APPENDIX C

C. FORMULAE

A. CHAPTER 1 RELATIONS
Gravitational acceleration g(r) = G mE/r2, r in m
G = 6.67x1014 m3/kg s2 (or kN m2/kg2)
mE, mass of earth = 5.97x1024 kg
rE, radius of earth = 6.37x106 m
At earth's surface g(rE) = 9.807 m/s2
gc = 32.174 lbm ft/s2 lbf
NAvog = 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 lbf/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 hP = 6.6251037 kJ s/molecule
Boltzmann's constant kB = 1.3801026 kJ/K molecule = R /NAvog
Speed of light in vacuum c0 = 2.998108 m/s, 9.836108 ft/s
One light year = 5.8751012 miles
StefanBoltzmann constant R = 5.6701011 kW/m2 K4, 0.1714108 Btu/h ft2 R4
Ideal gas law
P v = RT, PV =m R T
PV = nRT, Pv = R T
kPa m3 bar m3 ft lbf
R = 8.314 , 0.08314 ,1545
k mole K k mole K lbmoleo R
3 3
atm ft psia ft
R = 0.730 , 10.7
lbmole R lbmole R
pk/P = Nk/N = Xk.
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 ft3
Properties of pure substances
x = mg/(mf + mg)
v = x vg + (1 x)vf or vf + x(vg vf)
u, h, and s relations are similar to the v expression
Mathematical background
Point function or property
M N
For two variables dz = Mdx + Ndy, =
y x x y
Z x Y
Cyclic relation = -1
x y y z Z x

u (u / z )y z 1
Other useful relations = , =
x y (x / z )y x y (x / z )y

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 Homogeneous function
( x1 .... x s) = m ( x1 .... x s)

i

xi
x
= m , Euler equation

Z = Z(a,b,x,y) = xm 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+ 1g +
2h, F/x=0, F/y=0, F/z=0.
r r r r r
Stokes theorem F ds = cs ( F) dA
r r r r
Gauss divergence theorem cs F dA = cv ( F) dV
Microscopic thermodynamics
LJ Potential and Force
(l) = 4 ((l0/l)12 (l0/l)6)
F(l) =d/dl,
/kB in K 0.,77 Tc, 1.15 TBP, 1.9 TMP
(nm) 0.84 v c1/3, 1.66 v b1/3, 1.122 v m1/3
c:critical, b: boiling, m: melting
lmean = 1/(21/2n2)
Vrms = (3kBT/m))1/2= (3 R T/M))1/2
Vavg = {8/(3)}1/2Vrms, Vmps = (2kBT/m))1/2= (2 R T/M))1/2
2
where Vrms = Vx2 +Vy2 +Vz2 is based on the three velocity components
Sound Speed c = kRT / M
Kn = lmean/d

B. CHAPTER 2 RELATIONS
Closed systems
Q = W, Q W = dE, Q12 W12 = E2 E1
Wout positive, Qin positive
E = U + KE + PE
W rev = P dV
H = U + PV, h = u + Pv
cv = (u/T)v, cP = (h/T)P, (kJ/(kg K)), (cp/cv) = k
Ideal gases
cv,0 = du/dT, cP,0 = dh/dT, (cpo cvo) = R
(Note: Suffixes p and v are unnecessary for ideal gases. Instead let these be c10 and c20)
Monatomic gases
cP,0 = (5/2) R
2 2
(u0,2 - u0,1) = 1 cvo dT , (h0,2 - h0,1) = 1 cpo dT
Open systems
Mass accounting or conservation
dmcv/dt = m i m e
dmcv/dt = k mk,i k mk,e, multiple components, single inlet and exit
Energy accounting or conservation
dEcv/dt = Q cv + m
cv W i (h+ke+pe)i m
e (h + ke+ pe)e
mcv = dV / v , E cv = (u + ke + pe) dV / v

