Chapter 3

PROPERTIES OF A PURE,
SIMPLE COMPRESSIBLE
SUBSTANCE
 3.1. CONCEPTS
 Simple system – The term “Simple system”
is applied when there is only one way the
system energy can be significantly altered
by work as the system undergoes a
quasiequilibrium process.

 Although no system is ever truly simple,

many systems can be modeled as simple
systems for the purpose of thermodynamic
analysis.
 The most important of these models for
the application considered in this subject is
the “Simple compressible system”.

 Basic idea – Changes in volume can have

significant influence on the energy of
simple compressible systems.
I WANT TO RECALL YOU THAT…

 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 (Ex:
liquid water and water vapor).
 3.2. p-v-T SURFACE
 From experiment it is known that
temperature and specific volume can be
regarded as independent, and pressure
determined as a function of these two:
p = p(T, v) (3.1)
Eq. (3.1) is called p-v-T relation.

The graph of such a function is a surface,

“the p-v-T surface”.
P-v-T surface of a substance that
contracts on freezing

Solid-liquid

Liquid
Pre ssure

Critical
Solid point
P-v-T surface of a substance that
expands on freezing (like water)

Liquid
Critical
point
Pre ssure

Solid
 3.3. PHASE DIAGRAMS

 If the p-v-T surface is projected onto a plane, it

becomes PHASE DIAGRAM.

 We often pay our attention to: p-v diagram, T-v

diagram, p-T diagram and T-s diagram (h-s
diagram and logp-h diagram).
p-v DIAGRAM
p-v diagram of a substance that
contracts on freezing
p-v diagram of a substance that
expands on freezing
T-v DIAGRAM
p-T DIAGRAM
3.4. T-s diagram
3.5. PHASE CHANGE
 Let’s consider a piston-cylinder assembly.

 Let’s assume there is 1kg of pure water

inside at initial pressure 1atm and initial
temperature 20oC.

 Let’s do an experiment at constant

pressure.
 WHAT WE CAN OBSERVE???
 IMPORTANT TERMINOLOGIES
 Subcooled Liquid (Compressed Liquid)

 Saturated Liquid

 Wet Saturated Vapor

 Dry Saturated Vapor

 Superheated Vapor
 In the case of WET SATURATED VAPOR,
there is another important terminology,
that is QUALITY or DRYNESS
FRACTION.

mvapor
x
mliquid  mvapor (3.2)
 The value of the quality x ranges from
ZERO to UNITY.
0  x 1

 At saturated liquid states: x = 0

 At dry saturated vapor states: x = 1

 Although the phase change from liquid to
vapor (Vaporization) is the one of principal
interest in this lecture, it is also instructive
to consider the phase changes from solid
to liquid (Melting) and from solid to vapor
(Sublimation).
 Let’s consider a unit mass of ice at a
temperature below the TRIPLE POINT
temperature.

Case 1: Let’s begin with the case where

the pressure is greater than the triple point
pressure.
Case 2: Let’s begin with the case where
the pressure is less than the triple point
pressure.
 What we can see???
 Case 1
Suppose the system is slowly heated
(p=const): solid  liquid (Melting)

 Case 2
Suppose the system is slowly heated
(p=const): solid  vapor (Sublimation)
3.6. THERMODYNAMIC
PROPERTY DATA
 Thermodynamic property data for
engineering use appear in various forms,
including TABLES, GRAPHS and
EQUATIONS.
 TABLE

 Saturation Tables (Temperature table &

Pressure table)
+ They list property values for the
saturated liquid and vapor states.
+ The property values at these states are
denoted by the subscripts f and g.
+ The specific volume, the specific internal
energy, the specific enthalpy and the
specific entropy of a two-phase liquid-
vapor mixture can be also determined by
using the saturation tables.

  (1  x) f  x. g (3.3)

 - may be v, u, h and s
 If we are considering a two-phase liquid-
vapor mixture with property , we can
determine its quality by using the following
formula:
f
x
g   f (3.4)
 Vapor and Liquid Tables
+ These are often referred to as the
SUPERHEATED VAPOR TABLES and
COMPRESSED LIQUID TABLES.
+ In these tables, pressure and
temperature are independent properties.
+ The states encountered when solving
problems often do not fall exactly on the
grid of values provided by property tables.
Interpolation then becomes necessary.
 WARNING
 The values of u, h and s given in the
property tables are not obtained by direct
measurement, but are calculated from
other data that can be readily determined
experimentally.

 However, because they are calculated, the

matter of reference states and reference
values become important.
3.7. SPECIFIC HEATS
cv and cp
 Several properties related to internal
energy are important in Thermodynamics.
One of these is ENTHALPY, two others –
known as specific heats – are considered
in this section.

 cv and cp are intensive properties.

 For pure, simple compressible

substances, they (cv and cp) are defined as
partial derivatives of the functions u(T,v)
and h(T,p), respectively.
  u 
cv    (3.5)
 T v

 h 
cp   
 T  p (3.6)
 The property k, called the specific heat ratio,
is simply the ratio

cp
(3.7) k
cv

 In general, cv is a function of v and T (or p and

T), cp depends on both p and T (or v and T).
 3.8. APPROXIMATIONS FOR
LIQUID USING SATURATED
LIQUID DATA
 Referring to the compressed liquid table, it
shows that the specific volume and specific
internal energy change very little with pressure
at a fixed temperature.

