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Journal of Research of the National Bureau of Standards 41, 379–475 (1948), RP1932. DOI: doi.org/10.6028/jres.041.037

Section III.2 and table 12 give ortho–para equilibrium composition and compare state sums with spectral and thermal evidence. The compilation distinguishes fixed-composition normal hydrogen from equilibrium spin isomers of hydrogen mixtures. It supplies institutional thermodynamic data and theory, rather than answers to a particular examination.

A mixture whose orthohydrogen and parahydrogen mole fractions are fixed on the observation timescale, although each species can equilibrate over its own rotational levels. Its molar heat capacity is $x_o{C}_o+x_p{C}_p$. normal hydrogen retained during cooling has $x_o=3/4$ and $x_p=1/4$. A mixture initially prepared at some other equilibrium composition can also be frozen; its subsequent heat response does not include a changing-composition term.

Harold W. Woolley helped compile quantitative properties from thermodynamics of hydrogen, distinguishing its isotopic forms and spin isomers of hydrogen. The compilation compares orthohydrogen and parahydrogen equilibrium calculations with spectral and thermal evidence. It also distinguishes a fixed-composition sample of normal hydrogen from a mixture allowed to reach spin-isomer equilibrium.^[ref]

NBS author of the hydrogen thermodynamic compilation cited in Compilation of Thermal Properties of Hydrogen in Its Various Isotopic and Ortho-Para Modifications by Harold W. Woolley and others. The institutional article byline verifies this author name.

As $t\to 0$, the conditional mean rotational energies approach $U_{\mathrm{p}}/N=0$ and $U_{\mathrm{o}}/N=2k_{\mathrm{B}}{\theta }_r$, using the para $J=0$ level as the common zero. A frozen mixture with ortho fraction $x$ therefore retains $U_{\mathrm{fr}}/N\to 2x{k}_{\mathrm{B}}{\theta }_r$. If a bath keeps the sample at low temperature while a catalyst permits conversion to almost pure parahydrogen, the rotational heat delivered to the bath tends to $Q_{\mathrm{out}}/N=2x{k}_{\mathrm{B}}{\theta }_r$, or $3k_{\mathrm{B}}{\theta }_r/2$ for normal hydrogen.

One may shift the ortho ladder to its own lowest level for computing its conditional heat capacity, because a constant energy offset disappears on differentiation at fixed composition. That offset must be restored before comparing species or calculating conversion heat. Otherwise the calculation loses precisely the stored rotational energy that conversion releases. The expression above accounts for the internal rotor contribution at fixed bath temperature; it does not model liquid intermolecular energies, latent heat, or an adiabatic temperature rise.

A catalyst changes the conversion rate and allows heat removal during cooling; it does not change the free-gas equilibrium weights at a specified temperature. This connects the microscopic exchange rule to refrigeration: delayed conversion supplies a continuing internal heat source. Rotational Raman spectroscopy offers a complementary population probe because its $\Delta J=\pm 2$ transitions stay within the even or odd ladder; line intensities require the appropriate species populations and transition response, not a bare $3:1$ intensity rule.

Let $u_s=⟨ϵ{⟩}_s$ and $v_s={\mathrm{Var}}_s(ϵ)$ for the conditional distributions of parahydrogen and orthohydrogen, with $s=\mathrm{p},\mathrm{o}$. Differentiating the normalized Boltzmann factors gives $d{u}_s/dt=v_s/t^2$. Thus the rotational heat capacity at constant volume per molecule of a composition frozen at $x$ isAt conversion equilibrium, the law of total variance adds a nonnegative contribution from the changing species populations:The last term is the contribution from conversion. Compare the first two terms with a frozen sample at the same instantaneous composition; a frozen $3:1$ sample generally has different weights too. This formula follows directly from the variance of a mixture: subtract the overall mean inside each species, expand the square, and the cross terms vanish because each conditional deviation has zero mean. It also proves nonnegative rotational heat capacity in either model.

