APPENDIX C

C. FORMULAE
A. CHAPTER 1 RELATIONS
Gravitational acceleration g(r) = G m
E
/r
2
, r in m
G = 6.67x10
14
m
3
/kg s
2
(or kN m
2
/kg
2
)
m
E
, mass of earth = 5.97x10
24
kg
r
E
, radius of earth = 6.37x10
6
m
At earth's surface g(r
E
) = 9.807 m/s
2
g
c
= 32.174 lb
m
ft/s
2
lb
f
N
Avog
= 6.02310
26
molecules/kmole for a molecular substance
= 6.02310
26
atoms/k atom mole for an atomic substance
T(K) = T(C) + 273.15
T (R) = T(F) + 459.67
Joules equivalent of work J = 778.14 ft lb
f
/BTU
1 short ton (usually referred to as a ton in the US)= 2000 lb
1 metric ton = 1000 kg
1 long ton (English): 2240 lb
Planck constant h
P
= 6.62510
37
kJ s/molecule
Boltzmann's constant k
B
= 1.38010
26
kJ/K molecule = R/N
Avog
Speed of light in vacuum c
0
= 2.99810
8
m/s, 9.83610
8
ft/s
One light year = 5.87510
12
miles
StefanBoltzmann constant
R
= 5.67010
11
kW/m
2
K
4
, 0.171410
8
Btu/h ft
2
R
4
Ideal gas law
P v = RT, PV =m R T
PV = nRT, Pv = R T
R = 8.314
kPa m
k mole K
0.08314
bar m
k mole K
1545
ft lbf
lbmole R
R
3 3
o
, ,
=0.730
atm ft
lbmole R
, 10.7
psia ft
lbmole R

3 3
p
k
/P = N
k
/N = X
k
.
STP: 25C (60F), 101.325 kPa (14.696 psia), 760 mm of Hg (29.213 in of Hg at 32F, 10.3323
m of water at 4C)
1 kmole of ideal gas at STP occupies 24.8 m
3
1 lbmole of ideal gas at STP occupies 392 ft
3
Properties of pure substances
x = m
g
/(m
f
+ m
g
)
v = x v
g
+ (1 x)v
f
or v
f
+ x(v
g
v
f
)
u, h, and s relations are similar to the v expression
Mathematical background
Point function or property
For two variables dz = Mdx +Ndy,
M
y
=
N
x
x
y

Cyclic relation
y
z
x
Z
x

x
y

Y
Z
= -1

Other useful relations

y
y
y y y
u
x
=
( u / z)
( x / z )
z
x
=
1
( x / z )

,
2002 by CRC Press LLC
Homogeneous function
x .... x = x .... x
1 s
m
1 s
( ) ( )
i
i
x

x
= m

, Euler equation
Z = Z(a,b,x,y) = x
m
Z (a,b,y/x)
Lagrange multiplier
Optimize f(x,y,z) subject to g (x,y,z) = 0 and h(x,y,z) = 0. Then F = f+
1
g +

2
h, F/x=0, F/y=0, F/z=0.
Stokes theorem
r
r
r r r
F ds F dA
cs

( )
Gauss divergence theorem
r r r r
F dA F dV
cs cv

( )
Microscopic thermodynamics
LJ Potential and Force
(l) = 4 ((l
0
/l)
12
(l
0
/l)
6
)
F(l) =d/dl,
/k
B
in K 0.,77 T
c
, 1.15 T
BP
, 1.9 T
MP
(nm) 0.84 v
c
1/3
, 1.66 v
b
1/3
, 1.122 v
m
1/3
c:critical, b: boiling, m: melting
l
mean
= 1/(2
1/2
n
2
)
V
rms
= (3k
B
T/m))
1/2
= (3 RT/M))
1/2
V
avg
= {8/(3)}
1/2
V
rms
, V
mps
= (2k
B
T/m))
1/2
= (2 RT/M))
1/2
where V V V V
rms x y z
2 2 2 2
= + + is based on the three velocity components
Sound Speed c = kRT / M
Kn = l
mean
/d
B. CHAPTER 2 RELATIONS
Closed systems

Q =

W, Q W = dE, Q
12
W
12
= E
2
E
1
W
out
positive, Qin positive
E = U + KE + PE
W
rev
= P dV
H = U + PV, h = u + Pv
c
v
= (u/T)
v
, c
P
= (h/T)
P
, (kJ/(kg K)), (c
p
/c
v
) = k
Ideal gases
c
v,0
= du/dT, c
P,0
= dh/dT, (c
po
c
vo
) = R
(Note: Suffixes p and v are unnecessary for ideal gases. Instead let these be c
10
and c
20
)
Monatomic gases
c
P,0
= (5/2) R
(u - u ) = c dT
0,2 0,1
1
2
vo
, (h - h ) = c dT
0,2 0,1
1
2
po
Open systems
Mass accounting or conservation
dm
cv
/dt =

m
i

m
e
dm
cv
/dt =
k
m
k,i

k
m
k,e
, multiple components, single inlet and exit
Energy accounting or conservation
dE
cv
/dt =

Q
cv

W
cv
+

m
i
(h+ke+pe)
i

m
e
(h + ke+ pe)
e
cv cv
m = dV / v , E = (u +ke +pe) dV / v
2002 by CRC Press LLC
where, ke (kJ/kg) =V
2
/2000, pe(kJ/kg) = g Z/1000 (SI)
ke (BTU/lb) V
2
/(2 g
c
J), pe (BTU/lb) =g Z/(g
c
J)
methalpy, e
T
= = h + ke + pe
w
rev
= v dP
Bernoulli type of equation applied in fluid mechanics, (f
M
: Moody friction factor)
P V
gz
P V
gz u u
HeadLoss u u g f LV gD
i i
i
e e
e i e
i e M

