We are most accustomed to thinking of solutions as mixtures of a substance dissolved in water, but in fact the meaning of the term is broader than that. Certainly there is a special place in chemistry for solutions in which water—”the universal solvent”—provides the solvent medium. This is also true in daily life. Coffee, tea, soft drinks, and even water itself (since it seldom appears in pure form) are solutions, but the meaning of the term is not limited to solutions involving water. Indeed, solutions do not have to be liquid; they can be gaseous or solid as well. One of the most important solutions in the world, in fact, is the air we breathe, a combination of nitrogen, oxygen, noble gases, carbon dioxide, and water vapor. Nonetheless, aqueous or water-based substances are the focal point of study where solutions are concerned, and reactions that take place in an aqueous solution provide an important area of study.
HOW IT WORKS
Solutions belong to the category of substances identified as mixtures, substances with variable composition. This may seem a bit confusing, since among the defining characteristics of a solution are its uniformity and consistency. But this definition of a solution involves external qualities—the things we can observe with our senses—whereas a mixture can be distinguished from a pure substance not only in terms of external characteristics, but also because of its internal and structural properties.
At one time, chemists had a hard time differentiating between mixtures and pure substances (which are either elements or compounds), primarily because they had little or no knowledge of those “internal and structural properties.” Externally, a mixture and compound can be difficult to distinguish, but the “variable composition” mentioned above is a key factor. Coffee can be almost as weak as water, or so strong it seems to galvanize the throat as it goes down—yet in both cases, though its composition has varied, it is still coffee.
By contrast, if a compound is altered by the variation of just one atom in its molecular structure, it becomes something else entirely. When an oxygen atom bonds with a carbon and oxygen atom, carbon monoxide—a poisonous gas produced by the burning of fossil fuels—is turned into carbon dioxide, an essential component of the interaction between plants and animals in the natural environment.
Mixtures vs. compounds:three distinctions
Air (a mixture) can be distinguished from a compound, such as carbon dioxide, in three ways. First, a mixture can exist in virtually any proportions among its constituent parts, whereas a compound has a definite and constant composition. Air can be oxygen-rich or oxygen-poor, but if we vary the numbers of oxygen atoms chemically bonded to form a compound, the result is an entirely different substance.
Second, the parts of a mixture retain most of their properties when they join together, but elements—once they form a compound—lose their elemental characteristics. If pieces of carbon were floating in the air, their character would be quite
Water and oil droplets exposed to polarized light. Water and oil have very little miscibility with regard to one another, meaning that they tend to remain separate when combined.
different from that of the carbon in carbon dioxide. Carbon, in its natural form, is much like coal or graphite (graphite is pure carbon, and coal an impure form of the element), but when a carbon atom combines with an oxygen atom, the two form a gas. Pieces of carbon in the air, on the other hand, would be solid, as carbon itself is.
Third, a mixture can usually be created simply by the physical act of stirring items together, and/or by applying heat. Certainly this is true of many solutions, such as brewed coffee. On the other hand, a compound such as carbon dioxide can only be formed by the chemical reaction of atoms in specific proportions and at specific temperatures. Some such reactions consume heat, whereas others produce it. These interactions of heat are highly complex; on the other hand, in making coffee, heat is simply produced by an external source (the coffee maker) and transferred to the coffee in the brewing process.
Heterogeneous and homogeneous mixtures
There are two basic types of mixtures. One of these occurs, for instance, when sand is added to a beaker of water: the sand sinks to the bottom, and the composition of the sand-water mixture cannot be said to be the same throughout. It is thus a heterogeneous mixture. The same is true of cold tea when table sugar (sucrose) is added to it: the sugar drifts to the bottom, and as a result, the first sip of tea from the glass is not nearly as sweet as the last.
Wood is a mixture that typically appears in heterogeneous form, a fact that can be easily confirmed by studying wood paneling. There are knots, for instance—areas where branches once grew, and where the concentrations of sap are higher. Striations of color run through the boards of paneling, indicating complex variations in the composition of the wood. Much the same is true of soil, with a given sample varying widely depending on a huge array of factors: the concentrations of sand, rock, or decayed vegetation, for instance, or the activities of earthworms and other organisms in processing the soil.
In a homogeneous mixture, by contrast, there is no difference between one area of the mixture and another. If coffee has been brewed properly, and there are no grounds at the bottom of the pot, it is homogeneous. If sweetener is added to tea while it is hot, it too should yield a homogeneous mixture.
