Chemical Thermodynamics

LECTURE 2/14

Gerard Krooshof, Sr. Expert Thermodynamics @ DSM DEM

Lecturer of 2021 PPD Course TU/e

Chemical Engineering & Chemistry PPD TU/e

Content of Lecture 2

• Ideal gas theory (classic vs kinetic) 15 min

• The 4 laws of thermodynamics 20 min

• The thermodynamic potentials 10 min

• Summary

• Problems to work out

2 Chemical Thermodynamics 2
Ideal Gas theory (empirical)
P: pressure (Pa)
Volume format: V: container volume (m3)
= T: absolute temperature (K)
n: number of moles of gas in container (mol)
Density format: = R: universal gas constant (J/mol.K)
ρ: gas density (mol/m3)

Compression factor (Z):

≡ =1 (Eq. 2.42 & 2.43)

Definition: a gas is ideal when the compression factor is unity.

(non-ideal when Z<>1)

3 Chemical Thermodynamics 2
Ideal Gas (kinetic theory)
Maxwell & Boltzmann theory
’
Gas particles (atoms) collide elastically and exchange their kinetic energy ( = ).
’
Essential assumptions: Particles do not attract each other !
Particles have negligible size (point masses) !

At thermal equilibrium there will be a certain distribution of slow and fast

moving particles. The Maxwell-Boltzmann distribution for the velocity in de x-direction
is given by :

=
2

4 Chemical Thermodynamics 2
Ideal Gas (kinetic theory)
How do we read this function? The exponential term gives a measure for the probability
to find a particle with a velocity between and + d .

Exponent: Ratio of kinetic energy of a particle and

d = d the thermal energy (kBT). kB is Boltzmann’s constant.
2 Pre-exponential term normalizes:
d =1

What does the Eq. lead to?

Average squared velocity in x-direction: = d =

2

Average kinetic energy in a volume: 1 3

= + + =
2 2

5 Chemical Thermodynamics 2
Ideal Gas theory (kinetic theory)
The average kinetic energy of a system is a macroscopic property known as the
internal energy (U, u). For an ideal gas this is linear with temperature.

Uig(J)=N = = uig [J/mol] ≡

Slope:
∆u
= 8.314463 J/mol.K ∆T
uig(J/mol) = Heat capacity of
T [K] i.g. is constant.
Eq. 2.28
The temperature derivative of the internal energy 3
at constant volume is defined as the heat capacity ≡ ≡
mono-atomic 2
at constant volume.
molecule

6 Chemical Thermodynamics 2
Ideal Gas theory (kinetic theory)
Pressure is the bombardment of slow and fast particles against a wall:

∆ ∆ Elastic collision of a particle with

= = = = = wall, gives a change in momentum
∆ ∆

2
= 2 = = =
3
= Δ =2 = Δ

= Ideal gas law.

Eq. 2.30

7 Chemical Thermodynamics 2
Ideal Gas (kinetic theory)
• The average kinetic energy of an ideal gas particle
3
=
is mass independent 2

• The pressure of an ideal gas is linear to the average kinetic 2

= =
energy of the particles and temperature. 3
• The molar internal energy of ideal gas is linear with
uig = × uig=
temperature. For a monoatomic molecule:

• The temperature derivative of the internal energy equals

≡ Eq. 2.28
the heat capacity at constant volume.

• The heat capacity at constant pressure and volume are related. − = Eq. 2.41

8 Chemical Thermodynamics 2
First real gas-liquid equation of state
Johannes van der Waals adjusted the ideal gas equation of state
J. v.d. Waals
on two major points.

1) Particles are spherical and have a finite size, which reduces the volume.
2) Particles do attract each other, which reduces pressure.

b is covolume of particles
= − a is attraction energy
−
Eq. 2.130

(More in Lecture 5)

9 Chemical Thermodynamics 2
Laws of thermodynamics

Zeroth law: Thermal equilibrium and temperature

R.H.Fowler E.A. Guggenheim

If two assemblies are each in thermal equilibrium with a third

assembly, they are in thermal equilibrium with each other.
This is measured by the temperature.

The importance of this law is that the existence of a thermal equilibrium

can be determined by a temperature scale.

The thermodynamic toolbox of equations is only applicable when thermal

equilibrium exist.

