Thermodynamic

Properties

Property Table -from

direct measurement

Equation of State -any equations that relates

P,v, and T of a substance

Ideal -Gas Equation of State

Any relation among the pressure,

temperature, and specific volume of a
substance is called an equation of state. The
simplest and best-known equation of state is
the ideal-gas equation of state, given as

where R is the gas constant. Caution should be

exercised in using this relation since an ideal
gas is a fictitious substance. Real gases exhibit
ideal-gas behavior at relatively low pressures
and high temperatures.

Universal Gas Constant

Universal gas constant is given on
Ru = 8.31434 kJ/kmol-K
= 8.31434 kPa-m3/kmol-k
= 0.0831434 bar-m3/kmol-K
= 82.05 L-atm/kmol-K
= 1.9858 Btu/lbmol-R
= 1545.35 ft-lbf/lbmol-R
= 10.73 psia-ft3/lbmol-R

Example
Determine the particular gas constant
for air and hydrogen.
kJ
8.1417
kJ
R
u
kmol

K
0.287
R air M
kg
kg K
28.97
kmol

kJ
8.1417
kJ
kmol

K
4.124
R hydrogen
kg
kg K
2.016
kmol

Ideal Gas Law is a simple

Equation of State
PV mRT
Pv RT
PV NRuT
P v RuT, v V/N
P1V1 P2V2

T1
T2

Percent error for applying ideal gas

equation of state to steam

Question ...
Under what conditions is it
appropriate to apply the
ideal gas equation of state?

Ideal Gas Law

Good approximation for P-v-T
behaviors of real gases at low
densities (low pressure and high
temperature).
Air, nitrogen, oxygen, hydrogen,
helium, argon, neon, carbon
dioxide, . ( < 1% error).

Compressibility Factor
The

deviation from ideal-gas behavior

can be properly accounted for by using
the compressibility factor Z, defined as

Z represents the volume ratio

or compressibility.

Ideal
Gas

Real
Gases

Z=1

Z > 1 or
Z<1

Real Gases

Pv = ZRT or
Pv = ZRuT, where v is volume
per unit mole.

Z is known as the compressibility factor.

Real gases, Z < 1 or Z > 1.

Compressibility factor
What is it really doing?
It accounts mainly for two things

Molecular structure
Intermolecular attractive forces

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

Reduced Pressure
and Temperature
P
T
PR
; TR
Pcr
Tcr
where:

PR and TR are reduced values.

Pcr and Tcr are critical properties.

Compressibility factor for ten substances

(applicable for all gases Table A-3)

Where do you find critical-point properties?

Table A-7
Mol
(kg-Mol)

R
(J/kg.K)

Tcrit
(K)

Pcrit
(MPa)

Ar

28,97

287,0

(---)

(---)

O2

32,00

259,8

154,8

5,08

H2

2,016

4124,2

33,3

1,30

H2O

18,016

461,5

647,1

22,09

CO2

44,01

188,9

304,2

7,39

Reduced Properties
This works great if you are given a
gas, a P and a T and asked to find
the v.
However, if you are given P and v
and asked to find T (or T and v and
asked to find P), trouble lies ahead.
Use pseudo-reduced specific volume.

Pseudo-Reduced
Specific Volume
When

either P or T is unknown, Z can be

determined from the compressibility
chart with the help of the pseudo-reduced
specific volume, defined as

not vcr !

Ideal-Gas Approximation

The compressibility chart shows

the conditions for which Z = 1 and
the gas behaves as an ideal gas:

(a) PR < 0.1 and TR > 1

Exercise 3-21
Steam at 600 oC & 1 MPa. Evaluate
the specific volume using the steam
table and ideal gas law
To C

Tsat = 180 C therefore

is superheated steam 600
374
(Table A-3)
o

Volume = 0,4011
m3/kg

1MPa
Tcr

180

Solution - page 1
Part (b) ideal gas law
Rvapor = 461 J/kgK
v = RT/P , v = 461x873/106 = 0.403 m3/kg
Steam is clearly an ideal gas at this state.
Error is less than 0.5%

Check:
PR = 1/22.09 = 0.05
& TR = 873/647 = 1.35

TEAMPLAY
Find the compressibility factor to
determine the error in treating
oxygen gas at 160 K and 3 MPa as
an ideal gas.