Water and ethanol are completely miscible, whether the solution be 99% water and 1% ethanol, 50% of both, or 99% ethanol and 1% water. Shown here is a glass of beer-an example of a water-ethanol solution.
Solutions and Solubility
Virtually all varieties of homogeneous mixtures can be classified as a solution—that is, a homogeneous mixture in which one or more substances is dissolved in another substance. If two or more substances were combined in exactly equal proportions, this would technically not be a solution; hence the distinction between solutions and the larger class of homogeneous mixtures.
A solution is made up of two parts: the solute, the substance or substances that are dissolved; and the solvent, the substance that dissolves the solute. The solvent typically determines the physical state of the solution: in other words, if the solvent is a liquid, the solution will most likely be a liquid. Likewise if the solvent is a solid such as a metal, melted at high temperatures to form a metallic solution called an alloy, then when the solution is cooled to its normal temperature, it will be solid again.
Miscibility and solubility
Miscibility is a term describing 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. Oil and water, on the other hand (or substances based in either) have very low miscibility. The reasons for this will be discussed below.
Miscibility is a qualitative term like “fast” or “slow”; on the other hand, solubility—the maximum amount of a substance that dissolves in a given amount of solvent at a specific temperature—can be either qualitative or quantitative. In a general sense, the word is qualitative, referring to the property of being soluble, or able to dissolve in a solution.
At some points in this essay, “solubility” will be used in this qualitative sense; however, within the realm of chemistry, it also has a quantitative meaning. In other words, instead of involving an imprecise quality such as “fast” or “slow,” solubility in this sense relates to precise quantities more along the lines of “100 MPH (160.9 km/h).” Solubility is usually expressed in grams (g) (0.0022 lb) of solute per 100 g (0.22 lb) of solvent.
Other quantitative terms
Another quantitative means of describing a solution is in terms of mass percent: the mass of the solute divided by the mass of the solution, and multiplied by 100%. If there are 25 g of solute in a solution of 200 g, for instance, 25 would be divided by 200 and multiplied by 100% to yield a 12.5% figure of solution composition.
Molarity also provides a quantitative means of showing the concentration of solute to solution. Whereas mass percent is, as its name indicates, a comparison of the mass of the solute to that of the solvent, molarity shows the amount of solute in a given volume of solution. This is measured in moles of solute per liter of solution, abbreviated mol/l.
Saturation and Dilution
The quantitative terms for describing solubility that we have reviewed are useful to a professional chemist, or to anyone performing work in a laboratory. For the most part, however, qualitative expressions will suffice for the present discussion. Among the most useful qualitative terms is saturation.
When it is possible to dissolve solute in a solvent, the solution is said to be unsaturated— rather like a sponge that has not been filled to capacity with liquid. By contrast, a solution that contains as much solute as it can at a given temperature is like a sponge that has been filled with all the liquid it can possibly contain. It can no longer absorb more of the liquid; rather, it can only push liquid particles along, and the sponge is said to be saturated. In the same way, if tea is hot, it is easier to introduce sugar to it, but when the temperature is low, sugar will not dissolve as easily.
Saturation and temperature
With tea and many other substances, higher temperatures mean that a greater amount of solute can be added before the solution is fully saturated. The reason for this relationship between saturation and temperature, according to generally accepted theory, is that heated solvent particles move more quickly than cold ones, and as a result, create more space into which the solvent can fit. Indeed, “space” is a prerequisite for a solution: the molecules of solute need to find a “hole” between the molecules of solvent into which they can fit. Thus the molecules in a solution can be compared to a packed crowd: if a crowd is suddenly dispersed, it is easier to walk through it.
Not all substances respond to rises in temperature in the manner described, however. As a rule, gases (with the exception of helium) are more soluble at lower temperatures than at higher ones. Higher temperatures mean an increase in kinetic energy, with more molecules colliding with one another, and this makes it easier for the gases to escape the liquid in which they are dissolved.
Carbonated soft drinks get their “fizz” from carbon dioxide gas dissolved, along with sugar and other flavorings, in a solution of water. When the soft-drink container is opened, much of the carbon dioxide quickly departs, while a certain proportion stays dissolved in the cola. The remaining carbon dioxide will eventually escape as well, but it will do so more quickly if left in a warm environment rather than a cold one, such as the inside of a refrigerator.
dilution and concentration. Another useful set of qualitative terms for solutions also relates to the relative amount of solute that has been dissolved. But whereas saturation is an absolute condition at a certain temperature (in other words, the solution is definitely saturated at such-and-such a temperature), concentration and dilution are much more relative terms.
