MAE 501 course notes – Spring 2022 Copyrighted by R. D.

Gould

ADVANCED ENGR THERMODYNAMICS

V. PROPERTIES OBTAINED USING SPECIFIC HEATS

a.) Introduction
i.) Motivation behind specific heats:
• To allow the for the calculation of Δu or Δh in terms of ΔT and for the
calculation of Δs in terms of ΔT and Δv or Δp for materials which do not
undergo a phase change and for which we do not have thermodynamic
property data tables

ii.) Definitions:
Caloric:
• The amount of heat required per unit mass to raise the temperature of the
material by one degree.
• Since δQ is path dependent this definition would make the specific heat
path dependent –would not meet criteria of a thermodynamic property!
Modern day:
• The amount of energy required per unit mass to raise the temperature of
the material by one degree.
1  U  u  s  1  H  h s 
Cv        T   Cp        T  
m   T const   T v   T v m   T  pconst   T  p   T p

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ADVANCED ENGR THERMODYNAMICS

iii.) Observations:
• Should probably be called partial specific energy instead of specific heat
• Only defined for homogeneous phase
• Not defined during a phase change!
• Used to obtain Δu or Δh when you know ΔT and Δs when you know ΔT and
Δv or Δp

iv.) Units of specific heat:

kJ BTU
,
kg  K lbm  F

kJ
kg  C

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ADVANCED ENGR THERMODYNAMICS

1. Calculation of u for a pure SCS using specific heats :
We can represent u = u(T,v) and s = s(T,v). Using calculus of variations:
 u   u  and s  s
du    dT    dv ds    dT    dv
 T v  v T   T v   v T

Using the Fundamental Relation also gives du as: du  Tds  pdv

substituting the definition of Cv in the above equation gives:

 ds  
 u   s   s  
du  Cv T  dT    dv and
 v  T du  T  T  dT    dv  pdv
 v  v T 

 s    s  
du  T   dT  T    p  dv
 T v   v T 
 s   p 
using the Maxwell relation:      (Bejan, Table 4.4, p. 171) we get
 v T  T  v
  p  
du  Cv T  dT  T    p dv
  T  v  (5.1)

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ADVANCED ENGR THERMODYNAMICS

a.) Consider a solid or liquid (incompressible substances - dv  0):
liquid H2O @ 20 °C

duS ,L  Cv T  dT or uS ,L  u2  u1   Cv T  dT (5.2 a&b)

T2
P(kPa) v (m3/kg)
T1
2.339 0.0010018

b.) Consider an ideal gas ( pv = RgasT, Note: dv  0) 30,000 0.0009886

The term in the square brackets can be evaluated for an ideal gas as
  p     Rgas  
 
  T 
T  p  dv  
  v 
T   p  dv   p  pdv  0
 v   

u IG  u2  u1   Cv T  dT
T2
Thus, duIG  Cv T  dT or T1 (5.2 a&b)

for a gas that obeys the ideal gas equation of state. This is validated by
Joule’s experiment (rigid, insulated tanks). 1st law (closed system)
A
vac
A A Qnet,in,1-2 - Wnet,out,1-2 = U
P1,T1 open valve P2,T2 P2,T2

Initial final (V2 > V1, p2 < p1) 0 = U = mu

Note: These equations tell us that the internal energy is a function of temperature
only for incompressible solids and liquids and for ideal gases!

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ADVANCED ENGR THERMODYNAMICS

2. Calculation of h for a pure SCS using specific heats :
We can represent h = h(T,p) and s = s(T,p). Using calculus of variations:
 h   h  s  s 
dh    dT    dp and ds    dT    dp
 T  p  p    T p   p T
T

Using the Fundamental Relation also gives dh as: dh  Tds  vdp

substituting the definition of Cp in the above equation gives:
 
ds  
 h   s   s  
dh  C p  T  dT    dp and dh  T   dT    dp  vdp
 p  T
 T  p  p T 
 s    s  
dh  T   dT  T    v  dp
 T  p   p T 

 s 
  v
using the Maxwell relation:       (Bejan, Table 4.4, p. 171) we get
 p T  T  p
  v  
dh  C p  T  dT  v  T    dp
  T  p  (5.3)