 Because the values of v and u vary only

gradually as pressure changes at fixed
temperature, the following approximations are
reasonable for many engineering calculations:
v(T,p)  vf(T) (3.8)

u(T,p)  uf(T) (3.9)

It means, for liquids v and u may be

evaluated at the saturated liquid state
corresponding to the temperature at the
given state.
 An approximation value of h at liquid state can be
obtained by using Eqs. (3.8) and (3.9) in the
definition h = u + pv; thus

h(T,p)  uf(T) + p.vf(T) (3.10)

Equation (3.10) can be expressed alternatively

as

h(T,p)  hf(T) + vf(T)[p – psat(T)] (3.11)

where psat denotes the saturation pressure at the

given temperature.
 When the contribution of the last term of
Eq. (3.11) is small, the specific enthalpy
can be approximated by the saturated
liquid value,

h(T,p)  hf(T) (3.12)

 3.9. INCOMPRESSIBLE
SUBSTANCE MODEL

 As noted above, there are regions where

the specific volume of liquid water varies
little and the specific internal energy varies
mainly with temperature.

 The same general behavior is exhibited by

the liquid phases of other substances and
by solids.
 The approximation of Sec. 3.8 are based on
these observations, as is the incompressible
substance model under present consideration.

 To simplify evaluation involving liquids or solids,

the specific volume is often assumed to be
constant and the specific internal energy is
assumed to vary only with temperature.

 A substance idealized in this way is called

INCOMPRESSIBLE.
 In this case, the specific heat cv is also a
function of temperature alone,

du
cv (T )  (Incompressible) (3.13)
dT
 Although the specific volume is constant
and the internal energy depends on
temperature only, enthalpy varies with
both pressure and temperature,

h(T,p) = u(T) + p.v (Incompressible) (3.14)

 Differentiating Eq. (3.14) with respect to
temperature while holding pressure fixed, we
have:

 h  du
  
 T  p dT

 It says that, for a substance modeled as

incompressible, the specific heats cv and cp are
equal.

cp = c v (Incompressible) (3.15)
 CONCLUSION

 For an incompressible substance, it is

unnecessary to distinguish between cv and
cp.

 Specific heats depend on temperature

only.
  Using Eqs. (3.13) and (3.14), the changes in
specific internal energy and specific enthalpy
between two states are given, by

T2
u 2  u1   c(T ).dT (Incompressible) (3.16)
T1

h2  h1  u 2  u1  v( p 2  p1 )
T2
h2  h1   c(T ).dT  v.( p 2  p1 ) (Incompressible) (3.17)
T1
 Over limited temperature intervals the
variation of c with temperature can be
small. In this case, if the specific heat c is
taken as constant, we can write

u2 – u1 = c.(T2 – T1) (3.18)

h2 – h1 = c.(T2 – T1) + v.(p2 – p1) (3.19)
(Incompressible, constant c)
3.10. p-v-T RELATION FOR
GASES
3.10.1. UNIVERSAL GAS CONSTANT

 Let’s consider a piston-cylinder assembly

held at a constant temperature.

 Let’s move the piston to various positions

so that a series of equilibrium states at
constant temperature can be visited.
 Suppose the pressure p and the specific
volume per mole v are measured at each
state and the value of p.v / T determined.

 The ratios p.v / T can then be plotted versus

pressure at constant temperature (See
Fig.3.9, Shapiro).
 When the ratios are extrapolated to zero
pressure, precisely the same limiting value
is obtained,

pv
R  p lim o (3.20)
T
 R denotes the common limit for all
temperatures.
 If this procedure were repeated for other gases,
we can see that the limit p.v / T as p tends to zero
at fixed temperature is the same, namely R .

 R is called the universal gas constant.

 Its value as determined experimentally is

R = 8314J/kmol.K
 3.10.2. COMPRESSIBILITY FACTOR
pv
Z
 The dimensionless RT is called the
compressibility factor.

 Since v  M .v , where M is the molecular

mass, the compressibility factor can be
pv
expressed alternatively as Z 
RT

R
where R
M
 R is called gas constant.

 R (J/kg.K) is a constant for the particular

gas whose molecular mass is M.
pv
Z
 The compressibility factor RTtends to
unity as pressure tends to zero at fixed
temperature.
3.10.3. GENERALIZED COMPRESSIBILITY
CHART

 Generalized Compressibility Chart is the

chart of the form Z = f(pR, TR), where pR
and TR are Reduced pressure and
Reduced temperature, respectively.
 Thus, we have to study this chart to
determine Compressibility Factor.
 In order to determine Compressibility
Factor, we have to determine pR and TR
first.
 p
pR 
pC
T
TR 
TC

Where pC and TC denote the critical pressure

and temperature, respectively.
 CORRESPONDING STATES – when
different gases have nearly the same pR
and TR, we say they are under the same
corresponding states.

