Thermodynamics : The

Second law

FMIPA UGM – Februari 2020

Dr.rer.nat Niko Prasetyo

Thermodynamics : The Second law
 Spontaneous
 Disorderness (entropy)
 The Second law : spontanity
 What is spontanity ?
 The Second law : spontaneous

What is spontanity ?
 The direction of change that does not require work to be done to
bring the change
 In opposite : a process which is required works is called : non-
spontaneous

In thermodynamics ‘language’
‘No process is possible in which the sole result is the absorption of
heat from a reservoir and its complete conversion into work’
 The Second law : spontaneous
 In thermodynamics ‘language’
‘No process is possible in which the sole result is the
absorption of heat from a reservoir and its complete
conversion into work’
 The Second law : spontaneous
 Why it happens ?
 The Second law : spontaneous
 Why it happens ?
 Total energy ?
 First Law : energy is conserved
 The Second law : spontaneous
 Why it happens ?
 When a change occurs, the total energy is remains
conserved, but it is parcelled in different ways
 Something related to distribution
of energy
 The Second law : spontaneous
 Why it happens ?
 When a change occurs, the total energy is remains
conserved, but it is parcelled in different ways
 Something related to distribution
of energy
 How thermodynamics said about that ?
 The Second law : spontaneous
 Thermodynamics parameters :
U G H S A q W
 The Second law : spontaneous
 S (entropy)
 Signpost of spontaneous changes
 The second law
‘The entropy of an isolated system increases in
the course of a spontaneous change ΔStot > 0’
 The Second law : spontaneous

What is entropy :
 Degree of disorderness
 Remember :

energy/heat in thermodynamics is always ‘q’

Thermodynamics always about ‘two states’
 Definition :

The reversible transferred heat in the phase change
 The Second law : spontaneous
 What is entropy :
dqrev
dS= For adiabatic (NO HEAT TRANSFERRED)
T
For a spontaneous change, ΔSsurr = 0
dS Total>0
dS sys +dS surr >0
dq sys,rev
dS sys =
T sys
dq surr,rev
dS surr =
T surr
 The Second law : spontaneous
 What is entropy :
 From statistical point of view :
S = k ln W
k = Boltzmann Constant
W = number of microstate
 The Second law : spontaneous
 Entropy is state function
 Independent of the path
 Only cares about initial and final states
 The Second law : spontaneous
 Entropy is state function
 The Second law : spontaneous

Carnot cycle
 reversible isothermal expansion A to B

Entropy change ~ qh/Th
 Reversible adiabatic expansion B to C

No change in entropy
 Reversible isothermal compression C
to D

Entropy change ~ qc/Tc
 Reversible adiabatic compression D to A

No change in entropy
 The Second law : spontaneous
 Why Carnot cycle ?
 Efficiency of process Efficiency of Carnot cycle
Qin  Qout Qout
  1
Qin Qin
Tc
ε  1
Th
 The Second law : spontaneous
 Why Carnot cycle ? Note that for a Carnot cycle :
Qout WAB nRTc ln(VC / VD )
 Entropy is state function  
Qin WCD nRTh ln(VB / VA )
For adiabatic process
ThVB 1  TcVC 1
ThVA 1  TcVD 1
 VC / VD  VB / VA
Qout Tc
 
Qin Th
 The Second law : spontaneous

Entropy of process
 Expansion

 Again, entropy is state function. It does not care about the path
 But, the total change in entropy depend on the how expansion take
place

For example : in any process, the heat will transfer to the
surrounding (dqsur = - dq). For reversible changes,
 The Second law : spontaneous
 Entropy of process
 expansion

ΔStot = 0 = ΔSsys + ΔSsurr
 Phase transformation
 Heat at constant pressure (q = H)
 The Second law : spontaneous
 Entropy of process
 expansion