Other Thermodynamic Properties:

Isobaric (c. pressure) Coefficient
v

1 v

0
v T P

T P
T

Other Thermodynamic Properties:

Isothermal (c. temp) Coefficient
v

P T

1 v

0
v P T
T

Other Thermodynamic Properties:

We can think of the volume as being a function
of pressure and temperature, v = v(P,T).
Hence infinitesimal differences in volume are
expressed as infinitesimal differences in P and
T, using and coefficients
v
v
dv
dT
dP vdT vdP
T P
P T

If and are constant, we can integrate for v:

v
T T0 P P0
Ln
v0

Other Thermodynamic Properties:

Internal Energy, Enthalpy and
Entropy

u u T, v
h h T, P u Pv

s s u , v

Other Thermodynamic Properties:

Specific Heat at Const. Volume
u

u
Cv
0
T v

T v
T

Other Thermodynamic Properties:

Specific Heat at Const. Pressure
h

h
CP
0
T P

T P
T

Other Thermodynamic Properties:

Ratio of Specific Heat

Cp

Cv

Other Thermodynamic Properties:

Temperature
v

1
T

s 1
0

u v

Ideal Gases: u = u(T)

0
u
u
du
dT
dv
T

Therefore,

u
du
dT C v ( T )dT
T v

We can start with du and

integrate to get the change in u:
du C v dT, and

u u 2 u1

T2
T1

C v (T) dT

Note that Cv does change with temperature

and cannot be automatically pulled from
the integral.

Lets look at enthalpy

for an ideal gas:

h = u + Pv where Pv can be replaced

by RT because Pv = RT.

Therefore, h = u + RT => since u is

only a function of T, R is a constant,
then h is also only a function of T

so h = h(T)

Similarly, for a change in

enthalpy for ideal gases:
C p C p(T )

0
P

&

dh C p dT, and

h h2 h1

T2
T1

C p (T)dT

Summary: Ideal Gases

For ideal

gases u, h, Cv, and Cp are

functions of temperature alone.
For ideal gases, Cv and Cp are written
in terms of ordinary differentials as

du
Cv

dT

dh
; Cp

dT
ideal gas

ideal gas

For an ideal gas,

h = u + Pv = u + RT

dh du

R
dT dT
Cp = C v + R

kJ
kg K

Ratio of specific heats

is given the symbol,

Cp
Cv

Cp

Cp (T)
C v (T)

(T)

R
1
1
Cv
Cv

Other relations with the

ratio of specific heats which
can be easily developed:
R
R
Cv
and Cp
-1
-1

For monatomic gases,

5
3
C p R , Cv R
2
2
and both are constants.
Argon, Helium, and Neon

For all other gases,

Cp is a function of temperature and it may be

calculated from equations such as those in
Table A-5(c) in the Appendice

Cv may be calculated from Cp=Cv+R.

Next figure shows the temperature behavior

. specific heats go up with temperature.

Specific Heats for Some Gases

Cp = Cp(T)

function of
temperature

Three Ways to Calculate

u and h

u = u2 - u1 (table) h = h2 - h1 (table)

C v (T) dT

u =

u = Cv,av T

C p (T) dT

h =

h = Cp,av T

Isothermal Process

Ideal gas: PV = mRT

For ideal gas, PV = mRT

We substitute into the
integral
2

Wb PdV
1

2
1

mRT
dV
V

Collecting terms and integrating yields:

Wb mRT

2
1

V2
dV

mRT n
V
V1

Polytropic Process

PVn = C

Ideal Gas Adiabatic Process and

Reversible Work

1.
2.
3.
4.
5.

