ISOTHERMS OF BROMINE ON GRAPHITE

1959 ◽  
Vol 37 (5) ◽  
pp. 899-904 ◽  
Author(s):  
J. G. Hooley

The isotherms of bromine on eight carbon blacks and on natural graphite have been related to the known structures of these materials. The surface areas can be calculated from the adsorption isotherms and the size of the graphite crystals can be estimated from the extent of hysteresis on desorption. The isosteric heats of adsorption on the surface and between the layers are each 11 kcal mole−1. The formation of residue compounds displaces the isotherms equally at all pressures.

The adsorption of oxygen, hydrogen and carbon monoxide has been studied on evaporated films of nickel prepared under varied conditions with a view to defining more precisely the differences in behaviour between nickel films and nickel powder. Heats of adsorption on the films have been determined at room temperature using a resistance-thermometer calorimeter. The extent of the adsorption with oxygen and hydrogen has been assessed by means of krypton isotherms at 77°K, and by means of established correlations between activity and weight for equivalent films. The coverage with oxygen reaches a complete monolayer, but with hydrogen at 0·1 mm pressure, the coverage is estimated at 40%. Curves of differential heat versus coverage have been approximated by making heat measurements for small increments. With oxygen, a study over 15 increments shows a heat of adsorption which is constant near 150 kcal/mole for 80% of the uptake, but which falls ultimately to a value well below 50 kcal/mole. With hydrogen, there is a continuous, almost linear fall with coverage from an initial heat near 40 kcal/mole to a final heat near 10 kcal/mole. The reversibility of the hydrogen adsorption has been specifically examined. The films as originally prepared are porous with surface areas of 30 m 2 /g or higher, but the act of chemisorption appears to initiate sintering. The integral heats with each gas studied are, without exception, greater than those reported for nickel powders. From the collated results, it is suggested that the enhancement of the heat is related to the degree of disorder of the metal specimen, and attention is drawn to the possibility of release of stored energy from films on rapid chemisorption of gases. Heats of adsorption have also been measured on 'oxided' films obtained by heat treatment in vacuo of oxygenated surfaces. It is apparent that the behaviour of the nickel films approaches that of powders at high coverages of chemisorbed gases, or, equally, after sintering.


From 78 to 150°K, and at coverages < 8 x 10 14 molecules/cm 2 , the sticking probability s of nitrogen on tungsten films (= 0·9) is independent of both temperature and coverage, whereas at temperatures above 150°K it is a function of both these variables. These results are interpreted in terms of a physically adsorbed precursor state with a heat of adsorption of ca . 3 kcal/mole. It is concluded that only a fraction of molecules colliding with the surface enter this state and that it is this fraction which determines the initial value of s at low temperatures. The decrease of s with increasing temperature above 150°K is a consequence of the inactivity of some planes, such as the (110), at the higher temperatures. Desorption spectra were obtained by warming films from 78°K to room temperature and recording the subsequent pressure changes as a function of time. From these data the distribution of site energies for the weakly held adsorbate (the αγ state) was evaluated, indicating a continuous distribution with heats of adsorption varying between 6 and 20 kcal/mole.


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