CHEMICAL ENGINNERING

THERMODYNAMICS

Unit 1
INTRODUCTION AND
REFRESHING CONCEPTS
 CHEMICAL ENGINEERING
THERMODYNAMICS
Introduction and refreshing concepts
A process involving a pure substance or a constant composition mixture
For a closed system dE = d(U+Ec+Ep+…) = δQ – δW
As E, U, … variations do not depend on the process going from the initial
state to the final one, they will be the same for a reversible process,
dE = d(U+Ec+Ep+…) = δQ – δW = dQ – dW = TdS – PdV if only
volumentric work is interchanged
In most chemical engineering processes ΔEc and ΔEp << ΔU
Therefore
dU = TdS – PdV and dS = (1/T) dU + (P/T) dV

As H = U +PV, dH = TdS + VdP

As A = U –TS, dA = – SdT – PdV, energía libre de Helmholtz

As G = H – TS, dG = – SdT + VdP, energía libre de Gibbs

 CHEMICAL ENGINEERING
THERMODYNAMICS
Introduction and refreshing concepts
Besides
Cp = (∂H/∂T)P
Cv = (∂U/∂T)V
dU = TdS – PdV
(∂U/∂S)V = T, (∂U/∂V)s = -P
dS = (1/T) dU + (P/T) dV
(∂S/∂U)V = 1/T, (∂S/∂V)s = -P/T
dH = TdS + VdP
(∂H/∂S)P = T, (∂H/∂P)s = V
dA = – SdT – PdV
(∂A/∂T)V = -S, (∂A/∂V)T = -P
dG = – SdT + VdP
(∂G/∂T)P = -S, (∂G/∂P)T = V
 CHEMICAL ENGINEERING
THERMODYNAMICS
Introduction and refreshing concepts
As ∂2z/(∂x∂y) = ∂2z/(∂y∂x) and (∂z/∂x)(∂x/∂y)(∂y/∂z) = -1
(∂T/∂V)S = - (∂P/∂S)V (∂T/∂P)S = (∂V/∂S)P

(∂S/∂V)T = (∂P/∂T)V (∂S/∂P)T = - (∂V/∂T)P

As Cp = (∂H/∂T)P and dH = TdS + VdP

(∂H/∂T)P = T(∂S/∂T)P + V(∂P/∂T)P = T(∂S/∂T)P and (∂S/∂T)P = Cp/T

As Cv = (∂U/∂T)V and dU = TdS – PdV

(∂U/∂T)V = T(∂S/∂T)V - P(∂V/∂T)V = T(∂S/∂T)V and (∂S/∂T)V = Cv/T

Remember that P, T and V are the variables that can be experimentally

measured
 CHEMICAL ENGINEERING
THERMODYNAMICS
Introduction and refreshing concepts
From volumetric behavior (can be measured with high precision) to
thermodynamic behavior for real fluids
For ideal gases (∂H/∂P)T = (∂U/∂P)T = 0, (∂S/∂P)T = - R/P

For real fluids dH = (∂H/∂T)T dT + (∂H/∂P)T dP

(∂H/∂T)T = Cp, As dH = TdS + VdP, then

(∂H/∂P)T = T(∂S/∂P)T + V(∂P/∂P)T = -T(∂V/∂T)P + V, because (∂S/∂P)T = - (∂V/∂T)P

dH = Cp dT + [V - T(∂V/∂T)P] dP

For real fluids dS = (∂S/∂T)T dT + (∂S/∂P)T dP

(∂S/∂T)T = Cp/T and (∂S/∂P)T = - (∂V/∂T)P

dS = (Cp/T) dT - (∂V/∂T)P dP

Apply to IG where V = RT/P

 CHEMICAL ENGINEERING
THERMODYNAMICS
Introduction and refreshing concepts
Exercises:

1. Express for a real fluid and as a function of its volumetric behavior

a)Its Joule-Thompson coefficient, µ = (∂T/∂P) H

b)The difference Cp – Cv

2. Compare the variation of T experimented by a real fluid in an

expansion (same ΔP) for
a)An iso-enthalpic process

b)A reversible process

c)Compare both results with the ones obtained for an ideal gas

3. Develop the differential equations for H and S using as independent

variables T and V (instead of P)