What is the path for process with expand or

contract without heat flux? How P,v and T
behavior when Q = 0?
To develop an expression to the adiabatic
process is necessary employ:
Reversible work mode: dW = PdV
Adiabatic hypothesis: dQ =0
Ideal Gas Law: Pv=RT
Specific Heat Relationships
First Law Thermodynamics: dQ-dW=dU

Ideal Gas Adiabatic Process and

Reversible Work (cont)
First Law:

Using P = MRT/V

dQ

dW
0

PdV

dU

MC v dT

CV dT
dV

V
R T

1 1

Integrating from
(1) to (2)

T2 V2

T1 V1

Ideal Gas Adiabatic Process and

Reversible Work (cont)
Using the gas law :
Pv=RT, other
relationship amid
T, V and P are
developed
accordingly:

T2 V1

T1 V2
P2 V1

P1 V2
T2 P2

T1 P1

Ideal Gas Adiabatic Process and

Reversible Work (cont)
An expression for
work is developed
using PV =
constant.
i and f represent
the initial and final
states

W PdV PV i

dV
V

PV i 1

1
V V
W
1 f

PV f PV i

Ideal Gas Adiabatic Process and

Reversible Work (cont)

=0
Q
t.
ns
co
T=

The path representation

are lines where Pv =
constant.
For most of the gases,
1.4
The adiabatic lines are
always at the righ of the
isothermal lines.
The former is Pv =
constant (the exponent is
unity)

i
v

Polytropic Process
A frequently encountered process for gases
is the polytropic process:

PVn = c = constant
Since this expression relates P & V, we
can calculate the work for this path.

Wb

V2
V1

PdV

Polytropic Process
Process

Constant pressure
Constant volume
Isothermal & ideal gas
Adiabatic & ideal gas

Exponent n
0

1
k=C p/Cv

Boundary work for a gas which

obeys the polytropic equation
Wb

2
1

PdV c
v2

2
1

dV
n
V

1 n
1 n
V
V2 V1
c

1 n
1-n v1
1-n

n 1

We can simplify it
further
n

n
2

The constant c = P1V1 = P2V

n
2

) P1V 1n V 11 n
1-n

1 n
2

P
2 V (V
Wb

P2V2 P1V1

,
1 n

n 1

Polytropic Process
Wb

2
1

PdV

2
1

c
dV
n
V

P2V2 P1V1

, n 1
1 n
V2
, n 1
PVn
V1

Exercise 3-11
A bucket containing 2 liters of water at 100oC is
heated by an electric resistance.
a) Identify the energy interactions if the system
boundary is i) the water, ii) the electric coil
b) If heat is supplied at 1 KW, then how much
time is needed to boil off all the water to steam?
(latent heat of vap at 1 atm is 2258 kJ/kg)
c) If the water is at 25oC, how long will take to boil
off all the water (Cp = 4.18 J/kgC)

Solution - page 1
Part a)
If the water is the system then Q > 0
and W = 0. There is a temperature
difference between the electric coil and
the water.
If the electric coil is the system then Q
< 0 and W < 0. It converts 100% of the
electric work to heat!

Solution - page 2
Part b)
The mass of water is of 2 kg. It comes from 2liters
times the specific volume of 0.001 m3/kg
To boil off all the water is necessary to supply all
the vaporization energy:
Evap = 2285*2=4570 KJ
The power is the energy rate. The time necessary to
supply 4570 KJ at 1KJ/sec is therefore:
Time = 4570/1 = 4570 seconds or 1.27 hour

Solution
page
3
Part c)
The heat to boil off all the water initially at 25oC is
the sum of : (1) the sensible heat to increase the
temperature from 25oC to 100oC, (2) the vap. heat
of part (b)
The sensible heat to increase from 25oC to 100oC is
determined using the specific heat (CP = 4.18
kJ/kgoC)
Heat = 4.18*2*(100-25)=627 KJ
The time necessary to supply (4570+627)KJ at
1KJ/sec is :
Time = 5197/1 = 5197 seconds or 1.44 hour

Exercise 3-12
A bucket containing 2 liters of R-12 is left outside
in the atmosphere (0.1 MPa)
a) What is the R-12 temperature assuming it is in
the saturated state.
b) the surrounding transfer heat at the rate of
1KW to the liquid. How long will take for all R12 vaporize?

