1,

First law of thermodynamics

- For an isolated system which does not exchange work or heat with
its surroundings, the internal energy U is identical to the total
energy E of the system known from mechanics or electrodynamics.
- If the system is able to exchange work or heat with its
surroundings, an energy law holds which is extended with respect
to mechanics or electrodynamics.
- In infinitesimal form energy conservation reads
𝑑𝑈 = 𝛿𝑄 − 𝛿𝑊
Mayer’s relation for ideal gas
𝐶𝑝 = 𝐶𝑣 + 𝑛𝑅
Or 𝑐𝑝 = 𝑐𝑣 + 𝑅 for heat capacities per mole
Derive:
𝛿𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉
𝐹𝑜𝑟 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠: 𝑑𝑈 = 𝐶𝑣 𝑑𝑇 ( 𝑈 𝑎𝑠 𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛 𝑇 𝑎𝑛𝑑 𝑉)
→ 𝛿𝑄 = 𝐶𝑣 𝑑𝑇 + 𝑃𝑑𝑉
𝜕𝑉
𝑤𝑖𝑡ℎ 𝑑𝑉 = ( ) 𝑑𝑇
𝜕𝑇 𝑃
𝜕𝑉
→ 𝛿𝑄 = 𝐶𝑣 𝑑𝑇 + 𝑃 ( ) 𝑑𝑇
𝜕𝑇 𝑃
𝛿𝑄 𝜕𝑉
→ = 𝐶𝑣 + 𝑃 ( )
𝑑𝑇 𝜕𝑇 𝑃
𝛿𝑄 𝑛𝑅𝑇
( ) = 𝐶𝑝 ; 𝑉 =
𝑑𝑇 𝑃 𝑃
→ 𝐶𝑝 = 𝐶𝑣 + 𝑛𝑅
2, Adiabatic process
𝛿𝑄 = 0
𝑑𝑈 + 𝑃𝑑𝑉 = 𝛿𝑄 = 0
𝑑𝑉
→ 𝐶𝑣 𝑑𝑇 = −𝑃𝑑𝑉 = −𝑛𝑅𝑇
𝑉
𝐹𝑜𝑟 𝑝𝑒𝑟𝑓𝑒𝑐𝑡 𝑔𝑎𝑠 𝐶𝑣 = 𝑐𝑜𝑛𝑠𝑡
−𝑛𝑅
→ 𝑙𝑛𝑇 = 𝑙𝑛𝑉 + 𝑐𝑜𝑛𝑠𝑡
𝐶𝑣
𝑛𝑅 𝑛𝑅
→ 𝑙𝑛 (𝑇. 𝑉 𝐶𝑣 ) = 𝑐𝑜𝑛𝑠𝑡 → 𝑇. 𝑉 𝐶𝑣 = 𝑐𝑜𝑛𝑠𝑡(∗)
𝐶𝑝 𝑛𝑅
𝛾= =1+
𝐶𝑣 𝐶𝑣
𝛾−1
𝑇𝑉 = 𝑐𝑜𝑛𝑠𝑡
𝛾
(∗) → { 𝑃𝑉 = 𝑐𝑜𝑛𝑠𝑡
1
𝑇𝑃𝛾−1 = 𝑐𝑜𝑛𝑠𝑡
3,
Carnot engine: consists of two isotherms T1 and T2 and two adiabatics
(working body being ideal gas)
 𝑉𝐵
𝑄2 = 𝑄𝐴𝐵 = 𝑊𝐴𝐵 = 𝑛𝑅𝑇2 𝑙𝑛
𝑉𝐴
𝑉𝐶
𝒬1 = −𝑄𝐶𝐷 = 𝑊𝐶𝐷 = 𝑛𝑅𝑇1 𝑙𝑛 >0
𝑉𝐷
Mayer : 𝑇𝑉 𝛾−1 = 𝑐𝑜𝑛𝑠𝑡
𝛾−1 𝛾−1 𝛾−1 𝛾−1 𝑉𝐵 𝑉𝐶
𝑇2 𝑉𝐵 = 𝑇1 𝑉𝐶 𝑎𝑛𝑑 𝑇2 𝑉𝐴 = 𝑇1 𝑉𝐷 → =
𝑉𝐴 𝑉𝐷