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ADVANCED ENGR THERMODYNAMICS

a.) Consider a solid or liquid (dv  0) with zero pressure change (dp  0):

dhS ,L ,dP~0  C p T  dT hS ,L ,dP~0  h2  h1   C p T  dT

T2
or T1
(5.4 a&b)

b.) Consider a liquid (dv  0) with large pressure change (i.e. liquid pump):

Recall: h  u  pv thus dh  du  d  pv   du  pdv  vdp

For a liquid (dv  0) dh  du  vdp

dhLiq Pump  Cv T  dT  vdp or hLiq Pump  h2  h1   Cv T  dT  vp (5.5 a&b)
T2

T1

c.) Consider an ideal gas ( pv = RgasT, Note: dp  0)

The term in the square brackets can be evaluated for an ideal gas as
  v     Rgas  
 v  T   
 
dp   v  T    dp  v  vdp  0
 T p    p 
Thus, dhIG  C p T  dT or hIG  h2  h1   C p T  dT
T2

T1
(5.4 a&b)
for a gas that obeys the ideal gas equation of state.

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ADVANCED ENGR THERMODYNAMICS

Note: These equations tell us that the enthalpy is a function of temperature only for
incompressible solids and liquids (with small p process) and for ideal gases!

Consider the following processes for an ideal gas ( pv = RgasT) :

1 – 2a: constant v
1 – 2c: constant p
1 – 2b: linear p vs v

Isotherm, T2 = constant

Isotherm, T1 = constant

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ADVANCED ENGR THERMODYNAMICS

3. Relationship between Cp and Cv:

Recall: dh  du  d  pv  du  pdv  vdp

a.) Consider a solid or liquid

For an incompressible material (dv  0). Also, for most solids and liquids v is
small (v  0.00013  0.001 m3/kg)
dh  du  d  pv   du  pdv  vdp

Thus, dh  du (for incompressible substances over reasonable p!)

and C p  Cv (for incompressible substances!) (5.6a)

WARNING: THIS IS NOT TRUE FOR A GAS!

Note: For this reason only Cp is tabulated for incompressible substances!

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ADVANCED ENGR THERMODYNAMICS

b.) Consider an ideal gas

h  u  pv and dh  du  d  pv

but for an ideal gas: dh  Cp T  dT , du  Cv T dT , pv  Rgas T

Thus, C p T  dT  Cv T  dT  d  RgasT   Cv T  dT  Rgas dT  Cv T   Rgas  dT

C p T   Cv T   Rgas  kJ  for an ideal gas (mass basis) (5.6 b)

 kg  K 
 

C p T   Cv T   Ru  
kJ
 kmol  K  for an ideal gas (mole basis) (5.6 c)

Table A-4 gives values of Cp and Cv for 6 gases between 250 and 1000 K

For air at 300 K: Cp = 1.005 kJ/kg-K and Cv = 0.718 kJ/kg-K

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ADVANCED ENGR THERMODYNAMICS

4. Practical calculation of u and h using specific heats (for solid, liquid or IG):
• In general, Cp and Cv are functions of temperature

4.5 1.18
4 4.217 Water 1.16 N2 (Table A-4-1 data)
4.179 4.218

Cp (kJ/kg-K) for N2
3.5 1.14
1.12
Cp (kJ/kg-K)

3
2.5 1.1
2 1.08
Aluminum 1.06
1.5
1.04
1
1.02
0.5 0.797 0.859 0.902 0.929 0.949 0.973 0.997
1
0 200 400 600 800 1000
200 300 400 500
T (K)
Temperature (K)

h  h2  h1  T 2 C p T  dT
T
u  u2  u1  T 2 Cv T  dT (5.2b) (5.4b)
T
1 1

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ADVANCED ENGR THERMODYNAMICS

a.) Most accurate method:
• Perform integration accounting for temperature dependence of Cp or Cv
h  h2  h1  T 2 C p T  dT u  u2  u1  T 2 Cv T  dT
T T
1
or 1

1. These integrations have been performed for you [for ideal gases only] and
the results are tabulated for various values of T2 assuming that h1 and u1
are zero when T1 = 0 K. See Tables A-5 [air – Keenan & Kaye] through A-
11 [JANAF] for internal energies and enthalpies of ideal gases. Note: That
mass specific quantities are given in Table A-5 but that molar specific
quantities are given in all the other ideal gas tables!

