4 Properties of Materials, Chemical Reactions, and Heat

Figure 4.1 (a) Wax undergoes a physical change when solid wax is heated and forms liquid wax. (b) Steam condensing inside a cooking pot is a physical change, as water vapor is changed into liquid water. (credit a: modification of work by “95jb14”/Wikimedia Commons; credit b: modification of work by “mjneuby”/Flickr)

The change of one type of matter into another type (or the inability to change) is a chemical property. Examples of chemical properties include flammability, toxicity, acidity, and many other types of reactivity. Iron, for example, combines with oxygen in the presence of water to form rust; chromium does not oxidize (Figure 4.2). Nitroglycerin is very dangerous because it explodes easily; neon poses almost no hazard because it is very unreactive.

Figure 4.2 (a) One of the chemical properties of iron is that it rusts; (b) one of the chemical properties of chromium is that it does not. (credit a: modification of work by Tony Hisgett; credit b: modification of work by “Atoma”/Wikimedia Commons)

A chemical change always produces one or more types of matter that differ from the matter present before the change. The formation of rust is a chemical change because rust is a different kind of matter than the iron, oxygen, and water present before the rust formed. The explosion of nitroglycerin is a chemical change because the gases produced are very different kinds of matter from the original substance. Other examples of chemical changes include reactions that are performed in a lab (such as copper reacting with nitric acid), all forms of combustion (burning), and food being cooked, digested, or rotting (Figure 4.3).

Figure 4.3 (a) Copper and nitric acid undergo a chemical change to form copper nitrate and brown, gaseous nitrogen dioxide. (b) During the combustion of a match, cellulose in the match and oxygen from the air undergo a chemical change to form carbon dioxide and water vapor. (c) Cooking red meat causes a number of chemical changes, including the oxidation of iron in myoglobin that results in the familiar red-to-brown color change. (d) A banana turning brown is a chemical change as new, darker (and less tasty) substances form. (credit b: modification of work by Jeff Turner; credit c: modification of work by Gloria Cabada-Leman; credit d: modification of work by Roberto Verzo)

Balancing Equations

The chemical equation described in section 4.1 is balanced, meaning that equal numbers of atoms for each element involved in the reaction are represented on the reactant (left) and product (right) sides. This is a requirement the equation must satisfy to be consistent with the law of conservation of matter. It may be confirmed by simply summing the numbers of atoms on either side of the arrow and comparing these sums to ensure they are equal. Note that the number of atoms for a given element is calculated by multiplying the coefficient of any formula containing that element by the element’s subscript in the formula. If an element appears in more than one formula on a given side of the equation, the number of atoms represented in each must be computed and then added together. For example, both product species in the example reaction, CO2 and H2O, contain the element oxygen, and so the number of oxygen atoms on the product side of the equation is

(1 CO₂ molecule × 2 O atoms per CO₂ molecule) + (2 H₂O molecules × 1 O atom per H₂O molecule) = 4 O atoms

The equation for the reaction between methane and oxygen to yield carbon dioxide and water is confirmed to be balanced per this approach, as shown here: CH₄ + 2O₂⟶CO₂ + 2H₂O

A balanced chemical equation often may be derived from a qualitative description of some chemical reaction by a fairly simple approach known as balancing by inspection. Consider as an example the decomposition of water to yield molecular hydrogen and oxygen. This process is represented qualitatively by an unbalanced chemical equation: H₂O⟶H₂ + O₂ (unbalanced)

Comparing the number of H and O atoms on either side of this equation confirms its imbalance:

The numbers of H atoms on the reactant and product sides of the equation are equal, but the numbers of O atoms are not. To achieve balance, the coefficients of the equation may be changed as needed. Note that the coefficients must be whole numbers and cannot be fractions or decimals. Keep in mind, of course, that the formula subscripts define, in part, the identity of the substance, and so these cannot be changed without altering the qualitative meaning of the equation. For example, changing the reactant formula from H₂O to H₂O₂ would yield balance in the number of atoms, but doing so also changes the reactant’s identity (it’s now hydrogen peroxide and not water). The O atom balance may be achieved by changing the coefficient for H₂O to 2.

2H₂O⟶H₂ + O₂ (unbalanced)

The H atom balance was upset by this change, but it is easily reestablished by changing the coefficient for the H₂ product to 2.

