PROPERTIES OF PURE

SUBSTANCE
 AT THE END OF THIS TOPIC
YOU SHOULD BE ABLE TO
• Explain concept of a pure substance.
• Explain and differentiate the physics of phase-change
processes.
• Illustrate the P-v, T-v, and P-T property diagrams and P-v-T
surfaces of pure substances.
• Demonstrate the procedures for determining thermodynamic
properties of pure substances from tables of property data.
• Describe the hypothetical substance “ideal gas” and the ideal-
gas equation of state.
• Apply the ideal-gas equation of state in the solution of typical
problems.
WHAT IS PURE SUBSTANCE??
 PHASE OF
PURE SUBSTANCE

SOLID LIQUID GAS

 PHASE OF WATER

At what conditions do ice melt?

 PHASE OF WATER

Compressed Saturated
Liquid Liquid
 PHASE OF WATER

Saturated Saturated Superheated

Mixture Vapor vapor
 PHASE OF WATER

“Boiling temperature is depends on the pressure”

Temperature is dependent on Pressure during boiling

(phase change) process
 SATURATION
TEMPERATURE
T-v diagram for the
heating process of water
at constant pressure.
SATURATION
TEMPERATURE
At given P, the
temperature at
which pure
substance
change phase
T-v diagram for the heating
process of water at constant
pressure.
PROPERTIES DIAGRAM

Find Tsat for the

following
pressure:

1. 10 kPa
2. 100 kPa
3. 1000 kPa
4. 10 000 kPa
 PHASE OF WATER

SATURATION
PRESSURE
At given T, the
pressure at which
pure substance
change phase

P-v diagram for the heating process of water

at constant temperature.
 PROPERTIES TABLE

ymix = yf + x yfg
 f : fluid,
 g : gas
x: quality
 fg: gas minus fluid
x = mg/mtotal
 Terminology
Entropy S - a measure of molecular disorder, or molecular randomness.

where k is the Boltzmann constant

Internal energy U
1. a system is the sum of all the microscopic forms of energy.
2. a sum of the kinetic and potential energies of the particles that form the
system

Enthalpy H - is defined as the sum of the internal energy U and the PV product.
 PHASE OF WATER
Critical point
Saturated Liquid and saturated
vapor states identical
22.06MPa
Triple point
All three phases (solid, liquid,
gas) coexist in equilibrium
• No substance can be in liquid
form at P < PTP
0.6117 kPa
• High pressure substance can
be in liquid form at T < TTP
(Expand on freezing)

0.01oC 373.95 oC
 QUALITY
Quality; x should be between 0 to 1
x=0 : saturated liquid
x=1 : saturated vapor
0<x<1 : saturated mixture

x = mvapor/mtotal
mtotal = mvapor +mliquid
 Examples

A piston cylinder device contains 0.06m3 of

saturated water vapor at 350kPa pressure.
Determine the temperature and the mass of
the vapor inside the cylinder
 Examples
A 2 m3 rigid tank filled with water initially at 175 kPa
and specific enthalpy of 2300 kJ/kg is heated up until the
pressure reaches 400 kPa. Determine the
1. total mass of water in the tank (kg),
2. final temperature (oC).
Show the states and process on a P-v diagram.
 IDEAL GAS PROPERTIES
Ideal gas is a hypothetical gas whose molecules occupy
negligible space and have no interactions, and which
consequently obeys the gas laws exactly.
An ideal gas is a theoretical gas composed of many randomly
moving point particles whose only interactions are perfectly
elastic collisions.
Temperature, Pressure and Volume
Based on Equation of States.

* R is a gas constant
CAN WE ASSUME
WATER VAPOR AS IDEAL
GAS??
• YES!!!

• Only for water vapor with

pressure less than 10 kPa

• At sufficiently high-
temperatures / low-pressures,
all particles in a gas phase
obey the Ideal Gas Law.

19
 COMPRESSIBLITY
FACTOR?
• Measure of gas behaviour compared to ideal gas
(How much the deviation)
• Denoted by Z
• or

Z >1
Z=1
Z<1
Ideal gas
Real gas
Gases behave differently at a given temperature and
pressure, but they behave similar at temperatures and
pressures normalized (with respect to critical point).