Solution - page 1
Part a)
From table A-2, at the saturation
pressure of 0.1 MPa one finds:
Tsaturation = - 30oC
Vliq = 0.000672 m3/kg
vvap = 0.159375 m3/kg
hlv = 165KJ/kg (vaporization heat)

Solution - page 2
Part b)
The mass of R-12 is m = Volume/vL,
m=0.002/0.000672 = 2.98 kg
The vaporization energy:
Evap = vap energy * mass = 165*2.98 =
492 KJ
Time = Heat/Power = 492 sec or 8.2 min

Exercise 3-17
A rigid tank contains saturated steam
(x = 1) at 0.1 MPa. Heat is added to
the steam to increase the pressure to
0.3 MPa. What is the final
temperature?

Solution - page 1
P

Tcr = 374oC
superheated
0.3MPa
0.1MPa

133.55oC
99.63oC
v

Process at constant volume, search at the

superheated steam table for a temperature
corresponding to the 0.3 MPa and v = 1.690
m3/kg -> nearly 820oC.

Exercise 3-30
a)
b)
c)
d)

Air is compressed reversibly and adiabatically

from a pressure of 0.1 MPa and a temperature
of 20oC to a pressure of 1.0 MPa.
Find the air temperature after the compression
What is the density ratio (after to before
compression)
How much work is done in compressing 2 kg of
air?
How much power is required to compress 2kg
per second of air?

Solution - page 1

In a reversible and
adiabatic process P, T and
v follows:

P2 V1

P1 V2
T2 P2

T1 P1

=0
Q
t.
ns
co
T=

T2 V1

T1 V2

Solution - page 2
Part a)
The temperature after compression is
P
T2 T1 2
P1

T2 293

1 0.4 1.4
566K ( 293oC)

0.1

Part b)
The density ratio is
V2 1 P2

V1 2 P1

2 1 1 1.4

5.179

1 0.1

Solution - page 3
Part c)
The reversible work:
WREV

PV 2 PV 1 M R T2 T1

1
2 287 566 293

391KJ

Part d)
0.4
The power is:
R T2 T1
dW
M
P

391KW
1
dt

Exerccios Captulo 3
Propriedades das Substncias
Puras
Exerccios Propostos: 3.6 / 3.9 / 3.12 /
3.16 / 3.21 / 3.22 / 3.26 / 3.30 / 3.32 / 3.34
Team Play: 3.1 / 3.2 / 3.4

Ex. 3.1) Utilizando a Tabela A-1.1 ou A-1.2, determine se os estados

da gua so de lquido comprimido, lquido-vapor, vapor
superaquecido ou se esto nas linhas de lquido saturado ou vapor
saturado.
a) Vapor superaquecido
a) P=1,0 MPa; T=207 C
b) Lquido comprimido
b) P=1,0 MPa; T=107,5 C
c) P=1,0 MPa; T=179,91 C; x=0,0 c) Lquido saturado
d) P=1,0 MPa; T=179,91 C; x=0,45 d) Lquido-Vapor
e) T=340 C; P=21,0 MPa
e) Lquido comprimido
f) Vapor superaquecido
f) T=340 C; P=2,1 MPa
g) T=340 C; P=14,586 MPa; x=1,0 g) Vapor saturado
h) T=500 C; P=25 MPa h) Vapor superaquecido - Fluido
i) Lquido comprimido - Fluido
i) P=50 MPa; T=25 C

Ex. 3.2) Encontre o volume especfico dos

estados b, d e h do exerccio anterior.

b) P=1,0 MPa; T=107,5 C vvl=0,001050

(utilizar referncia T=107,5C)
d) P=1,0 MPa; T=179,91 C; x=0,45 v=0,08812
[v=(1-x)vl+x(vv)]
h) T=500 C; P=25 MPa v=0,011123 m3/kg
(Tabela A-1.3 Vapor Superaquecido)

Ex. 3.4) Amnia a P=150 kPa, T=0 C se

encontra na regio de vapor superaquecido
e tem um volume especfico e entalpia de
0,8697 m3/kg e 1469,8 kJ/kg,
respectivamente. Determine sua energia
interna especfica neste estado.

u =1339,345 kJ/kg
(u = h - P v)