Lecture 2: Enthalpy

• Reading: Zumdahl 9.2, 9.3

• Outline
– Definition of Enthalpy (DH)
– Definition of Heat Capacity (Cv and Cp)
– Calculating DE and DH using Cv and Cp
 Definition of Enthalpy
• Thermodynamic Definition of Enthalpy (H):

H = E + PV
E = energy of the system
P = pressure of the system
V = volume of the system
 Definition of Enthalpy (cont.)
• Consider a process carried out at constant
pressure.

• If work is of the form -PDV, then:

DE = qp + w
= qp - PDV
DE + PDV = qp

qp is heat transferred at constant pressure.

 Definition of Enthalpy (cont.)
• Recall: H = E + PV

DH = DE + D(PV)
= DE + PDV (P is constant)
= qp
• Or DH = qp

• The change in enthalpy is equal to the heat

transferred at constant pressure.
 Changes in Enthalpy
• Consider the following expression for a chemical
process:

DH = Hproducts - Hreactants

If DH >0, then qp >0. The reaction is endothermic

If DH <0, then qp <0. The reaction is exothermic

Enthalpy Changes Pictorally
• Similar to previous discussion
for Energy.

• Heat comes out of system,

enthalpy decreases (ex. Cooling
water).

• Heat goes in, enthalpy increases

(ex. Heating water)
 Heat Capacity at Constant V
• Recall from Chapter 5 (section 5.6):

(KE)ave = 3/2RT (ideal monatomic gas)

• Temperature is a measure of molecular speed.

• In thermodynamic terms, an increase in system

temperature corresponds to an increase in system
kinetic energy ( i.e., T is proportional to E)
 Heat Capacity at Constant V
• (KE)ave = 3/2RT (ideal monatomic gas)

• How much energy in the form of heat is required

to change the gas temperature by an amount DT?

Heat required = 3/2R DT

= 3/2R (for DT = 1K)

• Therefore, Cv = 3/2 R is the heat required to raise

one mole of an ideal gas by 1K at constant
volume. Cv is referred to as the constant volume
heat capacity.
 Heat Capacity at Constant P
• What about at constant pressure? In this case, PV
type work can also occur:

PDV = nRDT = RDT (for 1 mole)

= R (for DT = 1 K)

• Cp = “heat into translation” + “work”

= Cv + R = 5/2R (for an ideal monatomic gas)
Cv for Monatomic Gases
• What are the energetic
degrees of freedom for
a monatomic gas?

Ans: Just translations,

which contribute 3/2R
to Cv.
 Cv for Polyatomics
• What are the energetic
degrees of freedom for
a polyatomic gas?

Ans: translations,
rotations, and
vibrations. All of
which may contribute
to Cv (depends on T).
NO2 CV = 3R (approx.)
Variation in Cp and Cv
• Monatomics:
– Cv = 3/2 R
– Cp = 5/2 R
• Polyatomics:
– Cv > 3/2 R
– Cp > 5/2 R
– But….Cp = Cv + R
 Energy and Cv
• Recall from Chapter 5:
Eave = 3/2 nRT (average trans. energy)
DE = 3/2 nR DT
DE = n Cv DT (since 3/2 R = Cv)

• Why is it Cv? We envision heating our system at

constant volume. As such, all heat goes towards
increasing E (no work).
 Enthalpy and Cp
• What if we heated our gas at constant
pressure? Then, we have a volume change
such that work occurs.
q p = n Cp DT
= n (Cv + R) DT
= DE + nRDT = DE + PDV
= DH or DH = nCpDT
 Keeping Track
Ideal Monatomic Gas All Ideal Gases
• Cv = 3/2R
• Cp = Cv + R = 5/2 R • DE = nCvDT

Polyatomic Gas • DH = nCpDT

• Cv > 3/2R
• Cp > 5/2 R
 Example
• What is q, w, DE and DH for a process in which
one mole of an ideal monatomic gas with an initial
volume of 5 l and pressure of 2.0 atm is heated
until a volume of 10 l is reached with pressure
unchanged?

Pinit = 2 atm Pfinal = 2 atm

Vinit = 5 l Vfinal = 10 l
Tinit = ? K Tfinal = ? K
 Example (cont.)
• Since PDV = nRDT, we can determine DT.

• Then DV = (10 l - 5 l) = 5 l

• And:
(2atm)(5l) = 121.8K = DT
(
(1mol) .0821 l.atm mol.K )

†
 Example (cont.)
• Given this:

( )
DE = nCv DT = (1mol) 12.5 J mol.K (121.8K ) = 1522.5J

DH = nC DT = (1mol)(20.8 J mol.K )(121.8K ) = 2533.4J

p

†
( )
w = -Pext DV = -(2atm)(5l) 101.3 J l.atm = -1013.0J
†
q = DE - w = 1522.5J - (-1013.0J ) = 2535.5J
†