PRINCIPLES OF

ENTROPY

By : Herlina
 Spontaneous Chemical
Reaction

• Free energy (∆G) is driving force of chemical

reaction
– ∆G < 0 is spontaneous
– ∆G = 0 is equilibrium
– ∆G > 0 is nonspontaneous
∆G = ∆H -T∆S
• ∆G has negative value if
– ∆H (-) and ∆S (+)
– ∆H (-) and ∆S (-) then |∆H| > |T∆S|
– ∆H (+) and ∆S (+) then |∆H| < |T∆S|
PRINCIPLES OF ENTROPY
What is Entropy?
Entropy relates with “disorder”, true or false?

Which room that has bigger “entropy”?

Which that has bigger “entropy”, moon or sun?

 Possible
Arrangement
Or
Allowed
Position

ENTRROPY ≠ “Disorder”
 So…..

• Entropy, S , is a thermodynamic
quantity that is a measure of the
randomness or disorder or the
“available arrangements” for the
system or surroundings.
 ENTROPY is…

• Entropy is a thermodynamic property;

– It is a point function.
– It define the state of a system.
– It is independent of the path followed.
• it can be viewed as a measure of disorder.
• i.e. More disorganized a system the higher
its entropy.
Table 1. Entropy of Various Substances at 25°C (eu/g atom)
Substance Solid Liquid Gas
Na 12.30 13.83 36.71
P 9.82 10.28 38.98
Si 4.43 11.21 40.12
Pb 15.5 17.14 41.89
H2O - 16.72 45.11
CH3OH - 30.3 56.80
B2O2 12.91 18.55 64.42
SiO2 10.00 11.35 54.62
Li2O 8.98 9.86 56.03
BeO 3.38 10.50 47.21
TiO2 12.01 15.43 56.44
PbO 15.59 20.55 57.35
BCl3 45.3 - 85.3
SiCl4 - 57.2 79.2
PbCl2 32.50 38.34 76.63
NaCl 17.33 20.22 54.88
HgBr2 40.71 46.80 76.51
 Principle Number 1

• The gaseous state is more probable than the

liquid state, which in turn is more probable
than the solid state.
In the same substance:

> >
Entropy of Entropy of Entropy of

GAS LIQUID SOLID

Gas: Many allowed Solid: Only a few
positions, molecules “allowed” positions,
are far apart. molecules or atoms
close together
 Table 2. Entropy of Monoatomic and
Polyatomic Gases
(eu/g atom)

H 27.4 H2 15.6.5
N 36.6 N2 22.9
O 38.5 O2 24.5 O3 19.0
F 37.9 F2 24.4
Si 40.1 Si2 17.5
P 39.0 P2 26.1 P4 16.7
S 40.1 S2 27.3 S8 12.9
Cl 39.5 Cl2 26.6
NO2 57.5 N2O4 36.4
 Principles Number 2

• A monatomic gas is more probable than a

polyatomic molecular gas, and hence tends to
have higher entropy.

>
Entropy of Entropy of
Monoatomic Polyatomic
gas gas
 Principle Number 3

• An amorphous solid is more probable than a

crystalline solid, and a simple crystalline solid more
probable than a more complex crystalline solid.

>
Entropy of Entropy of
Amorphous Crystalline

>
Entropy of Entropy of
Simple Complex
Crystalline Crystalline
Structure of Amorphous and Crystalline
 Principle Number 4
• A molecular addition compound, or a
coordination complex, is less probable
than its separate components.

Ex:
2H2(g) + O2(g) → 2H2O(g) at constant pressure and 25°C
Decreases – simple molecules form more complex molecule, so ∆S system
is negative
Na(s) + heat → Na(l) at the m.p. temperature of Na
Increases – atoms of Na have more “available positions” in
the liquid state. ∆S system is positive
H2O
NaCl(s) → Na+(aq) + Cl-(aq) for 10 g NaCl in 1L H2O at 25°C
Increases – ions formed from NaCl are more simple in
structure and have more available position. ∆S system is positive
Table 3. Effect of Mass on Entropy of Gases 25°C (eu/g atom)

X F Cl Br I
HX 41.51 44.65
NaX 51.70 54.88
MgX2 55.80 61.50
PbX2 69.35 76.63 82.43 85.91
BX3 60.71 69.32
ZrX4 76.95 87.37 98.78 108.42

NOX 59.27 65.38 67.67

 Principle Number 5

• Compounds of elements of higher atomic

weight, or molecules of the free elements
themselves, tend to have higher entropy.

Glucose
Table 1. Entropy of Various Substances at 25°C (eu/g atom))
Substance Solid Liquid Gas
Na 12.30 13.83 36.71
P 9.82 10.28 38.98
Si 4.43 11.21 40.12
Pb 15.5 17.14 41.89
H2O - 16.72 45.11
CH3OH - 30.3 56.80
B2O2 12.91 18.55 64.42
SiO2 10.00 11.35 54.62
Li2O 8.98 9.86 56.03
BeO 3.38 10.50 47.21
TiO2 12.01 15.43 56.44
PbO 15.59 20.55 57.35
BCl3 45.3 - 85.3
SiCl4 - 57.2 79.2
PbCl2 32.50 38.34 76.63
NaCl 17.33 20.22 54.88
HgBr2 40.71 46.80 76.51
 Principle Number 6
• At ordinary temperatures, entropy
effects are commonly small enough to
have relatively little effect on the
direction of reaction unless the
difference in total bonding energy
between reactants and products is
relatively small.
• At zero absolute
temperature (0 K), the
value of entropy is also 0
 ∆Hf° and ∆Gf

• In low
temperature,
the effect of
entropy is
small
∆H and ∆G
 Number 7

• All chemical reactions that increase the

entropy occur spontaneously at high enough
temperatures.

• If temperature increases,
then the entropy is bigger
 Conclusion
• A reaction in which a molecule
The entropy 1 is broken into two or more
usually smaller molecules.
increases in
• A reaction in which there is an
the following 2
increase in the moles of gases.
situations:
• A process in which
3 • a solid changes to liquid or
• gas or a liquid changes to gas.