Energy and the first law of thermodynamics

 

Energy and the first law of thermodynamics

The concept of energy is a fundamental and familiar one in all the sciences. In simple terms, the energy of a body represents its ability to do work, and work itself is a force acting over a distance.

Chemical systems can have both kinetic energy (energy of motion) and potential energy (stored energy). The kinetic energy possessed by any collection of molecules in a solid, liquid, or gas is known as its thermal energy. Since liquids expand when they have more thermal energy, a liquid column of mercury, for example, will rise higher in an evacuated tube as it becomes warmer. In this way a thermometer can be used to measure the thermal energy, or temperature, of a system. The temperature at which all molecular motion comes to a halt is known as absolute zero.

Energy also may be stored in atoms or molecules as potential energy. When protons and neutrons combine to form the nucleus of a certain element, the reduction in potential energy is matched by the production of a huge quantity of kinetic energy. Consider, for instance, the formation of the deuterium nucleus from one proton and one neutron. The fundamental mass unit of the chemist is the mole, which represents the mass, in grams, of 6.02 × 1023 individual particles, whether they be atoms or molecules. One mole of protons has a mass of 1.007825 grams and one mole of neutrons has a mass of 1.008665 grams. By simple addition the mass of one mole of deuterium atoms (ignoring the negligible mass of one mole of electrons) should be 2.016490 grams. The measured mass is 0.00239 gram less than this. The missing mass is known as the binding energy of the nucleus and represents the mass equivalent of the energy released by nucleus formation. By using Einstein’s formula for the conversion of mass to energy (E = mc2), one can calculate the energy equivalent of 0.00239 gram as 2.15 × 108 kilojoules. This is approximately 240,000 times greater than the energy released by the combustion of one mole of methane. Such studies of the energetics of atom formation and interconversion are part of a specialty known as nuclear chemistry.

The energy released by the combustion of methane is about 900 kilojoules per mole. Although much less than the energy released by nuclear reactions, the energy given off by a chemical process such as combustion is great enough to be perceived as heat and light. Energy is released in so-called exothermic reactions because the chemical bonds in the product molecules, carbon dioxide and water, are stronger and stabler than those in the reactant molecules, methane and oxygen. The chemical potential energy of the system has decreased, and most of the released energy appears as heat, while some appears as radiant energy, or light. The heat produced by such a combustion reaction will raise the temperature of the surrounding air and, at constant pressure, increase its volume. This expansion of air results in work being done. In the cylinder of an internal-combustion engine, for example, the combustion of gasoline results in hot gases that expand against a moving piston. The motion of the piston turns a crankshaft, which then propels the vehicle. In this case, chemical potential energy has been converted to thermal energy, some of which produces useful work. This process illustrates a statement of the conservation of energy known as the first law of thermodynamics. This law states that, for an exothermic reaction, the energy released by the chemical system is equal to the heat gained by the surroundings plus the work performed. By measuring the heat and work quantities that accompany chemical reactions, it is possible to ascertain the energy differences between the reactants and the products of various reactions. In this manner, the potential energy stored in a variety of molecules can be determined, and the energy changes that accompany chemical reactions can be calculated.