The normalization is;

Reduced pressure Reduced temperature

Z factor for all gases is nearly same at the same reduced pressure and temperature.
By curve-fitting all the data, we 1. PR <<1, gases behave as an
ideal gas regardless of
temperature.
2. TR >2, ideal-gas behavior can be
assumed with good accuracy
regardless of pressure (except
when PR >>1).
3. Deviation of a gas from ideal-
gas behavior is greatest in the
vicinity of the critical point.
When P and v, or T and v, are given instead of P and T, the generalized
compressibility chart can still be used to determine the third property.

Therefore, it is necessary to define one more reduced property called the pseudo-
reduced specific volume vR as

Pseudo-reduced
specific volume

The compressibility factor can also be determined from a knowledge of PR and vR.

22
OTHER EQUATIONS OF STATE
The ideal-gas equation of state is very simple, but its range of applicability is limited.

We need equation that represent the P-v-T behavior of substances accurately over a
larger region with no limitations.

Van der Waals Equation of State

where
Van der Waals intended to improve the ideal-gas equation of state by including 2 of the
effects not considered in the ideal-gas model.

The term a/v2 accounts for the intermolecular forces, and b accounts for the volume
occupied by the gas molecules.

The determination of the two constants appearing in this equation is based on the
observation that the critical isotherm on a P-v diagram has a horizontal inflection
point at the critical

24
 Beattie-Bridgeman Equation of State
Beattie-Bridgeman equation is known to be reasonably accurate for densities up to
about 0.8ρcr, where ρcr is the density of the substance at the critical point.

where

Benedict-Webb-Rubin Equation of State

This equation can handle substances at densities up to about 2.5 cr.

Virial Equation of State

The coefficients a(T), b(T), c(T), and so on, that are functions of temperature
alone are called virial coefficients.

26
Error involved in various equations of state for nitrogen

27
 Example
Properties of Saturated Liquid–Vapor Mixture
An 80-L vessel contains 4 kg of refrigerant-134a at a
pressure of 160 kPa. Determine
(a) the temperature
(b) the quality
(c) the enthalpy of the refrigerant, and
(d) the volume occupied by the vapor phase.
 Assignment
1. Is iced water a pure substance? Why?
2. What is the difference between saturated vapor and
superheated vapor?
3. Is it true that water boils at higher temperatures at higher
pressures? Explain.
4. What is the difference between the critical point and the
triple point?
5. A rigid tank contains 10 kg of water at 90 °C. If 8 kg of the
water is in the liquid form and the rest is in the vapor form,
determine (a) the pressure in the tank and (b) the volume of
the tank.
6. Determine the mass of the air in a room whose dimensions
are 4 m 5 m 6 m at 100 kPa and 25 °C.
 Example
Pressure of Saturated Liquid in a Tank

A rigid tank contains 50 kg of saturated liquid

water at 90 °C. Determine the pressure in the tank
and the volume of the tank.

P  Psat @90C  70.183kPA Then the total volume of

the tank becomes
The specific volume of saturated liquid
V =mv =50 kg  0.001036 m3 /kg
v  v f @90C  0.001036m3 / kg
= 0.0518 m3
 Example
A piston–cylinder device contains 0.0566337 m3 of saturated water vapor at
344.738 kPa pressure. Determine the temperature and the mass of the vapor
inside the cylinder.

Pressure Temperature Saturated

(kPa) (°C) vapor (m3/kg)
325 136.27 0.56199
The specific volume of saturated liquid
344.738 Tsat @344.738 kPa Vg @344.738 kPa
350 138.86 0.52422 Vg  0.56199
344.738  325

350  325 0.52422  0.56199
Interpolation  344.738  325  0.52422  0.56199  
Vg  0.56199   
 350  325 
344.738  325 T  136.27 Vg  0.5322m / kg
3

350  325 138.86  136.27
Then the total volume of
 344.738  325 138.86  136.27  
T  136.27    the tank becomes
 350  325 
T  Tsat @344.738 kPa  138.315C 0.0566337
m= = 0.106kg
0.5322
 Example
A rigid tank contains 10 kg of water at 90 °C. If 8 kg of the water is in the liquid
form and the rest is in the vapor form, determine (a) the pressure in the tank
and (b) the volume of the tank.