+ + + + =
= =
2 2
2
2 2
2
( ) ( ) ,
( ) / / ( )
.
Uniform system and uniform flow processes
Q
cv
W
cv
= (m
2
u
2
m
1
u
1
)
cv
+ (m
e
h
e
m
i
h
i
), assumed, ke and pe =0
where m
i
m
e
= (m
2
m
1
)
cv
( w ) = ( w ) = - vdP
cv rev shaft rev

Differential forms
/ t V + =
r r
0, ( ) / ( )

" e t e V Q w
T cv
+ =
r r r
r
C. CHAPTER 3 RELATIONS
Performance of heat engines/heat pumps
Thermal efficiency (= sought/bought)
= sought/bought= w
cyc
/q
in
, w
cyc
= q
in
q
out
Carnot cycle q
out
/q
in
= T
L
/T
H
for heat engines, = 1 (T
L
/T
H
)
Coefficient of performance (= sought/bought)
(COP)
cooling
= sought/bought = |q absorbed from cooler body|/|w
cyc
|
(COP)
heating
= sought/bought = |q rejected to hotter body|/|w
cyc
|
Carnot heat pumps, q
L
/q
H
= T
L
/T
H
,
COP
cool
= T
L
/(T
H
T
L
), cop
heat pump
= T
H
/(T
H
T
L
),
HP/ton = 4.715/COP, 1 ton of refrigeration =211 kJ/min or 200 BTU/min
Entropy balance equation
Closed system ds = (q/T)
rev
ds = q/T
b
+ , s
2
s
1
= q/T
b
+
12
,
12
0
Open system
cv
cv
i i e e cv
dS
dt
=
Q
T
+ m s - m s +

Other relations Tds = du + pdv or ds = du/T + (p/T)dv,

Tds = dh vdp or ds = dh/T (v/T) dp
Entropy relations
Ideal gases
ds = (c
p0
/T) dT (R/p) dp, ds = c
v0
dT/T + (R/v) dv
Summary of processes involving ideal gases with the various specific heat assumptions
Constant specific heat Variable specific heat
Entropy s = c
p0
ln (T/T
ref
) R ln (P/Pref)
P
ref
=1 bar, P in bar, T
ref
= 273 K
or
s = c
v0
ln (T/T
ref
) + R ln (v/v
ref
)
where v
ref
= R T
ref
/T
ref
s = s

0
R ln (P/Pref)
P
ref
= 1 bar, s

0
= c
p0
(T) dT/T
Isentropic Proc-
ess
Pv
k
= C, Tv
(k1)
= C, T/P
(k1)/k
=
C
P
2
/P
1
= (T
2
/T
1
)
k/(k1)
v
2
/v
1
= (T
1
/T
2
)
1/(k1)
s
2
= s
2
0
R ln (P
2
/1)= s
1
= s
1
0
R ln
(P
1
/1)
P
2
/P
1
= p
r2
(T
2
)/p
r1
(T
1
)
v
2
/v
1
= v
r2
(T
2
)/v
r1
(T
1
)
2002 by CRC Press LLC
Constant specific heat Variable specific heat
Internal Energy u = c
v0
T
u =
T
T
ref

c
v0
(T) dT or from tables
Enthalpy h = c
p0
T
h =
T
T
ref

c
p0
(T) dT or from tables
Solids, liquids (ds) = c dT T
incomp
( / )
Mixtures
Dalton law P (N,V,T) = p
1
(N
1
,V, T) + p
2
(N
2
,V, T)+.,
Gibbs Dalton law U = N
1
u
1
(T,p
1
) + N
2
u
2
(T,p
2
) +
S = N
1
s
1
(T,p
1
) + N
2
s
2
(T,p
2
)+
Efficiencies: = w/w
s
,adiab.expansion, = w
s
/w, adiab.compress; = w/w
T
, w
T
/w, isothermal
Maximum entropy and minimum energy
dU = T
b
dS P dV (W
other
) T
b

dH = T
b
dS + VdP W
other
T
b

dA = SdT P dV W
other
T
b

dG = S dT + V dP W
other
T
b

dS
U,V,m
0, dS
H,P,,m
0, dU
S,V,m
0, dH
S,P,m
0, dA
T,V,m
0, dG
T,P,m
0
/dt = (1/T
A
1/T
B
) dU
A
/dt + (P
A
/T
A
P
B
/T
B
) dV
A
/dt + (
B1
/T
B

A1
/T
A
) dN
A1
/dt +
(
B2
/T
B

A2
/T
A
) dN
A2
/dt 0
D. CHAPTER 4 RELATIONS
Availability balance equation
Open system
d
dt
(E - T S ) =
Q
(1 -
T
T
) +m - m -
W
- T
c.v 0 c.v. j=1
N
R,j
0
R,j
i
i
e
e cv
cv

0
,
where the absolute stream availability (i.e open system) is defined as
(T,P,T
0
) = e
T
(T,P) T
0
s(T,P); e
T
= h + ke+pe
Stream exergy/availability or relative stream availability, ' =
0
For sssf, w
opt
=
i

e
Loss in stream availability/irreversibility i = w
opt
w = T
0

Closed systems
= u T
0
s + P
0
v, absolute closed system availability
' =
0
, closed system exergy or availability
w
u,opt
=
1

2
Loss in availability or irreversibility i = w
u,opt
w
u
= w
opt
w = T
0
, w
u
= w P
0
v
Availability or Exergetic( Work Potential) Efficiency
Heat engines
Avail
= W
cyc/
W
max,cyc,
W
max,cyc
=