10 Chemical Thermodynamics 2
Laws of thermodynamics

First law: Conservation of energy

H. Helmholtz. R. Clausius

In all cases, where work is generated by heat, the amount of generated

work is proportional to the quantity of heat consumed, and conversely,
that by using an equally large amount of work the same amount of heat
can be generated.

11 Chemical Thermodynamics 2
Laws of thermodynamics (1st law)
1st law defines the thermodynamic potential, called the internal energy (U).
A change (dU) can be caused by heat, mechanical work or chemical reactions.
dU = Q + W = Q + YdX + j j.dNj

Uinitial U is a state variable:

path 1
Not the process path but only the initial and final state matter.
U

∆U path 2
Ufinal final
∆ = d = final − initial
initial
states

12 Chemical Thermodynamics 2
Laws of thermodynamics (1st law)
Mechanical work in chemical engineering cases is usually expressed as:
W = YdX = -PdV. Other types of mechanical work:

Types of mechanical work W Y dX Process examples

Volume expansion -PdV -P dV Compressor, Supercritical extraction, evaporation.
Surface expansion dA dA Biaxial film extrusion, interfacial tension phenomena
Line elongation FdL F dL Polymer fiber drawing
Electric charge separation ede e de Electrodialysis
Torsion MTd MT d Torsion of string or metal bar
Electric work ⃗ ⃗ DNA trapping in a strong electric field
Magnetic work O2/N2 separation by magnetic dipole difference

13 Chemical Thermodynamics 2
Laws of thermodynamics
Second law:
R. Clausius. W. Thomson
(Lord Kelvin)

Clausius: Heat flows spontaneously from hot to cold, and not vice versa.
Kelvin: It is impossible to obtain mechanical work from heat alone.

Kinetic: Mechanical work is only obtained by a gradient in the kinetic

energy of moving/vibrating particles.

Only for a quasi-static reversible process, the state variable entropy can be
defined : dS = . For a spontaneous process dS > .

14 Chemical Thermodynamics 2
Laws of thermodynamics (2nd law)
Second law (Number of microstates): L. Boltzmann

Entropy (S) is a macroscopic measure for the number of equal probable

microscopic states (W) at thermal equilibrium.

= log

One microstate is characterized by the momentum and position of all particles

in a system. The Boltzmann equation holds only for large number of particles.

15 Chemical Thermodynamics 2
Laws of thermodynamics (2nd law)
Boltzmann’s concept only holds for a very large number of particle, say N>1000.
The example below has only educative purpose to explain the concept of L. Boltzmann

microstates.
A system of 5 particles which can occupy 3 positions and 5 energy levels.
L. Boltzmann
Microstate A: Microstate B: Microstate C: Microstate D: Microstate E:
E5 E5 E5 E5 E5 = ln

E4 E4 E4 E4 E4 W=73 (total # microstates)

E3 E3 E3 E3
E3 = ln 73 ≈ 4.3
E2 E2 E2 E2 E2
= −1.38 × 10 J/k
E1 E1 E1 E1 E1
= 5.9 × 10 J/k
# positional # positional # positional # positional # positional
configuration: 1 configuration: 27 configuration: 9 configuration: 9 configuration: 27

16 Chemical Thermodynamics 2
Laws of thermodynamics (2nd law)

The entropy of an ideal gas (Sackur-Tetrode Eq.)

5 3
= ln − ln + ln 2 − 3 ln ℎ
2 2

⁄
Only valid in the classical limit: ≫

It shows the dependencies to volume, temperature, number of particles and particle mass.

Mind that this formula is not applicable at very low T. The reason for this is that due to
quantum effects the particles no longer behave like independent individual particles.

17 Chemical Thermodynamics 2
Laws of thermodynamics
W. Nernst
Third law: absolute zero Kelvin
The entropy of a perfect crystal of many pure substance approaches zero
as the temperature approaches absolute zero
The 3rd law is essential in the calculation of reaction equilibria. gas Sfinal

The Gibbs free energy of reaction requires an exact value for the
entropy of formation of the pure components at any temperature.

S
liquid

By having S=0 at T=0, S can be calculated by: crystal

0
= d = + ∆
0 T

18 Chemical Thermodynamics 2
Thermodynamic potentials

The 4 thermodynamic laws define 2 thermodynamic potentials (state variables):

U: The internal energy – Applicable to processes in an enclosed volume
S: The entropy – Related to the number of microstates

Other thermodynamic potentials have been introduced to make process

evaluation on phase equilibria easier.

