Introduction to

Chemical Engineering
Thermodynamics
Seventh Edition

Smith Van Ness Abbott

Chapter 6 PowerPoint
Copyright the McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Thermodynamics Properties of fluids

We will try to find thermodynamic properties by use of these four
properties(T,P,V,m).
Qrev. + Wrev = d(nU)
Qrev = Td (nS)
Wrev = -P d(nV)
d(nU) = Td(nS) P d(nV)
Eq. 6-3
We had before HU + PV
Helmholtz Energy AU T S
Gibbs Energy
GH T S
We had before d(nH) = d(nU) +Pd(nV) +nVdP
Substituting d(nU) = Td(nS) P d(nV) in above equation
d(nH) = Td(nS) + nVdP
Eq. 6-4
Similarly A U T S or
d(nA) = Td(nU) T d(nS) - SdT

Substituting for internal energy U then we will have ;

d(nA) = -P d(nV) ( nS)dT
Eq. 6-5
similarly
d(nG) = nVdP n SdT
Eq. 6-6
So for homogenous fluid of constant composition we have;
dU = TdS P dV
Eq. 6-7
dH = TdS + VdP
Eq. 6-8
dA = - P dV SdT
Eq. 6-9
dG = VdP SdT
Eq. 6-10
From eq. 6-7 to 6-10 we can conclude that
U = U(S,V)
H = H(S,P)
A=A(V,T)
G=G(P,T) Therefore,
dU = (U/S)V dS + ( U/V)S dV Comparison of this equation
with Eq. 6-7 we can say that
T = (U/S)V and ( U/V)S = -P

 So we can write
(T/V)S = 2U/SV
-(P/S)V =2U/SV
therefore
(T/V)S= -(P/S)V
Eq. 6-13
Above equation is known as Maxwells equation
Similarly for H = H(S,P)
dH = (H/S)P dS + (H/P)SdP
We had dH = TdS + V dP So, T = (H/S)P
V=(H/P)S
(T/P)S = 2H/SP
(V/S)P= 2H/PS
therefore,
(T/P)S = (V/S)P
Eq. 6-14
similarly for A & G we can
write;
(P/T)V = (S/V)T
Eq. 6-15
(V/T)P = - (S/P)T
Eq. 6-16

(T/V)S= -(P/S)V
Eq. 6-13
(T/P)S = (V/S)P
Eq. 6-14
(P/T)V = (S/V)T
Eq. 6-15
(V/T)P = - (S/P)T
Eq. 6-16

Example 1
A cylinder piston device contains saturated liquid
water at 0oC. At constant temperature pressure
on the cylinder is increased, which of statement
given below is correct?
1)Entropy of saturated liquid at 0oC is less
than entropy of compressed liquid.
2) Entropy of saturated liquid at 0oC is
greater than entropy of compressed liquid.
3) Entropy of saturated liquid at 0oC is equal
to entropy of compressed liquid.
4) The change depends on final pressure.
Solution:
Since; (S/P)T = - (V/T)P and @ 0C
(V/T)P is negative therefore at higher
pressure entropy will increase.

Enthalpy and Entropy as Function of

Temperature
We had before CP = (H/T)P
Also dH= TdS+ VdP dividing
by dT we will have (H/T)P = T(S/T)P therefore one can say that
(S/T)P = (1/T)CP = 1/T (H/T)P Eq. 6-17
from Maxwells equation (S/T)P = -( V/T)P Also we had
dH = TdS +VdP dividing by dp
(H/P)T = T(S/P)T + V
as result above equation becomes
(H/P)T = V T ( V/T)P
Eq. 6-19
we know H= H(T,P) & S = S(T,P) so
dH = (H/T)P +(H/P)T dP and dS = (S/T)P dT + (S/P)TdP
substituting Eq. 6-16 and 6-17
dH = CP dT +[ V T (V/T)P] dP
and
dS = CP dT/T (V/T)P dP

Example 2

For an ideal gas show that dH = CP dT

Solution:
dH = CP dT +[ V T (V/T)P]dp
For ideal gas PV=RT therefore,
V=RT/P and (V/T)P = R/P
so
dH = CP dT +[ RT/P TR/P]dp
dH = CP dT