For an original worked example at $t=1/2$, summing the allowed ladders gives $q_{\mathrm{p}}\approx 1.00003072$, $q_{\mathrm{o}}\approx 0.05494692$, and $x_{\mathrm{o}}^{\mathrm{eq}}\approx 0.14150982$. The calculated rotational heat capacities are $c_{\mathrm{eq}}/k_{\mathrm{B}}\approx 1.94719633$ and $c_{\mathrm{fr}}/k_{\mathrm{B}}\approx 0.00110733$ for frozen normal hydrogen. The contrast is large because changing species accesses the $J=0$ to $J=1$ separation, whereas fixed species must use the larger $J=0$ to $2$ or $J=1$ to $3$ separations. These are model numbers at a chosen dimensionless temperature, not measured hydrogen data.

Both rotational heat capacities approach zero as $t\to 0$, although frozen normal hydrogen retains nonzero rotational internal energy. Both approach $k_{\mathrm{B}}$ as $t\to \infty$ within the rotor model. The high-temperature limit is a formal limit with all other excitations suppressed; actual molecular hydrogen eventually needs molecular vibration, nonrigidity, and dissociation. Multiplying the per-molecule result by the Avogadro constant gives rotational molar heat capacity in units of the molar gas constant $R$. A dilute classical ideal gas additionally contributes $3R/2$ from translation to its heat capacity at constant volume.

Normal hydrogen denotes the $3:1$ orthohydrogen-to-parahydrogen mixture, the high-temperature equilibrium limit. Near room temperature the equilibrium ratio is already close to this limit. Cooling an isolated sample need not change its composition on the measurement timescale: ordinary collisions can redistribute rotational populations within each spin species much faster than they interconvert the spin species. A kinetically frozen composition can therefore coexist with rotational thermal equilibrium separately within each species.

The distinction was historically decisive. The institutional account Die Entdeckung des para-Wasserstoffs, in its discussion of the rotational heat capacity, explains that assuming an equilibrating composition missed the observed behavior, whereas freezing the high-temperature ratio reproduced it. It also records Karl Friedrich Bonhoeffer and Paul Harteck's 1929 preparation using a catalyst and thermal conductivity detection.^[ref]

At low temperature, retain $J=0$ in the even sum and $J=1$ in the odd sum. Their weights are respectively $1$ and $3e^{-2{\theta }_{\mathrm{rot}}/T}$ before the nuclear-spin multiplicity, soEquilibrium hydrogen then becomes almost entirely parahydrogen. At high temperature, many even and odd rotational levels contribute, and their spatial sums have the same leading value. HenceThis is normal hydrogen. Its familiar high-temperature ratio is a nuclear-spin multiplicity ratio, not the $9:1$ ratio of the two lowest levels. Maintaining conversion is essential: a sample cooled without an effective conversion mechanism can retain its earlier composition instead of following $K(T)$. NBS thermodynamic data distinguish equilibrium composition from normal hydrogen and compare the state-sum prediction with spectroscopic and thermal evidence.^[ref]

The 1935 primary paper The Spin-Isomerization of Hydrogen at Paramagnetic and Diamagnetic Surfaces, pp. 1251–1252, describes evacuated catalyst samples cooled before admitting molecular hydrogen. Gas samples were analyzed in a glass cell in liquid air: a heated platinum wire and Wheatstone bridge converted changes in thermal conductivity into electrical resistance readings, calibrated against normal hydrogen.^[ref]

Its comparison of oxide surfaces supplied a control: specimens exhibiting strong paramagnetism converted the gas much faster than the comparison exhibiting diamagnetism despite all adsorbing molecular hydrogen. Contact time, pressure, and temperature were recorded. This supports a role for surface magnetic properties beyond adsorption alone; it does not identify every microscopic surface site or directly measure nuclear-spin orientations.^[ref]

The inference chain is preparation, contact with a specified surface, then a calibrated bulk transport readout of composition. It is distinct from a direct calorimetry measurement of heat capacity: transport and heat capacity can both depend on the spin populations, but they are different measured quantities. Changing the catalyst's own surface structure, introducing magnetic impurities, or changing the detector's gas pressure can confound an uncalibrated comparison. The free-rotor partition functions predict equilibrium populations and stored energy, not the conversion rate on a particular surface.