𝒬1 𝑇1
=
𝑄2 𝑇2
𝑊 𝑄2 − 𝒬1 𝒬1 𝑇1
𝑛= = =1− =1−
𝑄2 𝑄2 𝑄2 𝑇2
4, Second law of thermodynamics
5,
Carnot’s theorem
Efficiency of any reversible heat engine operating between heat
reservoirs with temperatures T1 and T2 is equal to the efficiency of
carnot engine
𝑇1
𝜂 =1−
𝑇2
While the efficiency of any irreversible heat engine is lower than this

Assume:𝜂𝑤𝑜𝑛𝑑𝑒𝑟 > 𝜂𝑐𝑎𝑟𝑛𝑜𝑡

→ 𝜂𝑤𝑜𝑛𝑑𝑒𝑟 − 𝜂𝑐𝑎𝑟𝑛𝑜𝑡 > 0
𝑊 𝑊′
→ − >0
𝑄2 𝒬2′
 𝑊 (𝒬2′ − 𝑄2 )
′ > 0 → 𝒬2′ − 𝑄2 > 0
𝑄2 𝒬2
According to second law 𝒬2′ − 𝑄2 < 0
→ Nothing beats a carnot engine
6,

7,
Change of entropy on isolated systems
8, Entropy of ideal gas
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
1 𝑃
𝑑𝑆 = 𝑑𝑈 + 𝑑𝑉
𝑇 𝑇
U function of T and V
 𝜕𝑈 𝜕𝑈
𝑑𝑈 = ( ) 𝑑𝑇 + ( ) 𝑑𝑉
𝜕𝑇 𝑉 𝜕𝑉 𝑇
1 𝜕𝑈 1 𝜕𝑈 𝑃
→ 𝑑𝑆 = ( ) 𝑑𝑇 + ( ) 𝑑𝑉 + 𝑑𝑉
𝑇 𝜕𝑇 𝑉 𝑇 𝜕𝑉 𝑇 𝑇
1 1 𝜕𝑈
𝑑𝑆 = 𝐶𝑉 𝑑𝑇 + [( ) + 𝑃] 𝑑𝑉
𝑇 𝑇 𝜕𝑉 𝑇
1 𝑃
𝑑𝑆 = 𝐶𝑉 𝑑𝑇 + 𝑑𝑉
𝑇 𝑇
1 𝑛𝑅
𝑑𝑆 = 𝐶𝑉 𝑑𝑇 + 𝑑𝑉
𝑇 𝑉
𝑆 = 𝐶𝑉 𝑙𝑛𝑇 + 𝑛𝑅𝑙𝑛𝑉 + 𝑆0
8,
Third law : in the limit T→0 entropy becomes constant, independent of
other thermodynamic parameters such as volume and pressure
𝜕𝑆 𝜕𝑆
( ) =( ) =0
𝜕𝑉 𝑇→0 𝜕𝑃 𝑇→0
Consequences:
1 𝑃
𝑑𝑆 = 𝑑𝑈 + 𝑑𝑉
𝑇 𝑇
1 𝑃
𝑑𝑆 = 𝐶𝑉 𝑑𝑇 + 𝑑𝑉
𝑇 𝑇
𝑑𝑆 𝐶𝑉
( ) =
𝑑𝑇 𝑉 𝑇
𝑇
𝐶𝑉
𝑆=∫ 𝑑𝑇 + 𝑆0
0 𝑇
T→0 𝐶𝑉 is not finite → S not constant→𝐶𝑉 = 0
 𝜕𝑆 𝜕𝑃
Maxwell relation ( ) = ( )
𝜕𝑉 𝑇 𝜕𝑇 𝑉

𝜕𝑃
→( ) | =0
𝜕𝑇 𝑉
𝑇→0
𝜕𝑉
( ) | =0
𝜕𝑇 𝑃 𝑇→0