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 where, ke (kJ/kg) =V2/2000, pe(kJ/kg) = g Z/1000 (SI)
ke (BTU/lb) V2/(2 gc J), pe (BTU/lb) =g Z/(gc J)
methalpy, eT = = h + ke + pe
wrev = v dP
Bernoulli type of equation applied in fluid mechanics, (fM: Moody friction factor)
Pi Vi2 P V2
+ + gz i ( e + e + gz e ) = (u i u e ) ,
2 2 .
Head Loss = (u i u e ) / g = fM LV2 / (2gD)
Uniform system and uniform flow processes
Qcv Wcv = (m2u2 m1u1)cv + (mehe mihi), assumed, ke and pe =0
where mi me = (m2 m1)cv
( wcv )rev = ( wshaft )rev = - vdP
Differential forms
r r r r r r
/ t + V = 0 , (e) / t + (e V) = Q " w
T cv

C. CHAPTER 3 RELATIONS
Performance of heat engines/heat pumps
Thermal efficiency (= sought/bought)
= sought/bought= wcyc/qin, wcyc = qin qout
Carnot cycle qout/qin = TL/TH for heat engines, = 1 (TL/TH)
Coefficient of performance (= sought/bought)
(COP)cooling = sought/bought = |q absorbed from cooler body|/|wcyc|
(COP)heating = sought/bought = |q rejected to hotter body|/|wcyc|
Carnot heat pumps, qL/qH = TL/TH,
COPcool= TL/(TH TL), cop heat pump = TH/(TH TL),
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/Tb + , s2 s1 = q/Tb + 12, 12 0
dScv Q
Open system = cv + m i si - m
e se + cv
dt T
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 = (cp0/T) dT (R/p) dp, ds = cv0 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 = cp0 ln (T/Tref) R ln (P/Pref) s = s 0 R ln (P/Pref)
Pref =1 bar, P in bar, Tref = 273 K Pref = 1 bar, s 0 = cp0 (T) dT/T
or
s = cv0 ln (T/Tref) + R ln (v/vref)
where vref = R Tref/Tref
Isentropic Proc- k s = s2 0 R ln (P2/1)= s1 = s1 0
R ln
Pv = C, Tv(k1) = C, T/P(k1)/k = 2
ess (P1/1)
C
k/(k1) P2/P1 = pr2(T2)/pr1(T1)
P2/P1 = (T2/T1)
1/(k1) v2/v1 = vr2(T2)/vr1(T1)
v2/v1 = (T1/T2)

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 Constant specific heat Variable specific heat
T
Internal Energy u = cv0 T
u= cv0 (T) dT or from tables
Tref

T
Enthalpy h = cp0 T
h= cp0 (T) dT or from tables
Tref

Solids, liquids (ds )incomp = c (dT / T)

Mixtures
Dalton law P (N,V,T) = p1(N1,V, T) + p2 (N2,V, T)+.,
Gibbs Dalton law U = N1 u 1 (T,p1) + N2 u 2 (T,p2) +
S = N1 s 1 (T,p1) + N2 s 2 (T,p2)+
Efficiencies: = w/ws,adiab.expansion, = ws/w, adiab.compress; = w/wT, wT/w, isothermal
Maximum entropy and minimum energy
dU = Tb dS P dV (Wother) Tb
dH = TbdS + VdP Wother Tb
dA = SdT P dV Wother Tb
dG = S dT + V dP Wother Tb
dSU,V,m 0, dSH,P,,m 0, dUS,V,m 0, dHS,P,m 0, dAT,V,m 0, dGT,P,m 0
/dt = (1/TA 1/TB) dUA/dt + (PA/TA PB/TB) dVA/dt + (B1/TB A1/TA) dNA1/dt +
(B2/TB A2/TA) dNA2/dt 0

