2.

0 THERMODYNAMIC RELATIONSHIPS

2.1 Properties of differential relationships of state functions

State functions have three important mathematical properties.

(1) Definite integrals

If you integrate a state function

𝐵

∆𝑈𝐴→𝐵 = ∫ 𝑑𝑈
𝐴
the integral must have a definite value that is independent of the path of integration from
A to B.

(2) We can write perfect differentials

If Z = Z (X, Y) (e.g., two degrees of freedom for single component, single phase), then:

𝜕𝑍 𝜕𝑍
𝑑𝑧 = (𝜕𝑋) 𝑑𝑋 + (𝜕𝑌) 𝑑𝑌
𝑌 𝑋

𝜕𝑃 𝜕𝑃
e.g. 𝑑𝑃 = ( ) 𝑑𝑇 + ( ) 𝑑𝑉
𝜕𝑇 𝑉 𝜕𝑉
𝑇

Example

Estimate the change in pressure of ole of ideal gas if the temperature is changed fro273.15K to 274.00 K and the
volume is changed from 10.00 L to 9.90 L.

Answer = 0.030 bar

(3) The order of differential for second derivatives

If Z = Z (X, Y)
For second derivatives of state functions, the order of differentiation does not matter:

CHE 311 Handout 3, page 1/13

2.2 Relationships between state functions

2.2.1 Fundamental Equations

Four Fundamental Equations relate functions of state to each other using the 1st and 2nd laws of
thermodynamics.

• 1st law with expansion work: dU = dq − Pext dV

nd
• Use 2 law: dqrev = Td S

• For the special case of a reversible process: 𝑃𝑒𝑥𝑡 = P and dqrev = Td S

NOTE:

(1) This fundamental equation only contains state variables, and this is true for the other
three.

(2) Although the equation was derived for a reversible process, the equation is always correct
and valid for a closed system, even in the presence of an irreversible process.

This is because U, T, S, p and V are all state functions and hence

independent of path

All of the primary thermodynamic properties (P, V, T, U, and S) are included in the equation
above. Additional thermodynamic properties arise only by definition in relation to these primary
properties.

Recall definitions:

H = U + PV

G = H – TS

A = U - TS

Each of these defined properties leads directly to an equation like dU = TdS - PdV

CHE 311 Handout 3, page 2/13

We can write a similar equation for enthalpy

• Similarly, from A = U - TS

• In analogous fashion, from G = H - TS

We have now introduced all our state functions. So, in general, for a closed system

U (S,V )  dU =TdS − pdV

H (S , p )  dH =TdS +Vdp Fundamental equations
A (T ,V )  dA = −SdT − pdV
G (T , p )  dG = −SdT +Vdp
(Note that these are function of changes in two state variables)

NOTE: These fundamental property relations are general equations for a homogeneous fluid of
constant composition (closed system).

CHE 311 Handout 3, page 3/13

 2.2.2 The Maxwell Relations

From the 3rd and 4th fundamental equations we obtain:

For second derivatives of state functions, the order of differentiation does not matter:

𝜕2𝐴 𝜕2𝐴 𝜕2 𝐺 𝜕2𝐺

= and =
𝜕𝑉𝜕𝑇 𝜕𝑇𝜕𝑉 𝜕𝑃𝜕𝑇 𝜕𝑇𝜕𝑃

Hence from the 4th Equation:

(and similar expressions from the other master equations)

These expressions are called the Maxwell relations and they are:

These are used to calculate changes in properties that are difficult to measure in terms of properties
that are easy to measure. They only feature S, T, V, P and no other temperature dependent variables.
They are thus useful to remove one of these (often S) from an expression.

We thus now have lots of equations! The important things are:

1. be able to write down/derive the four master equations and

2. be able to do the manipulations that give the other relationships

CHE 311 Handout 3, page 4/13

2.2.3 Enthalpy and Entropy as Functions of T and P

The most useful property relations for the enthalpy and entropy of a homogeneous phase result when
these properties are expressed as functions of T and P.