When a solution contains a relatively small amount of solute, it is said to be dilute; on the other hand, a solution with a relatively large amount of solute is said to be concentrated. For instance, hydrogen peroxide (H2O2) as sold over the counter in drug stores, to be used in homes as a disinfectant of bleaching agent, is a dilute 3% solution in water. In higher concentrations, hydrogen peroxide can cause burns to human skin, and is used to power rockets.
Chemists often keep on hand in their laboratories concentrated versions of various frequently used solutions. Maintaining them in concentrated form saves space; when more of a solution is needed, the chemist dilutes it in water according to desired molarity values. To do so, the chemist determines how much water needs to be added to a particular “stock solution” (as these concentrated solutions in a laboratory are called) to create a solution of a particular concentration. In the dilution with water, the number of moles of the solute does not change; rather, the particles of solute are dispersed over a larger volume.
“Like Dissolves Like”
In the molecules of a compound, the atoms are held together by powerful attractions. The molecules within a compound, however, also have an intermolecular attraction, but this is much weaker than the interatomic bonds in a molecule. It is thus quite possible for the molecules in a solution to exert a greater attractive force than the one holding the molecules of solute together with one another. When this happens, the solute dissolves.
A useful rule of thumb when studying solutions is “like dissolves like.” In other words, water dissolves water-based solutes, whereas oil dissolves oily substances. Or to put it another way, water and water-based substances are miscible with one another, as are oil and oil-based substances. Water and oil together, however, are largely immiscible.
polar water, nonpolar
oil. Water and oil and immiscible due to their respective molecule structures, and hence their inherent characteristics of intermolecular bonding. Water molecules are polar, meaning that the positive electric charge is at one end of the molecule, while the negative charge is at the other end. Oil, on the other hand, is nonpolar—charges are more evenly distributed throughout the molecule.
The oxygen atom in a water molecule has a much greater electronegativity than the hydrogen atoms, so it pulls negatively charged electrons to its end of the molecule. Conversely, most oils are composed of carbon and hydrogen, which have similar values of electronegativity. As a result, positive and negative charges are distributed evenly throughout the oil molecule. Whereas a water molecule is like a magnet with a north and south pole, an oil molecule is like a nonmagnetic metal. Thus, as most people know, “oil and water don’t mix.”
The immiscible quality of oil and water in relation to one another explains a number of phenomena from the everyday world. It is easy enough to wash mud from your hands under running water, because the water and the mud (which, of course, contains water) are highly miscible. But motor oil or oil-based paint will leave a film on the hands, as these substances bond to oily molecules in the skin itself, and no amount of water will wash the film off. To remove it, one needs mineral spirits, paint thinner, or soap manufactured to bond with the oils.
Everyone has had the experience of eating spicy foods and then trying to cool down the mouth with cold water—and just about everyone has discovered that this does not work. This is because most spicy substances contain emulsified oils that coat the tongue, and these oils are not attracted to water. A much better “solution” (in more ways than one) is milk, and in particular, whole milk. Though a great deal of milk is composed of water, it also contains tiny droplets of fats and proteins that join with the oils in spicy substances, thus cooling down the mouth.
Crossing the Oil/Water Barrier
The active ingredient in a dry-cleaning chemical usually has nonpolar molecules, because the toughest stains are made by oils and greases. But what about ordinary soap, which we use in water to wash both water- and oil-based substances from our bodies? Though, as noted earlier, certain kinds of oil stains require special cleaning solutions, ordinary soap is fine for washing off the natural oils secreted by the skin. Likewise, it can wash off small concentrations of oil that come from the environment and attach to the skin—for instance, from working over a deep fryer in a fast-food restaurant.
How does the soap manage to “connect” both with oils and water? Likewise, how does milk—which is water-soluble and capable of dilution in water—wash away the oils associated with spicy food? To answer these questions, we need to briefly consider a subject examined in more depth within the Mixtures essay: emulsions, or mixtures of two immiscible liquids.
Emulsifiers and surfactants
The dispersion of two substances in an emulsion is achieved through the use of an emulsifier or surfactant. Made up of molecules that are both water- and oil-soluble, an emulsifier or surfactant acts as an agent for joining other substances in an emulsion. The two words are virtually synonymous, but “emulsifier” is used typically in reference to foods, whereas “surfactant” most often refers to an ingredient in detergents and related products.
