Gasoline

Petroleum is converted to useful products such as gasoline in three steps: distillation, cracking, and reforming. Recall from Chapter 1 "Introduction to Chemistry" that distillation separates compounds on the basis of their relative volatility, which is usually inversely proportional to their boiling points. Part (a) in Figure 2.23 "The Distillation of Petroleum" shows a cutaway drawing of a column used in the petroleum industry for separating the components of crude oil. The petroleum is heated to approximately 400°C (750°F), at which temperature it has become a mixture of liquid and vapor. This mixture, called the feedstock, is introduced into the refining tower. The most volatile components (those with the lowest boiling points) condense at the top of the column where it is cooler, while the less volatile components condense nearer the bottom. Some materials are so nonvolatile that they collect at the bottom without evaporating at all. Thus the composition of the liquid condensing at each level is different. These different fractions, each of which usually consists of a mixture of compounds with similar numbers of carbon atoms, are drawn off separately. Part (b) in Figure 2.23 "The Distillation of Petroleum" shows the typical fractions collected at refineries, the number of carbon atoms they contain, their boiling points, and their ultimate uses. These products range from gases used in natural and bottled gas to liquids used in fuels and lubricants to gummy solids used as tar on roads and roofs.

Figure 2.23 The Distillation of Petroleum

(a) This is a diagram of a distillation column used for separating petroleum fractions. (b) Petroleum fractions condense at different temperatures, depending on the number of carbon atoms in the molecules, and are drawn off from the column. The most volatile components (those with the lowest boiling points) condense at the top of the column, and the least volatile (those with the highest boiling points) condense at the bottom.

The economics of petroleum refining are complex. For example, the market demand for kerosene and lubricants is much lower than the demand for gasoline, yet all three fractions are obtained from the distillation column in comparable amounts. Furthermore, most gasolines and jet fuels are blends with very carefully controlled compositions that cannot vary as their original feedstocks did. To make petroleum refining more profitable, the less volatile, lower-value fractions must be converted to more volatile, higher-value mixtures that have carefully controlled formulas. The first process used to accomplish this transformation is crackingA process in petroleum refining in which the larger and heavier hydrocarbons in kerosene and higher-boiling-point fractions are heated to high temperatures, causing the carbon–carbon bonds to break (“crack”), thus producing a more volatile mixture., in which the larger and heavier hydrocarbons in the kerosene and higher-boiling-point fractions are heated to temperatures as high as 900°C. High-temperature reactions cause the carbon–carbon bonds to break, which converts the compounds to lighter molecules similar to those in the gasoline fraction. Thus in cracking, a straight-chain alkane with a number of carbon atoms corresponding to the kerosene fraction is converted to a mixture of hydrocarbons with a number of carbon atoms corresponding to the lighter gasoline fraction. The second process used to increase the amount of valuable products is called reformingThe second process used in petroleum refining, which is the chemical conversion of straight-chain alkanes to either branched-chain alkanes or mixtures of aromatic hydrocarbons.; it is the chemical conversion of straight-chain alkanes to either branched-chain alkanes or mixtures of aromatic hydrocarbons. Using metals such as platinum brings about the necessary chemical reactions. The mixtures of products obtained from cracking and reforming are separated by fractional distillation.

Octane Ratings

The quality of a fuel is indicated by its octane ratingA measure of a fuel’s ability to burn in a combustion engine without knocking or pinging (indications of premature combustion). The higher the octane rating, the higher quality the fuel., which is a measure of its ability to burn in a combustion engine without knocking or pinging. Knocking and pinging signal premature combustion (Figure 2.24 "The Burning of Gasoline in an Internal Combustion Engine"), which can be caused either by an engine malfunction or by a fuel that burns too fast. In either case, the gasoline-air mixture detonates at the wrong point in the engine cycle, which reduces the power output and can damage valves, pistons, bearings, and other engine components. The various gasoline formulations are designed to provide the mix of hydrocarbons least likely to cause knocking or pinging in a given type of engine performing at a particular level.

Figure 2.24 The Burning of Gasoline in an Internal Combustion Engine

(a) Normally, fuel is ignited by the spark plug, and combustion spreads uniformly outward. (b) Gasoline with an octane rating that is too low for the engine can ignite prematurely, resulting in uneven burning that causes knocking and pinging.

The octane scale was established in 1927 using a standard test engine and two pure compounds: n-heptane and isooctane (2,2,4-trimethylpentane). n-Heptane, which causes a great deal of knocking on combustion, was assigned an octane rating of 0, whereas isooctane, a very smooth-burning fuel, was assigned an octane rating of 100. Chemists assign octane ratings to different blends of gasoline by burning a sample of each in a test engine and comparing the observed knocking with the amount of knocking caused by specific mixtures of n-heptane and isooctane. For example, the octane rating of a blend of 89% isooctane and 11% n-heptane is simply the average of the octane ratings of the components weighted by the relative amounts of each in the blend. Converting percentages to decimals, we obtain the octane rating of the mixture:

A gasoline that performs at the same level as a blend of 89% isooctane and 11% n-heptane is assigned an octane rating of 89; this represents an intermediate grade of gasoline. Regular gasoline typically has an octane rating of 87; premium has a rating of 93 or higher.