Therefore, the functional relations chosen here for H and S are:

H = H (T,P); S = S (T,P)

For a single component system, we can write

𝜕𝐻 𝜕𝐻 𝜕𝑆 𝜕𝑆
⇒ 𝑑𝐻 = ( 𝜕𝑇 ) 𝑑𝑇 + ( 𝜕𝑃 ) 𝑑𝑃 and 𝑑𝑆 = (𝜕𝑇) 𝑑𝑇 + (𝜕𝑃) 𝑑𝑃
𝑃 𝑇 𝑃 𝑇

The information on the variation of H and S with temperature and pressure is contained in the
derivatives:

𝜕𝐻 𝜕𝑆 𝜕𝐻 𝜕𝑆
( 𝜕𝑇 ) ; (𝜕𝑇) ; ( 𝜕𝑃 ) ; (𝜕𝑃)
𝑃 𝑃 𝑇 𝑇

Consider first the temperature derivatives.

𝜕𝐻
The constant heat capacity is defined as: 𝐶𝑃 = ( )
𝜕𝑇 𝑃
𝜕𝐻 𝜕𝑆
from 𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 ⇒ ( ) = 𝑇( )
𝜕𝑇 𝑃 𝜕𝑇 𝑃
𝜕𝑆 𝐶𝑃
⇒ (𝜕𝑇) =
𝑃 𝑇

CHE 311 Handout 3, page 5/13

We can also derive this expression though the chain rule:

Consider the pressure derivatives

𝜕𝑆 𝜕𝑉
• The Maxwell relationships: (𝜕𝑃) = − (𝜕𝑇 )
𝑇 𝑃

𝜕𝐻 𝜕𝑆
• From dH = TdS + VdP ( 𝜕𝑃 ) = 𝑇 (𝜕𝑃) + 𝑉
𝑇 𝑇

𝜕𝐻 𝜕𝑆
( 𝜕𝑃 ) = 𝑉 − 𝑇 (𝜕𝑃)
𝑇 𝑇

𝜕𝑉
• Hence dH = 𝐶𝑃 𝑑𝑇 + [𝑉 − 𝑇 (𝜕𝑇 ) ] 𝑑𝑃
𝑝

𝐶𝑃 𝜕𝑉
𝑑𝑆 = 𝑇
𝑑𝑇 − (𝜕𝑇 ) 𝑑𝑃
𝑝
These are general equations relating the properties of homogeneous fluids of a constant composition to
temperature and pressure.

𝑅𝑇 𝜕𝑉 𝑅
Special case: ideal gas ; 𝑃𝑉 = 𝑃
⇒ (𝜕𝑇 ) = 𝑃
𝑝

𝜕𝑉
⇒ dH = 𝐶𝑃 𝑑𝑇 + [𝑉 − 𝑇 (𝜕𝑇 ) ] 𝑑𝑃 = 𝐶𝑃 𝑑𝑇 + [𝑉 − 𝑉] 𝑑𝑃
𝑝

⸫ dH = 𝐶𝑃 𝑑𝑇 ⇒𝑑𝐻 = 𝑓(𝑇)
• Hence the enthalpy of an ideal gas is independent of pressure.
𝜕𝑉
• Real gases: we need to know 𝑉 − 𝑇 (𝜕𝑇 ) in terms of P to get pressure dependency (residual
𝑝
properties/ departure functions)
• We can use this equation to get entropy and enthalpy change of real substances using 𝐶𝑃 and an
euation of state. Remember that e need to define a T, P reference state at which 𝐻 = 0

2.2.3.1 Calculation of Enthalpies

▪ We wish to calculate the enthalpy change in going from point A to point B in

the diagram (point A may be a reference state)

▪ Note we can integrate the dT and dP terms separately as H is a state function.

▪ However, at low pressures, ALL gases behave ideally. Under these conditions Cp
is only a weak function of temperature, T and may be expressed as
𝐶𝑃 = 𝑎 + 𝑏𝑇 + 𝑐𝑇 2 + 𝑑𝑇 3

Where a, b, c, d are constants and can be looked up for different gases in

CHE 311 Handout 3, page 6/13

 reference books.

Thus, we can calculate ΔH easily at low P:

𝑇2
∆𝐻(𝑙𝑜𝑤 𝑃) = ∫ 𝐶𝑝𝑜 𝑑𝑇
𝑇1
This corresponds to the enthalpy change for step C → D in the diagram below.

