Measurements in daily life

 In daily life, many physical quantities are used in measurements such as temperature,
volume, length and pressure.

Pressure

Temperature Volume

2
 Thermodynamic measurements

 In thermodynamics, experimental measurements are also very important because

thermodynamics alone is generally not sufficient to solve engineering problems

 Unfortunately, not all thermodynamic properties are measurable.

 Let’s focus on the following main thermodynamic properties:

A U H T: Temperature
P: Pressure
Thermodynamic V: Volume
Properties U: Internal energy
T P V S : Entropy
H: Enthalpy
A : Helmholtz free energy
G : Gibbs free energy
G S

 Note that, two new thermodynamic properties (A & G) are introduced. 3

 Thermodynamic properties

 There are three types of thermodynamic properties:

1 Measured Properties P, V, T, composition

(measurable)

U (From the first law of thermodynamics)

2 Fundamental Properties

(not measurable) S (From the second law of thermodynamics)

3 Derived thermodynamic properties H, A, G

(not measurable)

Enthalpy Helmholtz energy Gibbs energy

𝐻 = 𝑈 + 𝑃𝑉 𝐴 = 𝑈 − 𝑇𝑆 𝐺 = 𝐻 − 𝑇𝑆
4
 More measurable properties

 The following thermodynamic properties are measurable:

 Cp : Heat capacity at constant pressure

𝐶𝑝 𝐶𝑣 𝛽
 Cv : Heat capacity at constant volume

𝜅  β : Volume expansivity

 κ: Isothermal compressibility

 Volume expansivity and isothermal compressibility are volumetric properties

 Heat capacity is a thermal property

5
 Thermodynamic properties

Process Main Problem Calculate heat & work?

HOW?
Heat and work are related to
changes of internal energy and
entropy.

 Are work and heat related to internal energy and entropy?!!

Yes. For example, you could see that from the 1st and 2nd laws in a closed system
and reversible process:

 1st law 𝑑𝑈 = 𝑑𝑄𝑟𝑒𝑣 + 𝑑𝑊 ( Q and W are related to ∆𝑈)

 2nd law 𝑑𝑄𝑟𝑒𝑣 = 𝑇𝑑𝑆 𝑑𝑈 = 𝑇𝑑𝑆 + 𝑑𝑊 ( Q and W are related to ∆𝑆)

6
 Thermodynamic properties

 The problem is now: how to obtain the change of internal energy and entropy?

Internal energy and entropy cannot directly be measured from experiment.

Therefore, we cannot find the values of Q and W for a process unless we

find the change of internal energy and entropy.

If internal energy and entropy cannot directly be measured, Is there a method

that would assist to find them indirectly?

Yes, this could be done by first relating

internal energy and entropy to measurable
properties such as T, P and V.

 This chapter sheds light on how to relate unmeasurable properties such as change in
internal energy, entropy, Helmholtz energy and Gibbs energy to measurable properties
such as T, P, V and Cp. 7
 Towards relating unmeasurable to measurable properties

 The change of thermodynamic potentials could be related in terms of measurable

properties
dU
dS T
dH P
dA V ..etc.
dG
 The initial step towards relating the unmeasurable to measurable properties is to
define the total differentials of energy functions (i.e. dU, dH, dA and dG) in terms
of two independent variables* which are called natural variables.

 The four fundamental thermodynamic potentials (U, H, A and G) are defined in

terms of their natural variables as follows:

Thermodynamic Natural
Why two potential variables
variables?
U S&V
H S&P
A T&V
G T&P

* Two variables because we consider a pure component and a single phase in this chapter. 8
 The differential expression of the potential U (dU)

 For a closed system and single phase

 The first law of thermodynamics for a closed system and reversible process is given by:

𝑑𝑈 = 𝑑𝑄𝑟𝑒𝑣 + 𝑑𝑊𝑟𝑒𝑣 (1)

 𝑑𝑊𝑟𝑒𝑣 and 𝑑𝑄𝑟𝑒𝑣 are defined as follows:

𝑑𝑊𝑟𝑒𝑣 = −𝑃𝑑𝑉 (2) 𝑑𝑄𝑟𝑒𝑣 = 𝑇𝑑𝑆 (3)

 From the above equations, we get the first fundamental equation:

𝑑𝑈 = 𝑇 𝑑𝑆 − 𝑃 𝑑𝑉 (4)

 Note that the change in dU is given in terms of the change of S and V (i.e dS and dV)
which arise naturally. This is why S and V are called the natural variables of U.