• Recall: mass and molar specific quantities are related (i.e. h  h M )

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ADVANCED ENGR THERMODYNAMICS

2. Use 4th order polynomial fit for C p T  in the above integrand. Table A-4-3
gives the coefficients for 15 gases :

Unitless, Cp here is molar quantity

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ADVANCED ENGR THERMODYNAMICS


C p T   Ru a  bT  cT 2  dT 3  eT 4  (5.7a) C p kJ kmol  K 
Cp 
M kg kmol 
T
1
 
h  h2  h1  Ru T 2 a  bT  cT 2  dT 3  eT 4 dT (5.7b)

 T b 2 T2 c 3 T2 d 4 T2 e 5 T2  h kJ kmol 
h  h2  h1  Ru aT T2  T  T  T  T  (5.7c) h 
 1 2 T1 3 T1 4 T1 5 T1  M kg kmol 

This method is efficient for use in computer programs

Note: Only C p is given in this table! However, recall the relation between Cp and Cv
for an ideal gas C p T   Cv T   Ru
b.) Good method:
• Use average specific heat value over the temperature range of your
problem.
u  T 2 Cv T  dT  Cv,avg T 2 dT
T T
1 1

u  Cv,avg T2  T1  (5.8a) h  h2  h1  C p, avg T2  T1  (5.8b)

where Cv, avg   Cv T1   Cv T2  2 and 

C p, avg  C p T1   C p T2  2 
Chapter 5 – Page 13
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ADVANCED ENGR THERMODYNAMICS

• Use Table A-4-1 for values of Cp and Cv in these expressions
• The ratio of specific heats k = Cp/Cv is also tabulated for convenience.
Note that k is less sensitive to temperature than Cp and Cv
• Ideal gas values of specific heat are also called zero-pressure specific
heats and are sometimes denoted as C op and Cvo
Noble gases (monatomic)
– no rotational or
Table A-4-1 vibrational energy storage
modes - only translational
and electronic energy
modes
• Helium
• Argon
• Neon
• Krypton
• Xenon
• Radon

• Use A-4-2

Chapter 5 – Page 14
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ADVANCED ENGR THERMODYNAMICS

5. Finding s for a pure substances using specific heats:
 We need to use the Fundamental Relations (simple, pure substance)

Tds  du  pdv (5.9) and Tds  dh  vdp (5.10)

dividing by T and integrating to find s for a pure SCS
2
2
du 2 pdv dh 2 vdp
s   s2  s1     (5.9a) and s   s2  s1      (5.10a)
1 T 1 T 1 T 1 T

a.) Consider a solid or liquid (dv  0), from Eq. (5.9a):

du Cv T  dT (5.11a )
2
Cv T  dT
dsS ,L   or sS ,L  s2  s1   (5.11b )
T T 1
T
If Cv(T)  constant over the temperature range of our process:
 T   kJ 
sS ,L  s2  s1  Cv ,avg ln  2    (5.12a) or S S ,L  S2  S1  mCv ,avg ln  T2   kJ  (5.12b)
 T1   kg  K   T1   K 
• Use to calculate S for a solid or liquid undergoing a temperature change
• NOTE: temperatures are ABSOLUTE!
• DO NOT use to calculating S for an isothermal heat reservoir!

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ADVANCED ENGR THERMODYNAMICS

b.) Consider an ideal gas ( pv = RgasT)

du IG  Cv T  dT, p T  Rgas v and dhIG  C p T  dT , v T  Rgas p

Substituting these into (5.9a) and (5.10a) gives

Cv T 
2 2
Rgas 2
dT v  (5.13a)
sIG   dT   dv   Cv T   Rgas ln  2 
1
T 1
v 1
T  v1 
2
C p T  2
Rgas 2
dT p 
sIG   dT   dp   C p T   Rgas ln  2  (5.13b)
1
T 1
p 1
T  p1 
1. If the specific heats are assumed constant over the temperature range of
our process we get
T  v 
sIG   s2  s1   Cv ,avg ln  2   Rgas ln  2  (5.14a)
 T1   v1 

