Thermodynamics

Enthalpy & specific heat, ideal gas

The Copperbelt University

Dr. L Siwale
 Enthalpy
• Enthalpy, H or h
– It’s a property H  U  PV
(depends on the state definition and change depends on end
states only)
– It’s the sum of internal energy (u) and potential energy
(Pυ) associated with “flow work”
h  u  P

– Specific enthalpy has units of energy/mass (kJ/kg or

Btu/lbm).

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 Example: Is Refrigerant really “Cooler,” than Water?
h of R22 T=12 ºC and u =144.58 kJ/kg

• R22

u uf
x
ug  u f

145  58.8
x  0.5
230  58.8
h  h f  xh fg

h  59.4  0.5  195 

h  157kJ / kg

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 Example: Is Refrigerant really “Cooler,” than Water?
h of H2O T=12 ºC and u =144.58 kJ/kg

• H2O u u f 144.58  50.41

x   0.0402
ug  u f 2393  50.41
h  h f  xh fg  50.41  0.0402(2473)  149.81 kJ / kg
Now

h  157kJ / kg ; x  0.5
R 22 R 22

h  149.81 kJ / kg ; x  0.0402
H 2O H 2O

Look up what else is the difference between the properties of H2O and R22
that makes one a better refrigerant than the other even at 12 oC

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 Example: “Boiler UP” or
“Boil the mixture to saturation”
• A piston-cylinder assembly contains • Find
1 kg of water, initially occupying a – Show the Process on a T-υ diagram.
– W = ? in kJ
volume of 0.5 m3 at 1 bar. Energy – ΔH = ? in kJ
transfer (for example by heat) to the
water results in an expansion at
constant temperature to a final • Sketch
volume of 1.69 m3. Kinetic and V1 = 0.5 m3
potential energy effects are 1 kg P1 = 1 bar
negligible. For the water, water
V2 = 1.69 m3
– (a) show the Process on a P-υ
diagram, T2 = T1
– (b) evaluate work, in kJ, and • Assumptions
– The water in the piston-cylinder
– (c) evaluate the change in enthalpy, assembly is the closed system.
in kJ. – The water expands at constant
temperature.
– Volume change is the only work
made.
– Kinetic and potential energy effects
play no role.

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 Example: “Boiler UP” or
“Boil the mixture to saturation”
• Given Solution
– m = 1 kg of water State 1
– V1 = 0.5 m3 P1 = 1bar, V1 = 0.5 m3
– P1 = 1 bar V1 0 .5m 3 m3
1  1  1  0.5
– T2 = T1 m 1kg kg
– V2 = 1.694 m3 Table A-3
At P1, υf < υ1 < υg liquid-vapor mixture
• Find T1 = Tsat = 99.63 ºC
– Show the Process on a T-υ diagram. 0.5   1.04  10 
3

x1  x1  0.295
– W = ? in kJ 1.69   1.04  103 
– ΔH = ? in kJ u1  417  0.295  2510  417  u1  1030kJ / kg
State 2
• Basic Equations T2 = T1, V2 = 1.694 m3
V 1.69m3 m3
W  VV2 PdV 2  2
m 2  2  1.69
1 1kg kg
Table A-3
At T, υ2 = υg saturated vapor
u2 = ug = 2510 kJ/kg
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 Example: “Boiler UP” or
“Boil the mixture to saturation”
• Solution
• Given
W  VV2 PdV
– m = 1 kg of water 1

– V1 = 0.5 m3 W12  P V2  V1 

– P1 = 1 bar N 1kJ
– W12  105 2  1.69  0.5  m3 3
T 2 = T1 m 10 N  m
– V2 = 1.694 m3
W12  119kJ
• Find
– Show the Process on a P-υ
diagram.
 
