Monday, September 13, 2021

Low-Temperature Heat Capacity of Hydrogen Molecules

 


ortho
H
2
para
H
2
3:1 mixture
equilibrium
H
2
HD

0
100
200
300
400
T (K)
0.0
0.5
1.0
1.5
2.0

Hydrogen is the lowest boiling molecular species, remaining a gas down to 20K. At and above room temperature, , the rotational degree of freedom is fully excited; thus the rotational contribution to heat capacity approaches its equipartition value, per mole. Owing to the exceptionally small moment of inertia of , rotation becomes inactive at temperatures below about 50K. However, the heat capacity behaves anomalously as the temperature is lowered. This anomaly was first explained by Dennison in 1927. Since is a homonuclear molecule, only half of its rotational states are accessible. In the singlet nuclear-spin state, known as parahydrogen (p-) only even- rotational states are accessible; in the triplet nuclear-spin state, known as orthohydrogen (o-) only odd- rotational states are accessible. The molecular partition functions representing the rotational and nuclear spin degrees of freedom are given by

[more]

Contributed by: S. M. Blinder (March 2011)
Open content licensed under CC BY-NC-SA


Snapshots


Details

Snapshot 1: ortho and para rotational heat capacities as functions of temperature

Snapshot 2: 3:1 mixture and equilibrium mixture with catalyst

Snapshot 2: rotational heat capacity of heteronuclear HD molecule

Reference: S. M. Blinder, Advanced Physical Chemistry; A Survey of Modern Theoretical Principles, New York: Macmillan, 1969 pp. 475–478.



 

https://demonstrations.wolfram.com/LowTemperatureHeatCapacityOfHydrogenMolecules/ 

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