J. A. Martin, P. B ~ U ~ J. 1. Monal, a n d M. F. Lejaille Universitd d e Noncy I B. P.

403-54001 Noncy Cddex

Fronce

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Synthesis of Sulfuric Acid by the Contact Process

A student laboratory experiment

The teaching of inorganic chemistry to groups of students such a s future pharmacists has to show how theory is applied in the methods of the heavy chemical industry and to draw on these methods to illustrate elementary technological notions. We have set u p in the laboratory several experiments which reproduce industrial syntheses of inorganic compounds and we present here,to illustrate the-concept of heterogeneous catalysis, the synthesis of sulfuric acid by the contact process, as we shall carry it out hefore o& students. The oxidation of sulfur dioxide by oxygen gives the trioxide, which, on hydrolysis, yields sulfuric acid

Figure 2. Laboratory apparatus. (A) Liquid sulfur dioxide battle: connection to the valve ''gas," control valve. (a) Sulfur dioxide flowmeter. ( 0 ) Oxygen cylinder: connection to pressure reducer. (b) Oxygen flowmeter. (C) Catalyst filled silica tubs, length 40 cm, i.d. 4 cm, load 300 g. (0) Tubular furnace regulated at 450'C when running. 550'C at the start of the reaction. (E) Stopper protected on the inside by asbestos. (F) Flask with coolant (glycol sealed vermiculite cooled in a refrigerator at -30%). (G)Empty flask. (H) Absorption flask filled with water. ( I ) Absorption flask filled with sulfuric acid, commercial aqueous solution d

The catalyst necessary for this reaction functions a t

450C and is a mixture of oxides of vanadium. The gaseous sulfur trioxide formed a t 450C condenses
on cooling and its dissolution, hydrolysis rather, is difficult in water. It is easier to dissolve SOXin a dilute aqueous solution of sulfuric acid, which can attain as high a concentration a s is desired and permits the formation of oleums.
SO,

by comparing the appearance of the white fumes a t the inlet and outlet of the bubbler. Procedure The furnace is regulated at 550C, then at 450C during the course of the reaction. First allow just oxygen to pass through the apparatus. Now admit the sulfur dioxide. Flow rates are adjusted so as to obtain a maximum of white fumes at the reactor tube exit: oxygen 0.45 l/mn-sulfur dioxide 0.2 l/mn. Experimental Results Partial condensation is obtained in the cooled flask F : Colorless or white needles of sulfur trioxide cover its walls. The white fumes pass through the empty flask G, are partially absorbed by the water in H, and almost completely absorbed by the sulfuric acid in I. The crystalline needles can be dissolved by cautious addition of water to the flask F This solution, like that obtained in flask H, may he used to carry out testsfor sulfates and strong acids. During the course of the reaction, observe the changes in color of the catalyst: yellow indicates vanadium with oxidation state V and green, lower oxidation states. Safety Precautions The components of the apparatus do not present any special dangers apart from those habitually encountered with a tubular furnace a t 500C and a bottle of liquid sulfur dioxide in normal usage. The only precaution to he observed is that of limiting the production of the solid trioxide to a small quantity (a few grams): Its dissolution in water should be carried out in a n externally cooled vessel and the possible danger of s~ittine should he borne in mind. Should a auantitv of s h f u r trioxide needles sufficient to present a real risk huring dissolution in water he produced, then the flask should he left open to the air in a fume cupboard until the h ~ d r O l ~ shas is slowly the humidity. The apparatus has functioned safely in our student lahoratory for three years.

+ HsO = H,SO,

The principles, thermodynamics, and kinetics of the procedure are widely known and well treated in the literature. We shall only describe our laboratory apparatus. Experimental Details Apparatus A comparison of the schematic diagram of a n industrial plant for the manufacture of sulfuric acid by the contact process (Fig. 1) and the diagram of our laboratory apparat u s (Fig. 2) will show the analogy existing between them. In the latter the sulfur trioxide is condensed by cooling below 0C:White or colorless needles of the crystalline form obtained in the presence of traces of water form on the walls of the receiving vessel. The trioxide mav also he collected in a soltttion oi~sulfurir acid in whirh it dissol\.es almust completely: Beforehand it will have been bubbled through water to demonstrate the feeble solubility 01 SOa

Figure 1. Schematic diagram of an industrial plant. (1) Drying tower: Porous filling down which flows concentrated sulfuric acid. (2) Converter. "catalytic drum": The catalyst is disposed an superposed screens, gases entering at the bottom and emerging at the top. (3) Coolant. (4) Oissoiution towers: porous filling down which flaws dilute sulfuric acid. his latter is enriched both by dissolution of sulfur trioxide and by evaporation of water due to the heat given by the gases and the heat of hydration.

188

Journalof Chemical Education

Acknowledgrnenl

General References

Acknowledgments are due to the Ugine-Kuhlmann Company, who kindly supplied us with their standard type catalyst and authorized us to reveal its origin. I t takes the form of cylinders 6 mm in diameter and about 10 mm in length whose color varies from yellow to green. When protected from humidity no variation in activity on the scale of the experiment is observed over at least three years.

Z & & .p bib].. (44rbf.l. Hacksill, L.. Bouon. J.. and Herold, A,. "Chimio min6oie;' Presses Univeritaircs dc F&e. Paris, ISM, t. I,pp.4&-8. Moukhlenou, I. P.. Koumetmv, D. A., Avsrburh, A. J., Toumarkina. E. C., and Fourmr. I. E.."Technolozie chimiavr #&nOmle." Ed. Eeola Suc4riewe. Mmow, 1969. ~

pp. 20615.

Winnaeker, K., and Kuchler, L., "Technoiogie min0rol%" Ed. Eyrolln, Paris. 1961, t.
3, pp.68-81.

Volume 52, Number 3, March 1975

189