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# 2

nd
Law of Thermodynamics
Entropy (part I)
Basic Physical Chemistry - Thermodynamics 1
■ Stated by Rudolph Clausius in 1854.
2 Basic Physical Chemistry - Thermodynamics
The Second Law of Thermodynamics
■ Heat can never pass from a colder to a warmer
body without some other change, connected
therewith, occurring at the same time.
DS = q
rev
/ T [10]
■ Lead to the definition of a new state function,
entropy, S. Entropy can be thought of as a
measure of disorder of a system. It is defined
as:
3 Basic Physical Chemistry - Thermodynamics
The Second Law of Thermodynamics
DS = q
rev
/ T [10]
T = 25 °C
T = 323 °C
596 J of heat pass from the hot copper bar to the copper bar at room temperature.
DS
HOT
= q
rev
/ T
DS
HOT
= –596 J / 596 K
DS
HOT
= –1 J K
–1
DS
RT
= q
rev
/ T
DS
RT
= +596 J / 298 K
DS
RT
= +2 J K
–1
DS = –1+2 J K
–1
= +1 J K
–1
4 Basic Physical Chemistry - Thermodynamics
Entropy
■ The entropy of an isolated system always
increases.
■ Calculate the probability of a 1% contraction of
one mole of a gas for just 1 ms over the entire
The probability for one atom to be found in 99% of
its original volume = 99% = 0.99
The probability for one mole of atoms to be found
in 99% of their original volume = 0.99
N
A
5 Basic Physical Chemistry - Thermodynamics
Entropy
P = (0.99)
6.022×10
23
= 10
–2,628,400,000,000,000,000,000

t = 13.75 ± 0.11 billion years
t = 4.336 × 10
23
ms
P = 10
–2,628,400,000,000,000,000,000
× 4.336 × 10
23

P = 4.336 × 10
(23 – 2,628,400,000,000,000,000,000)

P = 4.336 × 10
–2,628,400,000,000,000,000,977
≈ 0
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