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.
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.
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.
Click on this interactive simulation to view the effects of temperature on molecular motion.
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.
The following demonstration allows one to view the effects of heating and cooling a coiled bimetallic strip.
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).
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.
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 |  |
|---|---|---|
| 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 |  |
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
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- potential energy
- the energy an object has because of its relative position, composition or condition
