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**The Second Law of Thermodynamics
**

1. Why is there a need for the Second Law of

Thermodynamics?

2. Spontaneous and Non-spontaneous Processes

3. Entropy

4. Molecular Interpretation of Entropy

5. Entropy of the Universe, System and Surroundings

6. T dependence of Entropy

7. Standard Entropies

8. Conversion of Heat into Work

9. Carnot Engine

CM 1502 2

Why there is a need for the Second Law?

Limitations of the First Law of Thermodynamics

The total energy-mass of the universe is constant.

∆E

universe

= ∆E

system

+ ∆E

surroundings

= 0

+∆E

system

= -∆E

surroundings

-∆E

system

= +∆E

surroundings

or

The first law does not provide any information on the

spontaneity of a given process.

This is provided by the second law of thermodynamics.

CM 1502 3

The first law states that when absorbed heat is converted

into work, the work done is equivalent to the heat absorbed

and so ∆U = 0.

∆U = q + w

∆U = q + w = 0 then q = -w

Conversion of absorbed heat into work: q → w

Why there is a need for the Second Law?

Limitations of the First Law of Thermodynamics

CM 1502 4

Heat engine: a device that

converts heat energy into

work, by expansions and

compressions.

However, the second law says that the heat absorbed at

any one temperature cannot be completely transformed into

work without leaving some change in the system or its

surroundings.

*

q

2

q

1

w

Hot SOURCE

Cold SINK

CM 1502

5

Spontaneous

Non-spontaneous

Spontaneous processes are processes which can take place

without external intervention of any kind.

Examples of spontaneous physical and chemical processes:

water runs downhill, heat flows from hot to cold,

iron + water + O

2

→ rust.

Non-spontaneous processes are processes which require

external intervention to take place (under normal conditions).

Examples of non-spontaneous physical and chemical

processes: water running uphill, boiling and freezing of water.

Spontaneous Processes

CM 1502 6

Non-spontaneous

Spontaneous

Non-spontaneous Spontaneous

Gas molecules in closed container

Throw bricks

CM 1502 7

Mixing of gases

stopcock

closed

stopcock

opened

1 atm Evacuated

vacuum

0.5 atm 0.5 atm

Free expansion

Non-spontaneous

Spontaneous

Non-spontaneous

Spontaneous

CM 1502 8

Heat Transfer

Spontaneous

CM 1502 9

Chemical Reactions

potassium and water

K + H

2

O

iron and water

Fe + H

2

O

Spontaneous Spontaneous

CM 1502 10

Electrochemical Processes

www.public.asu.edu/.../lecture10.html

Galvanic cell Electrolytic cell

Non-spontaneous

Spontaneous

CM 1502 11

Entropy and the Second Law

The second law can be expressed as:

“The entropy of the universe increases (∆S

universe

> 0)

when a spontaneous process occurs and is not

changed in an equilibrium.”

So when ∆S

universe or total

≥ 0,

→ process is spontaneous

→ final states (products) more disordered

than initial states (reactants)

CM 1502

12

What is Entropy?

Entropy (symbol = S) is a measure of “disorder”, “mess” or

randomness”.

The greater the disorder, the higher the entropy, the higher the value

of S.

A microscopic interpretation is required for understanding

entropy. e.g. gases have higher entropy compared to

solids.

S is a state function

[∆S

system

= ΣS

final states (products)

– ΣS

initial states (reactants)

].

Feeling of entropy: Look at entropy of some systems.

Underline/Circle on the next seven slides.

CM 1502 13

http://wps.prenhall.com/wps/media/objects/602/616516/Media_Assets/Chapter08/Text_Images/FG08_13.J PG

Physical States and Phase Changes

More (∆S

system

> 0) or less (∆S

system

< 0) entropy?

CM 1502 14

Figure 20.6

Pure solid

Pure liquid

Solution

MIX

Dissolution of a Solid

More (∆S

system

> 0) or less (∆S

system

< 0) entropy?