D. CHAPTER 4 RELATIONS
Availability balance equation
d T0
Open system (E c.v - T 0 Sc.v.) = Nj=1 Q R,j (1 - i i - m
) +m e e - W
cv - T0 cv ,
dt T R,j
where the absolute stream availability (i.e open system) is defined as
(T,P,T0) = eT (T,P) T0 s(T,P); eT = h + ke+pe
Stream exergy/availability or relative stream availability, ' = 0
For sssf, wopt = i e
Loss in stream availability/irreversibility i = wopt w = T0
Closed systems
= u T0 s + P0 v, absolute closed system availability
' = 0, closed system exergy or availability
wu,opt = 1 2
Loss in availability or irreversibility i = wu,opt wu = wopt w = T0 , wu = w P0 v
Availability or Exergetic( Work Potential) Efficiency
Heat engines Avail = Wcyc/Wmax,cyc, Wmax,cyc = Wcyc + T0 cyc
Heat pumps: COP avail or Avail = Wmin,cyc/Wcyc, Wmin,cyc = Wcyc + T0 cyc
Work devices: Avail = W/Wmax, Wu/Wu,max, Wmin/W, Wu,min/Wu
Nonwork systems Avail = (Exergy leaving the system) (Exergy entering the
system).
Thermomechanical (TM) and chemical (C) equilibrium
Exit stream in TM equilibrium

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 W opt, TM = k k,i (T i , P i , X1,i X 2,i ...) N
k,i - k,e k,0 (T 0 , P 0 , X1,e , X 2,e ,...) N
k,e ,
)
where 1 = h k T0 s k (neglecting ke and pe)
Exit stream in TMC equilibrium
W opt, TMC = k k,i (T i , P i , X1,i X 2,i ...) N
k,i - k,e k,0 (T 0 , P 0 , X1, , X 2, ,...) N k,e
or W = W +W , where
Opt ,TMC Opt ,TM Chem

W Chem = [ k k,0 (T 0 , P 0 , x 1,e , x ,...) - k k,0 (T , P , x 1, , x 2, ,...) ] N

k,e ,
2,e

and where T = T0, P = P0, X1,e X1,,

' = Nk* (exergy relative when exit is at thermal and mechanical equilibrium
only)k+ ( Nk* (chemical availability)k)
) )
Chemical availability of component k = k,e k, = g k (T0,P0, X1,e,...) g k (T0,P0, X1,0,...)
Psychrometry
Specific Humidity, w = (Mv/Ma) (Pv/Pa) = 0.622 (pv/pa)
The degree of saturation = mv(T,P)/ msat sat
v (T,P) = Nv(T,P)/ N v (T,P)

The relative humidity RH = Xv(T,P)/ X sat sat

v (T,P) = (Nv(T,P)/N(T,P))/( N v (T,P)/
Nsat(T,P)) = Pv(T)/ Pvsat (T)
ln Pvsat(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 Xv) + Xv = /(1 X sat v (1 )).
Differential Forms:
r r r r
i
( (e Tos) / t ) + v = ((T)(1 To / T)) w
E. CHAPTER 5 RELATIONS
Fundamental equation S = S ( U, V, N1 ,..., Ns)
S S S
dS = dU + dV + dN k
U v V U K N k U ,V

(S/U)V = 1/T, (S/V)U = P/T, (S/Nk)U,V = k/T

Integrated form of U U = T S - P V + k Nk
1 S P S S
Equation of state = , = , k =
T U V, N T V N T Nk U, V, N
Legendre Transform = ( 0) = (x1 , x 2 ,.......x n ) , yi = ( / x i )
m
where (o) is the basis function . The mth Legendre Transform = -
(m) (0)
x y
i=1
i i

