By Bancroft W. D.
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X in C4HB,Dx or C4HIo7Dx % Composition as given by GLC analysis. 58 46 %4 Fig. 18. The effect of mercury coverage ( 6 ~upon ~ ) t h e rates of hydrogenation olefin exchange (@) and isomerisation ( 8 ) of but-l-ene over r h o d i u m s i l i c a at 4 . um at low temperatures (see Fig. 16 and ref. O, observed with the other noble Group VIII metals, may be explained by supposing that the conformations of the adsorbed but-2-yl group immediately before H-atom abstraction are important [ 1311. In an attempt t o understand further the mechanism of double bond migration, the reaction of but-l-ene with deuterium over mercury-poisoned rhodiumsilica catalysts was investigated [ 1291.
The preferential formation of cis-but-2-ene from but-1-ene, particularly noticeable with rhodi- -3 ; n 1 b P ," 4 1 TABLE 12 Product distributions from the reaction of the n-butenes with deuterium over palladiumalumina catalysts [ 1241 )-r 2 (J'R)o = (Pc~H&o = 60 torr _____________~~_ Reactant Conversion -- Temp. 0 36 a 2 a No species above - d ~were observed. x in C4HB,Dx or C4HIo7Dx % Composition as given by GLC analysis. 58 46 %4 Fig. 18. The effect of mercury coverage ( 6 ~upon ~ ) t h e rates of hydrogenation olefin exchange (@) and isomerisation ( 8 ) of but-l-ene over r h o d i u m s i l i c a at 4 .
Butane (%) 0 50 n -Butane 100 (O/d Fig. 1 6 . Distribution o f t h e n-butenes as a function of t h e extent of hydrogenation of but-l-ene a t 25OC over (a) rhodium-alumina and (b) r h o d i u m s i l i c a [ 1 2 5 ] . 0 , But-1ene; 3,t r a n s - b u t - l e n e ; f cis-but-2-ene. References p p . 0 ? 1 a ? 08 0 Catalyst Olefin Temp. o 0 0 ~~ Valid at low pressure; as P,, increased, m decreased. 4 Ref. 05 ? 4 124 103 43 The second method, derived by Hamilton and Burwell El271 for the hydroisomerisation of cis-but-2-ene over palladiumalumina, requires the assumption that the isomerisation and hydrogenation reactions have identical kinetic form and that the rates of hydrogenation of the butenes are identical.
Aromatic Substitution Products with Fluorine by Bancroft W. D.