• For an ideal gas, ∆𝐻(𝐴 →𝐶) and , ∆𝐻(𝐷 →𝐵) will be zero ( the enthalpy does not change with P)
• For real gases ∆𝐻(𝐴 →𝐶) and , ∆𝐻(𝐷 →𝐵) are termed residual enthalpies and they need to be found by
𝜕𝑉
integrating;[ 𝑉 − 𝑇 (𝜕𝑇 ) ]𝑑𝑃 using the equation of state.
𝑝
Example

𝜕𝑉
• dH = 𝐶𝑃 𝑑𝑇 + [𝑉 − 𝑇 (𝜕𝑇 ) ] 𝑑𝑃 ( derived in lectures; always true)
𝑝
𝑑𝐵
⇒ dH = 𝐶𝑃 𝑑𝑇 + [𝐵 − 𝑇 ] 𝑑𝑃
𝑑𝑇

(1) Step C→ D;

CHE 311 Handout 3, page 7/13

 𝑇𝐷 373
∆𝐻(𝐶 →𝐷) = ∫ 𝐶𝑃𝑜 𝑑𝑇 = ∫ (30.76 − 0.0099𝑇 + 1.55 𝑥 10−5 𝑇 2 ) 𝑑𝑇
𝑇𝐶 273

∆𝐻(𝐶 →𝐷) = 2929.2 𝐽/𝑚𝑜𝑙

(2) Step A→ C: T =273K
16500
𝐵 = 50.1 − = −10.34 𝑐𝑚3 /𝑚𝑜𝑙
273
𝑑𝐵 16500
= = 0.2214𝑐𝑚3 /𝑚𝑜𝑙 𝐾
𝑑𝑇 (273)2
0
∆𝐻(𝐴 →𝐶) = ∫ [−10.34 − (273 𝑥 0.214)] 10−6 𝑑𝑃 = 7.1𝐽/𝑚𝑜𝑙
105

(3) Step D → B T = 373K

𝐵 = 5.86 𝑐𝑚3 /𝑚𝑜𝑙

𝑑𝐵
= 0.1186𝑐𝑚3 /𝑚𝑜𝑙𝐾
𝑑𝑇
105
∆𝐻(𝐴 →𝐶) = ∫ [5.86 − (373 𝑥 0.2286)] 10−6 𝑑𝑃 = −38.4𝐽/𝑚𝑜𝑙
0

ℎ𝑒𝑛𝑐𝑒 𝐻 (100𝑜 , 10 bar) = 7.1 + 2919.2-38.4 = 2888 𝐽/𝑚𝑜𝑙

2.2.4 Internal Energy and entropy as Function of T and V

Temperature and volume often serves as more convenient independent variables than do
temperature and pressure, the most useful property relations are often for internal energy and
entropy.

The functional relations chosen here for 𝑈 and 𝑆 are; 𝑈 = 𝑈 (𝑇, 𝑉); 𝑆 = 𝑆 (𝑇, 𝑉)
For a single component system, we can rite
𝜕𝑈 𝜕𝑈 𝜕𝑆 𝜕𝑆
⇒ 𝑑𝑈 = ( 𝜕𝑇 ) 𝑑𝑇 + (𝜕𝑉 ) 𝑑𝑉 and 𝑑𝑆 = (𝜕𝑇) 𝑑𝑇 + (𝜕𝑉) 𝑑𝑉
𝑉 𝑇 𝑉 𝑇

Required here are the derivatives

CHE 311 Handout 3, page 8/13

 𝜕𝑈 𝜕𝑈 𝜕𝑆 𝜕𝑆
( 𝜕𝑇 ) , (𝜕𝑉 ) , (𝜕𝑇) , and (𝜕𝑉)
𝑉 𝑇 𝑉 𝑇

The following two of these follows directly from 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉

𝜕𝑈 𝜕𝑆 𝜕𝑈 𝜕𝑆
( 𝜕𝑇 ) = 𝑇 (𝜕𝑇) ( ) = ( ) −𝑃
𝑉 𝑉 𝜕𝑉 𝜕𝑉
𝑇 𝑇

𝜕𝑈 𝜕𝑃 𝜕𝑆
constant – volume heat capacity is defined as 𝐶𝑉 = ( 𝜕𝑇 ) and (𝜕𝑇 ) = (𝜕𝑉)
𝑉 𝑉 𝑇

