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
R u kmol  K kJ
R air  M  kg
 0.287
kg  K
28.97
kmol

kJ
8.1417
kmol  K kJ
R hydrogen  kg
 4.124
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 Real
Gas Gases
Z > 1 or
Z=1 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
 Thecompressibility 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 R Tcrit Pcrit

(kg-Mol) (J/kg.K) (K) (MPa)

Ar 28,97 287,0 (---) (---)

O2 32,00 259,8 154,8 5,08

H2 2,016 4124,2 33,3 1,30

H 2O 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

Other Thermodynamic Properties:
Isobaric (c. pressure) Coefficient

v P
1  v 
   0
v  T  P
 v 
 
 T  P

T
Other Thermodynamic Properties:
Isothermal (c. temp) Coefficient

v
1  v 
   0
v  P  T
 v 
 
 P  T
T

P
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 
Ln    T  T0     P  P0 
 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 v
 u 
Cv     0
 T  v

 u 
 
 T  v

T
Other Thermodynamic Properties:
Specific Heat at Const. Pressure

h P
 h 
CP     0
 T  P

 h 
 
 T  P

T
Other Thermodynamic Properties:
Ratio of Specific Heat

 Cp 
   
 Cv 
Other Thermodynamic Properties:
Temperature

s v 1

  s
T  0
 u  v

1
T

u
Ideal Gases: u = u(T)

0
 u   u 
du    dT    dv
 T  v  v  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
T2
u  u 2  u1   C v (T) dT
T1

Note that Cv does change with temperature

and cannot be automatically pulled from
the integral.
 Let’s 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:
 h 
C p  C p(T ) &  0
 P 

dh  C p dT, and
T2
h  h2  h1   C p (T)dT
T1
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   dh 
Cv    ; Cp   
 dT  ideal gas  dT  ideal gas
 For an ideal gas,
 h = u + Pv = u + RT
dh du
 R
dT dT
 kJ 
Cp = C v + R  kg  K 
 
Ratio of specific heats
is given the symbol, 
Cp Cp (T)
    (T)
Cv C v (T)
Cp 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) a
function of
temperature
 Three Ways to Calculate
Δu and Δh
 Δu = u2 - u1 (table)  Δh = h2 - h1 (table)

2 2
 Δu =  1
C v (T) dT  Δh =  1
C p (T) dT

 Δu = Cv,av ΔT  Δh = Cp,av ΔT
 Isothermal Process
 Ideal gas: PV = mRT
 For ideal gas, PV = mRT
We substitute into the
integral
2 2 mRT
Wb   PdV   dV
1 1 V
Collecting terms and integrating yields:

2 dV  V2 
Wb  mRT   mRT n 
1 V  V1 
 Polytropic Process
 PVn = C
 Ideal Gas Adiabatic Process and
Reversible Work
 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:
1. Reversible work mode: dW = PdV
2. Adiabatic hypothesis: dQ =0
3. Ideal Gas Law: Pv=RT
4. Specific Heat Relationships
5. First Law Thermodynamics: dQ-dW=dU
 Ideal Gas Adiabatic Process and
Reversible Work (cont)

First Law:   dW
dQ   dU

0 PdV MC v dT

 dV  CV  dT 
Using P = MRT/V    
 V  R  T 
 1    1
Integrating from  1  
 T2   V2 
(1) to (2)   
 T1   V1 
Ideal Gas Adiabatic Process and
Reversible Work (cont)
   1
Using the gas law :  T2   V1 
  
Pv=RT, other  T1   V2 
relationship amid 
 P2   V1 
  
T, V and P are  P1   V2 
developed
  1 
 T2   P2 
accordingly:   
 T1   P1 
 Ideal Gas Adiabatic Process and
Reversible Work (cont)

An expression for
work is developed

W   PdV  PV i    dV
V 

using PV =
W
 PV  i  1  
V  V   1  
constant.    1 f i

i and f represent 
  PV  f   PV  i 
   1
the initial and final
states
 Ideal Gas Adiabatic Process and
Reversible Work (cont)
 The path representation
are lines where Pv =
constant.
P f
 For most of the gases,  f
1.4

Q
 The adiabatic lines are

=0
T=
always at the righ of the

co
isothermal lines.

ns
t.
 The former is Pv = i
constant (the exponent is v
unity)
 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.
V2
Wb   PdV
V1
 Polytropic Process
Process Exponent n
 Constant pressure 0
 Constant volume 
 Isothermal & ideal gas 1
 Adiabatic & ideal gas k=Cp/Cv
Boundary work for a gas which
obeys the polytropic equation

2 2 dV
Wb   1
PdV  c 
1 V n

v2
V  1-n 1 n
V2  V1 1 n
 c    n  1
 1-n  v1 1 n
We can simplify it
further
n n
The constant c = P1V = P2V2
1

P
n
2 V (V
1 n
)  P1V 1n V 11 n 
Wb  2 2
1-n
P2V2  P1V1
 , n 1
1 n
Polytropic Process
2 2 c
Wb   PdV   n
dV
1 1 V
P2V2  P1V1
 , n1
1 n
V 2 
 PVn  , n  1
 V1 