Reactions of intermetallic clusters

Journal Article · Thu Feb 01 00:00:00 EST 1990 · Journal of Chemical Physics; (USA)

DOI:https://doi.org/10.1063/1.458060· OSTI ID:6950846

Farley, R W; Castleman, Jr, A W ^[1]

---

1. Department of Chemistry, Pennsylvania State University, University Park, Pennsylvania 16802 (US)

Reaction of bismuth--alkali clusters with closed-shell HX acids provides insight into the structures, formation, and stabilities of these intermetallic species. HC1 and HI are observed to quantitatively strip Bi{sub {ital x}}Na{sub {ital y}} and Bi{sub {ital x}}K{sub {ital y}}, respectively, of their alkali component, leaving bare bismuth clusters as the only bismuth-containing species detected. Product bismuth clusters exhibit the same distribution observed when pure bismuth is evaporated in the source. Though evaporated simultaneously from the same crucible, this suggests alkali atoms condense onto existing bismuth clusters and have negligible effect on their formation and consequent distribution. The indistinguishibility of reacted and pure bismuth cluster distributions further argues against the simple replacement of alkali atoms with hydrogen in these reactions. This is considered further evidence that the alkali atoms are external to the stable bismuth Zintl anionic structures. Reactivities of Bi{sub {ital x}}Na{sub {ital y}} clusters with HC1 are estimated to lie between 3{times}10{sup {minus}13} for Bi{sub 4}Na, to greater than 4{times}10{sup {minus}11} for clusters possessing large numbers of alkali atoms. Bare bismuth clusters are observed in separate experiments to react significantly more slowly with rates of 1--9{times}10{sup {minus}14} and exhibit little variation of reactivity with size. The bismuth clusters may thus be considered a relatively inert substrate upon which the alkali overlayer reacts.

• DOE Contract Number: FG02-88ER60648
• OSTI ID: 6950846
• Journal Information: Journal of Chemical Physics; (USA), Vol. 92:3; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BISMUTH COMPOUNDS
INTERMETALLIC COMPOUNDS
HYDRIODIC ACID
CHEMICAL REACTIONS
HYDROCHLORIC ACID
POTASSIUM COMPOUNDS
SODIUM COMPOUNDS
REACTIVITY
STABILITY
ALKALI METAL COMPOUNDS
ALLOYS
HALOGEN COMPOUNDS
HYDROGEN COMPOUNDS
INORGANIC ACIDS
IODINE COMPOUNDS
400201* - Chemical & Physicochemical Properties