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Chemical changes and their accompanying changes in energy are important parts of our everyday world (Figure 1). The macronutrients in food (proteins, fats, and carbohydrates) undergo metabolic reactions that provide the energy to keep our bodies functioning. We burn a variety of fuels (gasoline, natural gas, coal) to produce energy for transportation, heating and the generation of electricity. Industrial chemical reactions use enormous amounts of energy to produce raw materials (such as iron and aluminum). Energy is then used to manufacture those raw materials into useful products, such as cars, skyscrapers, and bridges.

Three pictures are shown and labeled a, b, and c. Picture a is a cheeseburger. Picture b depicts a highway that is full of traffic. Picture c is a view into an industrial metal furnace. The view into the furnace shows a hot fire burning inside.
The energy involved in chemical changes is important to our daily lives: (a) A cheeseburger for lunch provides the energy you need to get through the rest of the day; (b) the combustion of gasoline provides the energy that moves your car (and you) between home, work, and school; and (c) coke, a processed form of coal, provides the energy needed to convert iron ore into iron, which is essential for making many of the products we use daily. (credit a: modification of work by “Pink Sherbet Photography”/Flickr; credit b: modification of work by Jeffery Turner)

This chapter will introduce the basic ideas of an important area of science concerned with the amount of heat absorbed or released during chemical and physical changes—an area called thermochemistry. The concepts introduced in this chapter are widely used in almost all scientific and technical fields. Food scientists use them to determine the energy content of foods. Biologists study the energetics of living organisms, such as the metabolic combustion of sugar into carbon dioxide and water. The oil, gas, and transportation industries, renewable energy providers, and many others endeavor to find better methods to produce energy for our commercial and personal needs. Engineers strive to improve energy efficiency, find better ways to heat and cool our homes, refrigerate our food and drinks, and meet the energy and cooling needs of computers and electronics, among other applications. Understanding thermochemical principles is essential for chemists, physicists, biologists, geologists, every type of engineer, and just about anyone who studies or does any kind of science.

Energy

Energy can be defined as the capacity to supply heat or do work. One type of work (w) is the process of causing matter to move against an opposing force. For example, we do work when we inflate a bicycle tire—we move matter (the air in the pump) against the opposing force of the air already in the tire.

Like matter, energy comes in different types. One scheme classifies energy into two types: potential energy, the energy an object has because of its relative position, composition or condition, and kinetic energy, the energy that an object possesses because of its motion. Water at the top of a waterfall or dam has potential energy because of its position; when it flows downward through generators, it has kinetic energy that can be used to do work and produce electricity in a hydroelectric plant (Figure 2). A battery has potential energy because the chemicals within it can produce electricity that can do work.

Two pictures are shown and labeled a and b. Picture a shows a large waterfall with water falling from a high elevation at the top of the falls to a lower elevation. The second picture is a view looking down into the Hoover Dam. Water is shown behind the high wall of the dam on one side and at the base of the dam on the other.
(a) Water that is higher in elevation, for example, at the top of Victoria Falls, has a higher potential energy than water at a lower elevation. As the water falls, some of its potential energy is converted into kinetic energy. (b) If the water flows through generators at the bottom of a dam, such as the Hoover Dam shown here, its kinetic energy is converted into electrical energy. (credit a: modification of work by Steve Jurvetson; credit b: modification of work by “curimedia”/Wikimedia commons)

Energy can be converted from one form into another, but all of the energy present before a change occurs always exists in some form after the change is completed. This observation is expressed in the law of conservation of energy: during a chemical or physical change, energy can be neither created nor destroyed, although it can be changed in form. (This is also one version of the first law of thermodynamics, as you will learn later.)

When one substance is converted into another, there is always an associated conversion of one form of energy into another. Heat is usually released or absorbed, but sometimes the conversion involves light, electrical energy or some other form of energy. For example, chemical energy (a type of potential energy) is stored in the molecules that compose gasoline. When gasoline is combusted within the cylinders of a car’s engine, the rapidly expanding gaseous products of this chemical reaction generate mechanical energy (a type of kinetic energy) when they move the cylinders’ pistons.

According to the law of conservation of matter (seen in an earlier chapter), there is no detectable change in the total amount of matter during a chemical change. When chemical reactions occur, the energy changes are relatively modest and the mass changes are too small to measure, so the laws of conservation of matter and energy hold well. However, in nuclear reactions, the energy changes are much larger (by factors of a million or so), the mass changes are measurable, and matter-energy conversions are significant. This will be examined in more detail in a later chapter on nuclear chemistry. To encompass both chemical and nuclear changes, we combine these laws into one statement: The total quantity of matter and energy in the universe is fixed.

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 3). 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. In addition, 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.

Two molecular drawings are shown and labeled a and b. Drawing a is a box containing fourteen red spheres that are surrounded by lines indicating that the particles are moving rapidly. This drawing has a label that reads “Hot water.” Drawing b depicts another box of equal size that also contains fourteen spheres, but these are blue. They are all surrounded by smaller lines that depict some particle motion, but not as much as in drawing a. This drawing has a label that reads “Cold water.”
(a) The molecules in a sample of hot water move more rapidly than (b) those in a sample of cold water.

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. The operation of many thermometers depends on the expansion and contraction of substances in response to temperature changes.