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 F. CHAPTER 6 RELATIONS
Summary of PVT equations for real gases
PR = P/Pc, TR = T/TC, vR' = v/vc', vc' = RTc/Pc, Z(T,P) = v(T,P)/v0 (T,P)
Inflection conditions: (P/v)T = 0, (2P/v2)T = 0
b (2/3)NAvog 3.
Pitzer Factor w = 1.0 log10 (PRsat)TR=0.7 = 1 0.4343 ln (PRsat)TR=0.7. Z = Z(0) (TR, PR) + w Z(1) (TR, PR)
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 + B1P + C1P2 + D1P3 + ..., where B1, C1, D1 are called 2nd, 3rd, P/uT = Z
B1, C1, are functions of T or Pv = RT + B/ and 4th virial coefficients that
v + C/v2 + ... , and B, C, ... are functions of T. represent corrections to ideal gas
behavior
2. Approximate Pv/RT = Z = 1 + B(T)/P B*(T*) = B(T)/ b o, b 0 in
Virial Eq. m3/kmole, T* = T/(/k) For
Z = 1 + (PR/TR) (0.083 (0.422/Tr1.6))
where TR = T/Tc, PR = P/Pc bo, /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 P = RT/(vb) a/v2, b is a correction for a = (27/64)vc' 2 Pc = (27/64)R2 Does not agree with
(VW) volume occupied by molecular and repulsive Tc2/Pc 2.6673 NAvog, b = vc'/8 (Pcvc/RTc) exp = 0.2 to 0.3
forces, a/v2 is a correction for attractive forces =(1/8) RTc/Pc, Zc =3/8, A* = for most gases. Another
Z3 (B* +1) Z2 + A* Z A*B* = 0 (27/64) PR/TR2, B* = (1/8) PR/TR form:of the VW relation is
v 3 + v 2 ( b P R T)/P +
v ( a /P) ( a b /P) = 0
5. Berthelot P = RT/(vb) (a/T) (1/v2) a = (27/64)(vc'2TcPc) = = (27/64)R2
Tc3/Pc, b = vc'/8 = RTc/8Pc

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 Name State Equations Constants Remarks
6. Dieterici P = (RT/(vb)) exp {a/(RTv)} a = (4/e2) vc'2 Pc =(4/e2) R2 Tc2/Pc b Developed to provide better
= vc'/e2 = RTc/(e2Pc), Zc = 0.271, agreement with
e = exp(1)=2.3026 experiments.
7. RedlichKwong P = RT/(vb) a/(T1/2v (v + b)) a= 0.4275 vc'2 Tc0.5 Pc = 0.4275R2 Good accuracy over wide
(RK) Tc2.5/Pc, range and at high pressure.
or b = 0.08664 vc' = 0.08664 RTc/Pc,
Z3 Z2 + (A* B* 2 B*) Z A*B* = 0 Zc =1/3, A* = 0.4275 PR/TR 2.5, B* =
0.08664 PR/TR
8. Clausius II P = RT(vb)a/(T(v+c)2) a = 27/64 vc'2 Tc Pc =(27/64) R2
Tc3/Pc
b = vc'(Zc1/4) = (RTc/Pc) (Zc1/4)
c = vc'(3/8 Zc)= (RTc/Pc) (3/8 Zc)
2
9. Peng Robinson P = (RT/(vb)) (a (w,TR)/((v+b(1+2)) (v a = 0.45724 vc' Pc = 0.45724R2
+ b (12))) Tc2/Pc
(w,TR) = (1 + f(w) (1 TR(1/2)))2

f(w) = 0.37464 + 1.54226 w

0.26992 w2
b = 0.07780 vc' =0.0778 (RTc/Pc),
Zc = 0.26
10. SRK equation P = RT/(vb) a (w,TR)/(v(v+b)) A = 0.4275vc' 2 Pc = 0.4275R2
Tc2/Pc, b = 0.08664 vc' =0.08664
(RTc/Pc), Zc= 1/3
(w,TR) = (1 + f(w) (1 TR(1/2)))2

f(w) =(0.480 + 1.574 w 0.176 w2)

