Mixtures

CONCEPT

Elements and compounds are pure substances, but much of the material around us—including air, wood, soil, and even (in most cases) water— appears in the form of a mixture. Unlike a pure substance, a mixture has variable composition: in other words, it cannot be reduced to a single type of atom or molecule. Mixtures can be either homogeneous—that is, uniform in appearance, and having only one phase—or heterogeneous, meaning that the mixture is separated into various regions with differing properties. Most homogeneous mixtures are also known as solutions, and examples of these include air, coffee, and even metal alloys. As for heterogeneous mixtures, these occur, for instance, when sand or oil are placed in water. Oil can, however, be dispersed in water as an emulsion, with the aid of a surfactant or emulsifier, and the result is an almost homogeneous mixture. Another interesting example of a heterogeneous mixture occurs when colloids are suspended in fluid, whether that fluid be air or water.

HOW IT WORKS

Mixtures and Pure Substances

A mixture is a substance with a variable composition, meaning that it is composed of molecules or atoms of differing types. These may have intermolecular bonds, or bonds between molecules, but such bonds are not nearly as strong as those formed when elements bond to form a compound.
Examples of mixtures include milk, coffee, tea, and soft drinks—indeed, they include virtually any drink except for pure water, which is a rarity, because water is highly soluble and tends to contain minerals and other impurities. Air, too, is a mixture, because it contains oxygen, nitrogen, noble gases, carbon dioxide, and water vapor. Likewise metal alloys such as bronze, brass, and steel are mixtures.

Structural and phenomenological distinctions

Before chemists accepted the atomic theory of matter, it was often difficult to distinguish a mixture, such as air or steel, from pure substances, which have the same composition throughout. Pure substances are either elements such as oxygen or iron, or compounds—for example, carbon dioxide or iron oxide. An element is made up of only one type of atom, while a compound can be reduced to one type of bonded chemical species—usually either a molecule or a formation of ions.
A distinction between mixtures and pure substances based on atomic and molecular structures is called, fittingly enough, a structural definition. Prior to the development of atomic theory by English chemist John Dalton (1766-1844), and the subsequent identification of molecules by Italian physicist Amedeo Avogadro (17761856), chemists defined compounds and mixtures on the basis of phenomenological data garnered through observation and measurement. This could and did lead to incorrect suppositions.

Proust and the debate over constant composition

Around the time of Dalton and Avogadro, French
The wondrous invention known as soap is a mixture with surfactant qualities.
The wondrous invention known as soap is a mixture with surfactant qualities.
chemist Antoine Lavoisier (1743-1794) correctly identified an element as a substance that could not be broken down into a simpler substance. Later, his countryman Joseph-Louis Proust (1754-1826) clarified the definition of a compound, stating it in much the same terms that we have used: the composition of a compound is the same throughout. But with the very rudimentary knowledge of atoms and molecules that chemists of the early nineteenth century possessed, the distinctions between compounds and mixtures remained elusive.
Proust’s contemporary and intellectual rival Claude Louis Berthollet (1748-1822) observed that when metals such as iron are heated, they form oxides in which the percentage of oxygen increases with temperature. If constant composition is a fact, he challenged Proust, then how is this possible? Proust maintained that the proportions of elements in a compound are always the same, a hypothesis Berthollet countered by observing that metals can form variable alloys. Bronze, for instance, is an alloy of tin and copper at a ratio of about 25:75, but if the ratio were changed to, say, 30:70, it would still be called bronze.
At the time, the equipment—both in terms of knowledge and tools for analysis—simply did not exist whereby Berthollet’s assertions could be successfully proven wrong. Indeed, Berthollet, a student of Lavoisier who contributed to progress in the study of acids and reactants, was no anti-scientific villain: he was simply responding to the evidence as he saw it. Only with the discovery of subatomic particles in the late nineteenth and early twentieth centuries, discoveries that changed the entire character of chemistry as a discipline, did it truly become possible to answer Berthollet’s challenges.
Chemists now understand that the oxide formed on the surface of a metal is a compound separate from the metal itself, and that alloys (discussed later in this essay) are not compounds at all: they are mixtures.