CM 1502 15

Ethanol Water

Solution of

ethanol

and water

Dissolution of a Liquid

Figure 20.7

More (∆S

system

> 0) or less (∆S

system

< 0) entropy?

CM 1502 16

O

2

gas

Dissolution of a Gas

Figure 20.8

O

2

gas dissolved in water

More (∆S

system

> 0) or less (∆S

system

< 0) entropy?

CM 1502 17

Temperature Changes – Increase

Heating leads to greater degree of thermal motion of the

molecules thus greater entropy.

Molecular motion includes translation, vibration and rotation.

stretch

bend

More (∆S

system

> 0) or less (∆S

system

< 0) entropy?

CM 1502 18

Chemical Reaction

wps.prenhall.com/.../602/616516/Chapter_17.html

More (∆S

system

> 0) or less (∆S

system

< 0) entropy?

More (∆S

system

> 0) or less (∆S

system

< 0) entropy?

CM 1502 19

Figure 20.9

NO

NO

2

N

2

O

4

Atomic Size or Molecular Complexity

More (∆S

system

> 0) or less (∆S

system

< 0) entropy?

CM 1502 20

Predicting ∆S

sys

Values

4. Temperature changes

1. Physical states and phase changes

2. Dissolution of a solid or liquid

5. Atomic size or molecular complexity

3. Dissolution of a gas

S increases as the temperature rises.

S increases as a more ordered phase changes to a less

ordered phase.

S of a dissolved solid or liquid is usually greater than the S

of the pure solid or solute. However, the extent depends

upon the nature of the solute and solvent.

A gas becomes more ordered when it dissolves in a liquid or

solid.

In similar substances, increase in mass relate directly to

entropy.

In allotropic substances (same element, different molecular

forms), increase in complexity (e.g. bond flexibility) relate

directly to entropy.

CM 1502 21

Choose the member with the higher entropy in each of the

following pairs, and justify your choice [assume constant

temperature, except in part (e)]:

(a) 1mol of SO

2

(g) or 1mol of SO

3

(g)

(b) 1mol of CO

2

(s) or 1mol of CO

2

(g)

(c) 3mol of oxygen gas (O

2

) or 2mol of ozone gas (O

3

)

(d) 1mol of KBr(s) or 1mol of KBr(aq)

(e) Seawater in midwinter at 2

0

C or in midsummer at 23

0

C

(f) 1 mol of CF

4

(g) or 1mol of CCl

4

(g)

(a) 1mol of SO

3

(g) - larger mass

and more complex molecule

(b) 1mol of CO

2

(g) - gas > solid

(c) 3mol of O

2

(g) - larger number

of mols

(d) 1mol of KBr(aq) - solution > solid

(e) 23

º

C - higher temperature

(f) CCl

4

- larger mass

*

CM 1502 22

Molecular Interpretation of Entropy

Microstates (W) – position of atom.

Example: Expansion of a gas →

increase in number of microstates.

Increasing microstates happens

FAST!

How does this relate to entropy?

Increase the number of ways of

arranging the particles

→ Increase W

→ Increase disorder

→ Increase S

Figure 20.3

1 mol

2

n

No. of

compartments

No. of

atoms

CM 1502 23

Molecular Interpretation of Entropy

Entropy is a measure of how many different microscopic

states are consistent with a particular macroscopic state.

Macroscopic states which consists of many different

microscopic states have large entropies.

Expressed mathematically:

Boltzmann equation: S = (R/N

A

) ln W = k ln W

where S is entropy, k is the Boltzmann constant = R/N

A

.

(R is the gas constant, N

A

is Avogadro’s number) =

1.38 x 10

-23

JK

-1

and W is the number of microscopic

states.

CM 1502 24

1877 Ludwig Boltzmann

Boltzmann equation: S = k ln W

A system with relatively few equivalent ways to arrange its

components, has smaller W, has relatively less disorder and low

entropy.