W
cyc
+ T
0

cyc
Heat pumps: COP
avail
or
Avail
= W
min,cyc
/W
cyc
, W
min,cyc
=

W
cyc
+ T
0

cyc
Work devices:
Avail
= W/W
max
, W
u
/W
u,max
, W
min
/W, W
u,min
/W
u
Nonwork systems
Avai l
= (Exergy leaving the system) (Exergy entering the
system).
Thermomechanical (TM) and chemical (C) equilibrium
Exit stream in TM equilibrium
2002 by CRC Press LLC
opt, TM k k,i
i i
i k,i k,e k,0
0 0 1,e
k,e
W
= (T , P , X X ...)
N
- (T , P , X , X ,...)
N
1,i 2,e

,

2
,
where
)

1
=

h
k
T
0

s

k
(neglecting ke and pe)
Exit stream in TMC equilibrium
opt, TMC k k,i
i i
k,i k,e k,0
0 0
k,e
W
= (T , P , X X ...)
N
- (T , P , X , X ,...)
N
1,i 2,i 1, 2,




or

, ,
W W W
Opt TMC Opt TM Chem
= + , where
Chem k k,0
0 0 k k,0 k,e
W
= [ (T , P , x , x ,...) - (T , P , x , x ,...) ]
N
1,e 2,e 1, 2,




,
and where T

= T
0
, P

= P
0
, X
1,e
X
1,
,
' = N
k
*
(exergy relative when exit is at thermal and mechanical equilibrium
only)
k
+ ( N
k
*
(chemical availability)
k
)
Chemical availability of component k =
)

k,e

)

k,
=

g
k
(T
0
,P
0
, X
1,e
,...)

g
k
(T
0
,P
0
, X
1,0
,...)
Psychrometry
Specific Humidity, w = (M
v
/M
a
) (P
v
/P
a
) = 0.622 (p
v
/p
a
)
The degree of saturation = m
v
(T,P)/ m
v
sat
(T,P) = N
v
(T,P)/ N
v
sat
(T,P)
The relative humidity RH = X
v
(T,P)/ X
v
sat
(T,P) = (N
v
(T,P)/N(T,P))/( N
v
sat
(T,P)/
N
sat
(T,P)) = P
v
(T)/ P
v
sat
(T)
ln P
v
sat
(T) = A B/(T+C), T in K, For H2O (0<T<50 C), 0,25 C,50 C correlation
A = 12.21505207, B = 4119.460581, C = 35.208049
RH = (1 X
v
) + X
v
= /(1 X
v
sat
(1 )).
Differential Forms:
( ( ) / ) (( )( / ))

e T s t v T T T w i
o o
+ =
r
r r r
1
E. CHAPTER 5 RELATIONS
Fundamental equation S = S U, V, N ,... N
1 s
, ( )
dS =
S
U
dU +
S
V
dV+
S
N
dN
v U K
U V
k
k

,
(S/U)
V
= 1/T, (S/V)
U
= P/T, (S/N
k
)
U,V
=
k
/T
Integrated form of U U = T S - P V + N
k
k

Equation of state
1
T
=
S
U
,
P
T
=
S
V
,
T
=
S
N
V, N N
k
U, V, N
k

Legendre Transform = x x x
n
( )
, ,.......
0
1 2
= ( ) ,
i i
y = / x ( )
where
(o)
is the basis function . The mth Legendre Transform
(m) (0)
i = 1
m
i
i
= - x
y

2002 by CRC Press LLC
F. CHAPTER 6 RELATIONS
Summary of PVT equations for real gases
P
R
= P/P
c
, T
R
= T/T
C
, v
R
' = v/v
c
', v
c
' = RT
c
/P
c
, Z(T,P) = v(T,P)/v
0
(T,P)
Inflection conditions: (P/v)
T
= 0, (
2
P/v
2
)
T
= 0
b (2/3)N
Avog

3
.
Pitzer Factor w = 1.0 log
10
(P
R
sat
)
TR=0.7
= 1 0.4343 ln (P
R
sat
)
TR=0.7
. Z = Z
(0)
(T
R
, P
R
) + w Z
(1)
(T
R
, P
R
)
If R is a universal gas constant, then a, v, b are based upon mole basis. If R is simply a gas constant, then a, v, b are based upon mass basis
Summary of Equations of State
Name State Equations Constants Remarks
1. Virial Eq. Pv= RT + B
1
P + C
1
P
2
+ D
1
P
3
+ ..., where
B
1
, C
1
, are functions of T or Pv = RT + B/
v + C/v
2
+ ... , and B, C, ... are functions of T.
B
1
, C
1
, D
1
are called 2nd, 3rd,
and 4th virial coefficients that
represent corrections to ideal gas
behavior
P/
u
T = Z
2. Approximate
Virial Eq.
Pv/RT = Z = 1 + B(T)/P
Z = 1 + (P
R
/T
R
) (0.083 (0.422/T
r
1.6
))
where T
R
= T/T
c,
P
R
= P/P
c
B*(T*) = B(T)/ b
o
, b
0
in
m
3
/kmole, T* = T/(/k) For
b
o
, /k. See R.E. Sonntag
and G. Van Wylen
3. Clausius I P = RT/(vb) b = body volume Cannot satisfy inflection
conditions.
4. Van der Waals
(VW)
P = RT/(vb) a/v
2
,

b is a correction for
volume occupied by molecular and repulsive
forces, a/v
2
is a correction for attractive forces
Z
3
(B* +1) Z
2
+ A* Z A*B
*
= 0
a = (27/64)v
c
'
2
P
c
= (27/64)R
2
T
c
2
/P
c
2.667
3