Internal Energy as Function of Pressure

We had U = H P V differentiation yields
(U/P)T= (H/P)T P(V/P) V (P/P)
(U/P)T= (H/P)T P(V/P)T V
we had
(H/P)T = V T ( V/T)P
(U/P)T= -T P(V/P)T
Eq. 6-22
For ideal gas
PVig = RT (Vig/T)P=R/P
so
dS = CPig dT/T (V/T)P therefore,
dS = CPig dT/T R dP/P
Eq.6-24

Internal Energy and Entropy as

Function of T &V

From Eq. 6-7 we had dU=TdS P dV so

(U/T)V = T(S/T)V
Eq. A and (U/V)T = T(S/V)T P Eq. B
Combine Eq. A with Eq. 2-16 (U/T)V = CV so (S/T)V= CV/T
Combine Eq. B with Eq. 6-15 (P/T)V= (S/V)T so
(U/V)T = T (P/T)V P
Eq. 6-31
Also we said before
U = U(T,V) And S = S(T,V) Therefore,
dU = (U/T)V dT + (U/V)T dV
Eq. C
dS = (S/T)V dT + (S/V)T dV
Eq. D
Using Eq. 2-16, 6-30, 6-31, and 6-15 and also Eq. C & D can be
written as;
dU = CV dT + [T (P/T)V P ] dV
Eq. 6-32
dS = CV dT/T + (P/T)V dV
Eq. 6-33

Example 3
Slope of constant pressure line relative to slope of constant volume
line of water steam on T-S diagram is
1) smaller than one.
2) greater than one.
3) equal to one.
4) it depends on temperature could be smaller than one or greater
than one.
Solution:
We had dS = CP dT/T (V/T)P dP and
dS = CV dT/T + (P/T)V dV @ constant pressure
(V/T)P dP =0 therefore, [T/S]constant pressure = T/CP and @
constant volume (P/T)V dV =0
therefore,
[T/S]constant volume =T/ CV

so slope= T/CP T/ CV < 1

Expansion and Compressibility for

Liquid

We had =1/V (V/T)P

and k = -1/V (V/P)T
Also (s/p)T= -(V/T)P
(H/P)T =V T (V/T)P therefore;
(s/p)T= -V
Eq. 6-25
(H/P)T = V T (V/T)P = V(1 T )
Eq. 6-26
Also in Eq. 6-22 we had
( U/P)T = -T(V/T)P P (V/P)T
So ( U/P)T = -TV + PkV = V(kP T )
(V/T)P = v
can be replaced in Eq. 6-20 & 6-21
dH = CP dT +[ V T (V/T)P]dp = CP dT + V T V
dH = CP dT +(1-T)V dP
Eq. 6-28
dS = CP dT/T - (V/T)P dP = CP dT/T - V
Eq. 6-29
We had before dV/V = dT k dP for constant volume process
(P/T)V = - / k
We had dU= CV dT + [T(P/T)V P ]dV
dU = CV dT + [(/k)T P ]dV
Eq. 6-34
dS = CVdT + (P/T)V dV = CVdT + (/k) dV
Eq. 6-35

From Eq. 6-24,6-25, and 6-28

(S/P)T = -V......for incompressible flow (S/P)T = 0

(H/P)T = (1- T)V..for incompressible flow (H/P)T =V
(U/P)T = V(kP T )..for incompressible flow (U/P)T = 0
For ideal gas
dH = CPig dT
dU = CVig dT
dS = CPig dT/T
therefore;
We can conclude that for incompressible fluid only enthalpy is
function of pressure and internal energy and entropy is not
function of pressure, whereas, for ideal gas only entropy is
function of pressure, but enthalpy and internal energy are not
function of pressure.