9
 The differential expression of the potential U (dU)

 The first fundamental equation for a closed system is given by:

𝑑𝑈 = 𝑇 𝑑𝑆 − 𝑃 𝑑𝑉 (4)

 The first fundamental equation

 is a combination of the first and second laws of thermodynamics

 contains only properties of the system.

 represents a differential change between equilibrium states.

 Is the first fundamental equation limited to reversible processes?

 The equation was derived for a reversible process as seen in the previous
slide. However, it depends on the change between the properties and not
on the path of the process . Therefore, the equation can be applied to any
process whether it is reversible or irreversible process.

10
 The differential expression of the potential H (dH)

 Enthalpy is a derived thermodynamic property and defined as:

𝐻 = 𝑈 + 𝑃𝑉 (5)

 The enthalpy is defined this way because in open systems, two terms contribute
to the energy; internal energy and flow work (PV). This is why it is convenient to
define a property that includes both contributions.

 The change of enthalpy is given by the differential form of 5:

𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 (6)

 dU is defined by equation 4. Therefore, substitute 4 into 6:

𝑑𝐻 = 𝑇 𝑑𝑆 − 𝑃 𝑑𝑉 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 (7)

 Equation 7 is simplified to:
𝑑𝐻 = 𝑇 𝑑𝑆 + 𝑉𝑑𝑃 (8)

 Note that dS and dP appear naturally. This is why S and P are called natural variables of H.

11
 The differential expression of the potential A (dA)

 The Helmholtz free energy is defined as follows:

𝐴 = 𝑈 − 𝑇𝑆 (9)

 The change of the Helmholtz free energy is given by the following differential form :

𝑑𝐴 = 𝑑𝑈 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 (10)

 By using equation 4, equation10 becomes:

𝑑𝐴 = 𝑇 𝑑𝑆 − 𝑃 𝑑𝑉 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 (11)

 Finally, the change of the Helmholtz free energy is given by:

𝑑𝐴 = −𝑆𝑑𝑇 − 𝑃 𝑑𝑉 (12)

12
 The differential expression of the potential G (dG)

 The Gibbs free energy is defined as follows:

𝐺 = 𝐻 − 𝑇𝑆 (13)

 The change of the Helmholtz free energy is given by the following differential form :

𝑑𝐺 = 𝑑𝐻 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 (14)

 By using equation 8, equation 14 becomes:

𝑑𝐺 = 𝑇 𝑑𝑆 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 (15)

 Finally, the change of the Gibbs free energy is given by:

𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 (16)

13
Summary of the four fundamental thermodynamic potentials

dU  TdS  PdV

dH  TdS  VdP

dA  PdV  SdT

dG  VdP  SdT

 The above four equations are also called Gibbs equations.

14
Let’s review a little mathematics

15
 Total differential of F (dF)

 If F is a function of x and y (i.e. F(x,y)), the total differential of F is given by

𝜕𝐹 𝜕𝐹
𝑑𝐹 = 𝑑𝑥 + 𝑑𝑦 (17)
𝜕𝑥 𝑦
𝜕𝑦 𝑥

or 𝑑𝐹 = 𝑀 𝑑𝑥 + 𝑁𝑑𝑦 (18)

𝜕𝐹 𝜕𝐹
𝑀= 𝑁=
𝜕𝑥 𝑦
𝜕𝑦 𝑥

 Note that x and y is called independent variables and F is dependent function.

 If f is a function of x and y, the right hand side of 17 is called an exact differential expression
when:

𝜕𝑁 𝜕𝑀
= (19)
𝜕𝑥 𝑦
𝜕𝑦 𝑥

 Equation 19 is considered as the criterion of exactness.