2H2O⟶2H2 + O2 (balanced)

These coefficients yield equal numbers of both H and O atoms on the reactant and product sides, and the balanced equation is, therefore:

2H₂O⟶2H₂ + O₂

Check Your Learning: Write a balanced equation for the decomposition of ammonium nitrate to form molecular nitrogen, molecular oxygen, and water. (Hint: Balance oxygen last, since it is present in more than one molecule on the right side of the equation.)

ANSWER: 2NH₄NO₃⟶2N₂ + O₂ + 4H₂O

LINK TO LEARNING: Use this interactive tutorial by PhET for additional practice balancing equations: Balancing Chemical Equations.

Types of Chemical Reactions

Humans interact with one another in various and complex ways, and we classify these interactions according to common patterns of behavior. When two humans exchange information, we say they are communicating. When they hit each other with their fists, we say they are fighting. Faced with a wide range of varied interactions between chemical substances, scientists have likewise found it convenient (or even necessary) to classify chemical interactions by identifying common patterns of reactivity. This module will provide an introduction to three of the most prevalent types of chemical reactions: precipitation, acid-base, and oxidation-reduction.

Precipitation Reactions

A precipitation reaction is one in which dissolved substances react to form one (or more) solid products. Many reactions of this type involve the exchange of ions between ionic compounds in aqueous solution and are sometimes referred to as double displacement, double replacement, or metathesis reactions. These reactions are common in nature and are responsible for the formation of coral reefs in ocean waters and kidney stones in animals. They are used widely in industry for production of a number of commodity and specialty chemicals.

The extent to which a substance may be dissolved in water, or any solvent, is quantitatively expressed as its solubility, defined as the maximum concentration of a substance that can be achieved under specified conditions. Substances with relatively large solubilities are said to be soluble. A substance will precipitate when solution conditions are such that its concentration exceeds its solubility. Substances with relatively low solubilities are said to be insoluble, and these are the substances that readily precipitate from solution.

Lead iodide is a bright yellow solid that was formerly used as an artist’s pigment known as iodine yellow (Figure 4.4). The properties of pure PbI₂ crystals make them useful for fabrication of X-ray and gamma ray detectors.

Figure 4.4 A precipitate of PbI₂ forms when solutions containing Pb²⁺ and I⁻ are mixed. (credit: Der Kreole/Wikimedia Commons)

Acid-Base Reactions

An acid-base reaction is one in which a hydrogen ion, H⁺, is transferred from one chemical species to another. Such reactions are of central importance to numerous natural and technological processes, ranging from the chemical transformations that take place within cells and the lakes and oceans, to the industrial-scale production of fertilizers, pharmaceuticals, and other substances essential to society.

For purposes of this brief introduction, we will consider only the more common types of acid-base reactions that take place in aqueous solutions. In this context, an acid is a substance that will dissolve in water to yield hydronium ions, H₃O⁺. As an example, consider the equation shown here:   HCl(aq) + H₂O(aq)⟶Cl^–(aq) + H₃O⁺(aq)

The process represented by this equation confirms that hydrogen chloride is an acid. When dissolved in water, H₃O⁺ ions are produced by a chemical reaction in which H⁺ ions are transferred from HCl molecules to H₂O molecules (Figure 4.5).

 

Figure 4.5 When hydrogen chloride gas dissolves in water, (a) it reacts as an acid, transferring protons to water molecules to yield (b) hydronium ions (and solvated chloride ions).

The nature of HCl is such that its reaction with water as just described is essentially 100% efficient: Virtually every HCl molecule that dissolves in water will undergo this reaction. Acids that completely react in this fashion are called strong acids, and HCl is one among just a handful of common acid compounds that are classified as strong. A far greater number of compounds behave as weak acids and only partially react with water, leaving a large majority of dissolved molecules in their original form and generating a relatively small amount of hydronium ions. Weak acids are commonly encountered in nature, being the substances partly responsible for the tangy taste of citrus fruits, the stinging sensation of insect bites, and the unpleasant smells associated with body odor. A familiar example of a weak acid is acetic acid, the main ingredient in food vinegars (Figure 4.6).

 

Figure 4.6 (a) Fruits such as oranges, lemons, and grapefruit contain the weak acid citric acid. (b) Vinegars contain the weak acid acetic acid. (credit a: modification of work by Scott Bauer; credit b: modification of work by Brücke-Osteuropa/Wikimedia Commons)

A base is a substance that will dissolve in water to yield hydroxide ions, OH⁻. The most common bases are ionic compounds composed of alkali or alkaline earth metal cations (groups 1 and 2) combined with the hydroxide ion—for example, NaOH and Ca(OH)₂. Unlike the acid compounds discussed previously, these compounds do not react chemically with water; instead they dissolve and dissociate, releasing hydroxide ions directly into the solution. For example, KOH and Ba(OH)₂ dissolve in water and dissociate completely to produce cations (K⁺ and Ba²⁺, respectively) and hydroxide ions, OH⁻. These bases, along with other hydroxides that completely dissociate in water, are considered strong bases.