Mixtures and Compounds

With our modern knowledge of atomic and molecular properties, we can more fully distinguish between a compound and a mixture. First, a mixture can exist in virtually any proportion among its constituent parts, whereas a compound has a definite and constant composition. Coffee, whether weak or strong, is still coffee, but if a second oxygen atom chemically bonds to the oxygen in carbon monoxide (CO), the resulting
Bronze—an alloy of tin and copper—was one of the most important inventions in human history. This stone carving is from the period known as the Bronze Age.
Bronze—an alloy of tin and copper—was one of the most important inventions in human history. This stone carving is from the period known as the Bronze Age.
compound is not simply “strong carbon monoxide” or even “oxygenated carbon monoxide”: it is carbon dioxide (CO2), an entirely different substance. The difference is enormous: carbon dioxide is a part of the interactions between plant and animal life that sustains the natural environment, whereas carbon monoxide is a toxic gas produced, for instance, by automobiles.
Second, the parts of a mixture retain most of their properties when they join together, but elements lose their elemental characteristics once they form a compound. Sugar is still sweet, regardless of the substance into which it is dissolved. In coffee or another drink, it may no longer be dry and granular, though it could be returned to that state by evaporating the coffee. In any case, dryness and granularity are physical properties, whereas sweetness is a chemical one. On the other hand, when elemental carbon bonds with hydrogen and oxygen to form sugar itself, the resulting compound is nothing like the elements from which it is made.
Third, a mixture can usually be created simply by the physical act of stirring items together, and/or by applying heat. As discussed below, relatively high temperatures are sometimes needed to dissolve sugar in tea, for instance; likewise, alloys are usually formed by heating metals to much higher temperatures. On the other hand, the formation of a compound involves a chemical reaction, a vastly more complex interaction than the one required to create a mixture. Carbon, a black solid found in coal, can be mixed with hydrogen and oxygen—both colorless and odorless gases—and the resulting mess would be something; but it would not be sugar. Only the chemical reaction between the three elements, in specific proportions and under specific conditions, results in their chemical bonding to form table sugar, known to chemists as sucrose.

Homogeneous and Heteroge-neous Mixtures

Homogeneous mixtures and solutions

As we have seen, the composition of a mixture is variable. Coffee, for instance, can be weak or strong, and milk can be “whole” or low-fat. Beer can be light or dark in color, as well as “light” in terms of calorie content; furthermore, its alcohol content can be varied, as with all alcoholic drinks. Though their molecular composition is variable, each of the mixtures described here is the same throughout: in other words, there is no difference between one region and another in a glass of beer. Such a mixture is described as homogeneous.
A homogeneous mixture is one that is the same throughout, but this is not the same as saying that a compound has a constant composition. Rather, when we say that a homogeneous mixture is the same in every region, we are speaking phenomenologically rather than structurally. From the standpoint of ordinary observation, a glass of milk is uniform, but as we shall see, milk is actually a type of emulsion, in which one substance is dispersed in another. There are no milk “molecules,” and structural analysis would reveal that milk does not have a constant molecular composition.
Coffee is an example of a solution, a specific type of homogeneous mixture. Actually, most homogeneous mixtures can be considered solutions, but since a solution is properly defined as a homogeneous mixture in which one or more substances is dissolved in another substance, a 50:50 homogeneous mixture is technically not a solution. When particles are perfectly dissolved in a solution, the composition is uniform, but again, this is not a compound, because that composition can always be varied.

Heterogeneous mixtures

Anyone who has ever made iced tea has observed that it is easy to sweeten when it is hot, because temperature affects the ability of a solvent such as water—in this case, water with particles from tea leaves filtered into it—to dissolve a solute, such as sugar. Cold tea, on the other hand, is much harder to sweeten with ordinary sugar. Usually what happens is that, instead of obtaining a homogeneous mixture, the result is heterogeneous.
Whereas every region within a homogeneous mixture is more or less the same as every other region, heterogeneous mixtures contain regions that differ from one another. In the example we have used, a glass of cold tea with undissolved sugar at the bottom is a heterogeneous mixture: the tea at the top is unsweetened or even bitter, whereas at the bottom, there is an overly sweet sludge of tea and sugar.

From homogeneous to heterogeneous and back again

The distinction between homogeneous and heterogeneous solutions only serves to further highlight the difference between compounds and mixtures. Whereas the composition of a compound is definite and quantitative (so many atoms of element x bonded with so many atoms of element y in such-and-such a structure), there is less of a sharp dividing line between homogeneous and heterogeneous solutions.
When too much of a solute is added to the solvent, the solvent becomes saturated, and is no longer truly homogeneous. Such is the case when the sugar drifts to the bottom of the tea, or when coffee grounds form in the bottom of a coffee pot containing an otherwise uniform mixture of coffee and water.
Milk comes to us as a homogeneous substance, thanks to the process of homogenization, but when it comes out of the cow, it is a more heterogeneous mixture of milk fat and water. In fact, milk is an example of an emulsion, the result of a process whereby two substances that would otherwise form a heterogeneous mixture are made to form a homogeneous one.