N
Avog
, b = v
c
'/8
=(1/8) RT
c
/P
c
, Z
c
=3/8, A
*
=
(27/64) P
R
/T
R
2
, B* = (1/8) P
R
/T
R
Does not agree with
(P
c
v
c
/RT
c
)
exp
= 0.2 to 0.3
for most gases. Another
form:of the VW relation is
v
3
+ v
2
( bP RT)/P +
v ( a /P) ( a b/P) = 0
5. Berthelot P = RT/(vb) (a/T) (1/v
2
) a = (27/64)(v
c
'
2
T
c
P
c
) = = (27/64)R
2
T
c
3
/P
c
, b = v
c
'/8 = RT
c
/8P
c
2002 by CRC Press LLC
2002 by CRC Press LLC
Name State Equations Constants Remarks
6. Dieterici P = (RT/(vb)) exp {a/(RTv)} a = (4/e
2
) v
c
'
2
P
c
=(4/e
2
) R
2
T
c
2
/P
c
b
= v
c
'/e
2
= RT
c
/(e
2
P
c
), Z
c
= 0.271,
e = exp(1)=2.3026
Developed to provide better
agreement with
experiments.
7. RedlichKwong
(RK)
P = RT/(vb) a/(T
1/2
v (v + b))
or
Z
3
Z
2
+ (A* B*
2
B*) Z A*B
*
= 0
a= 0.4275 v
c
'
2
T
c
0.5
P
c
= 0.4275R
2
T
c
2.5
/P
c
,
b = 0.08664 v
c
' = 0.08664 RT
c
/P
c
,
Z
c
=1/3, A
*
= 0.4275 P
R
/T
R

2.5
, B* =
0.08664 P
R
/T
R
Good accuracy over wide
range and at high pressure.
8. Clausius II P = RT(vb)a/(T(v+c)
2
) a = 27/64 v
c
'
2
T
c
P
c
=(27/64) R
2
T
c
3
/P
c
b = v
c
'(Z
c
1/4) = (RT
c
/P
c
) (Z
c
1/4)
c = v
c
'(3/8 Z
c
)= (RT
c
/P
c
) (3/8 Z
c
)
9. Peng Robinson
P = (RT/(vb)) (a (w,TR)/((v+b(1+2)) (v
+ b (12)))
a = 0.45724 v
c
'
2
Pc = 0.45724R
2
T
c
2
/P
c
(w,T
R
) = (1 + f(w) (1 T
R
(1/2)
))
2
f(w) = 0.37464 + 1.54226 w
0.26992 w
2
b = 0.07780 v
c
' =0.0778 (RT
c
/P
c
),
Z
c
= 0.26
10. SRK equation
P = RT/(vb) a (w,T
R
)/(v(v+b))
A = 0.4275v
c
'
2
Pc = 0.4275R
2
T
c
2
/P
c
, b = 0.08664 v
c
' =0.08664
(RT
c
/P
c
), Z
c
= 1/3
(w,T
R
) = (1 + f(w) (1 T
R
(1/2)
))
2
f(w) =(0.480 + 1.574 w 0.176 w
2
)
11. Generalized Eq.
f
P
R
= T
R
/( v
R
b
*
) a
*
(w,T
R
)/(T
R
n
( v
R
+ c
*
)
a
*
= a/(P
c
v
c
2
T
c
n
), b
*
= b/ v
c
, c
*
=
*
2002 by CRC Press LLC
2002 by CRC Press LLC
Name State Equations Constants Remarks
of state ( v
R
+ d
*)
), c/ v
c
, and d
*
= d/ v
c
. See table
below
12. Compressibility
factor
Pv = ZRT or P
R
v
R
' = Z T
R
v
R
' = v/v
c
', v
c
' =RT
c
/P
c
P
R
= P/P
c
, T
R
= T/T
c
Also fv = ((T
R
, P
R
) Z(T
R
, P
R
)) RT (Chapter
07)
Z=v/v
ideal
for T
R
> 2.5, Z >
1, for T
R
< 2.5 Z < 1 and
has a minimum value. At
T
R
= 1, P
R
= 1, Z can vary
widely. For P
R
> 10 always
use real gas relations.
13. Benedict Webb
Rubin
P = RT/v + (B
2
RTA
2
C
2
/T
2
)/v
2
+ (B
3
R T
A
3
)/v
3
+ A
3
C
6
/v
6
+ (D
3
/(v
3
T
2
))(1+E
2
/v
2
)
exp(E
2
/v
2
)
8 constants. See Table 20A Good accuracy over wide
PVT condition.
14. MartinHou P = RT/(vb) + (A
2
+ B
2
+ C
2
e
KT
)/(vb)
2
+
(A
3
+ B
3
T + C
3
e
KT
)/(vb)
3
+ A
4
/(vb)
4
+ (A
5
+ B
5
T + C
5
e
KT
)/(vb)
5
12 constants evaluated from PvT
data of fluids
Mainly developed for
refrigerants, 1 % accuracy
for v > 0.67 v
c
and T < 1.5
T
c
15. Lee Kessler
P
R
=(T
R
/v
R
)(1+A/ v
R
+B/ v
R
2
+C/ v
R
5
+(D/ v
R
)(
+/ v
R
2
)exp(/ v
R
2
)), Z = P
R v
R
/T
R
See Table A21
16. Beattie
Bridgeman
equation
P v
2
= RT ( v + B
0
(1 ( b/ v)) (1 c/( vT
3
))
(A
0
/ v
2
)(1(a/ v))
See Table A20B
Accurate for v > 1.25 v
c
2002 by CRC Press LLC
2002 by CRC Press LLC
Generalized cubic equation of state P
R
= (T
R
/(v
R
' b
*
)) a
*
(w,T
R
)/(T
R
n
(v
R
' + c
*
)(v
R
*
+ d
*
)),
where a
*
= a/(P
c
v
c
'
2
T
c