The Gibbs Energy as a Generating

Function
We had (from Eq. 6-10)
dG= VdP SdT which G = G(P,T) ,
which P & T can be measured easily. An alternative form of Eq. 6-10
is d(G/RT) 1/(RT) dG G dT/(RT2) substituting Eq. 6-10 and Eq. 63 GH TS we will have
d(G/RT) = V/(RT) dP H dT/(RT2) Eq. 6-37
which at constant pressure &
constant Temperature
H/(RT) = - T[ (G/RT)/T]P
V/RT = [(G/RT)/P]T

Residual Properties

Residual property is defined as MR M M ig for example for volume

VR = V V ig = RT/P (Z -1 ) for instance Eq. 6-37
d(Gig /RT) = Vig /(RT) dP Hig dT/(RT2)
d(GR /RT) = V R/(RT) dP HR dT/(RT2)
Eq. 6-42 this
equation is applicable for fluid of constant composition.
HR /(RT) = - T[ (GR/RT)/T]P
Eq. 6-43
VR/RT = [(GR/RT)/P]T
Eq. 6-44
The residual Gibbs energy, a generating function for other residual
properties, has a direct link with experiment.
d(GR /RT) = V R/(RT) dP @ const. T from 0 P pressure
(GR
/RT) = (GR /RT)P=0 + P V R/(RT) dP @ Const. T
for
convenience, define
(GR /RT)P=0 J is a constant independent of T.
(GR /RT) = (GR /RT)P=0 + P V R/(RT) d = J + (Z-1) dP/P
Eq. 6-45
Derivative of this equation in combination of of eq. 6-43 gives
HR /(RT) = - T P (Z/T)P dP/P
from 0 p
Eq. 6-46

 Also, the definition of Gibbs energy G= H TS may also be written

as; Gig = Hig TSig by difference, GR = HR TSR and ,
SR/RT= HR/RT GR /RT Eq. 6-47
Combining this with eq. 6-45 and 6-46 gives
SR/RT= - T P (Z/T)P dP/P J P (Z-1) dP/P @ const T

Example 4 (problem 6-47)

From steam Table estimate values for the residual properties, VR,
HR, SR for steam at 225oC and 1600 kPa, and compare with values
found by a suitable generalized correlation.
Solution:
@ T= 225 C P= 1600 kPa v = 132.85 cm3/g , H= 2856.3 kJ/kg ,
s = 6.5503 kJ/kg K
(We choose P = 1 k pa as the lowest pressure available as ideal
gas values as P0,), therefore, From Table F-2 page 722
Hig = 2928.7 kJ/kg Sig =10.0681 kJ/kg K Note that: Enthalpy is
not function of pressure , whereas entropy is, therefore Sig = -R ln
(P/Po) = -( 8.314/18) ln (1600/1)= -3.408 kJ/kg K
SR = S (Sig +Sig) = 6.5503 (10.0681 3.408) = - 0.11 kJ/kg K
HR = 2856.3 2928.7 = - 72.4 kJ/kg K
VR = 132.85 (8.314 x 498.15)x103/[(18)(1600)] = -10.96 cm3/g

Solution of Problem 6-47 Cont.

Page 681 Table B-1 = 0.345 Tc = 647.1 K Pc= 220.556 bar

Tr = 498.15/647.1 = 0.7698
Pr= 16/220.556 = 0.07255
using generalized virial coefficient Z =1 +Bo Pr/Tr + B Pr/Tr also
Bo = 0.083 (0.422)/Tr1.6 = 0.083 [0.422 / (0.7698)1.6] = - 0.5583
B = 0.139 0.172/ ( 0.7698)4.2 = - 0.3771

Z = 1 (0.5583)(0.072546/0.7698) + (0.345)(- 0.3771)(0.07255/0.7698)

Z =0.935
VR = RT(Z 1) / MW P
VR = 8.314x498.15x10-3(0.935 -1)/[18x1600] = -9.33 cm3/g

Two Phase System

For 2 phase system & from Eq. 6-6 d(nG) = nVdP (nS)dT
for infinitismal change of one phase to another ( pure compound),
therefore, dP=0 , dT= 0 therefore, dG=0 so G = G or dG =dG
Also we had dG= VdP S dT for
dG = 0 So
VdPsat S dT =VdPsat S dT rearrangement of
this eq. (V V ) dPsat = (S S )dT
dPsat/dT = (S S ) / (V V ) = S/ V we also had (6-8)
dH = TdS + VdP
and integrating we will have H =T S thus
S = H /T substituting
dPsat/dT = H /( V T) This is Clapeyron Equation
From phase transition (liquid to Vapor)
dPsat/dT = Hlv /( Vlv T) but Vlv = RTZlv//Psat
Zlv = compressibility factor of vaporazation
dlnPsat/dT = Hlv/(RT2zlv)