𝜕𝑆 𝐶𝑉 𝜕𝑈 𝜕𝑃
⇒ (𝜕𝑇) = ( ) = 𝑇( ) −𝑃
𝑉 𝑇 𝜕𝑉 𝜕𝑇 𝑉
𝑇

𝜕𝑃 𝐶𝑉 𝜕𝑃
Hence: 𝑑𝑈 = 𝐶𝑉 𝑑𝑇 + [𝑇 (𝜕𝑇 ) − 𝑃] 𝑑𝑉 and 𝑑𝑆 = 𝑑𝑇 + (𝜕𝑇 ) 𝑑𝑉
𝑉 𝑇 𝑉

This is true for ANY substance (ideal or real) and it allows 𝑈 to be calculated as a function
of T and 𝑉 using the equation of state.

Special case: ideal gas

𝑑𝑃 𝑅
For an ideal gas; 𝑑𝑇 = and so 𝑑𝑈 = 𝐶𝑉 𝑑𝑇
𝑉

Hence the molar internal energy of an ideal gas is only dependent of temperature (i.e. it is
independent of pressure and volume).

Example 1
one mole of an ideal gas with 𝐶𝑣.𝑚 = 1.5𝑅 is heated from 300K to 400K along a
reversible path such as 𝑉 = 𝐴𝑇 𝑒𝑥𝑝[0.001𝑇], where A is a constant expressed in LK-1
compute ∆S.

Answer: 6.811J/K

2.2.5 Heat capacity relationship for ideal gases

Recall definition 𝐻 = 𝑈 + 𝑃𝑉

𝜕𝐻 𝜕𝑈 𝜕𝑉
Hence 𝐶𝑃 = ( 𝜕𝑇 ) = ( 𝜕𝑇 ) + 𝑃 (𝜕𝑇 )
𝑃 𝑃 𝑃

CHE 311 Handout 3, page 9/13

 For an ideal gas
𝜕𝑈
✓ ( 𝜕𝑇 ) = 𝐶𝑉 as 𝑑𝑈 = 𝐶𝑉 𝑑𝑇 derived above.
𝑃

𝜕𝑉 𝑅
✓ (𝜕𝑇 ) = directly from ideal gas la
𝑃 𝑃

✓ Hence 𝐶𝑃 = 𝐶𝑉 + 𝑛𝑅

2.2.6 ideal gases undergoing reversible adiabatic change.

𝐶𝑃 𝜕𝑉
Reversible and adiabatic ⇒ isentropic, 𝑑𝑆 = 0 ⇒0= 𝑑𝑇 − (𝜕𝑇 ) 𝑑𝑃
𝑇 𝑃

𝜕𝑉 𝑅 𝐶𝑃 𝑅
Ideal gas has (𝜕𝑇 ) = ⇒ 0= 𝑑𝑇 − 𝑑𝑃
𝑃 𝑃 𝑇 𝑃

If 𝐶𝑃 ≈ constant, we can integrate to get:

𝑅
𝑇 𝑃 𝑇 𝑃 𝐶𝑃
0 = 𝐶𝑃 ln 𝑇2 − 𝑅 ln 𝑃2 ⇒ ln 𝑇2 = 𝑙𝑛 (𝑃2 )
1 1 1 1

Note for an ideal gas 𝐶𝑃 = 𝐶𝑉 + 𝑅

𝑅 𝐶𝑉 1 𝛾−1
⇒ =1− =1− =
𝐶𝑃 𝐶𝑃 𝛾 𝛾

𝛾−1
𝑇2 𝑃 𝛾
⇒ 𝑇1
= (𝑃2 )
1

𝑃𝑉 𝛾 𝛾
Replacing T by 𝑅
gives ⇒ 𝑃1 𝑉1 = 𝑃2 𝑉2 𝑜𝑟 𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

2.2.7 P-V work done for ideal gases expanding.

Note that this will depend on the route as work is not a state function.
a) Isothermal expansion