A rigid tank contains saturated mixture.

Since the two phases coexist in equilibrium, we have a saturated mixture, and
the pressure must be the saturation pressure at the given temperature:

a)
P  Psat @90C  70.183kPA

b)
At 90 °C, we have vf = 0.001036 m3/kg and vg = 2.3593 m3/kg. One way
of finding the volume of the tank is to determine the volume occupied
by each phase and then add them:
mg 2
x   0.2
mt 10
m3
v  v f  xv fg  0.001036  0.2  2.3593  0.001036   0.473
kg
V  mv  10  0.473  4.73m3
 Example
An 0.08 m3 vessel contains 4 kg of refrigerant-134a at a pressure of 160 kPa.
Determine (a) the temperature, (b) the quality, (c) the enthalpy of the
refrigerant, and (d) the volume occupied by the vapor phase.

Obviously, vf <v<vg, the refrigerant V 0.08 m3

is in the saturated mixture region. v   0.02
m 4 kg
Tsat @160 kPA  15.60C
(b) Quality can be determined
v  vf 0.02  0.0007437
x   0.157
v fg 0.12348  0.0007437

(c) At 160 kPa, we also read from Table that hf = 31.21 kJ/kg and hfg = 209.90 kJ/kg

h  h f  xh fg  31.21  0.157  209.90   64.2 kJ / kg

(d) The mass of the vapor is

m g = xm t = 0.1572  4  = 0.628 kg

volume occupied by the vapor phase is

Vg = m g v g = 0.628 10.12348  = 0.0775 m 3

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

At 0.5 MPa, the enthalpy of saturated water vapor is

hg = 2748.1 kJ/kg. Since h = hg, as shown, we again
have superheated vapor. Under 0.5 MPa

Obviously, the temperature is between 200 and

250°C. By linear interpolation it is determined to be

T = 216.3°C
 Assignment
Determine the temperature of water at a state of P = 0.05 MPa
and h = 3333 kJ/kg.

email to assign_nazri@yahoo.com

for email's subject and file name (in pdf), please use "course
code_assignment2_MohdNazri".. dateline 21/11/2020
 Example
Predict the pressure of nitrogen gas at T = 175 K and v = 0.00375 m3/kg on the
basis of (a) the ideal-gas equation of state, (b) the van der Waals equation of
state, (c) the Beattie-Bridgeman equation of state, and (d) the Benedict-Webb-
Rubin equation of state. Compare the values obtained to the experimentally
determined value of 10,000 kPa.

The gas constant of nitrogen gas is 0.2968 kPa m3/kg K (Table A–1).

(a) Using the ideal-gas equation of state,

RT 10.2968 175 which is in error by 38.5 percent.

P=   13,851 kPa
v 0.00375

(b) The van der Waals constants for nitrogen

a= 0.175 m 6 kPa/kg 2 RT a
P=  2  9471 kPa which is in error by 5.3 percent.
3
b= 0.00138 m /kg v -b v
(c) Beattie-Bridgeman equation
The constants from Table 3–4  
v  Mv   28.013kg / mol   0.00375m3 / kg  0.10505m3 / kmol
A = 102.29 Then,
B = 0.05378 R uT  c  A
P= 2 
1  3   v  B   2  10110kPa
c = 4.2 104 v  vT  v

(d) Benedict-Webb-Rubin equation which is in error by 1.1 percent.

The constants from Table 3–4
R uT  C0  1 bRuT  a a c     / v 2
P= B R T  A      1  e
v  T 2  v 2
0 u 0
a  2.54 v3 v 6 v 3T 2  v 2 
b  0.002328 8.314  T    8.164 105   1
=   0.04074  8.314 175   106.73   2  2

c  7.379  104 0.10505   175  0.10505
  1.272 104 0.002328  8.314  T   2.54 
A0  106.73 0.105053
B0  0.04074  2.54 1.272 10  
4
7.379 104 
1 
0.0053  0.0053/0.105052
e  10, 009kPA
 2 
C0  8.164  105 0.105056  
0.105053 1752  0.10505 
  0.0053
which is in error by 0.09 percent.