11. Generalized Eq. PR = TR/( vR b*) a* (w,TR)/(TRn ( vR + c*) a* = a/(Pc vc 2 Tcn), b* = b/ vc , c* =
f *

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 Name State Equations Constants Remarks
of state ( vR + d*)), c/ vc , and d* = d/ vc . See table
below
12. Compressibility Pv = ZRT or PR vR' = Z TR Z=v/videal for TR > 2.5, Z >
factor vR' = v/vc ', vc' =RTc/Pc 1, for TR < 2.5 Z < 1 and
PR = P/Pc, TR = T/Tc has a minimum value. At
TR = 1, PR = 1, Z can vary
Also fv = ((TR, PR) Z(TR, PR)) RT (Chapter
widely. For PR > 10 always
07) use real gas relations.
13. Benedict Webb P = RT/v + (B2 RTA2C2/T2)/v2 + (B3R T 8 constants. See Table 20A Good accuracy over wide
Rubin A3)/v3 + A3C6/v6 + (D 3 /(v3T2))(1+E2/v2) PVT condition.
exp(E2/v2)
14. MartinHou P = RT/(vb) + (A2 + B2 + C2 eKT)/(vb)2 + 12 constants evaluated from PvT Mainly developed for
(A3 + B3T + C3 eKT)/(vb)3 + A4/(vb)4 + (A5 data of fluids refrigerants, 1 % accuracy
+ B5T + C5 eKT)/(vb)5 for v > 0.67 vc and T < 1.5
Tc
15. Lee Kessler PR=(TR/vR)(1+A/ vR +B/ vR 2+C/ vR 5+(D/ vR )( See Table A21
+/ vR 2)exp(/ vR 2)), Z = PR vR /TR

16. Beattie P v 2 = R T ( v + B0 (1 ( b / v )) (1 c/( v T3)) See Table A20B Accurate for v > 1.25 vc
Bridgeman (A0/ v 2)(1(a/ v ))
equation

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 Generalized cubic equation of state PR = (TR/(vR' b*)) a* (w,TR)/(TRn (vR ' + c*)(vR* + d*)),
where a* = a/(Pc vc'2 Tc n), b* = b/vc', c* = c/vc', d* = d/vc'

Equation c* = c/vc' d*=c/vc' n (w,TR) b*=b/vc a*=a/(PcTcn vc'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 (3/8Zc) (3/8Zc) 1 1 Zc 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: TR b'/vc'2 a'/vc'2

Note 2: c'/vc'2 TR
Note 3: = Zc 4.72/360, (1+(+1)1/3 +(+1)2/3)1, = ((1+f)2 (12ff2))/((1f)4(2+f)2), =
(12ff2)/((2+)+(2+4)f +(+22)f2)
Liquids and Solids dv = vP dT vT dP, P= (1/v)(v/T)P, T = (1/v) (v/P)T, T = 1/(T P)
= (v/P) (P/T)T
0.2857
Rackett equation for saturated liquid vsat / vc = Z(1-T
c
R )

G. CHAPTER 7 RELATIONS
Differentials
Exact are denoted as d()
Criterion for exactness
M N
If dZ = M(x,y) dx + N(x,y) dy, then =
y x x y
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

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 ( (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)
T P
= -
v s s v

T v
=
P s s P

P s
=
T v v T

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

dT v
= cp - dP
T T p
P
du = cv dT + T - P dv
T v
v
dh = cp dT + v - T dP
T p

cv
v = T ( P / T )v
2 2

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

T
2
v P
(cp - cv ) = - T = T v 2p / T
T p v T

Fugacity Coefficient
RT d ln () = vdP, = f/P
fk (T,P) = fk (T,Psat) POYk
P

POYk = exp ( (vk/RT)dP) for any given phase .

Psat
Other properties
Isobaric (volume) expansivity, p = (1/v) (v/T)p, 1/K or 1/R

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 isothermal compressibility, T = (1/v) (v /P)T, 1/bar, 1/atm
Isothermal bulk modulus, BT = 1/T, bar, atm
Isentropic compressibility, s = (1/v) v /P, 1/bar, 1/atm
v/P = v2/RT , as P 0
(u0(T) u(T,v))/P = + (3/2) (a/RT3/2) , as P 0
(h0 h)/P = (3/2) (a/RT3/2) v + v = (3/2) (a/RT3/2) , as P 0
Saturation properties and Joule Thomson coefficient
Correlations for hfg
hfg.n ( ln P c - 1)
Empirical correlations for hfg,n = 1.092
RTn ( 0.930 - T r n )
hfg,n = 13.52 , where Tn, normal boiling point, EK
hfg. n, heat of vaporization at Tn
Pc, critical pressure, bar
Trn = Tn/Tc
(1 - T R , 2)
0.38
hfg , 2
Correlation for any other T =
hfg , 1 (1 - T R , 1)
TR,2 = T2/Tc
Approximate relations
Saturation pressures based on real gas equations
ln PR = (dPR/dTR)C (1 1/TR)
where dPR/dTR for various state equations are tabulated below.
Zc (dPR/dTR)C
VW 3/8 4
Berthe 3/8 7
ClausII Zc 7
RK 1/3 5.582
SRK 1/3 4.0536+ 3.05362 fSRK(w)
PR 0.3214 4.1051+ 3.1051 fPR(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 hfg 1 1
= exp - or
P ref R T ref T
sat
ln P = A B/T, A = ln Pref + hfg/RTref and B =hfg/R.
Throttling coefficient
JT = (T / P )h
Joule Thomson effect (open system):
v
v - T
T P v[ P T - 1 ]
JT = - =
cp cp
Asymptotic limits: As pR 0, JT cP/vc' b/vc' 0.08664 for RK equation of state

