Lecture W09

Dr. Ammar Tariq

Gibbs (or Tds) Equations:
 1st Gibbs equation:
Tds = du + Pdv
 2nd Gibbs equation:

Tds = dh − vdP
 Based on these we now define some
Thermodynamic Property Relations including:
 Gibbs Function
 Helmholtz Function
Gibbs Function
 Also called the Gibbs thermodynamic potential, and
is represented by the symbol G.
 It is a measure of free energy available during a
chemical reaction at constant pressure.
 The change in G gives the heat of reaction during a
constant pressure process and is used in
preparation of vapor tables
 By definition: G = H – TS or (g = h – Ts)
(H = enthalpy; T = temperature; S = entropy)
 Gibbs Function
 Consider the relation: G = H – TS
 Differentiating:
dG = dH – TdS – SdT … (1)
 Now 2nd Gibbs equation:
dH = TdS + VdP
 For a constant-pressure (𝑑𝑃 = 0) process:
dH = TdS … (2)
 Combining (1) & (2):
dG = – SdT … (3)
 To prove G = H – TS, consider the TS
curve.
 Gibbs Function
 Area under isobaric line o-a-b-c:
∫Tds = H
 Area to the left of isobaric line o-a-b-c:
∫SdT = G
 But from eq (3):
−∫SdT = G or ∫SdT = −G
 Also, area of rectangle under isothermal
dc = TS
 Hence: TS = ∫Tds + ∫SdT
or TS = H + (−G) oa = heating of liquid
 Then: ab = evaporation of liquid to dry
G = H – TS saturated vapor
bc = superheating of vapor
dc = an isothermal at state c
Gibbs Function
 Consider again the 2nd Gibbs eqn:
dh = Tds + vdP
 Now, the coefficients T and v are partial derivative of
h(s,P) such that:
 h   h 
  = T and   =v
 s  P  P  s
 Since volume is always positive (v > 0), an isentropic
(ds=0) increase in pressure will result in an increase in
enthalpy.
Helmholtz Function
 We introduce Helmholtz function: A = U − TS or a = u – Ts such
that: da = (du – Tds – sdT)
 Combine 1st Gibbs eqn (Tds=du+Pdv) with the differential of a,
 da = (du – Tds – sdT) = (– Pdv – sdT) or da = (– Pdv – sdT)
 The coefficient –P and –s are the partial derivatives of a(v,T),
therefore:  a   a 
  = −P and   = −s
 v T  T  v
 Consider again: da = (– Pdv – sdT)
 For isothermal (dT=0) process, it becomes: Also
2 2
 da = – Pdv or dA = – PdV Hence A1 − A2 =  PdV W1− 2 =  PdV
1
1

 Thus, the decrease in A equals the amount of work done by a closed

system during a reversible-isothermal process!
Helmholtz Function
Q
 Also, since for a reversible isothermal process: S = ( S 2 − S1 ) = 
T0
 Thus, maximum amount of heat that can be transferred to the system
is: Qmax = T0 (S2 – S1)

 Using 1st Law, maximum work output of the system is:

 Wmax = [U1 – U2 + Qmax] = [U1 – U2 + T0 (S2 – S1)]

 = U1 – T0 S1 – (U2 – T0 S2 ) = A1 – A2 (since A = U – TS)

 Conclusion: if a close system passes from one state to another

isothermally while exchanging heat with only the surroundings at
temperature T0, the maximum work produced equals to decrease in
A (the Helmholtz function) of the system.
Gibbs Function and Helmholtz Function
 Note that if the system expands, part of work is done in pushing the
atmosphere back at pressure P0.

 This part of work is: P0 (V2 – V1)

 Useful work means the work done more than that required to push
back the atmosphere, thus: Wuseful = Wmax − P0 (V2 − V1 )

 The maximum useful work if system exchanges heat with only the
atmosphere at T0, is:
Wmax useful = U1 − U 2 + T0 ( S 2 − S1 ) − P0 (V2 − V1 )
= U1 + P0V1 − T0 S1 − (U 2 + P0V2 − T0 S 2 )
 If P2 = P1 = P0 and T2 = T1 = T0 (i.e. simultaneous isothermal & isobaric
process) then:
Wmax useful = H1 − T0 S1 − (H 2 − T0 S 2 ) = G1 − G2
Gibbs Function and Helmholtz Function
 Consider the relation:
Wmax useful = H1 − T0 S1 − (H 2 − T0 S 2 ) = G1 − G2
 Conclusion: If a closed system passes between two
states, in each of which it is at pressure and temperature
of the surrounding atmosphere, and exchanges heat only
with the atmosphere, then the maximum useful work that
can be produced is equal to decrease in G (the Gibbs
function).

