Chapter 2 Properties of Pure Substances

1. Introduction
2. The p-v-T surface
3. The liquid vapor region
4. Properties of steam
5. Equation of state
6. Equation of state for a non-ideal gas
 2.1 Introduction

• The relationship between pressure, specific

volume and temperature will be presented.
• A pure substance is homogeneous, but can be
in different phases.
• Air is usually regarded as a pure substance in
gas phase, but it is not a pure substance if in
multiple phases.
• A simple compressible substance is
considered in this course.
 2.2 The p-v-T surface
• A substance can exist in three different phases:
solid, liquid and gas.
• Consider an experiment such that pressure is
maintained at a constant value with heat added
to the cylinder.
 The T-v diagram for a substance under
constant-pressure heating

From Turns, Thermal and Fluid Science

 The p-v-T surface for a substance
The three variables, p, v, T form continuous surface
in a 3-D space. It is called a p-v-T surface, with
different shapes for different phases.
Note: These diagrams
are greatly distorted.
The p-v, T-v and p-T diagrams

superheated
vapor region

subcooled (or
compressed)
liquid region
Supercritical fluid (from www.criticalprocesses.com/SCF.html)

Below critical T, As T is raised, the At the critical point,

the liquid & vapor densities approach the densities
phases are distinct. each other and the become identical.
meniscus becomes The substance is
less distinct. now a supercritical
fluid.

Supercritical state is encountered when

T > Tc and p > pc.

video
Supercritical fluid sCO2 (Tc= 304 K, pc=73.9 bar)
• The relatively low temperature of the process and the stability
of CO2, in addition to its low toxicity and environmental impact,
allows most compounds to be extracted with little damage
or denaturing. (Wikipedia)

https://slideplayer.com/slide/5011717/
Supercritical fluid sCO2 (Tc= 304 K, pc=73.9 bar)

https://slideplayer.com/slide/5011717/
• With properties midway between a gas and a liquid,
CO2 can be used efficiently throughout the entire Brayton
cycle (https://www.powermag.com)
 p-v-T diagrams
Most substances contract on freezing, but water is an exception
which expands on freezing.
 The Three Phases of Water

Q: What do you think of

the relative magnitudes of
T, P, u associated with
these three phases?

From Turns, Thermal and Fluid Science

Critical Points of Substances
 2.3 Liquid vapor region
Let m be the total mass of a system: m=m f + mg
m f : mass of the liquid phase, mg : mass of the vapor phase
Quality: The ratio of the mass of saturated vapor to the total mass
mg
x=
m
m f = m - mg , v fg = vg − v f
The total volume V :
V = V f + Vg or mv = m f v f + mg vg
The specific volume v :
v = v f + x(vg − v f ) = v f + xv fg
 Properties of saturate water-vapor
Temperature Table
 Properties of saturate water-vapor
Temperature Table
 Properties of saturate water-vapor

Pressure Table
Properties of superheated water vapor
Ex. 2.2: Find the p, mass and volume of vapor
4 kg of water is placed in an enclosed volume 1 m3. Heat
is added till the temperature is 150oC.
specific volume v: ¼ = 0.25 m3 /kg
App. Table C.1: volume of 150oC saturated vapor 0.3928
m3/kg (> 0.25 m3/kg)
Thus, the state is in the saturated liquid-vapor region
(called quality region in the textbook).
At 150oC, the saturate pressure is p = 475.8 kPa
In the quality region, v = vf + x(vg - vf )
0.25 = 0.00109 + x(0.3928-0.00109) → x = 0.6354
mass of vapor mg = mx = 4 × 0.6354 = 2.542 kg
Vg = vgmg = 0.3928 × 2.542 = 0.9985 m3
Ex. 2.3: Find the volume of a mass under isobaric
heating
4 kg of water is heated at a pressure of 220 kPa to x=0.8.
Determine the final volume occupied by the mixture.
Table C.2: interpolating between 0.2 MPa and 0.3 MPa
220 − 200
g = (0.6058 − 0.8857) + 0.8857 = 0.8297 m3 /kg
300 − 200
 f = 0.00106 m3 /kg
→ v = vf + x(vg - vf ) = 0.00106+0.8(0.8297 - 0.00106)
=0.664 m3/kg
V = mv = 4 × 0.664 = 2.66 m3
 2.5 Equation of state
Equation of state relates p, v, and T, the three directly
measurable state properties.
Ideal-gas equation of state
• Ideal gas is assumed to have no intermolecular force
and particle volume.
• Practically, when the vapor of a substance has
relatively low density, the P, v and T are related by the
simple equation pv=RT, or
pV = mRT , p =  RT , pV = nRT
• The gas constant R (= R / M )
where R =8.314 kJ/(kmol K) is the universal gas
constant and M is the molecular weight.
• For air R=0.287 kJ/(kg．K)
FIGURE
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.

