TERMODINAMIKA

TEKNIK KIMIA 2
Dr. Ifa Puspasari
• Thermodynamics 1st law:
∆𝑈 = 𝑄 + 𝑊
2J
ΔU = 0 + 2 J
ΔU = 2 J

X
-2 J
ΔU = 0 + (-2 J)
ΔU = -2 J

• 1st law of thermodynamics does not tell if the above spontaneous

process is possible or not.
• 2nd law permits prediction on the direction of movement of a process.

1st law 2nd law

Thermodynamics 2nd Law
• Energy is spontaneously tend to flow only from concentrated in
one place to becoming diffused or dispersed or spread out.

• Thermal energy in the coffee has been given out to the surrounding,
so that it comes down to room temperature.
• Ice melting: energy from outside diffuse to the ice cube which has
lower energy, so that the water molecules melt.
Thermodynamics 2nd Law
• Energy is spontaneously tend to flow only from concentrated in one place
to becoming diffused or dispersed or spread out.

+
++ +
+ + + +
+ + + +
vacuum + +
+

• Charge on metallic sphere: electrostatic energy spreads out so that entire

surface has equal amount of electrostatic energy.
• When the knob is opened, air molecules in one of the chamber diffuse in both
chambers.
• Sound waves having high density spreads out, the intensity is gradually
decreasing because the energy is diffused or dispersed in atmosphere.
Entropy
• Entropy (ΔS): the extent of diffusion of energy.
𝑑𝑄𝑟𝑒𝑣
𝑑𝑆 =
𝑇
• If heat is given to a system, then entropy will increase.
• Taking out heat from a system, the entropy will decrease.
• When heat is given to a system, the heat is becoming more dispersed
and will be given to the molecules in the system, the heat will be
distributed => diffusion of energy => entropy is increased
• Change in entropy is inversely proportional to temperature.
10 J 10 J

T1 = 100 K T2 = 1000 K

• Entropy change is higher for lower temperature.

• At high temperature, the molecules are already very vigorous. Energy
content is already very high. Small amount of energy added, will not
change its state sufficiently. => dS is lower
Entropy
300 K
373 K

-100 J

−100 𝐽 100 𝐽
+ positive
373 𝐾 300 𝐾

• For this case, the net of entropy change is positive.

• So the proses is spontaneous.
373 K 300 K

−100 𝐽 100 𝐽
+ negative
300 𝐾 373 𝐾
• For this case, the net of entropy change is negative.
• So the proses is not possible.
Ideal Gas for Carnot Cycle
• path 1 – 2 (isothermal reversible expansion)

𝑑𝑈 𝑡 = 𝑑𝑄 + 𝑑𝑊
0

𝑄 = −𝑊 = 𝑃𝑑𝑉

𝑉2
𝑄 = 𝑅𝑇 ln
𝑉1

𝑉2
𝑄𝐻 = 𝑅𝑇𝐻 ln
𝑉1
Ideal Gas for Carnot Cycle
• path 1 – 2 (isothermal reversible expansion)
𝑉2
𝑄𝐻 = 𝑅𝑇𝐻 ln
𝑉1

• path 3 – 4 (isothermal reversible compression)

𝑉4
𝑄𝐶 = 𝑅𝑇𝐶 ln
𝑉3

• So,
𝑄𝐻 𝑇𝐻 ln 𝑉2 𝑉1
= 1
𝑄𝐶 𝑇𝐶 ln 𝑉4 𝑉3
Ideal Gas for Carnot Cycle
• path 2 – 3 (adiabatic reversible expansion)

𝑑𝑈 𝑡 = 𝑑𝑄 + 𝑑𝑊
0

𝐶𝑣 𝑑𝑇 = −𝑃𝑑𝑉

𝐶𝑣 1
𝑑𝑇 = − 𝑑𝑉
𝑅𝑇 𝑉

𝑇𝐶
𝐶𝑣 𝑉2
𝑑𝑇 = ln
𝑅𝑇 𝑉3
𝑇𝐻
Ideal Gas for Carnot Cycle
• path 2 – 3 (adiabatic reversible expansion)
𝑇𝐶
𝐶𝑣 𝑉2
𝑑𝑇 = ln
𝑅𝑇 𝑉3
𝑇𝐻

• path 4 – 1 (adiabatic reversible compression)

𝑇𝐻
𝐶𝑣 𝑉4
𝑑𝑇 = ln
𝑅𝑇 𝑉1
𝑇𝐶

𝑉2 𝑉1
ln = ln
𝑉3 𝑉4
Ideal Gas for Carnot Cycle
• from isothermal path (1 – 2 & 3 – 4)
𝑄𝐻 𝑇𝐻 ln 𝑉2 𝑉1
= 1
𝑄𝐶 𝑇𝐶 ln 𝑉4 𝑉3

• from adiabatic path (2 – 3 & 4 – 1)

𝑉2 𝑉1 𝑉2 𝑉3
ln = ln or = 2
𝑉3 𝑉4 𝑉1 𝑉4

• So,
𝑄𝐻 𝑇𝐻
=−
𝑄𝐶 𝑇𝐶
Quiz
• The working substance of an engine is 1.00 mol of a
monatomic ideal gas. The cycle begins at P1 = 1.00 atm
and V1 = 24.6 L. The gas is heated at constant volume to
P2 = 2.00 atm. It then expands at constant pressure until
its volume is 49.2 L. The gas is then cooled at constant
volume until its pressure is again 1.00 atm. It is then
compressed at constant pressure to its original state. All
the steps are reversible.
• (a) Show this cycle on a PV diagram. For each step of the
cycle, find the work done by the gas, the heat absorbed
by the gas, and the change in the internal energy of the
gas.
• (b) Find the efficiency of the cycle.