As shown in Figure 2.25 "The Octane Ratings of Some Hydrocarbons and Common Additives", many compounds that are now available have octane ratings greater than 100, which means they are better fuels than pure isooctane. In addition, antiknock agents, also called octane enhancers, have been developed. One of the most widely used for many years was tetraethyllead [(C₂H₅)₄Pb], which at approximately 3 g/gal gives a 10–15-point increase in octane rating. Since 1975, however, lead compounds have been phased out as gasoline additives because they are highly toxic. Other enhancers, such as methyl t-butyl ether (MTBE), have been developed to take their place. They combine a high octane rating with minimal corrosion to engine and fuel system parts. Unfortunately, when gasoline containing MTBE leaks from underground storage tanks, the result has been contamination of the groundwater in some locations, resulting in limitations or outright bans on the use of MTBE in certain areas. As a result, the use of alternative octane enhancers such as ethanol, which can be obtained from renewable resources such as corn, sugar cane, and, eventually, corn stalks and grasses, is increasing.

Figure 2.25 The Octane Ratings of Some Hydrocarbons and Common Additives

Production

The production of sulfuric acid today is likely to start with elemental sulfur obtained through an ingenious technique called the Frasch process, which takes advantage of the low melting point of elemental sulfur (115.2°C). Large deposits of elemental sulfur are found in porous limestone rocks in the same geological formations that often contain petroleum. In the Frasch process, water at high temperature (160°C) and high pressure is pumped underground to melt the sulfur, and compressed air is used to force the liquid sulfur-water mixture to the surface (Figure 2.26 "Extraction of Elemental Sulfur from Underground Deposits"). The material that emerges from the ground is more than 99% pure sulfur. After it solidifies, it is pulverized and shipped in railroad cars to the plants that produce sulfuric acid, as shown here.

Transporting sulfur. A train carries elemental sulfur through the White Canyon of the Thompson River in British Columbia, Canada.

Figure 2.26 Extraction of Elemental Sulfur from Underground Deposits

In the Frasch process for extracting sulfur, very hot water at high pressure is injected into the sulfur-containing rock layer to melt the sulfur. The resulting mixture of liquid sulfur and hot water is forced up to the surface by compressed air.

An increasing number of sulfuric acid manufacturers have begun to use sulfur dioxide (SO₂) as a starting material instead of elemental sulfur. Sulfur dioxide is recovered from the burning of oil and gas, which contain small amounts of sulfur compounds. When not recovered, SO₂ is released into the atmosphere, where it is converted to an environmentally hazardous form that leads to acid rain (Chapter 4 "Reactions in Aqueous Solution").

If sulfur is the starting material, the first step in the production of sulfuric acid is the combustion of sulfur with oxygen to produce SO₂. Next, SO₂ is converted to SO₃ by the contact process, in which SO₂ and O₂ react in the presence of V₂O₅ to achieve about 97% conversion to SO₃. The SO₃ can then be treated with a small amount of water to produce sulfuric acid. Usually, however, the SO₃ is absorbed in concentrated sulfuric acid to produce oleum, a more potent form called fuming sulfuric acid. Because of its high SO₃ content (approximately 99% by mass), oleum is cheaper to ship than concentrated sulfuric acid. At the point of use, the oleum is diluted with water to give concentrated sulfuric acid (very carefully because dilution generates enormous amounts of heat). Because SO₂ is a pollutant, the small amounts of unconverted SO₂ are recovered and recycled to minimize the amount released into the air.

Uses

Two-thirds of the sulfuric acid produced in the United States is used to make fertilizers, most of which contain nitrogen, phosphorus, and potassium (in a form called potash). In earlier days, phosphate-containing rocks were simply ground up and spread on fields as fertilizer, but the extreme insolubility of many salts that contain the phosphate ion (PO₄³⁻) limits the availability of phosphorus from these sources. Sulfuric acid serves as a source of protons (H⁺ ions) that react with phosphate minerals to produce more soluble salts containing HPO₄²⁻ or H₂PO₄⁻ as the anion, which are much more readily taken up by plants. In this context, sulfuric acid is used in two principal ways: (1) the phosphate rocks are treated with concentrated sulfuric acid to produce “superphosphate,” a mixture of 32% CaHPO₄ and Ca(H₂PO₄)₂·H₂O, 50% CaSO₄·2H₂O, approximately 3% absorbed phosphoric acid, and other nutrients; and (2) sulfuric acid is used to produce phosphoric acid (H₃PO₄), which can then be used to convert phosphate rocks to “triple superphosphate,” which is largely Ca(H₂PO₄)₂·H₂O.

Sulfuric acid is also used to produce potash, one of the other major ingredients in fertilizers. The name potash originally referred to potassium carbonate (obtained by boiling wood ashes with water in iron pots), but today it also refers to compounds such as potassium hydroxide (KOH) and potassium oxide (K₂O). The usual source of potassium in fertilizers is actually potassium sulfate (K₂SO₄), which is produced by several routes, including the reaction of concentrated sulfuric acid with solid potassium chloride (KCl), which is obtained as the pure salt from mineral deposits.