A system with many equivalent ways to arrange its components,

has larger W, has relatively more disorder and high entropy.

S = k ln W

∆S = S

final

– S

initial

∆S = k ln W

final

– k ln W

initial

∆S = k ln (W

final

/W

initial

)

*

CM 1502 25

Is the melting of ice or freezing of ice a spontaneous process?

Is this process spontaneous in the freezer? Yes No

Depends on ∆S

total/universe

, consider ∆S of system and surroundings.

CM 1502 26

exothermic

‘-’ ve ∆S

sys

:

system

becomes more

“ordered”

exothermic

‘+’ ve ∆S

sys

:

system becomes

more

“disordered”

endothermic

Exothermic and endothermic

reactions can be spontaneous.

Reactions that

have ∆S

sys

=

‘+’ve or ‘-’ve can

be spontaneous.

∆S

universe

*

ΔS

total/universe

= ΔS

system

+ ΔS

surroundings

≥ 0

Reactions that

have ∆S

surr

=

‘+’ve or ‘-’ve can

be spontaneous.

CM 1502 27

How to calculate ∆S

universe

?

ΔS

total/universe

= ΔS

system

+ ΔS

surroundings

1. Calculate ΔS

system

2. Calculate ΔS

surroundings

ΔS

total/universe

> 0: spontaneous.

ΔS

total/universe

< 0: non-spontaneous.

ΔS

total/universe

= 0: equilibrium process, which is

spontaneous.

For a spontaneous process,

∆S

universe

= ∆S

sys

+ ∆S

surr

≥ 0

The Second Law requires the

sum of ∆S

sys

+ ∆S

surr

to be ≥ 0

for spontaneous processes.

CM 1502 28

Ways to calculate ∆S

system

Most straight forward way to calculate ∆S

system

:

∆S

system

= Σ n S

products

– Σ n S

reactants

Another way to calculate the difference in S between two states is to

find a reversible path between them and integrate the energy (heat)

supplied at each stage of the path divided by the T at which heating

occurs:

At constant P, q

p

= ∆H,

thus ∆S

system

= ∆H

sys

/T .

T

q

dq

T

1

ΔS

rev

f

i

rev system

= =

∫

CM 1502 29

Another way to calculate ∆S

system

∆S

system

= q

rev

/T only applies if process is reversible, but what about

irreversible processes?

From First Law, conversion of q to w is possible: q = -w

w

rev

= -nRT In(V

f

/V

i

) => q

rev

= nRT In(V

f

/V

i

) => from ∆S

system

= q

rev

/T

∆S

sys

= nR In(V

f

/V

i

)

Because S, n and V are state functions, they do not depend on the

path. So, although the preceding calculation is derived for a reversible

process, ∆S has the same value for any reversible or irreversible

isothermal (T

i

= T

f

) path that goes between the same initial and final V.

So, ∆S

sys

for irreversible and reversible processes can be calculated

using:

∆S

sys

= nR In(V

f

/V

i

)

Expansion: ∆S

sys

> 0

Compression: ∆S

sys

< 0

CM 1502 30

∆S

surroundings

From First Law,

∆H

surr

= -∆H

sys

From second law, for a process at constant P,

∆S

sys

= ∆H

sys

/T

Applying to surroundings,

∆S

surr

= ∆H

surr

/T =>

∆S

surr

= -∆H

sys

/T

for all processes with the assumption that P of the surroundings is

constant.

At constant P, ΔS

total

= 0 equilibrium.

For irreversible isolated systems, ΔS

total

> 0

CM 1502 31

At 298K, the formation of ammonia has a negative ∆S

º

sys

;

Calculate ∆S

º

universe

and state whether the reaction occurs spontaneously at this

temperature.

N

2

(g) + 3H

2

(g) 2NH

3

(g) ∆S

º

sys

= -197J/K

Given ∆H

f

º

values: N

2

(g) = 0, H

2

(g) = 0 and NH

3

(g) = -45.9 kJmol

-1

.

