Appendix A.

General
Thermodynamic
Formulas
Systematic collections of thermodynamic formulas disso Table A l . Definitions and Symbols of Thermodynamic
ciated from their derivations and possible restrictions must be Quantities
used with caution, but they are nevertheless of value to the
initiate. Although no comprehensive summary of such for Thermal Quantity Symbol Definition
mulas appears to have been published, many tables of limited Heat Q
scope are available, for instance, in: Internal energy u
Entropy s
Enthalpy (also called
1. Bridgman, P.W. A Condensed Collection of Thermo heat content, heat
dynamic Formulas. Harvard University Press (1925). function, total heat) U+PV
Helmholtz function (also
Covers first and second derivatives of other thermo
called free energy and
dynamic quantities in terms of P, V, T, S, Cp, and their work function) U-TS
derivatives. (See Table A.7.) Gibbs function (also
2. Goranson, R.W. Thermodynamic Relations in Multi- called free energy, free
component Systems. Carnegie Institution of Washington enthalpy, thermodynamic
(1930). potential). H-TS
3. Shaw, A. N. The derivation of thermodynamical rela
Volume expansivity
tions for a simple system. Phil. Trans. Roy. Soc.
(coefficient of volume \*)
(London) A234, 299-328 (1935). Covers first and expansion).
second derivatives of one-component systems. The

-
method is much more flexible than that of Bridgman in
that any derivative also may be expressed in terms other Isothermal bulk B
than those involving only P, V, T, S, and Cp. The modulus

An
treatment relating to first derivatives also is presented
by T.K. Sherwood and C E . Reed, Mathematics in
Adiabatic bulk Bs
Chemical Engineering, McGraw-Hill (1939), and by
modulus
Carroll (1965) (/. Chem. Education 42(4), 218-221).
4. Tunneil, G. Relations between Intensive Thermody
namic Quantities and their First Derivatives in a Isothermal k
T
Binary System of One Phase. W.H. Freeman and compressibility
Company (1961).
5. Sage, B.H. Thermodynamics of Multicomponent
Systems. Reinhold Publishing Corporation (1965). An
Adiabatic
compressibility
** ~1
appendix lists formulas for systems of variable mass and

(SWS),
composition in Bridgman style.
6. Van Ness, H.C., M.M. Abbott. Classical Thermody
Heat capacity at cv
constant volume
namics of Non-Electrolyte Solutions. McGraw-Hill

(SMS),
(1982). Tables of formulas relating to mixtures are
scattered throughout the book and appendixes. Heat capacity at CP
constant pressure

Ratio of heat capacities y

Specialized tables of thermodynamic formulas are located Cy
throughout the book, particularly in Chapters 2, 3, 4, and 11.
The basic tables of this appendix are: Joule coefficient n
(S)
)
Table A. 1. Definitions and symbols of thermodynamic
quantities, Joule-Thomson
Table A.2. Some named relations in thermodynamics, (Kelvin) coefficient
Table A. 3. Thermodynamic formulas, X
'H
Table A.4. Directly measurable properties, Massieu function
Table A.5. Properties of the ideal gas and values of the gas T " T ~S
A U
constanti?, G H
Table A. 6. Ideal gas processes,
Table A. 7. A Bridgman method for first order derivatives.
Planck function
\ " "s

547
548 Appendix A. General Thermodynamic Formulas
Table A.2. Some Named Relations in Thermodynamics
1. First law: dQ = dU+dW.
2. Second law: dQ = TdS.
3. Third law: lim S = 0

4. Ideal-gas law: PV = RT.

5. Raoult's law: P, = yiPsiiii.
6. Henry's law: Pt kHXi oxJi kfjXj.
7. Lewis & Randall rule: }} = yifi or 0, = 0,.
dP AH
8. Clapeyron equation: ; = rviA rr .
dT TAV
d\nP AH,
9. Clapeyron-Clausius equation: vap (ideal vapor).
dT RT2

(dhf \ (dM
10. Gibbs-Duhem equation: xl dT+
/ T

(dAG \
11. Gibbs-Helmholtz equation: AG- AH.

12. Hess's law: Enthalpy change of a reaction is independent of the path.

idAH \ _
13. Kirchhoff equation: AC,.

14. Lorentz-Berthelot rules: For the parameters of cubic EOS such as the van der Waals, y/a = j^Vo/ and b = y fa (see
Rowlinson & Swinton, Liquids and Liquid Mixtures, 1982).
15. van't Hoff isochore: (d \nKce/dT)P = AH/RT2. (For chemical reaction.)

Table A.3. Basic Equations and Relations

Fundamental Equations:
nU = f(S, V,nl,n2,..., n k) internal energy,
nH=f{S, P, niin2,. . .,nk)
= n(U+PV) enthalpy,
nA=f(T, V,nlfn2,...,nk) \dTjyn \dTjpn \dTjp

= n(U- TS) Helmholtz energy,

nG=f(Tt P, n{,n2, . . . , n k) VJiE\ J\ _(
= n(U-TS + PV) Gibbs energy. \pjsn WJTn \dpJT
Differential Relations:
d(nU) = Td(nS) - Pd(nV) + &^
\d(UT) } v
d(nH) = Td(nS) + nVdP + ^dnh
d(nA) = -nSdT-Pd(nV) + ^dnh /*/> \
d(nG) = -nSdT + n VdP + ,/,. \d(l/T) Jp
Intensive Properties:

\es)Vn \dsjpn \ drii /SVrij \ drii /Spnj \ drij ' TVnj

 m
Appendix A. General Thermodynamic Formulas 549

(dnG\ ?T)
\drii /TPn
/d\ (dV
Maxwell Relations: \dP ) ~ \dT .
Chemical Reaction Equilibrium:
\dv)s \ds)v'
Keq= exp(-AG/RT),

-C-^)-(-
'dAG/T \
= -AH/T2.
dT

Table A.4. Directly Measurable Properties

1. Isothermal compressibility: kT

2. Adiabatic compressibility: ks
- - - ( - )

i fav\
3. Coefficient of thermal expansion, = (I I
V \dTjp

Heat capacity or specific heat:

4. at constant pressure. Cp
' \) T
\T)P \)\)5'

5. at constant volume,

6. C -Cr.T(i>\ \.*--((\._!\
\T/v\T)r R, \>Tr\)vT \T
,)/ \dv),

9. Joule-Thomson coefficient
ient_=
\dpK~ C
P L\*T)P J
550 Appendix A. General Thermodynamic Formulas

Table A.5. Properties of the Ideal Gas and Values of the Gas Constant in Various Units

pV=nRT
dT dp
(\ _2L f\ _ JL dG = nCpdT-nTCp + nRT~
\dTj~ T * \dT/v T

dU=nCvdT kT = \lp
ks - CylpCp

ea- &b fi- = VT

dH=nCpdT

a- fti- (a-
Energy Temperature Mole
2 2
lb-ft /sec Rankine lb 4.969 X10 4
ftlbf Rankine lb 1544
cu ft atm Rankine lb 0.7302
cu ft (lbf/sq in.) Rankine lb 10.73
Btu Rankine lb 1.987
Cp Cy = , C^ = _ , A: Cp/Cy hp-hr Rankine lb 7.805 X 10 - 4
k- 1
kwhr Rankine lb 5.819 X 10~4

dS = rdT-nR joule(abs) Kelvin gm 8.314

T P kg-m2/sec2 Kelvin 8.314 X10 3
kg
kgf m Kelvin kg 8.478 X10 2
dT dV cu cm atm Kelvin gm 82.0562
dA = nCydT- nTCy- nRT calorie Kelvin gm 1.987
Table A.6. Ideal Gas Processes (Weber & Meissner, Thermodynamics for Chemical Engineers, Wiley, 1957). PV=RT, constant heat
capacities Cp and C, k = Cp/Cv.
Condition Q= 0
of restraint V=C P=C T= C Reversible adiabatic
PV yi = y2 Pi-Pi PiVi=P2V2 ' PiV'i-PiV
relations

Pi V2

PT Pi 2 r 2 //>2 Y*- 1 )
relations Ti = T2
P\ \ ri - V'i )
V2 T2 Il (UT1
relations
Vi Ti \V2 )

-P{Vi-V\)
A(PV) = V(P2-PO = 0 [(*P-J
--) ~>[(*P-1
= 0
-<)
[ftP-]
-ft-) -7

Pi
= AU=cpAT "AH=epAT = - * . -
Q = 0
k-\ V\
k- 1 \~HPV) = -*TM-

Pi
Reversible = 0 - MPV)
-^[ftP-]
(Continued next page)
Table A.6. (continued)

vx -A(PV)
= P(V2-Vi) Jirin-

^non-flow
k
Reversible =Um~"' -']
= - AH cpAT

*2 kRTy / P 2 Y*~>/* I
Wfiow JWta.- =
= -jVdP = V(AP)= V(P2-PX) =0 -~LITT) -J
Reversible V\
W h , -

"nonflow ~~~ cvA 1

RTX (p2 V*-"^ I

= cvAT = cAT
AU =0
A(PV) A(PV) A(PV)
k~ 1 k- 1 k- 1

* iP2\k~l)/k 1

= -W = cpAT

kRT{ //>2 Y*")/* "I

= cpAT -cpAT
AH =0
=
^[{) -J
-J^MPV)

*^ Pi\k~i)lk 1
^^^^___^^_^_
Table A.7. A Bridgman-Type Table for First Derivatives of Thermodynamic Quantities. After P. W. Bridgman, A Condensed
Collection of Thermodynamic Formulas, Harvard University Press (1926).

(dT)P = ~(dP)T=l

m
(dV)p =
~ '=(i\ C
P
(dU)s =
--b(i);T&l]
(dS)P =
V
CD
(dH)s = -(SS)H=-^f-

(dU)p = -{dP)u=Cp-p(^T)p

{BH)p = -(dP)H=Cp
(dG)p = - (dP)G = - 5
(dG)s =
-(W)-i[KC'-5rf)J
(dA)p =
(dA)s =
--HC'{)T+"l
+8
(dV)T = -<to-(%)T &)
( -(dU)H=-v[cp-p(^)p]
(dS)T =
- ^-(f), (SH)u =

(dU)T =
-m-T&);p{7F\ A^)rm
-{dU)G=-V[Cp-P&)p]
(dG)u =
+r
(dH)T =
-"*-' ("l
+s T
(dG)T = -(dT)o--V
[ {fr);p&)T]
(dA)T =

(dS)v =
(dA)u =
-(dU)^P[(Cp + S){Vp)T+T{Vr)2}
(dV\
+ ST[
(dU)v =
- < i r
- c
' & ) ; T
& \
WJp
/ r)V\
( d G ) w - - (dH)G = - V(Cp + S) + TS I J
(dH)v =
-^=c'&);T(i)r
(dA)H =
-<-- H(f)J
");
(dG)v =
-<"*--K), ()J +i *H(i),H(-l
(dA)v =
-<"^-(s)r (dA)G =
^"''"^!