ENG3002 Topic 2: Gibbs Eqns & Maxwell Rels ENG3002 Topic 2: Gibbs Eqns & Maxwell Rels

ENG3002 – Thermodynamics II OBJECTIVES

BEng3M
• Review the definition and derivation of
entropy
Topic 02
• Derive the Gibbs Equations
Gibbs Equation & Maxwell Relations • Apply PDE principles to Gibbs Euations
• State the Maxwell Relations
Lecturer: Paul Campbell
• Derive the Clapeyron equation and related
to accompany expressions and use them to determine
Thermodynamics: An Engineering Approach, 5th edition (or approximate) the enthalpies of
by Yunus A. Çengel and Michael A. Boles vaporization and condensation of a
substance.
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ENG3002 Topic 2: Gibbs Eqns & Maxwell Rels ENG3002 Topic 2: Gibbs Eqns & Maxwell Rels

Deriving the 1st Gibbs Equation What is Entropy? (cont’d)

• Recall 1st Law. ∆Esystem = Qnet − Wby ,net
• …or if we ignore exteral/macroscopic energies
• …and when considering differential changes
• If we cannot measure heat and work directly, what property(ies) can we
measure that will only respond to heat. Similarly, what properties for work.
∆U system = Qnet − Wby ,net
• To answer, consider an rigid (const V) element that will undergo a cycle of
dU system = δQnet − δWby ,net heating then cooling

NOTE Fast (NQE) Slow (QE)

2 1
• Consider a small control mass element of a SCS undergoing a slow (or δQ δQ δQ
quasiequilibrium) differential change
• What fraction of energy change is caused by heat
1 ∫T CS
=∫
T
1 CS
+∫
2
TCS
1
Only heat & work affect SCS
• What fraction of energy change is caused by work
Qout = Qin Qout = Qin
• If we cannot measure heat and work directly, what property(ies) can we
measure that will only respond to heat. Similarly, what properties for work.

2 2

δQ δQ
3 ∫TCS NQE
<0 ∫TCS QE
⇒0 4
ENG3002 Topic 2: Gibbs Eqns & Maxwell Rels ENG3002 Topic 2: Gibbs Eqns & Maxwell Rels

What is Entropy? (cont’d) The 1st Gibbs Equation (cont’d)

• Since for a substance undergoing a cycle, the values of any arbitrary
property at the start MUST be the value at the finish, i.e.
∆ζ cyc = ∫ dζ = 0
• Recall our original question. For a SCS undergoing a slow quasiequilibrium
differential change
• What property change will indicate heat addition to (or removal from) the system
• What property change will indicate work on (or by) the system

dU system = δQnet − δWby ,net

δQ
• Therefore, this cannot represent a property change…
∫T
CS NQE
<0 NOTE

• Therefore, we can say… dU system = TdS − δWby ,net

δQ
• …but this can
∫T CS QE
=0 • What about work!

• Clausius defines this as the change in the property entropy, S

δQ
= dS
T QE
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ENG3002 Topic 2: Gibbs Eqns & Maxwell Rels ENG3002 Topic 2: Gibbs Eqns & Maxwell Rels

The 1st Gibbs Equation (cont’d) Generalized Thermodynamic

dU system = TdS − δWby ,net Property Relations
• For a simple compressible substance, there are four (4) Gibbs Equations.
• What about work! … energy transferred by a force acting through a distance The first is derived from the 1st and 2nd law of thermodynamics (previous
in the direction of the force. slide).
• To answer, consider a susbstance in an adiabatic piston undergoing QE
expansion. • The second, third and forth Gibbs equations are based on the definitions of
δWby = Fdx enthalpy-h, the Helmhotlz function-a, and the Gibbs function-g, respectively.
but
F = PA
δWby = PAdx = Pd ( Ax ) P

du = T ds − P dv
• Therefore δWby = PdV
dh = T ds + v dP (where h ≡ u + Pv )
• THUS THE FIRST GIBBS EQUATION, valid for all SCS. da = − s dT − P dv (where a ≡ u-Ts )
dU = TdS − PdV + α1dζ 1 + α 2 dζ 2 + L dg = − s dT + v dP (where g ≡ h-Ts )
(if not SCS)
• Valid for all control masses (CM) with uniform properties. E.g. (a) any CM
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undergoing a QE process, (b) any differential CM element.
ENG3002 Topic 2: Gibbs Eqns & Maxwell Rels ENG3002 Topic 2: Gibbs Eqns & Maxwell Rels
Some Mathematical Preliminaries
Generalized Thermodynamic • Thermodynamic properties are continuous point functions and have exact
differentials. A property of a single component system may be written as
Property Relations general mathematical function z = z(x,y). For instance, this function may be
the pressure P = P(T,v). The total differential of z is written as
• Some thermodynamic properties can be measured
directly, but many others cannot. Therefore, it is
necessary to develop some relations between these two
groups so that the properties that cannot be measured
directly can be evaluated.
where

