LECTURE 4

Spontaneous processes
Reversible and irreversible
processes
Entropy
2nd law of thermodynamics
https://www.boundless.com/chemistry/thermodynamics/
the-laws-of-thermodynamics/spontaneous-and-nonspontaneous-processes

By the end of this lecture you should

http://vippasstothespiritworld.blogspot.com.au/2012/10/entropy-explained.html

Understand the concept of spontaneity

Know what reversible and irreversible
processes are
Understand some basic
concepts of entropy
Understand the implications of the
2nd law of thermodynamics
Understand how entropy changes
with temperature (qualitatively)

Reading for this lecture

Chapters
4.9-4.10

Pages
153-159

Chapters
14.8-14.9

Pages
527-535

Spontaneous process
Occurs of its own accord, requires no interventions from the outside.
The reverse process is non-spontaneous

Cold

Hot

Warm

http://wpscms.pearsoncmg.com/wps/media/

Whether a process is spontaneous in a given direction

may depend on experimental conditions

Spontaneous melting
if tsurr > 0C
Spontaneous freezing
if tsurr < 0C

ice

liquid water

U1

U2

Vacuum

Gas

surr

sys

Step 1
The partition
is removed

U3=U1

Step 2
Gas expands
spontaneously
but does no
work. (psurr= 0)

Step 3
Gas is forcefully
(non-spontaneously)
compressed by
work. w > 0

The non-spontaneous process (step 3) required energy input, work w

overallU U fin U init U1 U1 0

overallU q w 0
q w

overallU q w

w0

q0

exothermic

Criterion for spontaneity

Bertholet : All exothermic changes are spontaneous.

However,
Melting ice is endothermic
Dissolution of some salts is endothermic
KNO3 (s) K (aq) NO3 (aq)

A key to understanding spontaneity

is understanding the concept of
reversible and irreversible processes

Other factors are at work

They relate to specific paths taken
between states during the change

Internal energy, enthalpy, temperature

are state functions
Work and heat are not

Reversible and irreversible processes

T T

T T

System

System

Surroundings, T

Surroundings, T

Surroundings

Surroundings

p p

p p

piston

piston

Gas, p

Gas, p

The direction of heat

flow can be reversed by
an infinitesimal change
in temperature

The direction of motion

of the piston can be
reversed by
an infinitesimal change
in pressure

Reversible process
A system is changed in such a way that the system and surroundings can be
restored to their original state by exactly reversing the change.
There is no net change to either the system or its surroundings.
Irreversible process is one that cannot be
reversed to restore the system and the
surroundings to their original states.

State 1
n1, p1 , V1 , T1

spontaneous
no work done

A reversible change produces maximum

amount of work
(done by system on the surroundings)

State 2

!! Any spontaneous
process is irreversible

n2, p2 , V2 , T2

non-spontaneous
some work done

Spontaneity --- Reversibility --- ????? --- Conditions (n, p, T, V)

(nothing done cannot

be reversed, let alone
by an infinitesimal
change)

Entropy, S
Entropy is a multifaceted concept, cannot be stated in one simple definition.

In this course :
As a measure of disorder
As a relation to heat transfer and temperature
As a number of possible microstates (arrangement of atoms/molecules/ions)
for a particular macroscopic state.

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http://www.dailydevotionblog.com/the-entropy-of-the-past/

S(gas)

>

S(liquid)

>

S(solid)

http://wps.prenhall.com/wps/media/objects/2478/2537811/Media-Portfolio/chapter_08/text_images/FG08_01a-c.JPG

Molecules in gases have much more possibilities how they can be

arranged in space then molecules in liquids or solids have.
1 2

3 4 5 6 7 8 9 10

Entropy
Is a state function S = Sfin - Sinit (path independent)
Depends on p, V, T, c
Is an extensive quantity S = nSm
Unlike U, H does have an absolute value
Is not conserved !!
Definition
For an isothermal process

S m (C (s,graphite), 298.15K) 5.69 J/K/mol

General definition

qrev
T

dS

dqrev
T

fin

Units
S J K 1

Sm J K 1 mol1
same units as R, Cp,m , CV,m

dS S

fin

Sinit S

init

dqrev
Tfin
C dT

ln
T init T
Tinit
init
fin

fin

S C ln

Tfin
Tinit

(constant C )