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 v
Inversion curve JT = 0, (T / P )h = 0, v = T
T P
Euken coefficient (closed system, throttling at constant volume)
E = (T/v)u = - (T (P/T)v - P) /cv

H. CHAPTER 8 RELATIONS
Mole and mass fractions
Mole fraction (number fraction) Xi = Ni/N
Mass fraction Yi = mi/m
Molecular mass of mixture Mm = Xi Mi
Conversion from Xi to Yi: Yi = XiMi/Mm,
Conversion from Yi to Xi: Xi = YiMm/Mi
Molality, Mo = 103kmole of solute kg of solvent.
Generalized relations
U = U (S, V, N1, N2 ... Nn)
H = H (S, P, N1, N2 ... Nn)
A = A (T, V, N1, N2 ... Nn)
G = G (T, P, N1 ........Nn)
Differentials
dU = Tds PdV + jdNj
dH = Tds + VdP + jdNj
dA = SdT PdV + jdNj
dG = SdT VdP + jdNj
Thermodynamc potentials
U H
T = =
S V, N ... Nn
S P, N1 , ... Nn
1

U H
P = - ,V =
V S , N1 ... Nn
P S N1 .... Nn
1

U H
1 = =
N1 S, V, N .... Nn
N1 S, P, N .... Nn
2 2

A G
= =
N1 T, V, N .... Nn
N1 T, P, N .... Nn
2 2

Partial molal property (B= U, A, H, G, etc.)

B V
= b1 , e.g., v1 = , g = (G / N1 )T,P,N2,N3,...
N1 T,P N ,N ,.. N2 T,P N ,N ,... 1
1 2 3 1 1 2

where g^1, partial molal Gibbs' function of species 1=1 = (G/N1) T,P, N2, N3..
Mixture Property
B = Nk b k , b 1 = b - X2 d b /dX2
Gibbs Duhem equation
db db K ) B B

K
dT + dP X k db k = 0 or dT + dP k =1 N k db k = 0
dT dP k =1
T P ,N P T ,N
Differentials of partial molal properties:
d g k = s k dT + v k dP, d h k = Td s k + v kdP,