ΔStot = 0 = ΔSsys + ΔSsurr
 Phase transformation
 Heat at constant pressure (q = H)
 The Second law : spontaneous
 Entropy of process
 Heating
 The Second law : spontaneous
 To be concluded in the second law
 Entropy is measurement of spontanity
 Entropy plays important role in thermodynamics
 We will see at the third law of thermodynamics
 The Third Law : “calmness”
 Third law
 Discuss about the motion at 0 K
 Maximum work
 The Third Law : “calmness”
 Third law
 Back to entropy
‘The entropy of all perfect crystalline substances is
zero at T = 0’
 Why ? At 0 K, everything is perfectly ordered, only
one way of arrangement (W=1)
 At 0 K, entropy is entropy
 The Third Law : “calmness”
 Third law
 At standard temperature entropy is standard
entropy
 Standard entropy reaction
 The Third Law : “calmness”
 Third law
 How to express the direction of changes to another
thermodynamics parameters
 Automatically taking entropy into account

 Claysius inequality
‘if a system in equilibrium with the surrounding with
temperature, T and then a change is occurred …
 The Third Law : “calmness”
 Claysius inequality
 Constant volume or pressure
 In constant volume
 Non expansion work

 Q = U
 The Third Law : “calmness”
 Claysius inequality
 Constant pressure
 Q=H
 The Third Law : “calmness”
 Claysius inequality
 We see, there are two forms

 Helmholtz free energy (A = U -TS)

 Gibbs free energy (G = U -TS)
 Spontaneous change, if ..
 The Third Law : “calmness”
 Helmholtz free energy

 System change spontaneously if total entropy

system and surrounding increases, not because
lower dU
 A, is the measure of ‘maximum work’
 The Third Law : “calmness”
 Gibbs free energy

 System change spontaneously if decreasing in dG

 G, is the measure of ‘maximum non expansion
work’
 The Third Law : “calmness”

Standard Gibbs reaction

 Very useful in theoretical and computational chemistry


For example : Hydration Gibbs free energy for single ion in
solution, binding free energy of protein -ligand
 The Third Law : “calmness”
 Standard Gibbs reaction
 The Third Law : “calmness”
 Standard Gibbs reaction
 The Third Law : “calmness”
 Standard Gibbs reaction

Cover Page :

Journal of Chemical Theory and

Computation, December 2018
 The Third Law : “calmness”
 Standard Gibbs reaction
 Interested to do final task in computational
chemistry ?
 Molecular dynamics simulation
 Molecular modelling
 Computer aided material / drug design
 Just mail me : [email protected]
 The Third Law : “calmness”
 Combining first and second laws
 Fundamental equation of thermodynamics
 The Third Law : “calmness”
 Combining first and second laws
 Properties of internal energy (U)
 U is function of S, and V
 The Third Law : “calmness”
 Combining first and second laws
 Properties of internal energy (U)
 U is function of S, and V
 The Third Law : “calmness”
 Maxwell Relations
 The Third Law : “calmness”
 Another properties of U
 It will change in isothermal process
 The Third Law : “calmness”
 Combining first and second laws
 Properties of G
 Function of P and T
 The Third Law : “calmness”
 Combining first and second laws
 Properties of G
 Function of P and T

 Fundamental equation of chemical thermodynamics

 The Third Law : “calmness”
 Properties of G
 Because S > 0 for all substances,
G always decreases when
the temperature is raised
(at constant pressure and composition)
 The Third Law : “calmness”
 Properties of G
 Because (∂G/∂T)p becomes
more negative as S increases,
G decreases most
sharply when the entropy of the
system is large.
 The Third Law : “calmness”
 Properties of G
 Because V > 0 for all substances,
G always increases when
the pressure of the system is increased
(at constant temperature and composition).
 The Third Law : “calmness”
 Properties of G
 Because (∂G/∂p)T increases with V,
G is more sensitive to pressure when the
volume of the system is large
 The Third Law : “calmness”
 Properties of G
 G as function of temperature
 Gibbs-Helmholtz equation
 The Third Law : “calmness”
 Properties of G
 G as function of pressure
 The Third Law : “calmness”
 Properties of G
 G as function of pressure
 The Third Law : “calmness”
 Properties of G
 G as function of pressure
Thank you