Derivatives of Sulfuric Acid

CHUCOOH + H2S04- HSOJ + CH3COOHf (CiHgJaO + H2S04 HSO7 + (C H ),0H+ 

A number of compounds yield more than two ions per molecule when dissolved in H2SO4 urea (NH2CONH2) has an i i factor of about 3, whereas sodium sulfate, sodium hydroxide, and nitric acid have H factors a bit less than 4  

NH2CONH2 + 2H2S04 NH C0NHJ+ + 2HSOJ Na S04 + H2S04 2Na+ + 2H80r 

NaOH + 2H2SO4 - Na4 + H80+ + 2HS07 HNOg + 2H2S04 H30+ + NOJ + 2HS07 

The metal sulfates are sufficiently familiar so that descriptions here are, for the most part, unnecessary. The sulfate ion tends to hold one molecule of anion water (p. 70) in many of the crystalline metal sulfates. Just as the hydrate of copper sulfate may be represented as (H20)4Cu24 H20 S04)2, so the hydrated sulfates of Mn2+, Fe2+, Co24, and Ni + may be represented (HgOJeM2 (H20 S04)2. A similar salt, (NH3)4Cu2+ (H20 S04)2 , may be crystallized from an ammoniacal solution of copper sulfate. 

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In this section, we examine the fate of hydrolyzable derivatives of sulfuric acid, namely ... 

The simple diesters dimethyl sulfate and diethyl sulfate are convenient and useful reagents for alkylation reactions. As derivatives of sulfuric acid. 

By far the most important derivative of sulfuric acid is phosphoric acid. It has been unknowingly used as fertilizer for hundreds of years. The wet process method of manufacture was important until 1920, when furnace acid began increasing in popularity. The wet process, however, has made a comeback because of plant design improvements 60% of phosphoric acid was made by this method in 1954, 88% in 1974, and over 90% currently. The furnace process is used only to make concentrated acid (75-85%) and pure product. It is very expensive because of the 2000 °C temperature required. In the furnace process phosphate rock is heated with sand and coke to give elemental phosphorus, which is then oxidized and hydrated to phosphoric acid. A simplified chemical reaction is ... 

Several important halogen derivatives of sulfuric acid are produced from S03. Some of these will be described in the next section, and some are discussed with the chemistry of sulfuric acid. 

Many derivatives of sulfuric acid are also important. In particular, sulfonates are used in the preparation of detergents such as CH3(CH2)nC6H4S03-Na+. Chlorosulfonic acid, HS03C1, can be prepared by the reaction of HC1 with S03 ... 

The sulfuryl halides may be considered, formally, as derivatives of sulfuric acid in which both OH groups have been replaced by halogen atoms. If only one OH group be replaced, the acids, FS03H (page 181), C1S03H and BrS03H, are obtained. 

Hydrolysis of this substance leads by intermediate steps to sulfamide (Scheme 1). Ammonolysis, on the other hand, yields a cyclic mixed derivative of sulfuric acid and carbonic acid (LXXXIII). Sulfuryl amide gives salts and also numerous organic derivatives. A silver salt (AgNH)2S02... 

Higher derivatives of sulfuric acid are 23-25% oleums, 65% oleums and pure SO3, as well as liquid SO2, which find applications in organic and petroleum processing. 

Acid derivatives of sulfuric acids are more complicated because there are two acidic protons and two OH units. If one OH unit is replaced with Cl, this... 

In this vein, sulfuryl chloride (SO2CI2) is an acid chloride derivative of sulfuric acid [H2SO4 or S02(0H)2] phosphorous oxychloride (POCI3) is an acid chloride derivative of phosphoric acid [H3PO4 or PO(OH)3], and so on. 

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