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Physical Properties Of Hydrogen

Hydrogen can be considered an ideal gas over a wide temperature range and even at high pressures. At standard temperature and pressure conditions, it is a colourless, odourless, tasteless, non-toxic, non-corrosive, non-metallic diatomic gas, which is in principle physiologically not dangerous. One of its most important characteristics is its low density, which makes it necessary for any practical applications to either compress the hydrogen or liquefy it. It is positively buoyant above a temperature of 22 K, i.e., over (almost) the whole temperature range of its gaseous state.

Hydrogen gas is highly diffusive and highly buoyant; it rapidly mixes with the ambient air upon release. The diffusion velocity is proportional to the diffusion coefficient and varies with temperature according to Tn with n in the range of 1.72-1.8. Corresponding diffusion rates of hydrogen in air are larger by about a factor of 4 compared to those of air in air. The rising velocity under the influence of (positively) buoyant forces cannot be determined directly, since they are dependent on the density difference between hydrogen and air as well as on drag and friction forces, shape and size of the rising gas volume, and atmospheric turbulence. The positive buoyancy of hydrogen is a favourable safety feature in unconfined areas, but it can cause a hazardous situation in (partially) confined spaces, where the hydrogen can accumulate, e.g., underneath a roof. Both diffusion and buoyancy determine the rate at which the gas mixes with the ambient air. The rapid mixing of hydrogen with the air is a safety concern, since it leads very soon to flammable mixtures, which on the other hand for the same reason also will quickly dilute to the non-flammable range. Therefore it is estimated that in a typical unconfined hydrogen explosion, only a fraction of the gas mixture cloud is involved releasing in fact not more than a few per cent of the theoretically available energy.

Because of its small size, its small molecular weight and its low viscosity, hydrogen can cause a problem with respect to the propensity of the gas to leak at a larger molecular flow rate than other gases. Diffusion in small amount is even possible through intact materials, in particular organic materials, which may lead to gas accumulation in confined spaces. Leakage rates are by a factor of 50 higher than for water and by a factor of 10 compared to nitrogen. The addition of an odorant or colorant would ease the detection of small leaks; however, this is not practicable in most situations, and not feasible for LH2.

Hydrogen gas dissolved in liquids will permeate into adjoining vessel materials. At elevated temperatures and pressures, hydrogen attacks mild steels severely, causing decarburization and embrittlement. This is a serious concern in any situation involving storage or transfer of hydrogen gas under pressure. Proper material selection, e.g., special alloy steels, and technology is required to prevent embrittlement.

Hydrogen coexists in two different forms, ortho and para hydrogen, whose partition is dependent on the temperature. Normal hydrogen at room temperature is 75 % ortho (nuclear spins aligned) and 25 % para (spins anti-aligned). In the lower temperature range < 80 K, para hydrogen is the more stable form. At 20 K, the thermal equilibrium concentrations are 99.821 % para and 0.179 % ortho. The transition takes place over a longer period (about 3-4 days), until a new equilibrium state is reached. However, magnetic impurities and also small oxygen concentrations are able to catalyze ortho-para conversions raising the rate by several orders of magnitude (very good: Fe(OH)3) to the order of hours. Any concentration of either spin state can be created at any temperature through the action of catalysts. Most physical properties are differing only slightly between the two spin states. Most important is the large energy difference between the two varieties, which results in major differences for the specific heats and thermal conductivities. The presence of a radiation field results in the generation of free hydrogen atoms and ions, which also act as catalysts before recombining. The recombination on the other hand produces excess ortho hydrogen.

Hydrogen also exhibits a positive Thompson-Joule effect at temperatures above 193 K, the inversion temperature. It means that the temperature of the hydrogen gas increases upon depressurization, which may lead to ignition. For example, the temperature change is six degrees, if a sudden pressure drop from 20 MPa to ambient pressure takes place. The chance of a spontaneous ignition just by that effect, however, is small; an explosion is more likely to occur because of electrostatic charging of dust particles during the depressurization or autoignition at high temperatures.

Liquid hydrogen (LH2) has the advantage of extreme cleanliness and the more economic type of storage, however, on the expense of a significant energy consumption of about one third of its heat of combustion. Another drawback is the unavoidable loss by boiloff which allows to maintain the cold temperature in the tank. The evaporation rate is even enhanced when ortho hydrogen is stored. The heat liberated during the ortho-para conversion at 20 K is huge with 670 kJ/kg compared to a figure of 446 kJ/kg for the latent heat of vaporization at the same temperature. This represents a safety issue requiring a design of the hydrogen loop which is able to remove the heat of conversion in a safe manner.

For open LH2 pools, it needs to be considered that cold hydrogen gas is less volatile compared to ambient gas and thus more prone to the formation of a flammable mixture with air. Furthermore LH2 quickly contaminates itself due to condensation and solidification of air constituents, which can particularly lead to oxygen-enriched zones to form shock-explosive mixtures. In confined areas, an additional hazard is given by the fact that due to the volume increase by a factor of 845, when LH2 is heated up to ambient conditions, the local atmosphere may change drastically. In an enclosed space, final pressure may rise to 172 MPa, which certainly over pressurizes systems to bursting.

A further temperature decrease below the boiling point eventually results in mixtures of liquid and solid hydrogen or slush hydrogen, SLH2. Slush offers the advantages of a higher density and a prolongation of the storage time of the cryogen as the solid melts and absorbs heat. A safety risk is arising from the decreasing vapour pressure even below atmospheric pressure, which demands protection against air ingress into the system. In addition, the conversion of ortho to para hydrogen connected with the release of the respective heat of conversion as the solid is form, needs to be taken into account (SonntagRE:1988). The triple point finally is the temperature (13.8 K) and pressure (7.2 kPa), at which all three phases can exist in equilibrium.

If hydrogen (or any other fluid) is maintained above its critical temperature and pressure is applied, a single phase "supercritical fluid" forms. It is gas-like in that it is compressible, it is liquid-like in that it has a comparable density, and there is some transitory state in between characterized by strong structural fluctuations causing the unusual behaviour of fluid properties near their critical point. It also exhibits higher flow rates as compared with liquids. There is a strong dependence of the thermophysical properties of cryogenic hydrogen on temperature and pressure in the supercritical state. They vary strongly especially in the near-critical region. Cp has a maximum at the then called the pseudo-critical temperature ("thermal spike phenomenon"). Supercritical hydrogen might undergo a turbulent-to-laminar transition due to the dependence of viscosity on temperature. Heat transfer coefficients are unpredictable in the transition regime, and are much lower in the laminar regime.

Hydrogen at extreme, but accessible pressures (2-3*105 MPa) and temperatures (~ 4400 K) will make a phase transition to metallic hydrogen which may be superconducting at room temperature. This effect predicted in 1935 was eventually proven in a shock compression test in 1996. Metallic hydrogen is accepted to exist in the interior of Saturn and Jupiter, but has no practical application on Earth so far.

Hydrogen is both in the gaseous and liquid phase essentially an insulator. Only above some critical "breakdown" voltage, where ionization occurs, it becomes an electrical conductor.

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Page last modified on January 30, 2009, at 09:11 AM