Lead-chamber process

Figure 10.5. The Lead Chamber process for the manufacture of sulphuric acid...

Sulfonic acids containing nitrogen have long been implicated as essential intermediates in the synthesis of H2SO4 by the lead-chamber process (p. 708) and, as shown by F. Seel and his group, the crucial stage is the oxidation of sulfite ions by the nitrosyl ion NO+ ... 

Nitrose, /. (Sulfuric Acid) a solution of nitro-sylsulfuric acid in sulfuric acid, formed in the lead-chamber process. 

The older process is called the lead chamber process. It uses a mixture of gaseous oxides of nitrogen—nitric oxide, NO, and nitrogen dioxide, N02—as the catalyst. This process has been in use and under development for over 200 years. It is named after the large room-like chambers lined with lead in which the gaseous reactions are carried out. The lead walls react with the acid and become coated with an inert protective coating of lead sulfate. 

It is believed that H2S04 was discovered in about the 10th century. In the 1800s most of the H2S04 was produced by the lead chamber process, although it was also produced by pyrolysis of FeS04-xH20. 

To date, the single most important commercial use of lead is in the manufacture of lead-acid storage batteries. However, for most of the twentieth century, the most important environmental source of Pb was gasoline combnstion. It is also used in alloys, such as fusible metals, antifriction metals, and solder. Lead foil is made with lead alloys. Lead is used for covering cables and as a lining for laboratory sinks, tanks, and the chambers in the lead-chamber process for the manufacture of sulfuric acid. It is used extensively in plumbing. Because it has excellent vibration-dampening characteristics, lead is often used to support heavy machinery. 

Late 1800s The lead chamber process for manufacturing sulfuric acid was prevalent in this period. Arsenic was a common contaminant in the pyrites used as a source of sulfur for this process. Now the cleaner contact process is used and most of the raw material is elemental sulfur. 

Nitrosylsulfuric acid is produced as an intermediate in the manufacture of sulfuric acid using the lead chamber process by the reaction of sulfur dioxide, nitrogen dioxide, oxygen, and water. 

While the lead-chamber process increased the amount of sulfuric acid that could be produced, it relied on a source of nitrate that usually had to be imported. The process also produced nitric oxide gas, NO, which oxidized to brown nitrogen dioxide in the atmosphere. To reduce the supply of nitrate required and the amount of nitric oxide produced, Gay-Lussac proposed that the nitric oxide be captured in a tower and recycled into the lead chamber. Although Gay-Lussac first proposed this modification to the lead-chamber method around 1830, it was not until the 1860s that John Glover (1801-1872) actually implemented Gay-Lussac s idea with the Glover tower. 

The lead-chamber process supplied the world s need for sulfuric acid for a century and a half. In the late nineteenth century, the contact process replaced the lead-chamber process. The contact process utilized sulfur dioxide, SOj, which was produced as a byproduct when sulfur-bearing ores were smelted. The contact process was named because the conversion of sulfur dioxide to sulfur trioxide, SO3, takes place on contact with a vanadium or platinum catalyst during the series of reactions ... 

As noted in Section 8.5, there are two important complications in the conversion of S02 to liquid H2S04 the oxidation of S02 is generally slow and must be catalyzed, and the direct reaction of SO3 with water tends to produce intractable aerosols (mists) of H2S04. The lead chamber process, which dates back to 1746, employs nitrogen oxides as the catalyst the intermediate HO—S02—O—NO, or nitrosylsulfuric acid, is easily... 

The reaction is exothermic (see Exercise 12.1), but, since it is very slow, a catalyst is necessary. Nitric oxide, once again, can serve as an oxygen carrier, as in the lead chamber process (Section 10.2) and in reaction 10.8, where (CH3)2S generated in the kraft process is converted to DMSO. Even so, at the elevated temperatures required, reaction 12.1 needs to be forced to completion by absorption of the steam in concentrated sulfuric acid or some other desiccant. In variants of the Deacon process, copper chloride acts as the catalyst or as an intermediate for chlorine regeneration. 

This commonest derivative of sulphur trioxide and the most important of all acids from a technical and commercial aspect, has been known from early times, although its production on a large scale and at a low price dates from the success of the lead chamber process of manufacture, which revolutionised chemical industry in the early part of the nineteenth century. 

The Pyrites Burners.—In the lead chamber process the first chemical action is the oxidation of sulphur to sulphur dioxide by atmospheric oxygen. The iron pyrites (or free sulphur, spent oxide from the gas works, or other sulphides such as zinc blende, as the case may be) is placed on shelves or bars in a series of ovens of suitable type. When iron pyrites or sulphur is used, the combustion when once started proceeds to completion without further assistance by external heat ... 

Nitrosulphonic Acid, Nitrosylsulphuric Acid or Nitroso-sulphuric Acid, NQ2.S02.0H.—In 1806, Clement and Desormcs, during the manufacture of sulphuric acid by the lead chamber process, observed the formation of a crystalline solid, to which the names nitrosulphonic acid and nitrosylsulphuric acid were later given the term chamber crystals, however, is still commonly applied to this acid.6 The composition and nature of the acid were first investigated by Weber,7 and by Michaelis and Schumann.8... 

It is fairly generally believed that nitrosulphonic acid plays an important part in the lead chamber process for the manufacture of sulphuric acid (see p. 153). The vapour pressures of mixtures of sulphuric acid with nitrous or nitric acid or with both these acids, within the range occurring in the chambers, increase with the nitrogen acid content and with rise in temperature, and the total pressure is always higher than the sum of the individual pressures, especially when the sulphuric acid is concentrated, for nitric acid - sulphuric acid mixtures this may be explained 1 by the occurrence of the following... 

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