Enthalpy (H) Combining EQN 1 and EQN 2:

• Extensive property
• State function

At constant P:

From 1st law:

EQN 1

And Work: EQN 2

• For isobaric (constant P) process: Change in Enthalpy at Constant T

• When a system is subjected to a constant P process, 0

and only expansion work can occur, the change in

enthalpy is equal to the energy supplied as heat.

For a closed system with constant composition, Change in Enthalpy at Constant P

0
H(T,P):

Change in Enthalpy at Constant V

 Recall:
expansion coefficient

Isothermal compressibility,
Divide both sides by
1

Using Euler’s Chain relationship:

Thus,
?

Using Euler’s Chain relationship: Thus,

At constant V,

= Joule-Thomson coefficient

ratio of the change in T to the change in P when
a gas expands under isenthalpic condition
 for Ideal Gas Isothermal Compressibility of Ideal Gas

divide by (߲P)T
1

for ideal gas
compressibility of ideal gas decreases with ↑P

Relationship between CP and CV CP – CV at constant P

0
(at constant P, dP = 0)
Two ways to derive :
1. at constant P → derive in terms of [dividing by ]
P, T, V and U
2. at constant V → derive in terms of
P, T, V and H (EQN 1)
Recall:
1
CP – CV at constant V
(dividing by )
(in terms of P, T, V and H)

(EQN 2)
Note:
Substituting EQN 2 to EQN 1:
• At constant P, the heat transferred to a gas may be
used in the W of expanding it besides heating.
• At constant V, all the heat produces only a rise in T.
• More heat is required in a constant P process than a
(in terms of P, T, V and U) constant V process.

For an ideal gas: For any substance:

• for an ideal gas:

Recall: • for monatomic gas (noble gases) under ideal conditions:

• for diatomic gas (H2, N2, O2, etc.) or linear polyatomic gas
(CO2) under ideal conditions:

• for non-linear polyatomic gas (NH3, CH4, etc.):

P4.1. A sample consisting of 1.0 mol Ar is
expanded isothermally at 0 °C from 12.8 L to
22.4 L
a) reversibly
b) against a constant pressure equal to the
final pressure of the gas
c) freely against zero external pressure
Calculate (in J) Q, W, ΔU and ΔH. Assume Ar
behaves ideally.