SOLUBILITY AND INTERACTION OF HYDROGEN GAS IN LIQUID LEAD LITHIUM EUTECTIC Introduction:

The lithium-lead eutectic is a tritium breeding material envisaged for use in fusion reactors. It also acts as cooler, multiplier. It also prevents the use of the highly toxic beryllium thus reducing the poisoning of internal structures and enabling safety. The eutectic does not show vigorous chemical reactions with air or water which is an important criterion in the choice of breeder materials. Possible disadvantages are related to high density. Worse compatibility, Compared to Li, with steels, tritium containment problems (due to its very low solubility) Solubility of hydrogen isotopes can be studied because of increasing interest in the use of Pb-Li in the fusion research.

1.1Solubility:
Solubility is the amount of a solute that will dissolve in a specific solvent under given conditions. The dissolved substance is called the solute and the dissolving fluid (usually present in excess) is called the solvent, which together form a solution. The process of dissolving is called solvation. Pressure and temperature are two external factors which influence solubility. Both affect the solubility of gases in liquid metals. The solubility of gases in a liquid is directly proportional to gas pressure (Henrys law).while the solubility of gases in metals / liq. Metals is governed by Sieverts law. 1.2Sieverts law: [1] According to the Sieverts law the solubility of a diatomic gas in al liquid metal is proportional to the square root of its partial pressure in the gas in equilibrium with the metal. S= P (gas) . Ks Here Ks= Sieverts constant (atm1/2) p= partial pressure of the gas applied on liq. Metal (atm) A diatomic gas, for example hydrogen dissociates into atoms when it dissolves in metal. The dissociation can be represented as ---- (1)

H2 (gas) 2H (dissolved species) The equilibrium constant for this process is Ks=C2H/PH2 Where CH = atomic hydrogen in the metal (equal to the atomic fraction of hydrogen present in the metal) PN2= partial pressure of hydrogen gas in equilibrium in the solution Hence, XH = (PH2)0.5 .KS --- (3) ---- (2)

The amount of a gas dissolved in a metal can be increased by increasing the partial pressure of gas.

1.3Limitations:
Sieverts law is applicable in pure liquid metals only when the solute gas is present in very low concentrations. At higher concentrations deviation from law occurs.

2.1 Solubility of hydrogen gas in lead lithium eutectic:

The solubility of hydrogen gas in liquid Pb-Li also obeys Sieverts law at low concentration. This eutectic contains reactive lithium metal in low concentration and inert lead in higher proportion. Lithium-lead eutectic contains 87 at. % Pb and 17 at. % Li. The data base for lead lithium is not complete and its physical and chemical properties are not well known.

2.2 Chemical interaction of lithium with hydrogen gas

Lead lithium eutectic (Li17Pb83) contains inert lead metal which is generally inert towards hydrogen gas. Lead generally forms lead tetra hydride (PbH4), is an extremely unstable gas produced by electrolytic reduction at a small lead cathode under a high current density. It breaks up into its elements with great ease even at ordinary temperature. [2] It is assumed that lead dissolves hydrogen endothermally. [3] Pb (l) + 2H2 (g) + energy PbH4 (g) (highly unstable)

2.3 Chemical interaction of lithium with hydrogen gas

Lithium can combine directly with hydrogen above 5000C temp. to give lithium hydride. Lithium hydride has a NaCl like cubic structure in which each Li atom is surrounded by 6 hydrogen atoms and vice versa. Lithium dissolves hydrogen exothermally. 2Li (l) + H2 (g) 2LiH (s) + energy This formed lithium hydride when heated, melts at 6800C and if melt is electrolyzed. Liquid lithium is formed at one electrode and hydrogen gas at other. Negative electrode: Li+ (melt) + e- = Li (liq.)

Positive electrode:

H-(melt) = H2 (g) + e$

This behavior, together with crystal structure, is characteristic of ionic compounds. [4]

2.4Charge on hydrogen in lead lithium eutectic [5]

Hydrogen existing in liquid lithiumlead was modeled using first-principles molecular dynamics. The chemical state of hydrogen was analyzed based on the trajectory and charge of hydrogen, and the HLi radial distribution function, as obtained from calculations. Results show that, in liquid lithiumlead, the charge state of hydrogen correlates with LiH interatomic distance: it becomes close to H- because of a binding interaction of LiH when the distance is short, whereas it becomes close to H0 as a hydrogen atom dissolved in liquid lead when the distance is long. Additionally, it was observed that hydrogen diffuses in liquid lithiumlead with jumping from one site to another where the binding interaction of LiH can be formed, which would be one of the main diffusion mechanisms. 2.5 Effect of pressure on the solubility of hydrogen gas in eutectic From the Sieverts law, solubility is dependent on the partial pressure of the gas. Hence as partial pressure of gas increases, solubility increases. According to le chateliers principle in a constant reaction space the pressure will depend upon the number of molecules of gas in that

space. An increase in the number of molecules in space will increase the pressure and decrease in number will decrease the pressure. If the pressure is increased the reaction will be favored is the one that will lower the pressure that is decrease the number of moles. (Higher number of moles to lower number of moles)[6] If we consider following reaction 2Li (l) + H2 (g) 2LiH (s) + energy

In condition of equilibrium, if we increase the pressure then the equilibrium will shift towards the lower number of moles i.e. amount of LiH in reacting vessel will increase. Equilibrium will shift in forward direction.

2.6 Effect of temperature on the solubility of hydrogen gas in eutectic In following reaction 2Li (l) + H2 (g) 2LiH (s) + energy

The formation of lithium hydride is an exothermic reaction. Hence if there is further increase in temperature of the reaction the reaction will be in backward direction according to le chateliers principle. Formation of lithium hydride is an exothermic reaction while formation of lead hydride is assumed to be endothermic reaction. [3] 2.7 conclusions: The solubility and interaction of hydrogen gas (hydride formation) depends upon the external temperature and pressure conditions, interatomic distance between atoms of hydrogen and lithium.

REFERENCES: 1. Chemical metallurgy: principles and practice By C. K. Gupta

2. Anil Kumar de (a text book of inorganic chemistry) 3. J.A. Blink, O.H. Krikorian and N.J. Hoffman, in: Metal Bonding and Interactions in High Temperature Systems, eds., J.L. Gole, W.C. Stwalley, ACS Symposium Series 179 (American Chemical Society, Washington D.C., 1982). 4. Metals and chemical change, Volume 1 by David Arthur Johnson 5. Chemical state and diffusion behavior of hydrogen isotopes in liquid lithiumlead (Daisuke Masuyama, Takuji Oda, Satoshi Fukada, Satoru Tanaka) 6. Chemistry the Easy Way By Joseph A. Mascetta