16
 Exact differential

 Test the following differential expression to determine if it is an exact differential:

 𝑑𝑧 = (𝑦 2 − 2𝑥)𝑑𝑥 + (2𝑥𝑦 + 1)dy

 The exactness criterion should be tested:

𝜕𝑀
𝑀 = 𝑦 2 − 2𝑥 = 2𝑦
𝜕𝑦 𝑥

𝜕𝑁
𝑁 = (2𝑥𝑦 + 1) = 2𝑦
𝜕𝑥 𝑦

𝜕𝑁 𝜕𝑀
=
𝜕𝑥 𝑦
𝜕𝑦 𝑥

2𝑦 = 2𝑦

 The above differential expression is an exact differential.

17
 Exact differential

 Test the following differential expressions to determine which one is an exact differential:
4
𝑥
 𝑑𝑧 = 𝑥 3 𝑦𝑑𝑥 + dy
4

 𝑑𝑧 = 𝑥 3 𝑦 3 𝑑𝑥 + 𝑥 3 𝑦 3 dy

 𝑑𝑧 = 𝑥 2 𝑦 3 𝑑𝑥 + 𝑥 3 𝑦 2 dy

18
 Why exact differential ?

 In thermodynamics, the exact differential criterion would help:

 to derive many thermodynamic relationships.

 to express thermodynamic properties in terms of measurable quantities

19
 Maxwell Equations

 Maxwell used the exact differential criterion with the four Gibbs energy:

 For example, the total differential of U (dU) is given by:

𝑑𝑈 = 𝑇 𝑑𝑆 − 𝑃 𝑑𝑉

 Maxwell used the criterion of the exact differential as follows

 T   P 
    
 V S  S V

20
 Maxwell relations

 Maxwell gave the exact differential for the four Gibbs equation:

dU  TdS  PdV  T   P 
    
 V S  S V

dH  TdS  VdP  T   V 
   
 P S  S P

 P   S 
dA  PdV  SdT    
 T V  V T

 V   S 
dG  VdP  SdT     
 T P  P T

21
 Internal energy as function of temperature and volume
𝑼 = 𝑼(𝑻, 𝑽)
𝜕𝑈 𝜕𝑈
𝑑𝑈 = 𝑑𝑇 + 𝑑𝑉
𝜕𝑇 𝑉
𝜕𝑉 𝑇

𝜕𝑈 𝜕𝑈
𝜕𝑇 𝑉
𝜕𝑉 𝑇

 The fundamental equation of dU is given by

dU = TdS − PdV

𝜕𝑈 𝜕𝑈 𝑇𝜕𝑆 − 𝑃𝜕𝑉 𝜕𝑆
𝐶𝑉 = = =𝑇 −𝑃
𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝜕𝑉 𝑇
𝜕𝑉 𝑇

 From Maxwell’s relations, we know that

𝜕𝑆 𝜕𝑃
=
𝜕𝑉 𝑇
𝜕𝑇 𝑉

 Recall: Cv is measurable property 𝜕𝑈 𝑇𝜕𝑆 − 𝑃𝜕𝑉 𝜕𝑃

= =𝑇 −𝑃
𝜕𝑉 𝑇
𝜕𝑉 𝑇
𝜕𝑇 𝑉

𝜕𝑈 𝜕𝑈 𝜕𝑃
𝑑𝑈 = 𝑑𝑇 + 𝑑𝑉 = 𝐶𝑉 𝑑𝑇 + 𝑇 − 𝑃 𝑑𝑉
𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝜕𝑇
𝑉

