Catalytic decomposition of formic acid

There is an extensive literature relating to the role of surface intermediates in the heterogeneous catalytic decomposition of formic acid on metals and oxides (see Refs. 36, 522,1030,1042—1045). 

Catalytic decomposition, of formic acid, 14 35 Catalytic effects, in isocyanate reactions, 13 393... 

Sabatier and Balandin had predicted a relationship between catal)dic activity and heat of adsorption. If a solid adsorbs the reactants only weakly, it will be a poor catalyst, but if it holds reactants, intermediates or products too strongly, it wiU again perform poorly. The ideal catalyst for a given reaction was predicted to be a compromise between too weak and too strong chemisorption. Balandin transformed this concept to a semiquantitative theory by predicting that a plot of the reaction rate of a catal)Tic reaction as a function of the heat of adsorption of the reactant should have a sharp maximum. He called these plots volcano-shaped curvesl This prediction was confirmed by Fahrenfort et al." An example of their volcano-shaped curve is reproduced in Fig. 9.1. They chose the catalytic decomposition of formic acid... 

The Catalytic Decomposition of Formic Acid P. Mars, J. J. F. Schollen, and P. Zwietering... 

Tamaru, K. Trans. Faraday Soc. 55 (1959) 824. Adsorption during the catalytic decomposition of formic acid on silver and nickel catalysts. 

Fig. 8. Similar change observed on kinetic measurement of the catalytic decomposition of formic acid with a Co-Pd alloy as catalyst (Curie interval 135° to 185°).

Sachtler, W. M. H., Fahrenfort, J. The Catalytic Decomposition of Formic Acid Vapor on Metals. Proc. Second. Intern. Congr. Catalysis. Technip. Paris 1961, p. 831. 

During the heterogeneous decomposition of formic acid on copper, the active metaUic phase undergoes sintering, sublimation and modifications of surface texture [25], By comparison with the behaviour of copper(II) formate [13], it is concluded that copper(l) formate is formed. Thus variations in the values of A and E, reported for the catalytic process may be attributed to a dependence of kinetic behaviour on the lifetime of the volatile participant, and thus upon metal mobility and reaction conditions [5], The decompositions of the copper formates and the catalytic decomposition of formic acid on copper metal thus include the participation of common intermediates, but these different reactions each consist of a sequence of several interdependent processes. 

Switchover of reaction paths in the catalytic decomposition of formic acid on TiO2(110) surface./. Catal., 146, 557-567. 

Ddring et al. [131] developed a reaction method for determining formic acid and its derivatives, based on the catalytic decomposition of formic acid into water and carbon monoxide. The decomposition is conducted at 200°C on a catalyst, BPO4, which is a mixture of boric and phosphoric acids. A sample (10/rl) is injected into a quartz tube (18 X 0.8 cm I.D.) filled with the catalyst. After the catalyst in the tube and beyond the oven are arranged absorber layers (molecular sieves 13X, alkaline asbestos, activated... 

The Role of Dislocations in the Catalytic Decomposition of Formic Acid... 

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