(from Cengel and Boles, Thermodynamics)

 Compressibility Factor Z
The compressibility factor Z helps to determine whether or not the
ideal gas equation can be used (when Z→1).
pv
Z= or pv = ZRT
RT
• From Fig. 2.6, nitrogen (or air) at 300 K can be regarded as
ideal gas up to a relatively high pressure.

Ideal gas assumption is

valid for
• Low pressure (p<<pc)
regardless of T.
• High T (>2Tc), except
when p>>pc.

Fig. 2.6
Generalized Compressibility
A generalized state relationship exists when actual
pressures and temperatures are normalized by their
respective critical values. That is, a “universal”
relationship exists for the compressibility factor Z
P
Z = Z ( PR , TR ), where PR = = reduced pressure
Pc
T
and TR = = reduced temperature.
Tc
pc and Tc of various substances are listed in Table B.3.
This idea is known as the principle of corresponding
states. Such plots are known as generalized
compressibility charts.
Sat. vapor

Critical point
Sat. liquid

From Turns, Thermal and Fluid Science

EX. 2.5: Find the mass in the tire
An auto tire with a volume of 0.6 m3 is inflated to a
gage pressure of 200 kPa. Calculate the mass of air in
the tire if the temperature is 20oC, assuming idela gas
behavior.
Pabs=Pgage+Patm=200+100=300kPa
T=Tc+273=293K
m=PV/RT=300000×0.6/(287×293)=2.14kg
2.6 Equation of State for a Non-Ideal Gas
Non-ideal gas behavior occurs when p is relatively high
(>2MPa for many gases) or when T is near the saturation
temperature.
The van der Waals equation of state
It is intended to account for the volume occupied by the
gas molecules and for the attractive forces between
molecules.
RT a 27 R 2Tc2 RTc
p= − 2, a= , b=
v−b v 64 pc 8 pc
Van der Waals equation of state
 a 
 p + 2 
( − b) = RT
  
correction for correction for 1
As ↑
intermolecular finite molecule 𝑣
attractive force • Collision freq.↑
volume
• Pull-back attraction↑
Based on the fact that isotherm T=Tc
exhibits an inflection point at the
critical point, Turns, Thermal and Fluid Science

p 2 p
= 0; = 0,
 Tc , pc  T , p
2
c c

we can derive
27 R 2Tc2 RTc pcc 3
a= , b= , Zc = =
64 pc 8 pc RTc 8
Other equations of state for a non-ideal gas

• Redlich-Kwong
RT a
p= − ,
v − b v ( v + b) T
R 2Tc2.5 RTc
a = 0.4275 , b = 0.0867
pc pc
• virial equation of state
B(T ) C (T )
p = RT + + 2 +
v v
EX 2.7: Find pressure of steam at T=500oC and density 24kg/m3
Three ways to determine P-v-T state relations for gases that do not
necessarily obey the ideal-gas equation of state:
1. use of tabular data,
2. use of nonideal-gas equation of state,
3. application of the concept of generalized compressibility.
• Ideal gas: P=ρRT=24×0.462×773=8570kPa, 7% error
• Van der Waals equation: a=1.703, b=0.00169
p=RT/(v-b)-a/v2=0.462×773/(1/24-0.00169) -1.703×242
=7950kPa >1% error
• Relich Kwong equation: a=43.9, b=0.00117
p=RT/(v-b)-a/[v(v+b)√(T)]=7930kPa >1% error
• Compressibility factor Z=0.93
TR=T/Tc=773/647.4=1.19, PR=P/PC=8570/22100=0.39
p=ZRT/v=0.93×0.462×774×24=7970kPa >1% error
• Steam table p=8000kPa
 2.7 Summary
• Saturated liquid; saturated vapor
• Saturated-liquid line; saturated-vapor line
• Critical point
• Triple point
• Compressed-liquid region/superheated region
• Quality region (saturated liquid-vapor region)
• Equation of state
ideal-gas: pv = RT ,…
non-ideal gas:
• Compressibility factor Z: pv = ZRT
• Quality: x = mg/m = mg/(mf+mg)
• Specific volume in quality region:
v = vf + x(vg - vf) = vf + xvfg