T  p 
sIG   s2  s1   C p ,avg ln  2   Rgas ln  2  (5.14b)
 T1   p1 

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ADVANCED ENGR THERMODYNAMICS

2.) If the specific heats vary significantly over the temperature range we
must evaluate the integral in the first term of (5.13b)
2 p 
dT
s   C p T   Rgas ln 2  (5.13b)
1 T  p1 

• This integral, with T1 = Tref = 0 K, is tabulated in the ideal gas tables

• Table A-5 for air (mass basis) or Tables A-6 thru A-11 (molar basis)
T T2
dT
  C p T 
dT
sTo (5.15a) thus sTo2  sTo1   C p T  (5.15b)
Tref T T1 T

To find the change s for an ideal gas with temperature dependent specific
heats (most accurate!) use
p  (5.16)
sIG   s2  s1   sTo2  sTo1  Rgas ln  2 
 p1 
T
dT
Note: sTo   Cv  T 
Tref T

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ADVANCED ENGR THERMODYNAMICS

Example Problem 5.1
Given: 1 kg of N2 (MN2 = 28.01 kg/kmol) initially at 0.2 MPa and 300 K is heated
during a constant pressure process to 800 K.

Find: Find the changes in enthalpy using, a.) polynomial curve fit to Cp(T), b.)
the average value of Cp over the temperature range, c.) the ideal gas tables.
Solution:

 T b 2 T2 c 3 T2 d 4 T2 e 5 T2 
h  h2  h1  Ru aT T2  T  T  T  T 
 1 2 T1 3 T1 4 T1 5 T1 

kJ



3.675T2  T1  
2

 1.205  10 3 2 2

T2  T1 
2.324  10 6 3
3

T2  T13  kJ
 8.3144    14989.82
kmol  K   0.632  10 9 4
 
4
T2  T1
4

5

 0.226  10 12 5
T2  T 1
5
 

kmol
h kJ
h   535.16
M kg

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ADVANCED ENGR THERMODYNAMICS

Example Problem 5.1 (cont)


C p ,avg  C p T1   C p T2  2 

C p ,avg 
1.039  1.121
2

kJ
C p ,avg  1.080
kg  K

h  C p ,avg T2  T1   1.080

kJ
800  300 K
kg  K

kJ
h  540
kg

Chapter 5 – Page 19
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ADVANCED ENGR THERMODYNAMICS

Example Problem 5.1 (cont)

kJ
h  h2  h1  23,714  8,723  14,991
kmol

h 14,991 kJ kmol kJ
h    535.2
M 28.01 kg kmol kg

Errors:

535.16  535.2
a.)  100  0.008%
535.2

540.0  535.2
b.)  100  0.89%
535.2

Chapter 5 – Page 20
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ADVANCED ENGR THERMODYNAMICS

recall 2nd law: S   Qnet
2
6. Isentropic (s = 0) relations for ideal gases:
Reversible & adiabatic
1 T
a.) Constant specific heats (Eqns. (5.14a) and (5.14b) with s = 0)
Cv , avg C p , avg

v2  T2  Rgas and p2  T2  Rgas
   
v1  T1  p1  T1 
Introducing the ratio of specific heats, k = Cp/Cv gives
Cp
Cv Cv 1 1 Cp Cp
   and  
Cv

k
Rgas C p  Cv C p k 1 C p  Cv Cp k 1
1 Rgas
1
Cv Cv
 1  k 1  k  k 1
v1  T2   k 1 T v  p2  T2   k 1
  or 2   1  (5.17a,b) and   or T2   p2  k
 (5.18a,b)
v2  T1  T1  v2  p1  T1  T1  p1 

Combining these to eliminate T gives p1v1k  p2 v2k  constant (5.18)

These equation is valid only for 1.) constant specific heats, 2.) ideal gas
behavior AND 3.) isentropic process (i.e. reversible & adiabatic).