n
), b
*
= b/v
c
', c
*
= c/v
c
', d
*
= d/v
c
'
Equation c
*
= c/v
c
' d
*
=c/v
c'
n
(w,T
R
)
b
*
=b/v
c
a
*
=a/(P
c
T
c
n
v
c
'
2
)
ClausiusI 0 0 0 0 0
VW 0 0 0 1 1/8 27/64
Berthlot 0 0 1 1 1/8 (27/64)
ClausiusII (3/8Z
c
) (3/8Z
c
) 1 1 Z
c
1/4 27/64
HorvathLin
(note 3)
0 1 1
(note 3) (note 3)
RK 0.08664 0 1/2 1 0.08664 0.4275
Lorentz 0 0 0 note 1 0
Martin 0 note 2
SRK 0 0 0 0.08664 0.42748
PR
(1+2)0.07780 (12)0.0778
0 0.07780 0.45724
Note 1: T
R
b'/v
c
'
2
a'/v
c
'
2
Note 2: c'/v
c
'
2
T
R
Note 3: = Z
c

4.72
/360, (1+(+1)
1/3
+(+1)
2/3
)
1
, = ((1+f)
2
(12ff
2
))/((1f)
4
(2+f)
2
), =
(12ff
2
)/((2+)+(2+4)f +(+2
2
)f
2
)
Liquids and Solids dv = v
P
dT v
T
dP,
P
= (1/v)(v/T)
P
,
T
= (1/v) (v/P)
T
,
T
= 1/(
T
P)
= (v/P) (P/T)
T
Rackett equation for saturated liquid
sat
c c
(1-T
v / v = Z
R
0.2857
)
G. CHAPTER 7 RELATIONS
Differentials
Exact are denoted as d()
Criterion for exactness
If dZ = M(x,y) dx + N(x,y) dy, then
x
y
M
y
=
N
x

j
(
,
\
,
(

j
(
,
\
,
(
Inexact are denoted by () and are path dependent functions
Thermodynamic relations
du = Tds Pdv
dh = Tds + vdP
da = Pdv sdT
dg = vdP sdT
Gibbs function g = hTs
Helmholtz function a = u Ts
(((a/T)/T))
v
= u, (a/v)
T
= P, and (a/T)
v
= s
2002 by CRC Press LLC
( (g/T)/ (1/T))
P
=h, (g/P)
T
= v, and (g/T)
P
= s
Maxwell's relations (or criteria for exact differential of thermodynamic relations)

j
(
,
\
,
(

j
(
,
\
,
(

j
(
,
\
,
(

j
(
,
\
,
(

j
(
,
\
,
(

j
(
,
\
,
(

j
(
,
\
,
(

j
(
,
\
,
(
T
v
= -
P
s

T
P
=
v
s

P
T
=
s
v

v
s
= -
s
P
s v
s P
v T
P T
Thermodynamic properties
Given the state equation P = P(T,V), properties can be determined using the relations
ds = c
dT
T
+
P
T
dv

= c
dT
T
-
v
T
dP
v
v
p
p
j
(
,
\
,
(

j
(
,
\
,
(
j
(
,
\
,
(

j
(
,
\
,
(
du = c dT + T
P
T
- P dv
v
v

j
(
,
\
,
(
,

,
]
]
]
dh = c dT + v - T
v
T
dP
p
p

j
(
,
\
,
(
,

,
,
]
]
]
]
T
v
2 2
v
c
v
= T ( P / T )

j
(
,
\
,
(

T
p
2 2
p
c
P
= - T ( v / T )

j
(
,
\
,
(

(c - c ) = - T
v
T

P
v
= T v /
p v
2
p
T
p
2
T

j
(
,
\
,
(
,

,
,
]
]
]
]

j
(
,
\
,
(
Fugacity Coefficient
RT d ln () = vdP, = f/P
f
k
(T,P) = f
k
(T,P
sat
) POY
k
POY
k
= exp (
P
P
sat

(v
k
/RT)dP) for any given phase .
Other properties
Isobaric (volume) expansivity,
p
= (1/v) (v/T)
p
, 1/K or 1/R
2002 by CRC Press LLC
isothermal compressibility,
T
= (1/v) (v /P)
T
, 1/bar, 1/atm
Isothermal bulk modulus, B
T
= 1/
T
, bar, atm
Isentropic compressibility,
s
= (1/v) v /P, 1/bar, 1/atm
v/P = v
2
/RT , as P 0
(u
0
(T) u(T,v))/P = + (3/2) (a/RT
3/2
) , as P 0
(h
0
h)/P = (3/2) (a/RT
3/2
) v + v = (3/2) (a/RT
3/2
) , as P 0
Saturation properties and Joule Thomson coefficient
Correlations for h
fg
Empirical correlations for h
fg,n

fg.n
n
c
r n
h
RT
= 1.092
P - 1
0.930 - T
ln ( )
( )
h
fg,n
= 13.52 , where T
n
, normal boiling point, EK
h
fg. n
, heat of vaporization at T
n
P
c
, critical pressure, bar
T
rn
= T
n
/T
c
Correlation for any other T
fg , 2
fg , 1
0.38
R , 2
R , 1
h
h
=
1 - T
1 - T

( )
( )