In an emulsion, millions of surfactants surround the dispersed droplets of solute, known as the internal phase, shielding them from the solvent, or external phase. 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 a water-based external phase. The emulsifiers in milk help to bond oily particles of milk fat (cream) and protein to the external phase of water that comprises the majority of milk’s volume.
As for soap, it is a mixture of an acid and a base—specifically, carboxylic acids joined with a base such as sodium hydroxide. Carboxylic acids, chains of hydrogen and carbon atoms, are just some of many hydrocarbons that form the chemical backbone of a vast array of organic substances. 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- (R stands for the hydrocarbon chain), whose two ends behave in different fashions, making it a surfactant.
The hydrocarbon end (R-) is said to be lipophilic, or “oil-loving”; 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 solution, due to the presence of the hydrocarbons, which attract one another to form 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.
When a hydrocarbon joins with other substances in one of the hydrocarbon functional groups, these form numerous hydrocarbon derivatives. Among the hydrocarbon derivatives is alcohol, and within this grouping is ethyl alcohol or ethanol, which includes a hydrocarbon bonded to the -OH functional group. The formula for ethanol is C2H6O, though this is sometimes rendered as C2H5OH to show that the alcohol functional group (-OH) is bonded to the hydroxyl radical (C2H5).
Ethanol, the same alcohol found in alcoholic beverages, is obviously miscible with water. Beer, after all, is mostly water, and if ethanol and water were not miscible, it would be impossible to mix alcohol with water or a water-based substance to make Scotch and water or a Bloody Mary (vodka and tomato juice.) In fact, water and ethanol are completely miscible, whether the solution be 99% water and 1% ethanol, 50% of both, or 99% ethanol and 1% water.
How can this be, given the fact that ethanol is a hydrocarbon derivative—in other words, a cousin of petroleum? The addition of the term “derivative” gives us a clue: note that ethanol contains oxygen, just as water does. As in water, the oxygen and hydrogen form a polar bond, giving that portion of the ethanol molecule a high affinity for water. Molecules of water and the alcohol functional group are joined through an intermolecular force called hydrogen bonding.
The term aqueous refers to water, and because water has extraordinary solvent qualities (discussed in the Osmosis essay) it serves as the medium for numerous solutions. Furthermore,reactions in aqueous solutions—though we can only touch on them briefly here—constitute a large and significant body of reactions studied by chemists.
Most of the solutions we have discussed up to this point are aqueous. We have referred, at least in an external or phenomenological way, to the means by which sugar dissolves in an aqueous solution, such as tea. Now let us consider, from a molecular or structural standpoint, the means by which salt does so as well.
Salt is formed of positively charged sodium ions, firmly bonded to negatively charged chlorine ions. To break these ionic bonds and dissolve the sodium chloride, water must exert a strong attraction. However, salt is not really composed of molecules but simply repeating series of sodium and chlorine atoms joined together in a simple face-centered cubic lattice which has each each sodium ion (Na+) surrounded by six chlorine ions (Cl-); at the same time, each chlorine ion is surrounded by six sodium ions.
In dissolving the salt, water molecules surround ions that make up the salt, holding them in place through the electrical attraction of opposite charges. Due to the differences in electronegativity that give the water molecule its high polarity, the hydrogen atoms are more positively charged, and thus these attract the negatively charged chlorine ion. Similarly, the negatively charged oxygen end of the water molecule attracts the positively charged sodium ion. As a result, the salt is “surrounded” or dissolved.
Plasma and aqueous-solution reactions in the body
Whereas saltwater is an aqueous solution that can eventually kill someone who drinks it, plasma is an essential component of the life process—and in fact, it contains a small quantity of sodium chloride. Not to be confused with the phase of matter also called plasma, this plasma is the liquid portion of blood. Blood itself is about 55% plasma, with red and white blood cells and platelets suspended in it.
Plasma is in turn approximately 90% water, with a variety of other substances suspended or dissolved in it. Prominent among these substances are proteins, of which there are about 60 in plasma, and these serve numerous important functions—for instance, as antibodies. Plasma also contains ions, which prevent red blood cells from taking up excess water in osmosis. Prominent among these ions are those of salt, or sodium chloride. Plasma also transports nutrients such as amino acids, glucose, and fatty acids, as well as waste products such as urea and uric acid, which it passes on to the kidneys for excretion.