S for phase changes

Phase changes
Freezing Fusion (melting)
Vaporization Condensation
Sublimation Deposition (desublimation)

freezing H fusion H
vaporization H condensation H
sublimation H deposition H

are reversible processes running at constant pressure and temperature

qrev phase change H

Example

phase change S

Enthalpy of fusion for water is

6.01 kJ/mol.
Calculate S of freezing
freezing S

freezing H

fusion H
T

T
6010
freezing S
22.00 J/K/mol
273.15

phase change H
T

Interesting Troutons rule

For many liquids
vap S 10.5 R

87 J/K/mol

surroundings

Melting of ice at laboratory conditions

is a spontaneous process
Heat flows from the surroundings
to the system
system

System
t = 0C T = 273 K
qrev fus H

T
T
6010

22.0 J/K
273

Surroundings
t = 25C T = 298 K
qrev fus H

T
T
6010

20.2 J/K
298

Ssys

Ssurr

Ssys

Ssurr

System + Surroundings = Universe

S univ Ssys Ssurr

S univ 22.0 (20.2) 1.8 J/K

For any irreversible process

S universe 0

Any spontaneous process is irreversible

For any spontaneous process

S univ 0

For any irreversible process Suniv > 0

One of the possible statements of

the second law of thermodynamics

Not very practical

It is easier to focus our
attention to the system only
reversible process
irreversible process

q
T
q
S
T

We need to know how the system

entropy changes

with temperature
with pressure/volume
with concentration
during a phase change
during a chemical reaction

Various statements of the 2nd law of thermodynamics

The entropy of an isolated system never decreases,
because isolated systems always evolve toward a state with maximum entropy
Thomson : It is impossible to construct a cyclic engine that would transform
heat fully to work (perpetuum mobile of the 2nd kind)
Clausius : Heat cannot spontaneously flow from cold regions to hot regions
without external work being performed on the system
Carnot : It is not possible to construct an engine
with greater efficiency than that of a Carnot engine

Perpetuum mobile
1st kind

Perpetuum mobile
2 nd kind

Real engine

Entropy and temperature

Low temperature: low average particle velocity and small range
High temperature: high average particle velocity and large range

The potential for disorder is greater at the

higher temperature
As temperature increases, S increases.

Mathematically
S

q
,
T

dS
for infinitesimal changes dS

dq
T
2

qp Cp T ,

C p dT

for infinitesimal changes dq Cp dT

dS S

C p dT
T

T
dT
Cp ln 2
T
T1
1

Cp

Entropy and temperature

Figure 4.31

Any substance will have zero entropy

(ideally, a perfectly ordered crystalline substance) at 0K
This is the third law of thermodynamics

Entropy and temperature

Mathematically
S (T )
Tf

Cp,solid
T

fusion H

Tf
Tb

Tf

Cp,liquid
T

dT

vaporization H
Tb
T

dT

Tb

Cp,gas
T

dT

Example
1 mol of liquid water at 25C was placed in the oven at 150C.
Calculate the change of enthalpy and entropy.
Is it a reversible process?
liquid water Cp,m 75.34 J K 1 mol1

150C

vapour Cp,m 35.92 J K 1 mol1

vap H 44 000 J mol1

25C

Lets split the overall process into three steps

1. Heating the liquid water from 25C to 100C
2. Vaporization of liquid water
3. Heating the vapour from 100C to 150C
H1 Cp,liquid T 75.34 100 25 5650.5 J

S1 Cp,liquid ln

H 2 vap H 44 000 J
S 2

H 3 Cp,vapour T 35.92 150 100 1796 J

vap H
Tb

Tb
100 273
75.34 ln
16.91 J K 1
Tinit
25 273
44 000
=117.96 J K 1
373
Tfin
150 273
35.92 ln
4.52 J K 1
Tb
100 273

H H1 H 2 H 3 5650.5 44 000 1796 51446.5 J

S3 Cp,vapour ln

H 51446.5

121.62 J K 1
T
423
S 139.39 J K 1

S S1 S 2 S3 16.91 117.96 4.52 139.39 J K 1

H
T

irreversible

How about letting the vapour at 150C escape

from the oven into the laboratory at 25C ?