In chemical engineering we use mainly S, the enthalpy H and the Gibbs free
energy G, which we will discuss next.

19 Chemical Thermodynamics 2
Thermodynamic potentials: Enthalpy

For a reversible process: dU = TdS - pdV = TdS - d(PV) + VdP

Rearrangement: d(U +PV)= TdS + VdP

It defines enthalpy H = U + PV Eq. 2.4

Eq. 2.5
The molar enthalpy eq.: h = u + Pv

Why ? To know the energy for processes at constant pressure.

ℎ
For isobaric process: dH = d(U+PV) = TdS-VdP=TdS. ≡ Eq. 2.32
dP=0

20 Chemical Thermodynamics 2
Thermodynamic potentials: Helmholtz free energy
H.Helmholtz

For a reversible process we have: dU = TdS - PdV = d(TS) -SdT - PdV

Rearrangement: d(U -TS)= SdT - PdV

Helmholtz free energy: A=U-TS Eq. 2.7

The molar Helmholtz fee energy: a = u -Ts

Why ? To know directly the available (free) energy in a system to do work.

For an isothermal process dA=SdT-PdV=-pdV Eq. 2.16

dT=0

21 Chemical Thermodynamics 2
Thermodynamic potentials: Gibbs free energy
J. Gibbs
For a reversible : dU = TdS - PdV = d(TS) -SdT – d(PV) + VdP
Rearrangement: d(U -TS+PV) = d(H -TS) = SdT + VdP

Gibbs free energy: G = U-TS+PV = H-TS = − Eq. 2.8

Molar Gibbs free energy: g = u -Ts + Pv = h - Ts

It is introduced to quantify phase equilibria between two or more states

For an isothermal isobaric process dG=SdT-VdP=0 Eq. 2.17

dT=0 dP=0

22 Chemical Thermodynamics 2
Thermodynamic potential natural variables:
Thermod. Name Natural Type of energy exchange
Potential variables Closed Coupled
S Entropy U, V, {Nj}

U Internal energy S, V, {Nj} Thermal, mechanical, chemical None

H = U + PV Enthalpy S, P, {Nj} Thermal, chemical Mechanical

A = U -TS Helmholtz energy T, V, {Nj} Mechanical, chemical Thermal

G = H -TS Gibbs energy T, P, {Nj} Chemical Thermal, Mechanical

= A− ∑ Grand potential T, V, { j} Mechanical Thermal, Chemical

Note: P (force) and V (displacement) are the most common variables in chemical engineering.
H,U,G,S are the most common state variables, but not directly measurable.
Maxwell invented relations to measurable variables.

23 Chemical Thermodynamics 2
Maxwell relations & auxiliary functions
Maxwell equations were invented to relate potentials to J. Maxwell

measurable properties.
Eq. 2.18-21. Isochoric heat capacity ≡
=+ =+

=+
P H S =+
Isobaric heat capacity ≡

G U 1
=− =− Isobaric thermal expansion ≡ Eq. 2.46
T A V
Isothermal compressibility 1
=− =− ≡− Eq. 2.47

24 Chemical Thermodynamics 2
The Carnot Cycle

− S. Carnot
= =1− =1−

Watt’s steam engine:

Operates with 1 atm steam pressure and is cools with river water.

Thigh = 373 K, Tlow = 283 K Therefore: ~1 − ~24%

When operated at 4 bar steam pressure and is cools with river water.

Thigh = 413 K, Tlow = 283 K Therefore: ~1 − ~31%

25 Chemical Thermodynamics 2
Carnot Cycle: An idealized process

1
1 Steam heating
Qin Carnot derives for an ideal gas
2 that a cycle of two isotherms
Adiabatic expansion and two adiabatic steps that:
2 −
3
= =1−
4 Water cooling
4
Qout 3
Adiabatic compression

26 Chemical Thermodynamics 2
Summary: Lecture 2

• Kinetic theory explains ideal gas properties (Pressure, Energy, Heat capacity)

• The four laws and the thermodynamics potentials (S,U,H,A,G) were introduced
to define changes from one to another (thermal equilibrium) state.

• Mechanical work is not only PdV

• Third law is essential in the calculation of Gibbs free energy changes caused by
reactions.

• The Carnot diagram is an idealized picture to show that the efficiency to convert heat into
work is related to the temperature difference of two isotherms.

27 Chemical Thermodynamics 2