Aqueous: A term describing a solution in which a substance or substances are dissolved in water.
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.
Concentrated: A qualitative term describing a solution with a relatively large ratio of solute to solvent.
Dilute: A qualitative term describing a solution with a relatively small ratio of solute to solvent.
Emulsifier: A surfactant. (Usually the term “emulsifier” is applied to foods, and “surfactant” to detergents and other inedible products.)
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.
Heterogeneous: A term describing a mixture that is not the same throughout; rather, it has various regions possessing different properties. One example of this is sand in a container of water. Rather than dissolving to form a homogeneous mixture as sugar does, 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.
Mass percent: A quantitative means of measuring solubility in terms of the mass of the solute divided by the mass of the solution, multiplied by 100%.
Miscibility: A term identifying the relative ability of two substances to dissolve in one another. Miscibility is qualitative, like “fast” or “slow”; solubility, on the other hand, can be a quantitative term.
Mixture: A substance with a variable composition, composed of molecules or atoms of differing types. Compare with pure substance.
Molarity: A quantitative means of showing the concentration of solute to solution. This is measured in moles of solute per liter of solution, abbreviated mol/L.
Pure substance: A substance— either an element or compound—that has an unvarying composition. This means that by changing the proportions of atoms, the result would be an entirely different substance. Compare with mixture.
Qualitative: Involving a comparison between qualities that are not precisely defined, such as “fast” and “slow” or “warm” and “cold.”
Quantitative: Involving a comparison between precise quantities—for instance, 10 lb vs. 100 lb, or 50 MPH vs. 120
Saturated: A qualitative term describing a solution that contains as much solute as it can dissolve at a given temperature.
Solubility: In a broad, qualitative sense, solubility refers to the property of being soluble. Chemists, however, usually apply the word in a quantitative sense, to indicate the maximum amount of a substance that dissolves in a given amount of solvent at a specific temperature. Solubility is usually expressed in grams of solute per 100 g of solvent.
Soluble: Capable of dissolving in a solvent.
Solute: The substance or substances that are dissolved in a solvent to form a solution.
Solution: A homogeneous mixture in which one or more substances (the solute) is dissolved in a solvent—for example, sugar dissolved in water.
Solvent: The substance or substances that dissolve a solute to form a solution.
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.
Unsaturated: A term describing a solution that is capable of dissolving additional solute, if that solute is introduced to it.
Much of the activity that sustains life in the body of a living organism can be characterized as a chemical reaction in an aqueous solution. When we breathe in oxygen, it is taken to the lungs and fed into the bloodstream, where it associates with the iron-containing hemoglobin in red blood cells and is transported to the organs. In the stomach, various aqueous-solution reactions process food, turning part of it into fuel that the blood carries to the cells, where the oxygen engages in complex reactions with nutrients.
A Miscellany of Solutions
Aqueous-solution reactions can lead to the formation of a solid, as when a solution of potassium chromate (K2CrO4) is added to an aqueous solution of barium nitrate (Ba[NO3]2 to form solid barium chromate (BaCrO4) and a solution of potassium nitrate (KNO3). This reaction is described in the essay on Chemical Reactions.
We have primarily discussed liquid solutions, and in particular aqueous solutions. It should be stressed, however, that solutions can also exist in the gaseous or solid phases. The air we breathe is a solution, not a compound: in other words, there is no such thing as an “air molecule.” Instead, it is made up of diatomic elements (those in which two atoms join to form a molecule of a single element); monatomic elements (those elements that exist as single atoms); one element in a triatomic molecule; and two compounds.
The “solvent” in air is nitrogen, a diatomic element that accounts for 78% of Earth’s atmosphere. Oxygen, also diatomic, constitutes an additional 21%. Argon, which like all noble gases is monatomic, ranks a distant third, with 0.93%. The remaining 0.07% is made up of traces of other noble gases; the two compounds mentioned, carbon dioxide and water (in vapor form); and, high in the atmosphere, the triatomic form of oxygen known as ozone (O3).
The most significant solid solutions are alloys of metals, discussed in the essay on Mixtures, as well as in essays on various metal families, particularly the Transition Metals. Some well-known alloys include bronze (three-quarters copper, one-quarter tin); brass (two-thirds copper, one-third zinc); pewter (a mixture of tin and copper with traces of antimony); and numerous alloys of iron—particularly steel—as well as alloys involving other metals.