REAL-LIFE APPLICATIONS

Colloids

In 1827, Scottish naturalist Robert Brown (17731858) was studying pollen grains under a microscope when he noticed that the grains underwent a curious zigzagging motion in the water. At first, he assumed that the motion had a biological explanation—in other words, that it resulted from life processes within the pollen—but later, he discovered that even pollen from long-dead plants behaved in the same way.
What Brown had observed was the suspension of a colloid—a particle intermediate in size between a molecule and a speck of dust—in the water. When placed in water or another fluid (both liquids and gases are called “fluids” in the physical sciences), a colloid forms a mixture similar both to a solution and a suspension. As with a solution, the composition remains homoge-neous—the particles never settle to the bottom of the container. At the same time, however, the particles remain suspended rather than dissolved, rendering a cloudy appearance to the dispersion.
Almost everyone, especially as a child, has been fascinated by the colloidal dispersion of dust particles in a beam of sunlight. They seem to be continually in motion, as indeed they are, and this movement is called “Brownian motion” in honor of the man who first observed it. Yet Brown did not understand what he was seeing; only later did scientists recognize that Brownian motion is the result of movement on the part of molecules in a fluid. Even though the molecules are much smaller than the colloid, there are enough of them producing enough collisions to cause the colloid to be in constant motion.
Another remarkable aspect of dust particles floating in sunlight is the way that they cause a column of sunlight to become visible. This phenomenon, called the Tyndall effect after English physicist John Tyndall (1820-1893), makes it seem as though we are actually seeing a beam of light. In fact, what we are seeing is the reflection of light off the colloidal dispersion. Another example of a colloidal dispersion occurs when a puff of smoke hangs in the air; furthermore, as we shall see, milk is a substance made up of colloids—in this case, particles of fat and protein suspended in water.

Emulsions

Miscibility is a qualitative term identifying the relative ability of two substances to dissolve in one another. Generally, water and water-based substances have high miscibility with regard to one another, as do oil and oil-based substances with one another. Oil and water, on the other hand (or substances based in either) have very low miscibility.
The reason is that water molecules are polar, meaning that the positive electric charge is in one region of the molecule, while the negative charge is in another region. Oil, on the other hand, is nonpolar, meaning that charges are more evenly distributed throughout the molecule. Trying to mix oil and water is thus rather like attempting to use a magnet to attract a nonmagnetic metal such as gold.

How surfactants aid the emulsion process

An emulsion is a mixture of two immiscible liquids such as oil and water—we will use these simple terms, with the idea that these stand for all oil- and water-soluble substances—by dispersing microscopic droplets of one liquid in another. In order to achieve this dispersion, there needs to be a “middle man,” known as an emulsifier or surfactant. The surfactant, made up of molecules that are both water- and oil-soluble, acts as an agent for joining other substances in an emulsion.
All liquids have a certain degree of surface tension. This is what causes water on a hard surface to bead up instead of lying flat. (Mercury has an extremely high surface tension.) Surfactants break down this surface tension, enabling the marriage of two formerly immiscible liquids.
In an emulsion, millions of surfactants surround the dispersed droplets (known as the internal phase), shielding them from the other liquid (the external phase). Supposing oil is the internal phase, then the oil-soluble end of the surfactant points toward the oils, while the water-soluble side joins with the water of the external phase.

Physical characteristics of an emulsion

The resulting emulsion has physical (as opposed to chemical) properties different from those of the substances that make it up. Water and most oils are transparent, whereas emulsions are typically opaque and may have a lustrous, pearly gleam. Oil and water flow freely, but emulsions can be made to form thick, non-flowing creams.
Emulsions are inherently unstable: they are, as it were, only temporarily homogeneous. A good example of this is an oil-and-vinegar salad dressing, which has to be shaken before putting it on salad; otherwise, what comes out of the bottle is likely to be mainly oil, which floats to the top of the water-based vinegar. It is characteristic of emulsions that eventually gravity pulls them apart, so that the lighter substances float to the top. This process may take only a few minutes, as with the salad dressing; on the other hand, it can take thousands of years.