𝜕𝑃
∆𝑈 = 𝐶𝑉 𝑑𝑇 + 𝑇 − 𝑃 𝑑V
𝜕𝑇 𝑉 22
 CV in terms of entropy

𝜕𝑈
𝐶𝑉 =
𝜕𝑇 𝑉

 The fundamental equation of dU is given by

dU = TdS − PdV

𝜕𝑈 𝜕𝑆 𝜕𝑉
𝐶𝑉 = =𝑇 −𝑃
𝜕𝑇 𝑉
𝜕𝑇 𝑉
𝜕𝑇 𝑉

0
𝜕𝑆
𝐶𝑉 = 𝑇
𝜕𝑇 𝑉

𝐶𝑉 𝜕𝑆
=
𝑇 𝜕𝑇 𝑉

23
Entropy as function of temperature and volume
𝑺 = 𝑺(𝑻, 𝑽)
𝜕𝑆 𝜕𝑆
𝑑𝑆 = 𝑑𝑇 + 𝑑𝑉
𝜕𝑇 𝑉
𝜕𝑉 𝑇

𝜕𝑆 𝜕𝑆
𝜕𝑇 𝑉
𝜕𝑉 𝑇

 From Maxwell’s relations, we know that

𝜕𝑆 𝐶𝑉
=
𝜕𝑇 𝑉
𝑇 𝜕𝑆 𝜕𝑃
=
𝜕𝑉 𝑇
𝜕𝑇 𝑉

𝐶𝑉 𝜕𝑃
𝑑𝑆 = 𝑑𝑇 + 𝑑𝑉
𝑇 𝜕𝑇 𝑉

𝐶𝑉 𝜕𝑃
∆𝑆 = 𝑑𝑇 + 𝑑𝑉
𝑇 𝜕𝑇 𝑉

24
 Enthalpy as function of temperature and pressure
𝑯 = 𝑯(𝑻, 𝑷)
𝜕𝐻 𝜕𝐻
𝑑𝐻 = 𝑑𝑇 + 𝑑𝑃
𝜕𝑇 𝑃
𝜕𝑃 𝑇

𝜕𝐻 𝜕𝐻
𝜕𝑇 𝑃
𝜕𝑃 𝑇

 The fundamental equation of dH is given by

dH = TdS + VdP

𝜕𝐻 𝜕𝐻 𝑇𝜕𝑆 + 𝑉𝜕𝑃 𝜕𝑆
𝐶𝑝 = = =𝑇 +𝑉
𝜕𝑇 𝑃
𝜕𝑃 𝑇
𝜕𝑃 𝑇
𝜕𝑃 𝑇

 From Maxwell’s relations, we know that

𝜕𝑆 𝜕𝑉
=−
𝜕𝑃 𝑇
𝜕𝑇 𝑃

 Recall: Cv is measurable property 𝜕𝐻 𝑇𝜕𝑆 + 𝑉𝜕𝑃 𝜕𝑉

= = −𝑇 +𝑉
𝜕𝑃 𝑇
𝜕𝑃 𝑇
𝜕𝑇 𝑃

𝜕𝐻 𝜕𝐻 𝜕𝑉
𝑑𝐻 = 𝑑𝑇 + 𝑑𝑃 = 𝑑𝐻 = 𝐶𝑝 𝑑𝑇 + −𝑇 + 𝑉 𝑑𝑃
𝜕𝑇 𝑃
𝜕𝑃 𝑇
𝜕𝑇
𝑃

𝜕𝑉
∆𝐻 = 𝐶𝑝 𝑑𝑇 + V−𝑇 𝑑𝑃
𝜕𝑇 𝑃 25
 Cp in terms of entropy

𝜕𝐻
𝐶𝑝 =
𝜕𝑇 𝑃

 The fundamental equation of dH is given by

dH = TdS + VdP

𝜕𝐻 𝜕𝑆 𝜕𝑃
𝐶𝑝 = =𝑇 +𝑉
𝜕𝑇 𝑃
𝜕𝑇 𝑃
𝜕𝑇 𝑃

0
𝜕𝑆
𝐶𝑝 = 𝑇
𝜕𝑇 𝑃

𝐶𝑝 𝜕𝑆
=
𝑇 𝜕𝑇 𝑃

26
Entropy as function of temperature and volume
𝑺 = 𝑺(𝑻, 𝑷)
𝜕𝑆 𝜕𝑆
𝑑𝑆 = 𝑑𝑇 + 𝑑𝑃
𝜕𝑇 𝑃
𝜕𝑃 𝑇

𝜕𝑆 𝜕𝑆
𝜕𝑇 𝑃
𝜕𝑃 𝑇

 From Maxwell’s relations, we know that

𝜕𝑆 𝐶𝑃
=
𝜕𝑇 𝑃
𝑇 𝜕𝑆 𝜕𝑉
=−
𝜕𝑃 𝑇
𝜕𝑇 𝑃

𝐶𝑃 𝜕𝑉
𝑑𝑆 = 𝑑𝑇 − 𝑑𝑃
𝑇 𝜕𝑇 𝑃

𝐶𝑃 𝜕𝑉
∆𝑆 𝑇, 𝑃 = 𝑑𝑇 − 𝑑𝑃
𝑇 𝜕𝑇 𝑃

27
Change of volume as a function of T and P

𝑉 = 𝑉(𝑇, 𝑃)

 Two new measurable intensive properties:

 Volume expansivity (𝛽)

 Isothermal compressibility(𝜅)

28
 Change of volume as a function of T and P

 If V is a function of T and P (i.e. 𝑉 = 𝑉(𝑇, 𝑃) ), the change in 𝑑𝑉 is given by:

𝜕𝑉 𝜕𝑉
𝑑𝑉 = 𝑑𝑇 + 𝑑𝑃
𝜕𝑇 𝑃
𝜕𝑃 𝑇

 There are two thermodynamic properties related to the above partial derivatives:

1 𝜕𝑉
 Volume expansivity: 𝛽=