Consider as an example the dissolution of lye (sodium hydroxide) in water: NaOH⟶Na⁺ + OH⁻

This equation confirms that sodium hydroxide is a base. When dissolved in water, NaOH dissociates to yield Na⁺ and OH⁻ ions. This is also true for any other ionic compound containing hydroxide ions. Since the dissociation process is essentially complete when ionic compounds dissolve in water under typical conditions, NaOH and other ionic hydroxides are all classified as strong bases.

CHEMISTRY IN EVERYDAY LIFE

Stomach Antacids

Our stomachs contain a solution of roughly 0.03 M HCl (molarity), which helps us digest the food we eat. The burning sensation associated with heartburn is a result of the acid of the stomach leaking through the muscular valve at the top of the stomach into the lower reaches of the esophagus. The lining of the esophagus is not protected from the corrosive effects of stomach acid the way the lining of the stomach is, and the results can be very painful. When we have heartburn, it feels better if we reduce the excess acid in the esophagus by taking an antacid. As you may have guessed, antacids are bases. One of the most common antacids is calcium carbonate, CaCO₃. The reaction: CaCO₃ + 2HCl⇌CaCl₂ + H₂O + CO₂  not only neutralizes stomach acid, it also produces CO₂, which may result in a satisfying belch.

CHEMISTRY IN EVERYDAY LIFE

Culinary Aspects of Chemistry

Examples of acid-base chemistry are abundant in the culinary world. One example is the use of baking soda, or sodium bicarbonate, in baking. NaHCO₃ is a base. When it reacts with an acid such as lemon juice, buttermilk, or sour cream in a batter, bubbles of carbon dioxide gas are formed from decomposition of the resulting carbonic acid, and the batter “rises.” Baking powder is a combination of sodium bicarbonate and one or more acid salts that react when the two chemicals come in contact with water in the batter.

Many people like to put lemon juice or vinegar, both of which are acids, on cooked fish (Figure 4.7). It turns out that fish have volatile amines (bases) in their systems, which are neutralized by the acids to yield involatile ammonium salts. This reduces the odor of the fish, and also adds a “sour” taste that we seem to enjoy.

 

Figure 4.7 A neutralization reaction takes place between citric acid in lemons or acetic acid in vinegar, and the bases in the flesh of fish.

Pickling is a method used to preserve vegetables using a naturally produced acidic environment. The vegetable, such as a cucumber, is placed in a sealed jar submerged in a brine solution. The brine solution favors the growth of beneficial bacteria and suppresses the growth of harmful bacteria. The beneficial bacteria feed on starches in the cucumber and produce lactic acid as a waste product in a process called fermentation. The lactic acid eventually increases the acidity of the brine to a level that kills any harmful bacteria, which require a basic environment. Without the harmful bacteria consuming the cucumbers they are able to last much longer than if they were unprotected. A byproduct of the pickling process changes the flavor of the vegetables with the acid making them taste sour.

LINK TO LEARNING: Explore the microscopic view of strong and weak acids and bases: PhET Acid-Base Solutions.

Oxidation-Reduction Reactions

Earth’s atmosphere contains about 20% molecular oxygen, O₂, a chemically reactive gas that plays an essential role in the metabolism of aerobic organisms and in many environmental processes that shape the world. The term oxidation was originally used to describe chemical reactions involving O₂, but its meaning has evolved to refer to a broad and important reaction class known as oxidation-reduction (redox) reactions. A few examples of such reactions will be used to develop a clear picture of this classification.

Some redox reactions involve the transfer of electrons between reactant species to yield ionic products, such as the reaction between sodium and chlorine to yield sodium chloride: 2Na + Cl₂⟶2NaCl

For redox reactions of this sort, the loss and gain of electrons define the complementary processes that occur:

Oxidation = loss of electrons

Reduction = gain of electrons

In this reaction, then, sodium is oxidized and chlorine undergoes reduction. Viewed from a more active perspective, sodium functions as a reducing agent (reductant), since it provides electrons to (or reduces) chlorine. The chlorine functions as an oxidizing agent (oxidant), as it effectively removes electrons from (oxidizes) sodium.

