ Value

Constant Pressure 0
Constant Temperature 1

Adiabatic k = Cp / C v
Constant Volume 

52
Specific Heat of Ideal Gases

du = Cv dT
2

Δ u =  Cv(T) dT = Cv,average (T2 – T1)

1

dh = Cp dT
2

Δ h =  Cp(T) dT = Cp,average (T2 – T1)

1

53
 Specific Heats of Incompressible Solids &
Liquids
Incompressible means  or v is essentially constant.
Similar to ideal gases, specific heat depends only on temperature.

h = u + Pv
Δ u = Cavg (T2 – T1) dh = du + d(Pv)

Δh = Δu+vΔP Cv = Cp = Cavg

Δ h = Cavg Δ T + v Δ P

Constant pressure process: ΔP = 0 Δ h = Cavg Δ T

Constant temperature process (for liquids):

ΔT = 0 Δh=vΔP

54