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The document discusses the molecular contributions to internal energy and heat capacity, focusing on the kinetic theory of matter and the behavior of ideal gases. It explains the degrees of freedom for monatomic, diatomic, and polyatomic molecules, as well as the equipartition theorem and its implications for heat capacities. Additionally, it covers the Dulong-Petit law and the modifications by Einstein and Debye to account for low-temperature behavior in solids.

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13 views8 pages

Very Hard

The document discusses the molecular contributions to internal energy and heat capacity, focusing on the kinetic theory of matter and the behavior of ideal gases. It explains the degrees of freedom for monatomic, diatomic, and polyatomic molecules, as well as the equipartition theorem and its implications for heat capacities. Additionally, it covers the Dulong-Petit law and the modifications by Einstein and Debye to account for low-temperature behavior in solids.

Uploaded by

ryuwodbs
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Molecular Contributions to

Internal Energy and Heat capacity


◆ Kinetic theory of matter
→ Bridge between thermodynamics
and mechanics of molecules
➢Total kinetic energy in n moles of
an ideal gas:
Ekin = ( 32 ) nRT
→ Internal energy of a monatomic gas

➢Molar heat capacity of a monatomic ideal gas


cP = cV + R = 32 R + R = 52 R = 20.785 J mol−1K −1
→ Good agreement with experiments!
106
➢ Diatomic molecules

 3 translational degrees of freedom: x-, y-, z-directions, Etrans = 12 M v 2


 2 rotational degrees of freedom: z-y, z-x planes,
Erot = 12 I  2
I : moment of inertia,  : angular velocity
 1 vibrational degree of freedom: Along y-axis,
2
1  dR 
( PE ) vib = k ( RAB − Re )
1
2
2
and ( KE ) vib =  AB  , Re: equilibrium bond length
2  dt 

Hook’s law Kinetic energy


107
➢ Polyatomic molecules

 Translational degrees of freedom: 3 (motion of the center of mass)


 Rotational degrees of freedom: 3 (nonlinear-), 2 (linear-) molecule
 Vibrational degrees of freedom: 3N – 6 (nonlinear) or 3N – 5 (linear)
Total degrees of freedom of N atoms of a molecule: 3N
Subtract the degrees of freedom for translation (3) and rotation (3 or 2)

108
◆ Equipartition theorem  classical concept
Each quadratic term that appears in the energy of
a molecule contributes RT/2 to the average energy
calculated from the Maxwell-Boltzmann distribution.

➢ Contributions to internal energy of a molecule:


Each translational degree of freedom: RT/2
Each rotational degree of freedom: RT/2
Each vibrational degree of freedom: RT
RT  KE ( 12 mv2 ) + PE ( 12 kx 2 )
➢ Contribution of each mode to the heat capacities
cV and cp (= cv + R) → Table 12.3

109
110
➢ Temperature dependence of contributions of each modes to cp
❑ Translation:
5R/2 at all temperatures above 0 K
❑ Rotation for H2:
Begins at low temperature
Reaches its equipartition value R
at room temperature
❑ Translation + Rotation for H2: 7R/2
❑ Vibration in H2, N2, O2:
Contributes only above room temp.
❑ Equipartition value for T+R+V, 9R/2
(= 37.41 J mol–1 K–1) reached at high T .

Equipartition values do not agree with


measured values at low temperature. Fig. 12.12. Temperature dependence
→ Quantum mechanical effect of cp for several gases.
111
◆ Heat capacities for solids

➢ Dulong-Petit’s law (1820):

cv = 3R (= 24.9 J K–1) for elemental solids at room temp


Classical 3D spring model for atoms in solid
→ 3 vibrational modes for each atom → 6 quadratic terms in PE & KE
→ 6R/2 = 3R to cv
Low experimental values for cv at low temperatures → QM effect!
 Einstein (1907) ~ Planck’s hypothesis for harmonic oscillators
→ Predicted low values of cv at low temperature
 Debye (1912) ~ Modified Einstein’s theory, better agreement with
experiment, cv approaches 0 as a T3-power law

112
Fig. 12.13. Temperature dependence of cv for solids. (a) Measured values
for elemental solids. (b) Debye and Einstein models for cv for Al.

113

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