Applications

Surfactants themselves are often used in laundry or dish detergent, because most stains on plates or clothes are oil-based, whereas the detergent itself is applied to the clothes in an aqueous solution. As for emulsions, these are found in a wide variety of products, from cosmetics to paint to milk.
In the pharmaceutical industry, for instance, emulsions are used as a means of delivering the active ingredients of drugs, many of which are not water soluble, in a medium that is. Pharmaceutical manufacturers also use emulsions to make medicines more palatable (easier to take); to control dosage and improve effectiveness; and to improve the usefulness of topical drugs such as ointments, which must contend with both oily and water-soluble substances on the skin.
The oils and other conditioning agents used in hair-care products would leave hair limp and sticky if applied by themselves. Instead, these products are applied in emulsions that dilute the oils in other materials. Emulsions are also used in color photography, as well as in the production of pesticides and fungicides.
Paints and inks, too, are typically emulsified substances, and these sometimes come in the form of dispersions akin to those of colloids. As we have seen, in a dispersion fine particles of solids are suspended in a liquid. Surfactants are used to bond the particles to the liquid, though paint must be shaken, usually with the aid of a high-speed machine, before it is consistent enough to apply.
As mentioned earlier, milk is a form of emulsion that contains particles of milk fat or cream dispersed in water. Light strikes the microscopic fat and protein colloids, resulting in the familiar white color. Other examples of emulsified foods include not only salad dressings, but gravies and various sauces, peanut butter, ice cream, and other items. Not only does emulsion affect the physical properties of foods, but it may enhance the taste by coating the tongue with emulsified oils.

Soap

The wondrous invention called soap, which has made the world a cleaner place, exhibits several of the properties we have discussed. It is a mixture with surfactant qualities, and in powdered form, it can form something close to a true solution with water. Discovered probably by the Phoenicians around 600 B.C., it was made in ancient times by boiling animal fat (tallow) or vegetable oils with an alkali or base of wood ashes.
This was a costly process, and for many centuries, only the wealthy could afford soap—a fact that contributed to the notorious lack of personal hygiene that prevailed among Europeans of the Middle Ages. In fact, the situation did not change until late in the eighteenth century, when the work of two French chemists yielded a more economical manufacturing method.
In 1790, Nicholas Leblanc (1742-1806) developed a process for creating sodium hydroxide (called caustic soda at the time) from sodium chloride, or ordinary table salt. This made for an inexpensive base or alkali, with which soap manufacturers could combine natural fats and oils.
Then in 1823, Michel Eugene Chevreul (17861889) showed that fat is a compound of glycerol with organic acids, a breakthrough that led to the use of fatty acids in producing soaps.

The chemistry of soap

Soap as it is made today comes from a salt of an alkali metal, such as sodium or potassium, combined with a mixture of carboxylic acids (“fatty acids”). These carboxylic acids are the result of a reaction called saponification, involving triglyc-erides and a base, such as sodium hydroxide. Saponification breaks the triglycerides into their component fatty acids; then, the base neutralizes these to salts. This reaction produces glycerin, a hydrocarbon bonded to a hydroxyl (-OH) group. (Hydrocarbons are discussed in the essays on Organic Chemistry; Polymers.)
In general, the formula for soap is RCOOX, where X stands for the alkali metals, and R for the hydrocarbon chain. Because it is a salt (meaning that it is formed from the reaction of an acid with a base), soap partially separates into its component ions in water. The active ion is RCOO-, whose two ends behave in different fashions, making it a surfactant. The hydrocarbon end (R-) is said to be lipophilic, or “oil-loving,” which is appropriate, since most oils are hydrocarbons. On the other hand, the carboxylate end (-COO-) is hydrophilic, or “water-loving.” As a result, soap can dissolve in water, but can also clean greasy stains.
When soap is mixed with water, it does not form a true homogeneous mixture or solution due to the presence of hydrocarbons. These attract one another, forming spherical aggregates called micelles. The lipophilic “tails” of the hydrocarbons are turned toward the interior of the micelle, while the hydrophilic heads remain facing toward the water that forms the external phase.

Alloys

We have primarily discussed liquid mixtures, but in fact mixtures can be gaseous or even solid—as for example in the case of an alloy, a mixture of two or more metals. Alloys are usually created by melting the component metals, then mixing them together in specific proportions, but an alloy can also be created by bonding metal powders.
The structure of an elemental metal includes tight “electron sea” bonds, which are discussed in the essay on Metals. These, combined with the metal’s crystalline structure, create a situation in which internal bonding is very strong, but nondirectional. As a result, most metals form alloys, but again, this is not the same as a compound: the elemental metals retain their identity in these metal composites, forming characteristic fibers, beads, and other shapes.