 The conditions specified are met by a system undergoing

a chemical reaction in an open vessel.
Gibbs Function and Helmholtz Function
 In other words:
 The decrease in Helmholtz function (𝑨) of a system sets an upper limit to the
work done (𝑊𝑚𝑎𝑥) in any process between two equilibrium states at the same
temperature during which the system exchanges heat only with a single
reservoir at this temperature.
 Since the decrease in the Helmholtz potential represents the potential to do
work by the system, it is also a thermodynamic potential.
 The decrease in Gibbs function of a system sets an upper limit to the work,
exclusive of “Pdv” work in any process between two states at the same
temperature and pressure, provided:
 The system exchanges heat only with a single reservoir at this temperature and
 The surroundings are at a constant pressure equal to that in the end states of the
pressure.
 The maximum work is done when the process is isothermal as well as
isobaric.
 Gibbs function is also called Chemical Potential.
Conclusions
 An isentropic (ds=0) increase in pressure will result in an increase in
enthalpy.
 Decrease in A (the Helmholtz function) equals the amount of work done by a
closed system during a reversible-isothermal process.
 If a close system passes from one state to another isothermally while
exchanging heat with only the surroundings at temperature T0, the maximum
work produced equals to decrease in A (the Helmholtz function) of the
system.
 If a closed system passes between two states, in each of which it is at
pressure and temperature of the surrounding atmosphere, and exchanges
heat only with the atmosphere, then the maximum useful work that can be
produced is equal to decrease in G (the Gibbs function).
 The maximum work is done when the process is isothermal as well as
isobaric.
 A Little Math-Partial Derivatives and
Associated Relations
• State postulate: state of a simple, compressible substance is completely
specified by any two independent, intensive properties.
• All other properties at that state can be expressed in terms of those two
properties.

• where x and y are the two independent

properties that fix the state, and z represents
any other property.
• Consider a function f that depends on a single
variable x, that is,

The derivative of a function f(x) with respect to x

represents the rate of change of f with x.
 Example
The cp of ideal gases depends on temperature only, and it is expressed as
cp(T)=dh(T)/dT.
Determine the cp of air at 300 K, using the enthalpy data from Table A-17, and
compare it to the value listed in Table A-2b.
 Partial Differentials
• Consider a function that depends on two (or more) variables, such as z = z(x, y).

• The variation of z(x, y) with x when y is held constant is called the partial
derivative of z with respect to x

• ∂ represents the partial differential change due to the variation of a single

variable.

• Relation for the total differential change in z(x, y) for simultaneous changes in x
and y
If specific volume had remained constant

If temperature had remained constant

 Partial Differentials Relations

• Taking the partial derivative of M with respect to y and of N with respect to

x yields

Inverse of a partial derivative is equal to its reciprocal.

𝜕𝑧 𝜕𝑥 𝜕𝑧 𝜕𝑧 𝜕𝑥 𝜕𝑦
=− → = −1
𝜕𝑥 𝑦
𝜕𝑦 𝑧
𝜕𝑦 𝑥
𝜕𝑥 𝑦
𝜕𝑦 𝑧
𝜕𝑧 𝑥
 The Maxwell Relations
• The equations that relate the partial derivatives of properties P, v, T, and s of a
simple compressible system to each other are called the Maxwell relations.
• They are obtained from the four Gibbs equations:

• Also called the Gibbs thermodynamic potential, is a measure of free energy

available during a chemical reaction at constant pressure.

• The Helmholtz free energy is a thermodynamic potential that measures the

“useful” work obtainable from a closed thermodynamic system at a
constant temperature and volume.
 The Maxwell Relations

Simplifying the above relations

 The Maxwell Relations
Gibbs equations Gibbs relations are of the form

Applying generalized form to each of the Gibbs relations

These relations provide a means of determining the change in entropy, which cannot
be measured directly, by simply measuring the changes in properties P, v, and T.
 The Clapeyron Equation
• Used to determine the enthalpy change associated with a phase change (such
as the enthalpy of vaporization hfg) from a knowledge of P, v, and T data alone.