CHE 311 Handout 3, page 10/13

 𝑉 𝑉 𝑅𝑇 𝑉
P-V work = − ∫𝑉 2 𝑃𝑑𝑉 = ∫𝑉 2 𝑑𝑉 = −𝑅𝑇 ln (𝑉2 ) as temperature is constant
1 1 𝑉 1

b) Reversible adiabatic expansion

𝑉 𝑉 𝑃𝑉 𝛾
P-V work = − ∫𝑉 2 𝑃𝑑𝑉 = ∫𝑉 2 𝑑𝑉
1 1 𝑉𝛾
𝑉 𝑑𝑉
= −𝑃𝑉 ∫𝑉 2 𝑉 𝛾
1

As 𝑃𝑉 𝛾 is a constant for adiabatic reversible change (ideal gas)

𝑉2
𝑉 𝛾+1 1
𝑃𝑉 𝛾 [−𝛾+1] = 𝛾−1 (𝑃2 𝑉2 − 𝑃1 𝑉1 )
𝑉1
1
= 𝛾−1 (𝑇2 − 𝑇1 )
𝑅
For ideal gas, 𝐶𝑃 = 𝐶𝑉 + 𝑅 and 𝛾−1 = 𝐶𝑉 . Hence P-V work =𝐶𝑉 (𝑇2 − 𝑇1 )

Alternative derivation for adiabatic expansion PV-work:

1st la : 𝑑𝑈 = 𝑑𝑄 + 𝑑𝑊𝑠 + 𝑃𝑑𝑉
As adiabatic: 𝑑𝑄 = 0
No shaft work: 𝑑𝑊𝑠 = 0
Hence the P-V work will just be the change in internal energy. As the internal energy of an ideal
gas depends only on the temperature, then:
Hence P-V work = ∆𝑈 = 𝐶𝑉 (𝑇2 − 𝑇1 ) as above

2.2.7 Absolute entropy of an ideal gas

𝐶𝑃 𝜕𝑉
Recall: 𝑑𝑆 = 𝑑𝑇 − (𝜕𝑇 ) 𝑑𝑃
𝑇 𝑃
𝑅𝑇 𝜕𝑉 𝑅
For an ideal gas: 𝑃𝑉 = 𝑅𝑇 ⇒ 𝑉 = ⇒ (𝜕𝑇 ) = 𝑃
𝑃 𝑃
𝐶𝑃 𝑅
⇒ 𝑑𝑆 = 𝑑𝑇 − 𝑑𝑃
𝑇 𝑃
𝑅
At constant temperature, T: dT = 0 ⇒ 𝑑𝑆 = − 𝑑𝑃
𝑃

For an arbitrary pressure, P,

CHE 311 Handout 3, page 11/13

 𝑃
𝑜
𝑅 𝑃
𝑆(𝑃, 𝑇) = 𝑆(𝑃 , 𝑇) − ∫ 𝑑𝑃 = 𝑆(𝑃𝑜 , 𝑇) − 𝑅 ln ( 𝑜 )
𝑃𝑜 𝑃 𝑃
Here 𝑃𝑜 is the same reference pressure which e set at 1 bar
NOTE:
• In thermodynamics e often relate properties to standard state, a reference state usually
denoted by the symbol “o”
• The standard state of a substance is the ost stable for under pressure of 1 bar and at the
temperature specified. It is usually tabulated for 298K. at one tie a value of 1 at as used
for 𝑃𝑜

Hence e needs a value for 𝑆 𝑜 (𝑇) in order to find 𝑆(𝑃, 𝑇)

Supposed e had 𝑆 𝑜 (𝑇) = 0𝐾, standard molar entropy at zero kelvin
𝜕𝑆 𝐶𝑃
Then e should get 𝑆 𝑜 (𝑇) using (𝜕𝑇) = 𝑇

e.g., consider the following sequence of the processes for the substance A:

CHE 311 Handout 3, page 12/13

 • If we take So (T = 0K) = zero for every pure substance in its crystalline
solid state, then we could calculate the entropy at any other temperature.
This leads us to the Third Law of Thermodynamics

CHE 311 Handout 3, page 13/13