KEY TERMS

Alloy: A mixture of two or more metals.
Aqueous: A term describing a solution in which a substance or substances are dissolved in water.
Atom: The smallest particle of an element.
Chemical species: A generic term used for any substance studied in chemistry—whether it be an element, compound, mixture, atom, molecule, ion, and so forth.
Compound: A substance made up of atoms of more than one element, which are chemically bonded and usually joined in molecules. The composition of a compound is always the same, unless it is changed chemically.
Dispersion: A term describing the distribution of particles in a fluid.
Element: A substance made up of only one kind of atom. Unlike compounds, elements cannot be chemically broken down into other substances.
Emulsifier: A surfactant.
Emulsion: A mixture of two immiscible liquids such as oil and water, made by dispersing microscopic droplets of one liquid in another. In creating an emulsion, surfactants act as bridges between the two liquids.
Fluid: A substance with the ability to flow. In physical sciences such as chemistry and physics, “fluid” refers both to liquids and gases.
Heterogeneous: A term describing a mixture that is not the same throughout; rather, it has various regions possessing different properties. An example of a mixture is sand in a container of water. Rather than dissolving to form a homogeneous mixture, as sugar would, the sand sinks to the bottom.
Homogeneous: A term describing a mixture that is the same throughout, as for example when sugar is fully dissolved in water. A solution is a homogenous mixture.
Immiscible: Possessing a negligible value of miscibility.
Ion: An atom or group of atoms that has lost or gained one or more electrons, and thus has a net electric charge.
Miscibility: A qualitative term identifying the relative ability of two substances to dissolve in one another.
Mixture: A substance with a variable composition, meaning that it is composed of molecules or atoms of differing types. Compare with pure substance or compound.
Molecule: A group of atoms, usually but not always representing more than one element, joined in a structure. Compounds are typically made of up molecules.
Phenomenological: A term describing scientific definitions based purely on experimental phenomena. These only convey part of the picture, however— primarily, the part a chemist can perceive either through measurement or through the senses, such as sight. A structural definition is therefore usually preferable to a phenomenological one.
Pure substance: A substance that has the same composition throughout. Pure substances are either elements or compounds, and should not be confused with mixtures. A homogeneous mixture is not the same as a pure substance, because although it has an unvarying composition, it cannot be reduced to a single type of atom or molecule.
Solution: A homogeneous mixture in which one or more substances is dissolved in another substances—for example, sugar dissolved in water.
Structural: A term describing scientific definitions based on aspects of molecular structure rather than purely phenomenological data.
Surfactant: A substance made up of molecules that are both water- and oil-soluble, which acts as an agent for joining other substances in an emulsion.
Suspension: A term that refers to a mixture in which solid particles are suspended in a fluid.

Some famous alloys

One of the most important alloys in early human history was a 25:75 mixture of tin and copper that gave its name to an entire stage of technological development: the Bronze Age (c. 3300-1200 B.C.). This combination formed a metal much stronger than either copper or tin, and bronze remained dominant until the discovery of new iron-smelting methods ushered in the Iron Age in about 1200 B.C.
Another important alloy of the ancient world was brass, which is about one-third zinc to two-thirds copper. Introduced in the period c. 1400-c. 1200 B.C, brass was one of the metals that defined the world in which the Bible was written. Biblical references to it abound, as in the famous passage from I Corinthians 13 (read at many weddings), in which the Apostle Paul proclaims that “without love, I am as sounding brass.” Some biblical scholars, however, maintain that some of the references to brass in the Old Testament are actually mistranslations of “bronze.”
Tin, copper, and antimony form pewter, a soft mixture that can be molded when cold and beaten regularly without turning brittle. Though used in Roman times, it became most popular in England from the fourteenth to the eighteenth centuries, when it offered a cheap substitute for silver in plates, cups, candelabra, and pitchers. The pewter turned out by colonial American metalsmiths is still admired for its beauty and functionality.
As for iron, it appears in nature as an impure ore, but even when purified, it is typically alloyed with other elements. Among the well-known forms of iron are cast iron, a variety of mixtures containing carbon and/or silicon; wrought iron, which contains small amounts of various other elements, such as nickel, cobalt, copper, chromium, and molybdenum; and steel. Steel is a mixture of iron with manganese and chromium, purified with a blast of hot air. Steel is also sometimes alloyed with aluminum in a one-third/two-thirds mixture to make duraluminum, developed for the superstructures of German zeppelins during World War I.

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