T
R,2
= T
2
/T
c
Approximate relations
Saturation pressures based on real gas equations
ln P
R
= (dP
R
/dT
R
)
C
(1 1/T
R
)
where dP
R
/dT
R
for various state equations are tabulated below.
(dP
R
/dT
R
)
C
VW 3/8 4
Berthe 3/8 7
ClausII Z
c
7
RK 1/3 5.582
SRK 1/3 4.0536+ 3.05362 f
SRK
(w)
PR 0.3214 4.1051+ 3.1051 f
PR
(w)
Clapeyron Equation
(dP/dT)
sat
= h

/(T v

)

h = h - h v = v - v , , phase, phase
ClausiusClayperon (vapor/ideal gas) an approximate relation

P
P
= exp
h
R

1
T
-
1
T
ref
fg
ref
,

,
]
]
]
j
(
,
\
,
(
or
ln P = A B/T, A = ln P
ref
sat
+ h
fg
/RT
ref
and B =h
fg
/R.
Throttling coefficient
Joule Thomson effect (open system):
JT h
JT
P
p
P
p
= ( T / P)

= -
v - T
v
T

c
v T -
c

j
(
,
\
,
(
,

,
]
]
]

[ ] 1
Asymptotic limits: As p
R
0,
JT
c
P
/v
c
' b/v
c
' 0.08664 for RK equation of state
Z
c
2002 by CRC Press LLC
Inversion curve
JT h
P
= 0, ( T / P) = 0 v = T
v
T

j
(
,
\
,
( ,
Euken coefficient (closed system, throttling at constant volume)

E
= (T/v)
u
= - (T (P/T)
v
- P) /c
v
H. CHAPTER 8 RELATIONS
Mole and mass fractions
Mole fraction (number fraction) X
i
= N
i
/N
Mass fraction Y
i
= m
i
/m
Molecular mass of mixture M
m
= X
i
M
i
Conversion from X
i
to Y
i
: Y
i
= X
i
M
i
/M
m
,
Conversion from Y
i
to X
i
: X
i
= Y
i
M
m
/M
i
Molality, Mo = 10
3
kmole of solute kg of solvent.
Generalized relations
U = U (S, V, N
1
, N
2
... N
n
)
H = H (S, P, N
1
, N
2
... N
n
)
A = A (T, V, N
1
, N
2
... N
n
)
G = G (T, P, N
1
........N
n
)
Differentials
dU = Tds PdV +
j
dN
j
dH = Tds + VdP +
j
dN
j
dA = SdT PdV +
j
dN
j
dG = SdT VdP +
j
dN
j
Thermodynamc potentials
T =
U
S
=
H
S
V, N ... N P, N , ... N
1 n 1 n

j
(
,
\
,
(

j
(
,
\
,
(
P = -
U
V
, V =
H
P
S , N ... N S N .... N
1 n 1 1 n

j
(
,
\
,
(

j
(
,
\
,
(
1
S, V, N .... N
1
S, P, N .... N
1
T, V, N .... N
1
T, P, N .... N
1
=
U
N
=
H
N
A
N
=
G
N
2 n 2 n
2 n 2 n

j
(
,
\
,
(

j
(
,
\
,
(

j
(
,
\
,
(

j
(
,
\
,
(
Partial molal property (B= U, A, H, G, etc.)
T,P N ,N ,..
1
1
1
T,P N ,N ,...
2
1
1 T,P,N ,N ,...
1 2 3 1 1 2
2 3
B
N
b
e.g., v =
V
N
g = ( G / N )

j
(
,
\
,
(

j
(
,
\
,
(

, ,

where ^ g
1
, partial molal Gibbs' function of species 1=
1
= (G/N
1
)
T,P, N2, N3..
Mixture Property
B = N
k

b

k
,

b
1
= b - X
2
d b/dX
2
Gibbs Duhem equation

db
dT
dT
db
dP
dP X db
k
K
k k
+

1
0
)
or

j
(
,
\
,
( +

j
(
,
\
,
(

B
T
dT
B
P
dP N db
P N T N
k k
k
K
, ,

1
0
Differentials of partial molal properties:
d

g
k
=

s
k
dT +

v
k
dP, d

h
k
= Td

s
k
+

v
k
dP,
2002 by CRC Press LLC
d

u
k
= T d

s
k
P d

v
k
, d

h
k
= Td

s
k
+

v
k
dP.

c
pk
=

h
k
/T = T (

s
k
/T)
P
,

c
vk
= T(

s
k
/T)

v
k
Generalized Thermodynamic Relations
d

u
k
=

c
v,k
dT + (T(P/T) P) d

v
k
, d

h
k
=

c
p,k
dT + (

v
k
T (

v
k
/T)) dP,
d

s
k
= (

c
pvk
/T)dT + (P/T)

v
k
dP, d

s
k
= (

c
p,k
/T)dT (

v
k
/T) dP.
PVT relations for ideal or real gas mixtures
Dalton's law (LAP) P = p
k
(T, V, N
k
)
Amagat Leduc law (LAV) V = V
k
(T, P, N
k
)
For ideal gases, volume fraction vf
k
/ X
k
Partial pressure for ideal gases p
k
= X
k
P
Gibbs Dalton law U = N
1
u
1
(T,p
1
) + N
2
u
2
(T,p
2
) +, H = U+PV
S = N
1
s
1
(T,p
1
) + N
2
s
2
(T,p
2
)+,

s
k
= s
k
(T,P,X
k
)
= s
k
0
R ln (p
k
/1)= = s
k

(T,P) R ln X
k
Ideal solution/ideal mixture
Any property other than g, a, or s
If b
k
= h
k
, u
k
, v
k
then