A picture labeled a is shown as well as a pair of drawings labeled b. Picture a shows the lower portion of an alcohol thermometer. The thermometer has a printed scale to the left of the tube in the center that reads from negative forty degrees at the bottom to forty degrees at the top. It also has a scale printed to the right of the tube that reads from negative thirty degrees at the bottom to thirty five degrees at the top. On both scales, the volume of the alcohol in the tube reads between nine and ten degrees. The two images labeled b both depict a metal strip coiled into a spiral and composed of brass and steel. The left coil, which is loosely coiled, is labeled along its upper edge with the 30 degrees C and 10 degrees C. The end of the coil is near the 30 degrees C label. The right hand coil is much more tightly wound and the end is near the 10 degree C label.
(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 (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 (Figure 5).

Three drawings are shown and labeled a, b, and c, respectively. The first drawing labeled a depicts two boxes, with a space in between and the pair is captioned “Different temperatures.” The left hand box is labeled H and holds fourteen well-spaced red spheres with lines drawn around them to indicate rapid motion. The right hand box is labeled L and depicts fourteen blue spheres that are closer together than the red spheres and have smaller lines around them showing less particle motion. The second drawing labeled b depicts two boxes that are touching one another. The left box is labeled H and contains fourteen maroon spheres that are spaced evenly apart. There are tiny lines around each sphere depicting particle movement. The right box is labeled L and holds fourteen purple spheres that are slightly closer together than the maroon spheres. There are also tiny lines around each sphere depicting particle movement. A black arrow points from the left box to the right box and the pair of diagrams is captioned “Contact.” The third drawing labeled c, is labeled “Thermal equilibrium.” There are two boxes shown in contact with one another. Both boxes contain fourteen purple spheres with small lines around them depicting moderate movement. The left box is labeled H and the right box is labeled L.
(a) Substances H and L are initially at different temperatures, and their atoms have different average kinetic energies. (b) When they are put into contact with 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.

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 (Figure 6). 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.

Two pictures are shown and labeled a and b. Picture a shows a metal railroad tie being cut with the flame of an acetylene torch. Picture b shows a chemical cold pack containing ammonium nitrate.
(a) An oxyacetylene torch produces heat by the combustion of acetylene in oxygen. The energy released by this exothermic reaction heats and then melts the metal being cut. The sparks are tiny bits of the molten metal flying away. (b) A cold pack uses an endothermic process to create the sensation of cold. (credit a: modification of work by “Skatebiker”/Wikimedia commons)

Historically, energy was measured in units of calories (cal). A calorie is the amount of energy required to raise one gram of water by 1 degree C (1 kelvin). However, this quantity depends on the atmospheric pressure and the starting temperature of the water. The ease of measurement of energy changes in calories has meant that the calorie is still frequently used. The Calorie (with a capital C), or large calorie, commonly used in quantifying food energy content, is a kilocalorie. The SI unit of heat, work and energy is the joule. A joule (J) is defined as the amount of energy used when a force of 1 newton moves an object 1 meter. It is named in honor of the English physicist James Prescott Joule. One joule is equivalent to 1 kg m2/s2, which is also called 1 newton–meter. A kilojoule (kJ) is 1000 joules. To standardize its definition, 1 calorie has been set to equal 4.184 joules.

Chemists are concerned with both physical and chemical change, and the energy associated with each. Chemical reactions involve the making and breaking of covalent bonds and these transformations have energy consequences. Heat is the most common form of energy introduced into or released from chemical reactions, but light, electrical current and sound may also be involved. Also, if gases are produced in a reaction, the work done on the surroundings by volume expansion becomes part of the energy balance, and in explosive reactions may be the major consequence. Of course, reactions that consume a gas undergo an opposite volume change and work is done on the system by the surroundings.

The covalent bond of a chlorine molecule provides a simple example of the energy changes associated with bond breaking and bond making. This bond may be broken by the introduction of heat or light energy and it has been determined that 57.9 kcal/mol (242.3 kJ/mol) is required to do so. This is shown in the first of the following reactions; the second reaction describes the reverse bond-forming process. The energy absorbed or released in these reactions is referred to as the bond dissociation energy. If the bond dissociation energy is introduced from the surroundings in the form of heat, the transformation is said to be endothermic. If heat passes from the system to the surroundings, the transformation is termed exothermic. Using our initial terminology, we may say that the covalently bonded system has a lower potential energy than the unbonded diatomic system. Indeed, it is helpful to think of exothermic reactions as proceeding from a higher energy (less stable) reactant state to a lower energy (more stable) product state, as shown in the diagram on the right. Some basic principles of reaction energetics were discussed earlier.

Cl_Cl   +   heat   ____>   2Cl •  An Endothermic Transformation image
2Cl •   ____>   Cl_Cl   +   heat  An Exothermic Transformation

In more complex chemical reactions some (or even all) of the bonds that hold together the atoms of reactant and product molecules may be broken while other bonds are formed. Energy is required to break bonds and since different bonds have different bond dissociation energies, there is often a significant overall energy change in the course of a reaction. In the combustion of methane, for example, all six bonds in the reactant molecules are broken and six new bonds are formed in the product molecules (equation 1). To analyze such reactions we need to keep track of and evaluate heat changes in a precise and systematic manner.

(1)   CH4   +   2 O2 image CO2   +   2 H2O   +   heat
Reactants Products

Glossary

bond dissociation energy
The energy absorbed or released in these reactions

exothermic process
A change that releases heat
endothermic process
A change that absorbs heat
kinetic energy
the energy that an object possesses because of its motion
potential energy
the energy an object has because of its relative position, composition or condition

 

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