2002 by CRC Press LLC

 d u k = T d s k P d v k, d h k = Td s k + v kdP.
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 = pk (T, V, Nk)
Amagat Leduc law (LAV) V = Vk (T, P, Nk)
For ideal gases, volume fraction vfk / Xk
Partial pressure for ideal gases pk = Xk P
Gibbs Dalton law U = N1 u 1 (T,p1) + N2 u 2 (T,p2) +, H = U+PV
S = N1 s 1 (T,p1) + N2 s 2 (T,p2)+, s k= s k (T,P,Xk)
= s k0 R ln (pk/1)= = s k (T,P) R ln Xk
Ideal solution/ideal mixture
Any property other than g, a, or s
If bk = hk, uk, vk then b k = b k(T,P)
For gk, ak, sk
b k = b k (T,pk) for ideal mix of real gases
b k= b k (T,P, Xk) for ideal mix of liquids and solids
b k= b k(T,P) ln Xk,
b k = k(T,P) ln Xk ideal or real gases
s k(T, P, Xk) s k(T, P) = R ln Xk, g kid g k (T, P) = R T ln Xk.
Fugacity of k
d g k = v k dP = R T d ln ( f k(T, P, Xk))
Lewis Randall rule f kid(T, P, Xk) = Xk fk(T, P)
Henrys law f 1id(HL) = X1(d f 1/dX1) x1 0
Fugacity coefficient
k = f k/(Xk P)
( f kid/fk)) = Xk = kid, i.e., f kid = Xk fk = Xk k P, ideal mix of real gases
For ideal gas mixtures, f kig = P Xk = pk
Activity k
k = ( f k(T, P, Xk)/fk(T, P)), k id = Xk
g k(T, P,Xk) g k (T, P) = R T ln k= ( v k (T, P,Xk) v k(T, P))dP
g k (T,P, Xk) g k(T, Po) = R T ln (( k(T,P)/ k(T,Po; T,P))
= R T ln ( f (T, P)/ f (Po,T))
k k
Activity coefficient, k
k = k/ kid
g k g kid = R T ln (k) = R T ln ( k/k)
DuhemMargules relation kNk d ln (Xkk) or kXk d ln (Xkk) = 0
Excess Property b E = (b b id ) , BE = BBid=kNk( b k b k)
k k 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

 = kXkk, = (kXkk1/2)2, = (kXkk1/3)3
= (1/4) kXkk + (3/4) (kXkk1/3)(kXkk2/3), = kXjXkkj,
Kays rule Tcm = X1 Tc1 + X2 Tc2 + ..., and Pcm = X1Tc1 + X2Tc2 + .
RK and Other rules: a m = (kXk a k1/2)2, b m = kXk b k
a m = ijXiXj a ij, b m = iXi b i,
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 = f .
k(f) k(g)
Ideal solution model Xk() fk() (T,P) = Xk() fk())
fk (T,P) = fk (T,Psat) POY,
P

POY = exp ( (v/RT)dP for any given phase .

Psat
Ideal liquid solution but vapor is an ideal gas (Rauolt;s law: pk = Xk() Pksat)
Boiling point elevation T = ( Tpure
2
R/hfg) ln Xk(l) or T kb Mosolute,
Azeotropic Xk(g) = Xk(l)
Dissolved gases = Xk (l) = pk/(Pksat)
Henrys law pk = Xk,l Hk(T,P), Hk(T,P) = Pksat (POY)k(l).
Deviation from Rauolts law: pk = k(l) Xk,l p sat
k or k,l = pk/pk,Raoult

J. CHAPTER 10 RELATIONS
Criteria
dSU,V,m = 0, (d2S) U,V,m < 0, dSH,P,,m = 0, d2S HPV,m < 0,
dUS,V,m = 0, d2US,V,m > 0, dHS,P,m = 0, d2HS,P,m > 0
dAT,V,m = 0, d2 A T,V,m > 0, dGT,P,m = 0, d2GT,P,m > 0
S UUS UV
D2 = = S UU S VV S VU 2 > 0
S VUS VV
Thermal stability 2S/U2 < 0 or cv > 0
Mechanical stability (P/V)T < 0
Kestin formulae
If dS = (1/T) dU + (P/T) dV =SU (U,V) dU +SV (U,V) dV, then
d2S = d(1/T) dU + d(P/T) dV = d(SU(U,V)) dU + d(SV(U,V)) dV,
= (gmetastable/unstable gstable)/T
Spinodal Points : (P/V)T = 0

K. CHAPTER 11 RELATIONS
Thermochemistry
Air composition mole%: N2 = 79%, O2 = 21 %
mass %: N2 = 77%, O2 = 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 O2 in products

A:F (mass basis) air required in kg

kg of fuel

A:F (mole basis) air required in k moles

k mole of fuel

Excess air % A:F - ( A:F )stoich

x 100
( A:F )stoich

Air supplied as % theoretical air or air supplied

stoichiometric Ratio (SR) x 100
theoretical stoich. air

Equivalence ratio () = 1/(SR) ( A:F)stoich ( F:A)