b
k
= b
k
(T,P)
For g
k
, a
k
, s
k

b
k
= b
k
(T,p
k
) for ideal mix of real gases

b
k
= b
k
(T,P, X
k
) for ideal mix of liquids and solids

b
k
= b
k
(T,P) ln X
k
,
b
k
=
k
(T,P) ln X
k
ideal or real gases

s
k
(T, P, X
k
) s
k
(T, P) = R ln X
k
,

g
k
id g
k
(T, P) = RT ln X
k
.
Fugacity of k
d

g
k
=

v
k
dP = RT d ln (

f
k
(T, P, X
k
))
Lewis Randall rule

f
k
id
(T, P, X
k
) = X
k
f
k
(T, P)
Henrys law

f
1
id
(HL) = X
1
(d

f
1
/dX
1
)
x
1
0
Fugacity coefficient

k
=

f
k
/(X
k
P)
(

f
k
id
/f
k
)) = X
k
=

k
id
, i.e.,

f
k
id
= X
k
f
k
= X
k

k
P, ideal mix of real gases
For ideal gas mixtures,

f
k
ig
= P X
k
= p
k
Activity

k
= (

f
k
(T, P, X
k
)/f
k
(T, P)),

k

id
= X
k

g
k
(T, P,X
k
) g
k
(T, P) = RT ln

k
= (

v
k
(T, P,X
k
) v
k
(T, P))dP

g
k
(T,P, X
k
)

g
k
(T, P
o
) = RT ln ((

k
(T,P)/

k
(T,P
o
; T,P))
= RT ln (

f
k
(T, P)/

f
k
(P
o
,T))
Activity coefficient,
k

k
=

k
/

k
id

g
k

g
k
id
= R T ln (
k
) = R T ln (

k
/
k
)
DuhemMargules relation
k
N
k
d ln (X
k

k
) or
k
X
k
d ln (X
k

k
) = 0
Excess Property

(

) b b b
k
E
k k
id
, B
E
= BB
id
=
k
N
k
(

b
k
b
k
)
( g
E
/T)/(1/T) = h
E
,
( g
E
/P)
T
= v
E
, and s
E
= ( g
E
/T)
Mixing rules
2002 by CRC Press LLC
=
k
X
k

k
, = (
k
X
k

k
1/2
)
2
, = (
k
X
k

k
1/3
)
3
= (1/4)
k
X
k

k
+ (3/4) (
k
X
k

k
1/3
)(
k
X
k

k
2/3
), =
k
X
j
X
k

kj
,
Kays rule T
cm
= X
1
T
c1
+ X
2
T
c2
+ ..., and P
cm
= X
1
T
c1
+ X
2
T
c2
+ .
RK and Other rules: a
m
= (
k
X
k
a
k
1/2
)
2
, b
m
=
k
X
k bk
a
m
=
i

j
X
i
X
j
a
ij
, b
m
=
i
X
i bi
,
I. CHAPTER 9 RELATIONS
Phase rule
F = K + 2 , F: degrees of freedom, K: components, : phases

g
1(1)
=

g
1(2)
=

g
1(3)
= ... =

g
1()
,

g
2(1)
=

g
2(2)
=

g
2(3)
= ... =

g
1()
,
, and

g
k(1)
=

g
k(2)
=

g
k(3)
= ... =

g
1()
,
or

f
k(f)
=

f
k(g)
.
Ideal solution model X
k()
f
k()
(T,P) = X
k()

f
k())
f
k
(T,P) = f
k
(T,P
sat
) POY,
POY = exp (
P
P
sat

(v/RT)dP for any given phase .

Ideal liquid solution but vapor is an ideal gas (Rauolt;s law: p
k
= X
k()
P
k
sat
)
Boiling point elevation T = ( T
pure
2
R/h
fg
) ln X
k(l)
or T k
b
Mo
solute
,
Azeotropic X
k(g)
= X
k(l)
Dissolved gases = X
k (l)
= p
k
/(P
k
sat
)
Henrys law p
k
= X
k,l
H
k
(T,P), H
k
(T,P) = P
k
sat
(POY)
k(l)
.
Deviation from Rauolts law: p
k
=
k(l)
X
k,l
p
k
sat
or
k,l
= p
k
/p
k,Raoult
J. CHAPTER 10 RELATIONS
Criteria
dS
U,V,m
0, (d
2
S)
U,V,m
< 0, dS
H,P,,m
0, d
2
S
HPV,m
< 0,
dU
S,V,m
= 0, d
2
U
S,V,m
> 0, dH
S,P,m
= 0, d
2
H
S,P,m
> 0
dA
T,V,m
= 0, d
2
A
T,V,m
> 0, dG
T,P,m
= 0, d
2
G
T,P,m
> 0
D
S S
S S
S S S
UU UV
VU VV
UU VV VU 2
2
0 >
Thermal stability
2
S/U
2
< 0 or c
v
> 0
Mechanical stability (P/V)
T
< 0
Kestin formulae
If dS = (1/T) dU + (P/T) dV =S
U
(U,V) dU +S
V
(U,V) dV, then
d
2
S = d(1/T) dU + d(P/T) dV = d(S
U
(U,V)) dU + d(S
V
(U,V)) dV,
= (g
metastable/unstable
g
stable
)/T
Spinodal Points : (P/V)
T
= 0
K. CHAPTER 11 RELATIONS
Thermochemistry
Air composition mole%: N
2
= 79%, O
2
= 21 %
mass %: N
2
= 77%, O
2
= 23%
Molecular weight of air: 28.97 kg/kmol or 28.97 lb/lbmol
2002 by CRC Press LLC
Process/Variable Formulae
Stoichiometric combustion Complete combustion and no O
2
in products
A:F (mass basis)
air required in kg
kg of fuel
j
(
,
\
,
(
A:F (mole basis)
air required in k moles
k mole of fuel
j
(
,
\
,
(
Excess air %
A:F - A:F
A:F
x 100
stoich
stoich
( )
( )