∆H

º

sys

= [(2mol)(∆H

º

f

NH

3

)] - [(1mol)(∆H

º

f

N

2

) + (3mol)(∆H

º

f

H

2

)]

∆H

º

sys

= -91.8 kJ

∆S

º

surr

= -∆H

º

sys

/T = -(-91.8x10

3

J /298 K) = 308 J /K

∆S

º

universe

= ∆S

º

sys

+ ∆S

º

surr

= (-197 J /K) + 308 J /K = 111 J /K

∆S

º

universe

> 0 so the reaction is spontaneous.

*

32

T Dependence of ∆S

If process occurs at a particular T, for example, in the case of a phase

change:

For example, fusion/melting, q

p

= ∆H

fus

(the enthalpy of fusion) and if

the process has been carried out at T

fus

=> ∆S

sys

= ∆H

fus

/T

fus

. (1 of the 4 ways to express ∆S

sys

)

If process occurs over a range of T’s, then

∆S

sys

= q

rev

/T 1

and q

p

= ∆H = C

p

x n x ∆T 2

(refer to first law: coffee cup calorimeter)

=> substitute 2 into 1:

∆S

sys

= C

p

n ∆T/T = C

p

n ln(T

f

/T

i

)

This equation assumes that the T interval is small enough that the T

dependence of C

p

can be neglected.

*

Integrate w.r.t. T

V and T change

CM 1502 33

Calculate the entropy change when argon at 25 °C and 1 atm in a

container of volume 0.5 L is allowed to expand to 1 L and is

simultaneously heated to 100 °C. C

p,m

= 20.79 J mol

-1

K

-1

∆S

sys

= nR In(V

f

/V

i

) = (P

i

V

i

/T

i

) In(V

f

/V

i

)

∆S

sys

= C

v

n ln(T

f

/T

i

)

Step 1: Increase V (expand)

Step 2: Increase T (heat)

∆S

sys

= C

v

n ln(T

f

/T

i

) = (C

p

– R) (P

i

V

i

/RT

i

) In(T

f

/T

i

)

Overall,

∆S

sys

= (P

i

V

i

/T

i

) In(V

f

/V

i

) +

(C

p

– R) (P

i

V

i

/RT

i

) In(T

f

/T

i

)

= (0.17) In(2) +

(12.476) (0.02) In(1.252)

= 0.17 J K

-1

CM 1502 34

Entropy Change of Chemical Reactions

Most straight forward way to calculate ∆S

system

∆S

system

= Σ n S

products

– Σ n S

reactants

If standard conditions (1 atm, 298 K) apply, this is indicated with the

superscript

o

,

∆S

o

= ∑ n S

o

products

− ∑ n S

o

reactants

So for example, the entropy change of the following reaction is

CaCO

3

(s) → CaO(s) + CO

2

(g)

∆S

o

= [S

o

(CaO) + S

o

(CO

2

)] − S

o

(CaCO

3

)

= (39.75 + 213.8) − 92.88 = 160.7 J K

-1

How to determine S

o

for substances?

CM 1502 35

Standard Entropies (S°)

How to determine S

o

for substances?

This is different as for H and G which are derived from ∆H°

f

and ∆G°

f

,

respectively. [∆G° will be discussed in next lecture.]

There is NO entropy of formation.

From the Boltzmann equation: S = k ln W, a zero entropy can be

calculated if W = 1. In a perfect crystal, each atom occupies one of the

crystal lattice sites and has the lowest possible energy.

When is W = 1?

W = 1 at absolute zero temperature (0 K).

So at absolute zero of temperature (0 K), in a perfect crystal there is

only one distinguishable microscopic state and the entropy is zero.

This is used as the “standard point”. (Third law of thermodynamics)

CM 1502 36

Calculation of Standard Entropies (S°)

For example, calculate S° of a

substance at 393 K. Need to

extrapolate from 0 K.

