Thermodynamic

Properties
Š Property Table --
from direct measurement
Š Equation of State --
any equation that relates
P,v, and T of a substance
jump
 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
R-12 vaporize?
See R-12 (diclorindifluormethane) on Table A-2
 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
GAS PROPERTIES
Ideal -Gas Equation of State
M
PV = nR u T; n =
mol
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 (28.97 kg/kmol) and hydrogen (2.016
kg/kmol).
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 = NR u T
P1 V1 P2 V2
=
T1 T2
 Question …...
Under what conditions is it appropriate to
apply the ideal gas equation of state?

Š Good approximation for P-v-T

behaviors of real gases at low densities
(low pressure and high temperature).

Š Air, nitrogen, oxygen, hydrogen,

helium, argon, neon, carbon dioxide,
…. ( < 1% error).
Percent error for applying ideal gas
equation of state to steam
Compressibility Factor
Š It accounts mainly for two things
• Molecular structure
• Intermolecular attractive forces

Ideal Real
Gas Gases
Z > 1 or
Z=1 Z<1

Š What is it really doing?

 Compressibility Factor
Š 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: Z =1;
•Real Gases: Z>1 or Z<1. jump
 Principle of
corresponding states
ŠThecompressibility 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)
 OTHER

THERMODYNAMIC

PROPERTIES
Other Thermodynamic Properties:
Isobaric (c. pressure) Coefficient

v P
1  ∂v 
β=   >0
v  ∂T  P
 ∂v 
 
 ∂T  P For ideal gas,
β = 1/T

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

v
1  ∂v 
κ=−   >0
v  ∂P  T
 ∂v 
 
 ∂P  T For ideal gas,
T
κ = 1/P

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 κ and β
coefficients

 ∂v   ∂v 
dv =   dT +   dP ≡ β vdT − κvdP
 ∂T  P  ∂P  T

For ideal gas: dv/v = dT/T- dP/P →VP/T = const!

For substances other than ideal gas, it can be approximated by:

 v 
Ln  = β(T − T0 ) − κ (P − P0 )
 v0 
If κ and β are nearly constant,
Other Thermodynamic Properties:

u = u (T , v ) - Internal Energy

h = h(T, P) ≡ u + Pv - Enthalpy

s = s(u, v ) - Entropy
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
 Specific Heats for Some Gases

Š Cp = Cp(T)
a function of
temperature
 Ideal Gases: u = u(T)
 ∂u 
du = 
 ∂u 
 dT +   dv
0
 ∂T  v  ∂v T

Therefore,
 ∂u 
du =   dT = C v ( T )dT
 ∂T  v
The internal energy change is:
T2
∆u = u 2 − u1 = ∫ T C v (T) dT
1

As Cv changes with temperature it cannot

be pulled out from the integral (for general
cases).
 Enthalpy for an Ideal Gas

Š h = u + Pv where Pv can be replaced

by RT because Pv = RT.

Š 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!

Š 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
Š Forideal gases u, h, Cv, and Cp are
functions of temperature alone.

Š Forideal gases, Cv and Cp are written in

terms of ordinary differentials as

 du   dh 
Cv =   ; Cp =  
 dT  ideal gas  dT  ideal gas
 Three Ways to Calculate
∆u and ∆h
Š ∆u = u2 - u1 (table) Š ∆h = h2 - h1 (table)

2 2
Š ∆u = ∫ 1
C v (T) dT Š ∆h = ∫ 1
C p (T) dT

Š ∆u = Cv,av ∆T Š ∆h = Cp,av ∆T
Problem 3.31 – N2 is heated from 373K to
1773K at constant pressure. Evaluate the
specific entalpy change (KJ per kg).

