Scribd
Upload
138 views

Introductory Chemical Engineering Thermodynamics: by J.R. Elliott and C.T. Lira

The document discusses fundamental concepts in classical thermodynamics including: 1) The fundamental property relationship of dU=(Q+W)dt and its implications for deriving the Maxwell relations and expressions for changes in enthalpy, Helmholtz free energy, and Gibbs free energy. 2) Applications of these relationships including determining enthalpy changes and entropy changes with respect to temperature and pressure. 3) The use of generalized fluid properties like heat capacities and equations of state to extend these relationships to real gases using the triple product rule.

Uploaded by

Aman Singh
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
138 views

Introductory Chemical Engineering Thermodynamics: by J.R. Elliott and C.T. Lira

The document discusses fundamental concepts in classical thermodynamics including: 1) The fundamental property relationship of dU=(Q+W)dt and its implications for deriving the Maxwell relations and expressions for changes in enthalpy, Helmholtz free energy, and Gibbs free energy. 2) Applications of these relationships including determining enthalpy changes and entropy changes with respect to temperature and pressure. 3) The use of generalized fluid properties like heat capacities and equations of state to extend these relationships to real gases using the triple product rule.

Uploaded by

Aman Singh
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 9

Introductory Chemical

Engineering
Thermodynamics

By J.R. Elliott and C.T. Lira


The fundamental property relation
Piston+Cylinder ⇒ Closed system ⇒ dU=(Q+W)dt
For the heat exchange: Qdt=TdS (macroscopic definition)
For the work Wdt = -PdV (W = Fdx)
⇒dU =TdS - PdV This is the fundamental property relationship.

H = U + PV ⇒ dH = dU + d(PV) = dU + PdV + VdP


Substitution of the fundamental property relationship:
⇒ dH = (TdS - PdV) + PdV + VdP
⇒ dH = TdS + VdP
dA = -SdT - PdV
dG = -SdT + VdP
We can integrate these expressions to find that
A ≡ U - TS Helmholtz free energy
G ≡ H - TS Gibbs free energy

Elliott and Lira: Chapter 5 – Classical Thermodynamics Slide 1


Example. Enthalpy of H2O above its saturation pressure
Determine the enthalpy of H2O at 20°C and 100 MPa. Note that values of pressure this
high do not appear in the steam tables.
Solution The expression for a change in enthalpy should remind us that shaft work for an
adiabatic, reversible process (dS=0) is ∆H =∫ VdP. But,

VL ≈ constant = 1.003 cm3/g ⇒ ∆H=1.003(100-.00234)8.314/8.314=100.30 J/g.


⇒ H=83.96 + 100.30 = 184.25 J/g.
NOTE: W=∆H = 100 J/g ~ P (MPa)

Elliott and Lira: Chapter 5 – Classical Thermodynamics Slide 2


Maxwell's Relations
By recognizing that any variable is a function of any two other variables,
U = U(S,V) ⇒ dU = (∂U/∂S)V dS + (∂U/∂V)S dV
But the fundamental property relationship says:
dU = T dS - PdV
∂ 2U ( S ,V )  ∂  ∂U ( S ,V )    ∂  ∂U ( S ,V )   ∂ 2U ( S ,V )
=    =     =
∂S∂V  ∂S ∂ ∂ ∂ ∂V∂S
  V  S V  V  S V  S
∂ 2U ( S ,V )  ∂   ∂  ∂ 2U ( S ,V )
=  ( − P)  =  (T )  =
∂S∂V  ∂S V  ∂V S ∂V∂S
dH = (∂H/∂S) dS + (∂H/∂P)S dP = TdS + VdP
∂2H ∂ 2 H  ∂  ∂H    ∂  ∂H    ∂V   ∂T 
= =    =       =  
∂S∂P ∂P∂S  ∂S  ∂P  S  p  ∂P  ∂S  p  S ⇒  ∂S  p  ∂P  S
dU = TdS - PdV ⇒ -(∂P/∂S)V = (∂T/∂V)S
dH = TdS + VdP ⇒ (∂V/∂S)p = (∂T/∂P)S MAXWELL'S
dA = -SdT - PdV ⇒ (∂P/∂T)V = (∂S/∂V)T RELATIONS
dG = -SdT + VdP ⇒ -(∂V/∂T)p = (∂S/∂P)T

Elliott and Lira: Chapter 5 – Classical Thermodynamics Slide 3


Example. Entropy change vs. T at constant P
Evaluate (∂S/∂T)p in terms of Cp , Cv , T, P, and V
Solution:
Recall, dH = TdS + VdP
If P is constant, then dP=0. Dividing through by dT,
 ∂H   ∂S   ∂H 
  = T   Cp ≡  
 ∂T  p  ∂T  p But, the definition of Cp is:  ∂T  p
 ∂S  Cp
Therefore,  ∂T  =
p T