𝑉 𝜕𝑇 𝑃

1 𝜕𝑉
 Isothermal compressibility: 𝜅 = −
𝑉 𝜕𝑃 𝑇

 The change of volume could be given in terms of 𝛽 and 𝜅 as:

𝑑𝑉
= 𝛽𝑑𝑇 − 𝜅𝑑𝑃
𝑉

29
 Volume expansivity

1 𝜕𝑉
 Volume expansivity: 𝛽=
𝑉 𝜕𝑇 𝑃

 volumetric property

 intensive property

 Measurable property

 dimension is 1/T
 Always positive (except for liquid water between 0 and 4 oC)

 The volume expansivity is an indication of the change in volume that

occurs when temperature changes while pressure remains constant.

 At normal boiling point,

𝛽 = 270 ∗ 10−5 𝐾 −1 for water vapor

𝛽 = 75 ∗ 10−5 𝐾 −1 for water liquid

 The above values indicate that if you heat a substance at fixed pressure, it is:
 easier to change the volume of the gas (bigger value).
 more difficult to change the volume of a liquid.
30
 Isothermal compressibility

1 𝜕𝑉
 Isothermal compressibility: 𝜅 = −
𝑉 𝜕𝑃 𝑇
 volumetric property

 intensive property

 Measurable property

 dimension is 1/P
 positive

 The isothermal compressibility is an indication of the change in volume that

takes place when pressure changes while temperature remains constant. The
value is always positive for all substances in all phases.

 At normal boiling point,

𝜅 = 1 𝑏𝑎𝑟 −1 for water vapor

𝜅 = 4.9 ∗ 10−7 𝑏𝑎𝑟 −1 for water liquid

 The values indicates that it is easy to change the volume of vapour but difficult
for liquid

31
 Methods for transforming derivatives

More mathematical tricks for partial

derivatives to proceed towards relating
unmeasurable in terms of measurable
properties

 The following mathematical methods are very helpful in relating the

thermodynamic variables in terms of more convenient variables

 Derivative inversion

 Triple Product

 Chain rule expansion to add another independent variable z.

