Beruflich Dokumente
Kultur Dokumente
Spring 2015
Dr. Jean M. Standard
February 2, 2015
Substance C p, m Substance C p, m
(J mol1K1) (J mol1K1)
He (g) 20.79 CH4 (g) 35.31
Ne (g) 20.79 C2H6 (g) 52.63
H2 (g) 28.82 C2H5OH (g) 65.44
O2 (g) 29.36 C2H5OH (l) 111.46
CO2 (g) 37.11 C4H10, n-butane (g) 97.45
H2O (g) 33.58 C6H14, n-hexane (g) 143.09
H2O (l) 75.29 C8H18, n-octane (g) 188.87
Equipartition theorem
The equipartition theorem states that each degree of freedom contributes 12 RT to the molar internal energy, U m , of
a gas.
U m = ( dof ) ( 12 RT ) .
For example, the monatomic gas exhibits only 3 degrees of freedom. Therefore, the prediction from the
equipartition theorem for the molar internal
energy is
(
U m = ( dof ) 12 RT )
(
= ( 3) 12 RT )
U = 23 RT .
The constant volume molar heat capacity C v,m can be calculated using the definition,
# U &
C v,m = % m ( .
$ T 'v
The constant pressure molar heat capacity can then be obtained using the relation
C p,m = C v,m + R .
Substituting the value of R, the theoretical prediction for the constant pressure heat capacity of a monatomic gas is
C p,m = 52 R
(
= 52 8.314 J mol1K 1 )
1 1
C p,m = 20.79 J mol K .
This matches the experimental values of the heat capacities of He and Ne reported in the table above.
Beyond monatomic gases
For diatomic molecules along with linear and nonlinear polyatomic molecules in the gas phase, the number of
degrees of freedom can be determined and therefore the theoretical internal energy and heat capacity can be
predicted. In addition to the 3 translational degrees of freedom, contributions from rotational and vibrational
degrees of freedom must be considered.
For diatomic and linear polyatomic molecules, rotational motion contributes 2 degrees of freedom to the total, while
for nonlinear polyatomic molecules, rotational motion contributes 3 degrees of freedom. For diatomic and linear
polyatomic molecules, vibrational motion contributes 2(3N5) degrees of freedom to the total, while for nonlinear
polyatomic molecules, vibrational motion contributes 2(3N6) degrees of freedom, where N is the number of atoms
in the molecule. Using these prescriptions, the total number of degrees of freedom may be determined and the
equipartition theorem may then be employed to determine a theoretical prediction for the molar internal energy and
the heat capacities.