H  m u  u  P (V2  V1)
2 1
– W = ? in kJ  1kg (2510  1030)kJ / kg  119 kJ
– ΔH = ? in kJ  1590 kJ
• Basic Equations
V
W   2 PdV
V1 The energy transfer needed for process 1 to 2 to
H  U  ( PV ) take place happens to be equal to the change in enthalpy
PV  PV  VP that we just calculated. We could have been asked to
calculate that energy transfer (for example by heat).
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 Example: “Boiler UP” or
“Boil the mixture to saturation”
Given • Solution
m = 1 kg of water
V1 = 0.5 m3
T
P1 = 1 bar (ºC) 1 bar
T 2 = T1
V2 = 1.694 m3
Find 99.6
1 2
Show the Process on a P-υ
diagram.
W = ? in kJ
ΔH = ? in kJ
0.5 1.69 υ (m3/kg)

Basic Equations
V The energy transfer needed for process 1 - 2 to
W   2 PdV take place happens to be equal to the change in enthalpy
V1
H  U  ( PV ) that we just calculated. We could have been asked to
calculate that energy transfer (for example by heat*).
PV  PV  VP
*“Boiler UP”

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 Example 3: Boiler
A closed, rigid tank contains 2 kg • Find
of water initially at 80 ºC and a
quality of 0.6. Heat transfer occurs – ΔH in kJ
until the tank contains only – ΔU in kJ
saturated vapor at a higher • System
pressure. Kinetic and potential T1 = 80 ºC
energy effects are negligible. For 2 kg
x1 = 0.6
water
the water as the system, determine state 2: sat. vapor
the change in enthalpy and the
change in internal energy of the
system that occurred because of • Assumptions
energy transfer by heat, in kJ. – υ2 = υ1.
Given
• Basic Equations
– m = 2 kg of water H  m h2  h1 
–
U  m u2  u1 
T1 = 80 ºC
– x1 = 0.6
– state 2: sat. vapor u1  u f 1  x1u fg1
– P2 > P 1
h1  h f 1  x1h fg1
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 Example 3: Boiler
From Table A-3
• Solution
kJ
T1=80C, x1=0.6, P2  0.82bar u2  u g  2500
kg
P1 = Psat = 0.4739 bar
v2=v1, P2 = Psat @ v2=v2g
P2 = ? From Tables.

u1  335  0.6  2480  335 

u1  1620kJ / kg  2 1

H  m h  h  2 (2667  1900)
1   2
 1534 kJ
1  1.03 10  0.6  3.41  1.03 10
3 3

1  2.04m3 / kg  2 1

U  m u  u  2 (2500  1620)

2   g  1  2.04m3 / kg
 1760 kJ
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 Specific heat
• From 1st Law at constant volume

• Q=ΔU (internal energy)

• Constant pressure
Q= Δ H= Δ U+ Δ PV (flow work)
 RE CAP Closed System Energy Balance
►The energy concepts introduced thus far are
summarized in words as follows:
change in the amount net amount of energy net amount of energy
of energy contained transferred in across transferred out across
within a system the system boundary by the system boundary
during some time heat transfer during by work during the
interval the time interval time interval

►Using previously defined symbols, this can be

expressed as: E22-E
– E1 =QQ– –WW (Eq. 2.35a)
E2-E1 1==Q–W
►Alternatively, KE + PE + U = Q – W (Eq. 2.35b)
In Eqs. 2.35, a minus sign appears before W because energy
transfer by work from the system to the surrounding is taken as
positive.
 Specific Heats
• Specific heats were defined to rate substances for their
capacity to store energy supplied in the form of
“heat.”
• Substances that take a lot of heat without becoming
hot have high “specific heat!”
• Physical description: The increase in energy storage
(heat) a body undergoes when its temperature rises by
1 degree.
• Particularly useful for thermodynamic calculations
involving the ideal gas model.
• Units of kJ/kg-K, kJ/kg-ºC, Btu/lbm-ºF, and Btu/lbm-
ºR.