Elliott and Lira: Chapter 5 – Classical Thermodynamics Slide 4


Example . Entropy change as a function of T and P
Derive a general relation for entropy changes of any fluid with respect to temperature and
pressure in terms of Cp, Cv, P, V, T and their derivatives.
dS = (∂S/∂T)p dT + (∂S/∂P)T dP but (∂S/∂T)p = Cp/T as derived above,
and Maxwell's Relations show that (∂S/∂P)T = -(∂V/∂T)P .

⇒ dS(T,P)p = Cp dT/T - (∂V/∂T)p dP (eqn. 5.35, a useful, general equation)

Similarly

dS(T,V) = Cv dT/T + (∂P/∂T)V dV (eq 5.36)

dH(T,P) = Cp dT + [V-T(∂V/∂T)P]dP (eq 5.37)

dU(T,V) = Cv dT + [T(∂P/∂T)V -P]dV (eq 5.38)

Elliott and Lira: Chapter 5 – Classical Thermodynamics Slide 5


II. Generalized Fluid Properties
What is so important about the variables Cp, Cv, P, V, T?
As a sample application, we can assume the ideal gas equation of state.
V = RT/P ⇒ (∂V/∂T)P = R/P. Substitution ⇒ ∆S = Cp ln(T2/T1) - Rln(P2/P1)

Applying ∆S = 0 ⇒ ln(T2/T1) = R/Cp ln(P2/P1)⇒ (T2/T1) = (P2/P1) (Cp-Cv)/Cp


1−1 / γ −1/ γ 1/ γ
T2 P2V2  P2  V2  P2   P1 
= =  ⇒ =  = 
T1 PV
1 1  P1  V1  P1   P2 

Once again, we arrive at this familiar relation, but this time, it is easy to recognize the
necessary changes for applications to real gases. That is, we must simply replace the
PVT relation by a more realistic equation of state.

e.g. V = RT/(P+C) which we may refer to as the “bogus” equation of state.


⇒ (∂V/∂T)P = R/(P+C)
Substitution ⇒ ∆S = Cp ln(T2/T1) - Rln[(P2+C)/(P1+C)]
Applying ∆S = 0 ⇒ ln(T2/T1) = R/Cp ln[(P2+C)/(P1+C)]⇒
(T2/T1) = [(P2+C)/(P1+C)] R/Cp

Elliott and Lira: Chapter 5 – Classical Thermodynamics Slide 6


II. Generalized Fluid Properties
Triple Product Rule (a.k.a. Chain Rule)
Suppose: F = F(A,B)
then dF = (∂F/∂A)B dA + (∂F/∂B)A dB.
Consider what happens when dF = O (ie. at constant F). Then,
 ∂F   ∂A 
−  − 
 ∂ F   ∂ A  ∂ F  ∂
  A  ∂ B A  ∂F B
0=    +  ⇒  = =
 ∂A  B  ∂B  F  ∂B  A  ∂B  F  ∂F   ∂B 
   
 ∂A  B  ∂F  A
But, because C is some fourth property and F is constant.
 ∂A 
 
∂
 A  ∂ C  F  ∂A   ∂C 
  = =   
 ∂B  F  ∂B   ∂C  F  ∂B  F
 
 ∂ C F
Now the negative sign has disappeared. Did you notice the difference?

Elliott and Lira: Chapter 5 – Classical Thermodynamics Slide 7


II. Generalized Fluid Properties
Example. Application of the triple product relation.
Evaluate (∂S/∂V) in terms of Cp, Cv , T, P, and V. Your answer may include absolute
values of S if it not associated with a derivative.
Solution: This problem illustrates a typical situation where the triple product rule is
necessary because the free energy is held constant. It is easiest to express changes in the
free energies as changes in other variables.
Applying the triple product rule: (∂S/∂V)A = -(∂A/∂V)S /(∂A/∂S)V
dA = -PdV-SdT ⇒ (∂A/∂V)S = -P-S(∂T/∂V)S and (∂A/∂S)V = 0 - S(∂T/∂S)V
T  ∂P   ∂T  T
5.35 ⇒ (∂T/∂V)S = Cv ∂T−   and   =
 V  ∂S V Cv
Substitution
 ∂S  − PCv  ∂P 
⇒  = + 
 ∂V  A ST  ∂T V

Elliott and Lira: Chapter 5 – Classical Thermodynamics Slide 8

You might also like