Air supplied as % theoretical air or

stoichiometric Ratio (SR)
air supplied
theoretical stoich. air
x 100
Equivalence ratio () = 1/(SR)
stoich
stoich
A:F
A:F
=
F:A
F:A
( )
( )
( )
( )
Lean mixture
< 1
Rich mixture
> 1
Partial pressure of water vapor in products
, where denotes number of gaseous moles in
products.
Total enthalpy, h
( )
Enthalpy of formation h
f
0
( )
+ thermal enthalpy

h
298 to T
( )
Enthalpy of reaction, H
R

( ) PROD,T REACT,T
H - H
Enthalpy of combustion,
c
H
( )
H H
C R

Heating value (HV)
HV = - H
R,298

= H - H
REACT,298 PROD,298
Higher heating value, HHV = HV with H
2
O in liquid form
Lower heating value, LHV = HV with H
2
O in gaseous state
Internal energy for use u h P v h RT if species i is ideal gas
i i i i
,
Combustion efficiency
comb
=
Actual heat release
Theoretical heat release

Boiler efficiency
boiler
=
Heat transferred to water / Kg of fuel
Higher heating value / Kg of fuel

2002 by CRC Press LLC

Overall thermal efficiency
thermal
=
Elec. work / kg of fuel
Higher heating value / kg of fuel

Energy and entropy balance for reacting systems

dE
cv
/dt =

Q
cv

W
cv
+
k,i

Nk
e
T,k

k,e

Nk
e
T,k
, e
T,k
= ( h+ k e + p e)
k
dS
cv
/dt =

Q
cv
/T
b
+
k,i

Nk

sk

k,e

Nk

s
k
+

Mole balance
dN
k
/dt =

N
k,i
+

N
k, gen

N
k, e
L. CHAPTER 12 RELATIONS
dU = TdS P dV T
dH = T dS + V dP T
dA = S dT P dV T
dG = S dT + V dP T
T (S/N
k
)
U,V
=T (S/N
k
)
H,P
= (U/N
k
)
S,V
= (A/N
k
)
T,V
= (G/N
k
)
T,P
=

g
k
=
k
Process/Variable/Condition Formula
Direction of reaction
0, dG
T,P
0 or (
k
dN
k
)

0,
dG
T, P
= (
k k
dN
k
)

0,
G = N g T, p , g T, p
k
k
k k k k
( ) ( )

Equilibrium condition
= 0,


g d N = g d N =
k
k
k
k
dG = 0 , dA
T,P T,V
0
Chemical potential
j
j T,P,N ...
j
j T,V,n ...
= ( G / N )
= ( A / N )
2
2

Chemical force potential (e.g.
H
2
+ 1/2 O
2
H
2
O)
chem, react
H O chem, prod
H O
F = g -
1
2
g F = g
2 2 2
,
F
chem, react
> F
chem Prod
Gibbs function useful for
chemical reactions, P in bars
i i i i
o
i
o
i
i i
o
i
i
o
i i
i
g =
h
- T s =
h
- T s - R T (PX )
g g T RT (PX ) see TableA to A for g
g g T P R T X

{ } ln /

( ) ln / ,

( , ) ln
1
1 8 19
]
+
+
Equilibrium constant, K
0
(T)
K T = (- G /R T )
o 0
( ) exp , G
0
= G
0
RHS
G
0

LHS
Equilibrium constant, K
0
(T) from
elementary reactions
K
0
(T)exp (A (B/T)), T in K, A=
k
A
k
, B=
k
B
k
, (e.g.: CO
2
CO +1/O
2
, A = 1A
CO
+(1/2) A
O
2

1A
CO
2
), use Table A28A
Vant Hoff relation
ln K
0
(T) = A B/T, A = A = ln K
ref
o
+ (H
R
o
/ R) (1/T
ref
), B
= (H
R
o
/ R).
2002 by CRC Press LLC
8 1 19
M. CHAPTER 13 RELATIONS
g = h Ts
a = u Ts
d(E
cv
T
0
S
cv
)/dt =

( )
,
,
Q
T
T
R j
R j
1
0
+ (

N
k
)
k
)
i
(

N
k

)

k
)
e

W
cv

I
Variable Formula
Entropy
s T, P = s T - R
P
1
( )

( ) ln , P in bar
Absolute availability of species j (not
availability)
j j
o j
=
h
- T s

Exergy or availability

j

j,0
Chemical availability
^ g
k
(T
0
,P
0
, X
1,e
,..)^ g
k
(T
0
,P
0
, X
1,
,..)
Fuel availability, avail
f
with fuel at 1
bar, air at 1 bar
N
k,i
^ g
k,i
(T
0
,P
0
, X
1,0
,..) N
k,e
^ g
k,e
(T
0
,P
0
, Y
1,
,..)
Irreversibility/lost availability, I I = W
opt
W
act
W
opt, TM
, W
chem
but not of fuel only w
opt, TM
= - T P X X
i e e e
( , , , ..)
0 0 1 2
w T P X X - T P X X
e
chem e e

( , , , ..) ( , , , ..)
0 0 1 2 1 2
Availability efficiency

avail
= W/Avail
F
.
Voltage in fuel cell, number of
electrons from C
x
H
y
is (4x+y).
(volts)
-5
V =
G in kJ / K mole x 1.036 x 10
No of electrons per molecule of fuel
( )
( )
2002 by CRC Press LLC