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ADVANCED ENGR THERMODYNAMICS

b.) Variable specific heats (i.e. temperature dependent Cp and Cv)
 p2  sT2  sT1 1 T2 C p T dT
o o
(Eq. (5.13a) with s = 0): ln    
 1
p R gas Rgas T1 T

1 T dT '
 C p T ' 
T'
Introducing the relative pressure: pr  p  e Rgas T
o  f T  (5.20)
po

• pr is a complicated function of temperature for each gas which has been

tabulated for you.
• po is some reference pressure that corresponds to the reference sTo
temperature To. If To is chosen to be 0 K, we get p R
pr   e gas
po

• Between two states along an 1.) isentropic process of an 2.) ideal gas
having 3.) temperature dependent specific heats:
 p1 
 
p1  po  s p (5.21)
  r ,1
p2  p2  pr,2
  s  constant
 po  s

Chapter 5 – Page 22
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ADVANCED ENGR THERMODYNAMICS

1 T dT '
  Cv T ' 
T'
Introducing the relative specific volume: vr  v  e Rgas T
o  g T  (5.22)
vo

• Between two states along an 1.) isentropic process of an 2.) ideal gas having
3.) temperature dependent specific heats:
 v1 
 
v1  vo  s v (5.23)
  r,1
v2  v2  vr,2
  s  constant
 vo  s

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ADVANCED ENGR THERMODYNAMICS

Example Problem 5.2
Given: Air is compressed in an isentropic process giving a pressure ratio of 8.56:1.
The initial air temperature is 300 K.

Find: The final temperature of the air assuming: a.) constant specific heats, b.)
temperature dependent specific heats (Table A.5), and c.) the relative
pressure concept
Solution: For isentropic process, s = 0
k 1
a.) T2  p2  k Table A-4-1 at 300K → kair = 1.40
 
T1  p1  k 1
p2  k
T2  T1     300 K 8.56 1.41 1.4  300 K 8.56.2857  554.04 K
 p1 

b.) sIG   s2  s1   sTo  sTo  Rgas ln  p2 

kJ
Table A-5 at 300K → sT1  1.70203
o
kg  K
 p1 
2 1

p  kJ kJ kJ
For s  0 sTo2  sTo1  Rgas ln 2   1.70203  .287 ln 8.56   2.31824
 p1  kg  K kg  K kg  K
Interpolating in Table A-5 → T2 = 550 K

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ADVANCED ENGR THERMODYNAMICS

Example Problem 5.2 (cont) p 
c.) pr ,2  pr ,1  2 
 p1 
pr ,2  1.3868.56

pr ,2  11.864
Interpolating
→ T2 = 550 K

Chapter 5 – Page 25
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ADVANCED ENGR THERMODYNAMICS

7. NIST-JANAF Thermochemical Tables – 4th edition:
“NIST-JANAF Thermochemical Tables – 4th edition,” Journal of Physical and
Chemical Reference Data, Monograph 9, 1998.
• NIST – National Institute of Standards and Technology (formally NBS)
• JANAF – Joint Army, Navy and Air Force
• NSRDS – National Standard Reference Data System
• Initiated in the late 1950’s to help researchers calculate propellant and combustion
system performance.

a.) Data provided in NIST-JANAF tables as a function of temperature:

T
H T    C op T dT
o T
dT
and S T    C p T  T
o o
• 0
(enthalpy) (part of entropy)
0

• G T   H Tr  T   S o T   H o T   H o Tr  T
o o
(Gibbs energy)

•
 
 f H o T    f H o 298  H o T   H o 298  compound (enthalpy of formation) –
 
compound formed from its elements
  H T   H 298 elements
o o

o o o

•  f G T    f H T   T S T compound   S T elements
o
 (Std. state Gibbs func.
change for reaction)
• ln K f    f G o T  RT  2.30258 log K f (equilibrium constant)

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NIST-JANAF thermochemical table (4th ed.) reference conditions:
• Reference temperature: Tr = 298.15 K Wark’s table (1971 JANAF)
• Standard state pressure: po = 100 kPa (Note: older JANAF tables: po = 1 atm)
1
N N2
Monatomic Nitrogen, N (M = 14.0067) 2 1600
JK-1mol-1 kJmol-1
T (K) Cop So -[Go-Ho(Tr)]/T Ho-Ho(Tr)  f Ho  f Go Log Kf
0 0. 0. Infinite -6.197 470.820 470.820 Infinite

