LECTURE 5

Entropy and volume/pressure

Molecular interpretation
of entropy
Standard molar entropy
Standard entropy of reaction
http://commons.wikimedia.org/wiki/File:Entropie.png

By the end of this lecture you should

Be able to estimate qualitatively
the influence of
volume/pressure/temperature
structure
concentration
on the change of entropy
Understand the concept of a microstate
and its influence on entropy
Be able to calculate the entropy changes
in chemical reactions
http://en.wikipedia.org/wiki/Boltzmann's_entropy_formula

Reading for this lecture

Chapters
4.11-4.12

Pages
160-167

Chapters
14.10-14.11

Pages
535-544

Entropy and volume

http://wps.prenhall.com/wps/media/objects/3312/3392504/blb1902.html

The state when molecules

spread out over the whole
volume is the most probable

Smaller volume
1 possible
arrangement

Larger volume
4 possible
arrangements

4 molecules

N molecules

16 possible
arrangements

2N possible
arrangements

Expansion (increasing the

systems volume) leads to
increased randomness
and thus to an increased
entropy

Mathematically
Vfin
S R ln
Vinit

Entropy and pressure

At constant temperature the pressure increase is equivalent to volume
decrease. Thus increasing pressure leads to lower entropy and vice versa.

Lower pressure
Larger volume

Higher pressure
Smaller volume

Mathematically

Higher entropy

Lower entropy

S R ln

pfin
pinit

Entropy and Molecular Theory

Substances store heat as a kinetic energy of motion of molecules and atoms

Not only positions of molecules within a system play a role

but also their orientation.
Based on 1 mole : S big molecules Ssmall molecules

Entropy and Molecular Theory

Entropy of n-alkanes (T = 298 K)
450

S (J/K/mol)

400

350

(g )

300

(l)

250
200
150
0

4
6
8
n - number of carbon atoms

10

12

Entropy increases with increasing molecular complexity

Isomers of pentane

S o 263.47 J/K/mol

S o 260.41 J/K/mol

S o 217 J/K/mol

Boltzmanns equation and microstates

Microstate is a snapshot ,
a single possible
arrangement of the
positions, orientations and
kinetic energies of particles
(molecules, atoms, ions, )
at given instant.

(p, T, n, V)

Boltzmann : Entropy is a measure of how many microstates

are associated with a particular macrostate

S k ln W
k (also k B ) ... Boltzmann's constant
k 1.3806 1023 J K 1
k NA R

1.3806 10

(universal gas constant)

23

J K 1 6.022 1023 mol 1 8.314 J K 1 mol 1

S k ln Wfin k ln Winit
S k ln

Wfin
Winit

Number of microstates
is proportional to the volume
S R ln

Vfin
Vinit

Microstates and phase changes

Rigid structure

Loose structure

molecules restricted
to vibration only

molecules have
increased
freedom to move,
vibrate
and rotate

Smallest number
of microstates

Larger number
of microstates

BLB Figure 14.27

No structure at all
molecules have
complete freedom
for translation,
vibration
and rotation

Largest number
of microstates

Microstates and dissolution

Similar to fusion
NaCl (s) Na (aq) Cl (aq)

NaCl (l)

Moreover, dissolution provides more

freely moving particles which leads
to an increased number of microstates

Why do solids have limited solubility if dissolution is a spontaneous process

accompanied by entropy increase?
Because water molecules have lost some freedom of motion.
They are held around ions by electrostatic forces.
(See later in lecture on entropy & equilibrium)

Microstates and concentration

More molecules in the system means

more microstates.
Thus the reaction
2 NO(g) O2 (g) 2 NO2 (g)

leads to a decrease in the entropy

nfin 2 mol

ninit 3 mol

n 1 mol

However, in a closed volume, fewer moles will result in lower pressure

which is equivalent (at constant temperature) to larger volume.
From the perspective of the molecules there is more volume for themselves.
Larger volume leads to an increase in the entropy.
The two opposite effects will balance out in equilibrium (see next lecture)

Microstates and the 3rd law of thermodynamics

Perfect crystal at T = 0 K (t = -273.15 C)

Atoms are fixed (locked) at certain positions
have no kinetic energy (no translation, no rotation,
no vibrations)
Every snapshot at any time is exactly the same =>
=> there is one and single possible arrangement

Boltzmann : S k ln W k ln1 0

This makes it possible to determine

an absolute value of entropy at given
conditions (T, p)
Area below the curve
T

S (T )
0

http://chemwiki.ucdavis.edu/Under_Construction/chem1/Thermodynamics_of_Chemical_Equilibrium/Entropy

Cp
T

dT

Standard molar entropy, S mo

Absolute entropy of 1 mol of a substance
at standard conditions
298.15 K, 25C
1 atm, 1 bar, 101.325 kPa, 760 mm Hg
1 mol/L
Standard molar entropy is a change in
entropy when 1 mol of a substance
is heated from absolute zero
temperature to 298.15 K (at 1 atm)

Standard molar entropies are

determined from experimental data
and are tabulated for many substances.
Lowest standard molar entropy
Diamond

S mo 2.43 J K 1 mol 1

Substance

S mo / J K 1 mol1

H2(g)

130.6

N2(g)

191.5

O2(g)

205.0

NH3(g)

192.5

H2O(l)

69.91

CH3OH(l)

126.8

C6H6(l)

172.8

Hg(l)

200.6

Li(s)

29.1

Na(s)

51.4

K(s)

64.7

Fe(s)

27.2

NaCl(s)

72.3

Entropy changes in chemical reactions

Based on the fact that entropy is a state function
S Sfin Sinit

for a chemical reaction (initial state = reactants, final state = products)

r S S products S reactants

At standard conditions standard reaction entropy change

r S o

o
ni S m,
i

products

reactants

Analogy with Hesss law

for

o
mi S m,
i

R k1 R1 k2 R2 ...

Unlike enthalpies of formation of elements

the entropies of elements have not zero value

r S k1 r S1 k2 r S 2 ...

Example
2S ( s ) 3O2 ( g ) 2 SO3 ( g )

o
o
o
r S o 2Sm,
SO3 2 S m,S 3S m,O2

2 256.2 2 31.88 3 205 166.36 J/K

o
r H o 2 f H SO
2 395.2 = 790.4 kJ
3

r H o 790 400

2 651 J/K
T
298.15

r H o
r S
T
o

irreversible process

C s, diamond C s, graphite
o
o
r S o S m,graphite
S m,diamond
5.69 2.43 3.26 J K 1

o
o
r H o f H m,graphite
f H m,diamond
0 1.88 1.88 kJ K 1

r H o
r S
T
o

spontaneous decay of diamond