S°

393 K

=

C

p

In(T

2

/T

1

) +

C

p

In(T

3

/T

2

) +

C

p

In(T

4

/T

3

)

T

1

= 0 K

T

2

T

3

T

4

= 393 K

∆H

fus

/T

fus

+

∆H

vap

/T

vap

+

*

Equation assumes that the T

interval is small enough that

the T dependence of C

p

can

be neglected.

T

1

has to be ~0 K, e.g. 0.0001 K

37

Conversion of Heat into Work

In a heat engine, two reservoirs, one hot and the other cold are in turns

brought into contact with the cylinder.

Hot reservoir (“source”) – expansion, input of heat which is converted

into work.

Cold reservoir (“sink”) – compression, outflow of heat which allows work.

Linear motion that is mechanically converted to rotary motion.

CM 1502

CM 1502 38

Efficiency (ε)

Efficiency is the fraction of the heat that is transformed into work.

Efficiency (ε) = w/q

H

For the most efficient heat engine, q

H

= w, and so ε = 1.

Higher T

Source

q

H

Lower T

Sink

q

C

Heat engine

w

CM 1502 39

The Second Law

Kelvin statement:

It is impossible for a system to

convert heat completely into work.

Clausius statement:

Heat cannot flow spontaneously

from a cooler to a hotter object.

*

CM 1502 40

Carnot Engine −

the most efficient heat engine cycle

Nicolas Léonard Sadi Carnot

Heat in

Work done Heat out

q

C

< q

H

universe-review.ca/option2.htm

Work done

q

H

q

C

Heat engine: a device that converts

heat energy into work.

CM 1502 41

Carnot Engine − the most efficient heat engine cycle

universe-review.ca/option2.htm

4 reversible steps:

1. Rev. isothermal expansion from a to b at T

H

. ∆S = q

H

/T

H

, q enter from hot source.

2. Rev. adiabatic expansion from b to c. ∆S = 0 as q = 0, T

H

decreases to T

C

.

3. Rev. isothermal compression from c to d at T

C

. ∆S = -q

C

/T

C

, q release to cold sink.

4. Rev. adiabatic compression from d to a. ∆S = 0 as q = 0, T

C

increases to T

H

.

T

H

T

C

CM 1502

Entropy in the Carnot Cycle

0

T

q

T

q

ΔS

C

c

H

H

sys

= + = →

q

H

T

H

T

C

Rev. isothermal

expansion

∆S = q

H

/T

H

Rev. isothermal

compression

∆S = -q

C

/T

C

Rev. adiabatic

expansion

q = 0

q

C

∆S

sys

only involves

the isothermal steps

C

c

H

H

sys

T

q

T

q

S − = = ∆

For a reversible cyclic

process,

Rev. adiabatic

compression

q = 0

In a generalized cycle ∫ dS = 0

CM 1502 43

H

C

H

C

H

C H

q

q

1

q

q

1

q

q q

q

w

absorbed heat

performed work

ε − = + =

+

= = =

Efficiency (ε) for a Carnot Cycle

H

C

H

C

C

H

C

H

T

T

q

q

T

T

q

q

− = ⇒ − =

H

C

T

T

- 1 ε =

C

H

C

H

C

C

H

H

T

T

q

q

T

q

T

q

− = ⇒ − =

∆S

sys

=

CM 1502 44

100% Efficiency from a Carnot Cycle

The efficiency of a heat engine depends on the Ts of the

hot source and the cold sink.

– The lower the T

c

and the higher the T

h

, the greater the

efficiency.

To achieve 100% efficiency the T

c

/T

h

term has to be 0.

Theoretically, to do this:

– Have the cold sink at absolute zero of T (0 K).

– Have the hot source at infinite T.

CM 1502 45

Carnot Cycle

Any reversible cycle can be

approximated as a

collection of a large number

of Carnot cycles, with

alternating isothermal and

adiabatic segments.

So, for a cyclic process, ∆S = 0

In fact, for any cyclic process, the

change in any state function is

zero.

Isotherms

Adiabatic

processes

*

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