Š ∆h ≈ Cp,300k ∆T = (tab. A-7)

1,0416x(1773-373) = 1457kJ/kg

∆h = ∫ 1 Cp(T) dT tab A-5, θ = t(K)/100

2
Š
Cp = 39,060 - 512,79θ -1.5+1072,7θ -2-820,40θ -3
∆h =1635.98 kJ/kg

There is an error of 11% for using Cp constant when the

temperature span is of 1400K!
 Cp x Cv Relationship
for an Ideal Gas,
Šh = u + Pv = u + RT
dh du
= +R
dT dT
 kJ 
C p = Cv + R  kg ⋅ K 
 
 Ratio of Specific Heats γ
Cp Cp (T)
γ≡ = = γ (T)
Cv C v (T)
For most gases γ is almost constant
with temperature and equals to 1.4
Cp R
= 1+ = γ >1
Cv Cv

R γR
Cv = and Cp =
γ-1 γ-1
 ISOTHERMAL,
POLITROPIC AND
ADIABATIC PROCESSES
FOR AN IDEAL GAS
 Isothermal Process
Š Ideal gas: PV = mRT = constant
 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 An 
1 V  V1 
 Polytropic Process: PVn = C; 1 ≤ n ≤ γ
Isothermal …………… n = 1
Adiabatic (Q=0)………. n = γ = Cp/Cv
Others:
Constant pressure………n = 0
Constant volume ……… n = ∞
PV1 = c

PVγ = c

The politropic lines are always to the right of the

isothermal lines.
 P, v and T Relationship in a
Polytropic Process, 1≤n ≤1
Š The path is described by: Pvn = C
Š The ideal gas state equation is: Pv = RT
Š Combining these two expressions is possible to
relate the initial to the final states
n n −1
 P2   v1   T2   v1 
 =   = 
 P1   v 2   T1   v 2 
n −1
 T2   P2  n
 = 
 T1   P1  jump
Boundary work for a gas which
obeys the polytropic equation

2 dV
Wb = ∫ 1 PdV = c ∫ 12
Vn
v2
V 1-n   V21− n − V11− n 
= c  = c  para (n ≠ 1)
 1-n  v  1− n 
1

Where C stands for the constant Pvn = C

We can further simplify
n n
The constant c = P1V1 = P2V2

P
n
2 V (V ) − P1V 1n (V 11− n )
1− n
Wb = 2 2
1-n
P2V2 − P1V1
= , n ≠1
1− n
 Summary for
Polytropic Process
2 2 c
Wb = ∫ PdV = ∫ n
dV
1 1 V
P2V2 − P1V1
= , n ≠1
1− n
V 2 
= PVAn  , n = 1
 V1 
 Ideal Gas Adiabatic Process and
Reversible Work

Š
γ
Why Pv = C
represents a process P
f f

where the volume is

Q
expanding or

=0
T=
co
contracting without

ns
t.
heat flux, Q = 0? i

v
 Ideal Gas Adiabatic Process and
Reversible Work (cont)
First Law: N − dW
dQ N = dU
N
=0 PdV MC v dT

Substituting  dV  CV  dT 
P = MRT/V  =−  
 V  N 
R T 
(1− γ )−1

Integrating from (1− γ ) γ

 T2   V2   P2   V1 
(1) to (2)   =   ⇒   =  
 T1   V1   P1   V2 

Which are the polytropic relations seen before!

 Exercise 3-30
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.

a) Find the air temperature after the compression

b) What is the density ratio (after to before compression)
c) How much work is done in compressing 2 kg of air?
d) How much power is required to compress 2kg per
second of air?
 Solution - page 1
Š In a reversible and
adiabatic process P, T and
v follows:
P f
( γ −1) f
 T2   V1 
 = 
 T1   V2 

Q
=0
T=
γ

co
 P2   V1 

ns
 = 

t.
 P1   V2  i

( γ −1) γ v
 T2   P2 
 = 
 T1   P1 
 Solution - page 2
Part a)
The temperature after compression is
( γ −1) γ 0.4 1.4
P   1 
T2 = T1 ⋅  2  → T2 = 293 ⋅   = 566K ( 293oC)
 P1   0.1 

Part b)
The density ratio is
−1 γ
 V2   ρ1   P2   ρ 2   1 1 1.4
 ≡ =  → =  = 5.179
 V1   ρ 2   P1   ρ1   0.1 
 Solution - page 3
Part c)
The reversible work:

WREV =−
[(PV )2 − (PV )1 ] M ⋅ R (T2 − T1 )
≡ =
( γ − 1) ( γ − 1)
2 ⋅ 287 ⋅ (566 − 293 )
= = 391KJ
Part d) 0.4
The power is:
dW  R (T2 − T1 )
M
P= =− = 391KW
dt ( γ − 1)
 Exercícios – Capítulo 3
Propriedades das Substâncias
Puras

Exercícios 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