=
( A:F) ( F:A)stoich

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 hf 0 + thermal enthalpy
( h298 to T)
Enthalpy of reaction, ( H R) HPROD,T - HREACT,T

Enthalpy of combustion, ( Hc) H C H R

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

Higher heating value, HHV = HV with H2O in liquid form

Lower heating value, LHV = HV with H2O in gaseous state

Internal energy for use ui = hi P vi , = hi RT if species i is ideal gas

Actual heat release
Combustion efficiency comb =
Theoretical heat release
Heat transferred to water / Kg of fuel
Boiler efficiency boiler =
Higher heating value / Kg of fuel

2002 by CRC Press LLC

 Elec. work / kg of fuel
Overall thermal efficiency thermal =
Higher heating value / kg of fuel
Energy and entropy balance for reacting systems
cv W
dEcv/dt = Q cv + k,i N ke T,k k,e N ke T,k, e T,k = (h+ k e + p e )k
cv/Tb + k,i N
dScv/dt = Q k s k k,e N k s k +
Mole balance
k,i + N
dNk/dt = 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/Nk)U,V =T (S/Nk)H,P = (U/Nk) S,V= (A/Nk)T,V = (G/Nk)T,P = g k =k

Process/Variable/Condition Formula
Direction of reaction 0, dGT,P 0 or (k dNk) 0,

dGT, P = (k k dNk) 0,
G = Nk gk ( T,pk), g k ( T,pk) k
Equilibrium condition = 0,
g k d Nk = dG T,P = 0 , g k d Nk = dA T,V = 0

Chemical potential j = (G / Nj )T,P,N2 ...

j = (A / Nj )T,V,n 2 ...

Chemical force potential (e.g. 1

F chem, = gH 2 - gO 2 , F chem, = g H 2O
H2+ 1/2 O2 H2O) react
2 prod

Fchem, react > Fchem Prod

Gibbs function useful for
chemical reactions, P in bars
g i = h i - T s i = { hoi - T si o } - R T ln (PXi / 1) ]
g i = gi (T) + RT ln (PX i / 1) ,see TableA88 to A119
o
9 for g i
o

g i = gi (T, P) + R T ln Xi
Equilibrium constant, K0(T) K 0 (T) = exp (- G o /R T ) , G0 = G0RHS G0 LHS

Equilibrium constant, K0(T) from K0(T)exp (A (B/T)), T in K, A= k Ak, B= k

elementary reactions Bk, (e.g.: CO2 CO +1/O2, A = 1ACO +(1/2) A O2
1A CO2 ), use Table A28A
Vant Hoff relation
ln K0(T) = A B/T, A = A = ln K oref + (H oR / R ) (1/Tref), B
= (H oR / R ).

2002 by CRC Press LLC

M. CHAPTER 13 RELATIONS
g = h Ts
a = u Ts
k ) k)i ( N
(1 T0 ) + ( N )
k
d(Ecv T0 Scv)/dt = Q R ,j k)e Wcv I
TR ,j

Variable Formula
Entropy P
s ( T,P) = s ( T ) - R ln , P in bar
1
Absolute availability of species j (not j = hj - T o sj
availability)
Exergy or availability j j,0

Chemical availability g^k(T0,P0, X1,e,..)^g k(T0,P0, X1,,..)

Fuel availability, availf with fuel at 1 Nk,ig^ k,i(T0,P0, X1,0,..) Nk,eg^ k,e(T0,P0, Y1,,..)
bar, air at 1 bar
Irreversibility/lost availability, I I = Wopt Wact
Wopt, TM, Wchem but not of fuel only wopt, TM = i - e (T0 , P0 , X1e , X 2e ..)

w chem = e (T0 , P0 , X1e , X 2e ..) - (T , P , X1 , X 2 ..)

Availability efficiency avail= W/AvailF.

Voltage in fuel cell, number of ( G in kJ / K mole) x 1.036 x 10-5

V(volts) =
electrons from Cx Hy is (4x+y). ( No of electrons per molecule of fuel )

2002 by CRC Press LLC