Reducing agent = species that is oxidized

Oxidizing agent = species that is reduced

Thermal Energy, Temperature, and Heat

Thermal energy is kinetic energy associated with the random motion of atoms and molecules. Temperature is a quantitative measure of “hot” or “cold.” When the atoms and molecules in an object are moving or vibrating quickly, they have a higher average kinetic energy (KE), and we say that the object is “hot.” When the atoms and molecules are moving slowly, they have lower average KE, and we say that the object is “cold” (Figure 4.8). Assuming that no chemical reaction or phase change (such as melting or vaporizing) occurs, increasing the amount of thermal energy in a sample of matter will cause its temperature to increase. And, assuming that no chemical reaction or phase change (such as condensation or freezing) occurs, decreasing the amount of thermal energy in a sample of matter will cause its temperature to decrease.

 

Figure 4.8 (a) The molecules in a sample of hot water move more rapidly than (b) those in a sample of cold water.

LINK TO LEARNING: Click on this interactive simulation to view the effects of temperature on molecular motion: PhET States of Matter.

Most substances expand as their temperature increases and contract as their temperature decreases. This property can be used to measure temperature changes, as shown in Figure 4.9. The operation of many thermometers depends on the expansion and contraction of substances in response to temperature changes.

 

Figure 4.9 (a) In an alcohol or mercury thermometer, the liquid (dyed red for visibility) expands when heated and contracts when cooled, much more so than the glass tube that contains the liquid. (b) In a bimetallic thermometer, two different metals (such as brass and steel) form a two-layered strip. When heated or cooled, one of the metals (brass) expands or contracts more than the other metal (steel), causing the strip to coil or uncoil. Both types of thermometers have a calibrated scale that indicates the temperature. (credit a: modification of work by “dwstucke”/Flickr)

Heat Transfer – Conduction, Convection and Radiation

Heat transfer can happen three different ways; through conduction, convection and radiation. Conduction is heat transfer through contact between atoms. The conductivity of materials is influenced by their atomic structure and bonds. For example, metals are very conductive because they have free flowing electrons that can easily transfer thermal energy. Convection is heat transfer through the movement of gases or liquids. When these fluids are heated and move away from the heat source, they carry the thermal energy with them. A great example of convection is a space heater; the air is heated and then blown out of the heater, sending thermal energy with it out into the room and heating it up. Radiation is the heat transfer through electromagnetic waves. We experience heat from radiation every day from the sun, which transfers heat to the earth through solar radiation. Radiation is the only type of heat transfer that can travel through empty space, because both conduction and convection require a medium to transfer the thermal energy through.

LINK TO LEARNING: The following demonstration allows one to view the effects of heating and cooling a coiled bimetallic strip: Bimetallic strip gif.

Heat (q) is the transfer of thermal energy between two bodies at different temperatures. Heat flow (a redundant term, but one commonly used) increases the thermal energy of one body and decreases the thermal energy of the other. Suppose we initially have a high temperature (and high thermal energy) substance (H) and a low temperature (and low thermal energy) substance (L). The atoms and molecules in H have a higher average KE than those in L. If we place substance H in contact with substance L, the thermal energy will flow spontaneously from substance H to substance L. The temperature of substance H will decrease, as will the average KE of its molecules; the temperature of substance L will increase, along with the average KE of its molecules. Heat flow will continue until the two substances are at the same temperature and therefore reach thermal equilibrium(Figure 4.10).

 

Figure 4.10 (a) Substances H and L are initially at different temperatures, and their atoms have different average kinetic energies. (b) When they contact each other, collisions between the molecules result in the transfer of kinetic (thermal) energy from the hotter to the cooler matter. (c) The two objects reach “thermal equilibrium” when both substances are at the same temperature and their molecules have the same average kinetic energy.

 

LINK TO LEARNING: Click on this PhET simulation to explore energy forms and changes: PhET Energy Forms and Changes. Visit the Energy Systems tab to create combinations of energy sources, transformation methods, and outputs. Click on Energy Symbols to visualize the transfer of energy.

Matter undergoing chemical reactions and physical changes can release or absorb heat. A change that releases heat is called an exothermic process. For example, the combustion reaction that occurs when using an oxyacetylene torch is an exothermic process—this process also releases energy in the form of light as evidenced by the torch’s flame. A reaction or change that absorbs heat is an endothermic process. A cold pack used to treat muscle strains provides an example of an endothermic process. When the substances in the cold pack (water and a salt like ammonium nitrate) are brought together, the resulting process absorbs heat, leading to the sensation of cold.