 Principle of CORRESPONDING STATES

– when different gases are under the
same corresponding states, they have
nearly the same Compressibility Factor. It
means, the Z factor for all gases is
approximately the same at the same
reduced pressure and temperature.
GENERALIZED COMPRESSIBILITY CHART FOR
VARIOUS GASES
 Using the critical pressure and critical
temperature of a substance of interest, the
generalized compressibility chart can be
entered with various pairs of TR, pR and
v’R: (TR, pR), (pR, v’R), or (TR, v’R).

 Where v’R is the pseudoreduced specific

volume, v
v 
,
R
R.TC / pC
 NOTE 1 – For correlation purpose, the
pseudoreduced specific volume has been
found to be preferable to the reduced
specific volume vR,

v
vR 
vC
 NOTE 2 – The generalized compressibility
chart should not be used as a substitute
for accurate p-v-T data for a given
substance as provided by a table or
computer software.
 3.11. IDEAL GAS MODEL
 By considering the generalized
compressibility chart, it can be concluded
that:
- The compressibility factor is
approximately unity when the reduced
pressure pR is less than about 0.05 or
when the reduced temperature TR is
greater than 15.
- For TR in the interval from about 2 to 3, Z
is closely equal to unity over a wide range
of reduced pressure.
 Hence, the pressure, specific volume, and
temperature relationship for gases at many
states is given approximately by

pv
(3.21) Z 1
RT

or
(3.22) pv  RT
 Equation (3.22) is called the ideal gas
equation of state.

 Alternative forms,
pV  mRT (3.23)

p v  RT (3.24)

pV  n RT (3.25)
 For any gas whose equation of state is
given exactly by pv=RT, the specific
internal energy and the specific enthalpy
depend on temperature only.
 The ideal gas model is summarized as
follows,

pv = RT (3.26)

u = u(T) (3.27)

h = h(T) = u(T) + RT (3.28)

 NOTE
1. The specific internal energy and
enthalpy of gases generally depend on
two independent properties, not just
temperature as presumed by the ideal gas
model.
2. The ideal gas equation of state does not
provide an acceptable approximation at all
states. To verify a gas can be modeled as
an ideal gas, the states of interest can be
located on a compressibility chart to
determine how well Z = 1 is satisfied.
 NOTE
From the microscopic point of view, the
ideal gas model adheres to several
idealizations:
- The gas consists of molecules that are in
random motion and obey the laws of
mechanics;
- The total number of molecules is large,
but the volume of molecule is a negligibly
small fraction of the volume occupied by
the gas;
- No appreciable forces act on the
molecules except during collisions.
 3.12. INTERNAL ENERGY,
ENTHALPY, and SPECIFIC
HEATS of IDEAL GASES

 Specific heat cv of ideal gas

du
c v (T ) 
dT T2
u 2 (T )  u1 (T )   cv (T )dT
du  cv (T )dT T1
 Specific heat cp of ideal gas

T2
dh
c p (T )  h2 (T )  h1 (T )   c p (T )dT
dT T1

dh  c p (T )dT
 Relationship between the ideal gas
specific heats

c p (T )  cv (T )  R

c p (T )  c v (T )  R

c p (T )
k
cv (T )
 Since cp > cv, it follows that k > 1. It is also
a function of temperature only
3.13. POLYTROPIC PROCESS OF
AN IDEAL GAS
 The pressure-volume relationship of a
polytropic process of a closed system,

pV  const
n (3.29)

where n is a constant called polytropic index.

The exponent n may take on any value from - 
to +.
2. Particular processes

Isobaric process (Constant-pressure process),

n = 0.

Isometric process (Constant-volume process),

n = .

Isothermal process (Constant-temperature

process), n = 1.

Adiabatic process, n = k (k is called adiabatic

index)
 EXERCISE 1
 Two tanks are connected by a valve. One tank
contains 2kg of carbon monoxide gas at 77oC
and 0.7bar. The other tank holds 8kg of the
same gas at 27oC and 1.2bars. The valve is
opened and the gases are allowed to mix while
receiving energy by heat transfer from the
surroundings. The final equilibrium temperature
is 42oC. Using the ideal gas model, determine
(a) the final equilibrium pressure, in bars
(b) the heat transfer for the process, in kJ
 SOLUTION 1
 Assumptions: (1) The total amount of carbon
monoxide gas is a closed system, (2) The gas is
modeled as an ideal gas, (3) The gas initially in
each tank is in equilibrium. The final state is an
equilibrium state, (4) No energy is transferred to,
or from, the gas by work, (5) There is no change
in kinetic or potential energy.

 The final equilibrium pressure pf

(m1  m2 ) RT f
pf 
V1  V2
 (m1  m2 ) RT f
pf 
m1 RT1 m2 RT2
( )( )
p1 p2

(10kg )315K
pf   1.05bars
(2kg )(350K ) (8kg )(300K )
{ )( }
0.7bar 1.2bar
 The heat transfer can be found from an
energy balance
U  Q  W

Q  U f Ui U i  m1u (T1 )  m2 u (T2 )

U f  (m1  m2 )u (T f )
Q  m1cv (T f  T1 )  m2 cv (T f  T2 )