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Specific heat capacity definition
Specific heat at constant pressure
 Specific Heats
u h
c  cp 
T  T P

U  mcv T  kJ 

H  mc p T  PV  U  kJ  16
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 Specific Heats
• Specific heats
– They are properties.
– Although their definition comes from two
different paths, they work for any Process.
• Both du = cυ dT and dh = cp dT work for isobaric,
isochoric, isenthalpic, isentropic, …
– cp > cυ
– Cp-Cv= R
– Their ratio is also a property called specific heat
ratio.
cp
k
c
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 Incompressible Substances
• We have some approximations for
incompressible substances.
uT , p   u f T 
 T , p    f T 

h T , p   h f  T    f  T   p  p sat  T  
h T , p   h f  T 

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 Incompressible Substances
• If specific heats are constant:
2
u   c dT u  c T
1
2
h   c p dT h  c p T
1

c p  c

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 Closure
• In this lecture, we
– Introduced the concept of specific heats.
– Provided mathematical definitions for cυ and cp.
– Presented units for specific heats.
– Evaluated u and h changes for the energy
analysis of incompressible substances.

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 Thermodynamics
Ideal Gas
The Copperbelt University

Dr. L Siwale
 Ideal Gas

PV  mRT

PV  nR T

• What is R?
• What are the units of R?

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 When is a Gas not Ideal?
• When the gas is very
near the saturated
vapor line.

• Ideal gas behavior will

occur when the density
is “low”.

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 What Can We Do?

P  ZRT

• The Principle of Corresponding States says that p-

-T behavior of many gases is identical if T and p
are scaled (divided) by the critical properties Tc and
Pc which gives Reduced property e.g. Pr = P / Pc
•
Z  f  T Tc , P Pc 

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 Z - factor
• As with many problems in engineering, we prefer
to have our equations in dimensionless form.

• To do this, we define a reduced P (PR) and a

reduced T (TR).

PR  P Pc
Z  f  PR , TR 
TR  T Tc

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 Z - factor
• Z is a
complicated
function so
it’s provided
in graphical
form.

P
Z
RT

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 Z - factor
• Ideal gas
range is
Z~1 (say,
Z=1±0.1)


 R 
R Tc Pc

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 Solution Procedure
• Typically
– Look up pc and Tc in tables A-1 or A-1E
– Use p and T to calculate pR and TR
– Use pR and TR to find Z from Z-chart
– Use pυ = ZRT to find “unknown” properties

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 Example 1
• At 34 bar and 30 ºC, are the following gases
ideal or not?
– CO2
– Air P
Z
RT
CO2 air
p T p T
pR  TR  pR  TR 
pc Tc pc Tc
303K 303K
34bar TR  34bar TR 
pR  304 K pR  133K
73.9bar 37.7bar
TR  0.997 TR  2.28
p R  0.460 p R  0.902
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 Example 1
Air, Z ~ 1.0
p R  0.902
TR  2.28

CO2, Z ~ 0.83
p R  0.460
TR  0.997

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 Ideal Gas Equation of State
P
Z
RT
p
Z

• If p < pc and T > Tc

RT

T  Tc
Z ~1
p  pc
P  RT
PV  mRT
P  R T
PV  nR T
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 Example 2
A closed, rigid tank is filled • Basic Equations
with a gas modeled as ideal,
initially at 27 ºC with a gage PV  mRT
pressure of 300 kPa. If the
gas is heated to 77 ºC, • Solution
determine the final pressure, p1 mR
expressed as gage, in kPa. p1V1  m1 RT1 
The local atmospheric T1 V
pressure is 1 bar.
p 2V2  m2 RT2 p 2 mR
•Find 
T2 V
–P2 = ? in kPa (gage)
•System
T1 = 27 ºC
P1 = 300 kPa (gage)
Gas T2 = 77 ºC
P2 = ? 32
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Patm = 1 atm
 Example 2
• Solution
p1 mR
 p1
T1 V p2
 p2  468kPa
p 2 mR T1 T2

T2 V p abs  patm  p gage
T1  300 K T2  350 K p2, gage  468kPa  101kPa

p1,abs  101kPa  300kPa p 2, gage  367kPa

p1,abs  401kPa

p2 
 401kPa  350 K
300 K 33
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 Closure
• In this lecture, we
– Noted that gases do not always exhibit ideal
behavior.
– Learned how to determined when non-ideal
behavior is important.
– Outlined the solution procedure for finding
non-ideal gas properties.
– Studied the compressibility chart and the ideal
gas model.

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