• Consider the third Maxwell relation

• During a phase-change process, the pressure is the saturation pressure, which

depends on the temperature only and is independent of the specific volume.
That is,

which is the slope of the saturation curve on a P-T

diagram at a specified saturation state.

• This slope is independent of the specific volume,

and thus it can be treated as a constant during the
integration of the above Maxwell relation between
two saturation states at the same temperature.
 The Clapeyron Equation
For an isothermal liquid–vapor phase-change process, for
example, the integration yields

During this process, the pressure also remains constant.

Therefore, from Equation:

• Thus, the enthalpy of vaporization hfg at a given temperature can be determined

by simply measuring the slope of the saturation curve on a P-T diagram and the
specific volume of saturated liquid and saturated vapor at the given temperature.

• The Clapeyron equation is applicable to any phase-change process that occurs at

constant temperature and pressure. It can be expressed in a general form as:

where the subscripts 1 and 2 indicate the two phases.

 Example
Evaluating The hfg Of a Substance From the P-v-t Data
Using the Clapeyron equation, estimate the value of the enthalpy of vaporization of
refrigerant-134a at 20oC, and compare it with the tabulated value.

The tabulated value of hfg at 20oC is 182.33 kJ/kg.

The small difference between the two values is due to the approximation used in
determining the slope of the saturation curve at 20oC.
 Clapeyron–Clausius equation
• The Clapeyron equation can be simplified for liquid–vapor and solid–vapor
phase changes by utilizing some approximations.
• At low pressures vg >> vf, and thus

• By treating the vapor as an ideal gas, we have vg = RT/P.

• Substituting these approximations into

• For small temperature intervals hfg can be treated as a constant at some

average value.
• Then integrating this equation between two saturation states yields

• used to determine the variation of saturation pressure with temperature.

• It can also be used in the solid–vapor region by replacing hfg by hig (the enthalpy
of sublimation) of the substance.
EXAMPLE 12–6: (page-667)
 Estimate the saturation pressure of refrigerant-134a at
−45°C, using the data available in the refrigerant tables.
Solution: Table A–11 lists saturation data at temperatures
−40°C and above. Therefore, we use extrapolation to
obtain saturation data at lower temperatures. Or we can
consider Equation 12–24:

In our case T1 = −40°C and T2 = −45°C .

For refrigerant-134a, R = 0.08149 kJ/kg K
Also, from Table A–11 at −40°F:
hfg = 225.86 kJ/kg
P1 = Psat @ −40°C = 51.25 kPa.
 EXAMPLE 12–6: (page-667)
 Estimate the saturation pressure of refrigerant-134a at
−45°C, using the data available in the refrigerant tables.
 We had:
 hfg = 225.86 kJ/kg
 P1 = Psat @ −40°C = 51.25 kPa.
 Substituting these values into eq. 12.24
 P2  225.86 kJ/kg  1 1 
ln   −  → P2 = 39.48 kPa
 51.25 kPa  0.08149 kJ/kg.K  233 K 228 K 
• Analysis:
• The actual value, obtained from another source = 39.15 kPa
• Value predicted by Eq. 12–24 = 39.48 kPa (error by about 1%)
• The linear extrapolation returns the value = 37.23 kPa (error by 5%)
 General Relations for du, dh, ds, cv and cP
• Develop general relations for changes in internal energy, enthalpy,
and entropy in terms of pressure, specific volume, temperature, and
specific heats alone.

• Develop some general relations involving specific heats.

• The relations developed will enable us to determine the changes in

these properties.
Internal Energy Changes

The change in internal energy of a simple compressible system associated

with a change of state from (T1, v1) to (T2, v2) is determined by:
 General Relations for du, dh, ds, cv and cP
Enthalpy Changes
The change in enthalpy of a simple compressible system associated with a change of
state from (T1, P1) to (T2, P2) is determined by

Entropy Changes

Two general relations for the entropy change of a simple compressible system.

Choice depends on the available data.

Important Assignment
Important Assignment
Important Assignment
Important Assignment