Taking the partial derivative of M with respect to y and of N with respect to x yields
• The 8 fundamental properties are: P, v, T, u, h, s, g and a

• The measurable properties are: P, v and T

Since properties are continuous point functions and have exact differentials, the
• Recall the state postulate. What is it’s basis. Consider following is true
the following calculus principles.
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ENG3002 Topic 2: Gibbs Eqns & Maxwell Rels ENG3002 Topic 2: Gibbs Eqns & Maxwell Rels
The Clapeyron Equation
• Setting the second mixed partial derivatives equal for these four functions
yields the Maxwell relations The Clapeyron equation enables us to determine the enthalpy change associated
with a phase change, hfg, from knowledge of P, v, and T data alone.
Consider the third Maxwell relation
du = T ds − P dv
dh = T ds + v dP
da = − s dT − P dv
dg = − s dT + v dP During phase change, the pressure is the saturation pressure, which depends on the
temperature only and is independent of the specific volume. That is Psat = f(Tsat).
∂P/∂
Therefore, the partial derivative (∂ ∂T)v can be expressed (dP/dT)sat, which is the
slope of the saturation curve on a P-T diagram at a specified state.
• There is another relationship based on other principles. If z = z(x,y), then P

LIQUID
SOLID
Can you relate
these to the Psat(T)
Gibbs equations?  ∂P 
 
VAPOR  ∂T  sat
11 T 12
ENG3002 Topic 2: Gibbs Eqns & Maxwell Rels ENG3002 Topic 2: Gibbs Eqns & Maxwell Rels

Image a unit mass of a substance going from the liquid phase to the vapour phase.
The temperature of the liquid-vapor system is being held constant. Therefore, the
integration yields

During the phase-change process, the pressure also remains constant. Therefore,
from the enthalpy relation
dh = T ds + v dP
g g g
∫ f
dh = ∫ T ds = T ∫ ds
f f

hg − h f = h fg = T s fg

Now we obtain the Clapeyron equation expressed as

h fg  dP 
=  v fg
T  dT  sat
 dP  h fg
  =
13  dT  sat T v fg 14

ENG3002 Topic 2: Gibbs Eqns & Maxwell Rels ENG3002 Topic 2: Gibbs Eqns & Maxwell Rels
Example 12-1  dP 
h fg = Tv fg  
o  dT  sat
Using only P-v-T data, estimate the enthalpy of vaporization of water at 45 C.
m3 kPa kJ
= (40 + 273.15) K (15.250 )(0.4965 )
The enthalpy of vaporization is given by the Clapeyron equation as kg K m3 kPa
kJ
= 2371.1
kg
The actual value of hfg is 2394.0 kJ/kg. The Clapeyron equation approximation is low
Using the P-v-T data for water from Table A-4 by about 1 percent due to the approximation of the slope of the saturation curve at
45oC.
m3
v fg = (vg − v f )@ 45o C = (15.251 − 0.001010)
kg Clapeyron-Clausius Equation
m3
= 15.250 For liquid-vapor and solid-vapor phase-change processes at low pressures, an
kg
approximation to the Clapeyron equation can be obtained by treating the vapor phase
 dP   ∆P  Psat @50o C − Psat @ 40o C as an ideal gas and neglecting the specific volume of the saturated liquid or solid
  ≅  =
 dT  sat  ∆T  sat , 45o C 50o C − 40o C phase compared to that of the vapor phase. At low pressures
(12.35 − 7.385)kPa kPa v g >> v f
= o
= 0.4965
10 K K v fg ≅ v g
RT
vg =
15 P 16
ENG3002 Topic 2: Gibbs Eqns & Maxwell Rels

For small temperature intervals, hfg can be treated as a constant at some average
value. Then integrating this equation between two saturation states yields

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