100 20.786 130.593 171.780 -4.119 471.448 466.379 -243.611

200 20.786 145.001 155.201 -2.040 472.071 461.070 -120.419

250 20.786 149.639 153.642 -1.001 472.383 458.283 -95.753

298.15 20.786 153.300 153.300 0. 472.683 455.540 -79.809

300 20.786 153.429 153.300 0.038 472.694 455.434 -79.298

350 20.786 156.633 153.554 1.078 473.005 452.533 -67.537

400 20.786 159.408 154.116 2.117 473.314 449.587 -58.710

450 20.786 161.857 154.843 3.156 473.621 446.603 -51.840

500 20.786 164.047 155.655 4.196 473.923 443.584 -46.341

600 20.786 167.836 157.379 6.274 474.510 437.461 -38.084

700 20.786 171.041 159.108 8.353 475.067 431.242 -32.180

800 20.786 173.816 160.777 10.431 475.591 424.945 -27.746

900 20.786 176.264 162.364 12.510 476.081 418.584 -24.294

1000 20.786 178.454 163.866 14.589 476.540 412.171 -21.530

T T
Note : C op  f (T ) o
Cp T  dT H T   H 298.15 
o o
 C p T dT
o

0 T 298.15 Chapter 5 – Page 27

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ADVANCED ENGR THERMODYNAMICS

Diatomic Nitrogen, N2 (M = 28.0134) 1621

T (K) Cop So -[Go-Ho(Tr)]/T Ho-Ho(Tr) fHo fGo log Kf

0 0. 0. Infinite -8.670 0. 0. 0.
100 29.104 159.811 217.490 -5.768 0. 0. 0.
200 29.107 179.985 194.272 -2.857 0. 0. 0.
250 29.111 186.481 192.088 -1.402 0. 0. 0.
298.15 29.124 191.609 191.609 0. 0. 0. 0.
300 29.125 191.789 191.610 0.054 0. 0. 0.
350 29.165 196.281 191.964 1.511 0. 0. 0.
400 29.249 200.181 192.753 2.971 0. 0. 0.
450 29.387 203.633 193.774 4.437 0. 0. 0.
500 29.580 206.739 194.917 5.911 0. 0. 0.
600 30.110 212.176 197.353 8.894 0. 0. 0.
700 30.754 216.866 199.813 11.937 0. 0. 0.
800 31.433 221.017 202.209 15.046 0. 0. 0.
900 32.090 224.757 204.510 18.223 0. 0. 0.
1000 32.697 228.170 206.708 21.463 0. 0. 0.

Note for N 2 : C op  f (T )

Chapter 5 – Page 28
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ADVANCED ENGR THERMODYNAMICS

Tables in Wark’s appendix

• Tables A-6 through A-11: Ideal gas enthalpy, internal energy, absolute entropy
for N2, O2, CO, CO2, H2O, H2, O, OH. Based on JANAF tables, NSRDS-NBS-
37, 1971. Note: po = 1 atm in these tables

•  
Table A-33: Enthalpy of formation  f H o , Gibbs function of formation  f G o ,  
absolute entropy (so), and enthalpy of vaporization at 25C and 1 atm (hfg) for
42 substances. Based on JANAF Thermochemical tables, Dow Chemical Co.,
1971. Note: po = 1 atm in these tables.

• Table A-35: Log10 of equilibrium constants for 8 reactions as a function of

temperature. Based on JANAF tables, NSRDS-NBS-37, 1971. Note: po = 1 atm
in these tables.

Chapter 5 – Page 29
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ADVANCED ENGR THERMODYNAMICS

Table A-6 diatomic nitrogen – partial listing (po = 1atm = 1.01 bar)
T (K) h (kJ/kmole) u (kJ/kmole) so (kJ/kmole-K)
Similar to
0 0 0 0
NIST-JANAF
220 6,391 4,562 182.639
table 1621
230 6,683 4,770 183.938
(with po = 1bar)
240 6,975 4,979 185.180
250 7,266 5,188 186.370
260 7,558 5,396 187.514
270 7,849 5,604 188.614
280 8,141 5,813 189.673
290 8,432 6,021 190.695
298 8,669 6,190 191.502
300 8,723 6,229 191.682

1000 30,129 21,815 228.057

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Example Problem 5.3
Given: Monotonic nitrogen gas.