32
 Methods for transforming derivatives

 Derivative inversion (It is also called reciprocal relation)

𝜕𝐹 1
=
𝜕𝑦 𝑥
𝜕𝑦/𝜕𝐹 𝑥

 Example:

𝜕𝑆 1
=
𝜕𝑃 𝑇
𝜕𝑃/𝜕𝑆 𝑇

33
 Methods for transforming derivatives

 Triple Product (it is also called xyz-1 rule or cyclic relation)

𝜕𝐹 𝜕𝑥 𝜕𝑦
= −1
𝜕𝑥 𝑦
𝜕𝑦 𝐹
𝜕𝐹 𝑥

 Example:

𝜕𝐻 𝜕𝑇 𝜕𝑃
= −1
𝜕𝑇 𝑃
𝜕𝑃 𝐻
𝜕𝐻 𝑇

 Practice: Prove that the ideal gas law satisfy xyz-1 rule?

34
 Methods for transforming derivatives

 Chain rule expansion to add another independent variable z:

𝜕𝐹 𝜕𝐹/𝜕𝑧 𝑥 𝜕𝐹 𝜕𝑧
= =
𝜕𝑦 𝑥
𝜕𝑦/𝜕𝑧 𝑥 𝜕𝑧 𝑥
𝜕𝑦 𝑥

 Example:

𝜕𝑆 𝜕𝑆/𝜕𝑇 𝑃 𝐶𝑝 /𝑇 1
= = =
𝜕𝐻 𝑃
𝜕𝐻/𝜕𝑇 𝑃 𝐶𝑝 𝑇

35
 Jacobian Transformation
Jacobian transformation is a useful technique used to relate thermodynamic properties
and their derivatives

The Jacobian transformation could be

used as an alternative method to what
was given in previous slides

36
 Jacobian Transformation

 Assume f is a function of x and y and g is also a function of x and y:

f  f ( x, y)

g  g ( x, y)

 The Jacobian of f and g with respect to x and y is defined as follows:

f f
 f, g  x y  f g f g 
J   g    
 x, y  g  x y y x 
x y

 For simplicity, the Jacobian is given by:

determinant

 f, g   f , g 
J  
 x, y  x, y 
37
 Jacobian Transformation

 From the properties of the determinants, the following important Jacobian properties
could be defined:

f , f  0

 f , g    g, f 

 f , h   f 
g , h  g h

 f , g  x, y    f , g 
x, y  m, n m, n
38
 Jacobian Transformation

 Example Write the Jacobian for the following partial derivative:

𝜕𝐹
𝑀=
𝜕𝑥 𝑦

 Solution

 Apply the third Jacobian property in in slide 38:

𝜕𝐹 𝐹, 𝑦
𝑀= =
𝜕𝑥 𝑦
𝑥, 𝑦

39
 Jacobian Transformation

 Example Write the Jacobian for the following equations:

𝐶𝑝 𝜕𝑆
 =
𝑇 𝜕𝑇 𝑃

𝐶𝑉 𝜕𝑆
 𝑇
=
𝜕𝑇 𝑉

 Solution

𝐶𝑝 𝜕𝑆 Cp

S , P 
 𝑇
=
𝜕𝑇 𝑃 T T , P 

𝐶𝑉 𝜕𝑆 CV

S ,V 
 𝑇
=
𝜕𝑇 𝑉
T T ,V 
 Jacobian Transformation

 The Jacobians for the isothermal compressibility and volume expansivity are
given as follows:

1 𝜕𝑉 
V , P
𝛽=
 Volume expansivity
𝑉 𝜕𝑇 V T , P 
𝑃

1 𝜕𝑉
 
V , T 
 Isothermal compressibility 𝜅=−
𝑉 𝜕𝑃 𝑇
V P, T 

41
 Jacobian Transformation

 Example Write the Jacobian for the following total differential:

𝜕𝐹 𝜕𝐹
𝑑𝐹 = 𝑑𝑥 + 𝑑𝑦
𝜕𝑥 𝑦
𝜕𝑦 𝑥

 Solution

𝜕𝐹 𝐹, 𝑦 𝜕𝐹 𝐹, 𝑥
𝑀= = 𝑁= =
𝜕𝑥 𝑦
𝑥, 𝑦 𝜕𝑦 𝑥
𝑦, 𝑥

𝐹, 𝑦 𝐹, 𝑥
𝑑𝐹 = 𝑑𝑥 + 𝑑𝑦
𝑥, 𝑦 𝑦, 𝑥
 Multiply each term by 𝑥, 𝑦

x, ydF  F , ydx  F , xdy

 Take all terms to the left hand side:

x, ydF  y, F dx  F , xdy  0

 Jacobian Transformation

 A cyclic relation with four variables F, x, y and b:

𝑥, 𝑦 𝐹, 𝑏 + 𝑦, 𝐹 𝑥, 𝑏 + 𝐹, 𝑥 𝑦, 𝑏 = 0

 An important Jacobian form for the exact differentials is given by:

𝐹, 𝑏 = 𝑀 𝑥, 𝑏 + 𝑁[𝑦, 𝑏]
 The Four Fundamental equations in the Jacobian form

 The last equation in the previous slide could be used to write the Gibbs equations
in the Jacobian form:

dU  TdS  PdV [U , x]  T S , x  PV , x

dH  TdS  VdP [ H , x]  T S , x  V P, x

dA  PdV  SdT [ A, x]  S T , x  PV , x

dG  VdP  SdT [G, x]  S T , x  V P, x

 Note that x is a dummy variable

 Maxwell Relations in the Jacobian form

 All Maxwell Relations could be converted to one equation in the Jacobian form:

 T   P 
    
 V  S  S V

 T   V 
    
 P S  S P
T , S   P,V 
 P   S 
   
 T V  V T

 V   S 
    
 T P  P T

Practice: Try to verify that all Maxwell relations are converted into [T,S]=[P,V]
 𝑆, 𝑉 Cv
𝑆, 𝑃 Cp

𝑆, 𝑇 Maxwell’s
Think this way
𝑃, 𝑉, 𝑇 𝛽, 𝜅

46
 Jacobian Transformation

 Example:

 Use the Jacobian method to derive the following relation:

 T 
dU  CV dT    P  dV
  
 Solution:
𝑈 = 𝑈(𝑇, 𝑉)
𝜕𝑈 𝜕𝑈 𝑈, 𝑉 𝑈, 𝑇
𝑑𝑈 = 𝑑𝑇 + 𝑑𝑉 𝑑𝑈 =
𝑇, 𝑉
𝑑𝑇 +
𝑉, 𝑇
𝑑𝑉 (1)
𝜕𝑇 𝑉
𝜕𝑉 𝑇

 From the first Gibbs equation: use the dummy variable as V

[U , x]  T S , x  PV , x 𝑈, 𝑉 = 𝑇 𝑆, 𝑉 − 𝑃 𝑉, 𝑉 𝑈, 𝑉 = 𝑇 𝑆, 𝑉 (2)
0
 From the first Gibbs equation: use the dummy variable as T
[U , x]  T S , x  PV , x 𝑈, 𝑇 = 𝑇 𝑆, 𝑇 − 𝑃 𝑉, 𝑇 (3)
 Insert 2 and 3 into 1:
𝑇 𝑆, 𝑉 𝑇 𝑆, 𝑇 − 𝑃 𝑉, 𝑇
𝑑𝑈 = 𝑑𝑇 + 𝑑𝑉
𝑇, 𝑉 𝑉, 𝑇
 Jacobian Transformation

 Example:
𝑇 𝑆, 𝑉 𝑇 𝑆, 𝑇 − 𝑃 𝑉, 𝑇
𝑑𝑈 = 𝑑𝑇 + 𝑑𝑉
𝑇, 𝑉 𝑉, 𝑇

CV S ,V 
 We know that: 
T T ,V 

 From Maxwell relations: T , S   P,V 

𝑇 𝑉, 𝑃 − 𝑃 𝑉, 𝑇 𝑇 𝑉, 𝑃
𝑑𝑈 = 𝐶𝑉 𝑑𝑇 + 𝑑𝑉 𝑑𝑈 = 𝐶𝑉 𝑑𝑇 + − 𝑃 𝑑𝑉
𝑉, 𝑇 𝑉, 𝑇

 T 
dU  CV dT    P  dV
  