Find: Evaluate the specific heat as a function of temperature for N using the
method described in the NIST-JANAF monograph
Solution: N is a monotonic gas (see p. 17 & 18 of Monograph 9)

Translation: C op tr  5 2 Ru  5 2  8.3144 kmolekJ  K  20.786 kmolekJ  K (1)

C op   2 d 2 ln Q d ln Q  c  
Electronic:  T  2T  (2) where Q   gi exp 2 i  (3)
Ru   dT 2 dT   T 
e i

  c2 i 
  i gi exp 
thus, d ln Q c2  T 
 2 i
(4)
dT T c  
 gi exp 2 i 
i  T 

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ADVANCED ENGR THERMODYNAMICS

Example Problem 5.3 (cont.)
and 2
  c2 i    c2 i     c2 i 
  g exp    2
g exp      g exp 
d 2 ln Q  2c2 i i i T  c22 i T  c22
i i i i
  i  T 
 3  4  4 (5)
dT 2
T   c     c      c2 i 
2
 g i exp 2 i  T  gi exp 2 i  T  g exp 
 T   T   i
i i
i  T 
Putting (4) and (5) into (2) gives:
 c2 i   c2 i 
C  2c2 i
o   i gi exp 
 T  c2
 2   i2 gi exp 
 T 

  
p i

 c2 i  T 2  c  
i gi exp  T  i gi exp  T2 i 
Ru e T

2
 c    c2 i 
 g exp  2 i  
2  i i   g exp  
 T  2c2 i i
T 
 22  i
c
 i
T   c2 i  
2
 c  
i gi exp  T2 i 
T
 i g exp 
 T  

 i

Canceling 1st and 4th terms gives

Chapter 5 – Page 32
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ADVANCED ENGR THERMODYNAMICS

Example Problem 5.3 (cont.)
2
 c2 i    c2 i  
Cp 
o 2   i g i exp 
c2 i
2

 T  c2
 2  
 i
 i g i exp 
 T  

  
Ru e T 2  c2 i  T 2   c2 i  
2

i gi exp  T    gi exp  T  
 i 

c2 (cm-K) 1.438786 Ru (kJ/kmole-K) 8.3144

e_i (cm^-1) g_i

1 0.000 4

2 19224.464 6

3 19233.177 4

4 28838.920 2

5 28839.306 4

T Q sum (e_i*Q_i) sum(e_i^2*Q_i) Cp,elec/Ru Cp,elec Cp,trans Cp,total

1000 4 1.85877E-07 0.003574031 1.84E-09 1.53E-08 20.786 20.786

2000 4.0000098 0.189219216 3639.919735 0.000470 0.0039 20.786 20.790

3000 4.0009946 19.18238781 370475.1272 0.021292 0.1770 20.786 20.963

4000 4.0101031 196.0658821 3821922.264 0.123000 1.0227 20.786 21.809

5000 4.0410349 803.3678923 15860962.53 0.321731 2.6750 20.786 23.461

6000 4.1053902 2083.656299 41714568.78 0.569470 4.7348 20.786 25.521

Agrees with NIST-JANAF table 1600

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Example Problem 5.3 (cont.)
Expanding the summations (assuming 5 energy levels) gives the
following at each prescribed temperature value:

 c    c    c    c    c    c  
A T    gi exp  2 i   g1 exp  2 1   g 2 exp  2 2   g3 exp  2 3   g 4 exp  2 4   g5 exp  2 5 
i  T   T   T   T   T   T 

 c    c    c    c    c    c  
B T     i gi exp  2 i   1 g1 exp  2 1    2 g 2 exp  2 2    3 g3 exp  2 3    4 g 4 exp  2 4    5 g5 exp  2 5 
i  T   T   T   T   T   T 

 c    c    c    c    c    c  
C T     i2 gi exp  2 i   12 g1 exp  2 1    22 g 2 exp  2 2    32 g 3 exp  2 3    42 g 4 exp  2 4    52 g 5 exp  2 5 
i  T   T   T   T   T   T 

C po  c22  C B 2 
  2  2
Ru e T  A A 

Chapter 5 – Page 34