# 3: Thermodynamics

• 3.1: Prelude to Thermochemistry
Useful forms of energy are also available from a variety of chemical reactions other than combustion. For example, the energy produced by the batteries in a cell phone, car, or flashlight results from chemical reactions. This chapter introduces many of the basic ideas necessary to explore the relationships between chemical changes and energy, with a focus on thermal energy.
• 3.2: Energy Basics
Energy is the capacity to do work (applying a force to move matter). Heat is energy that is transferred between objects at different temperatures; it flows from a high to a low temperature. Chemical and physical processes can absorb heat (endothermic) or release heat (exothermic). The SI unit of energy, heat, and work is the joule (J). Specific heat and heat capacity are measures of the energy needed to change the temperature of a substance or object.
• 3.3: Calorimetry
Calorimetry is used to measure the amount of thermal energy transferred in a chemical or physical process. This requires careful measurement of the temperature change that occurs during the process and the masses of the system and surroundings. These measured quantities are then used to compute the amount of heat produced or consumed in the process using known mathematical relations. Calorimeters are designed to minimize energy exchange between the system and its surroundings.
• 3.4: Enthalpy
If a chemical change is carried out at constant pressure and the only work done is caused by expansion or contraction, q for the change is called the enthalpy change with the symbol ΔH. Examples of enthalpy changes include enthalpy of combustion, enthalpy of fusion, enthalpy of vaporization, and standard enthalpy of formation.   If the enthalpies of formation are available for the reactants and products of a reaction, the enthalpy change can be calculated using Hess’s law.
• 3.5: Spontaneity
Chemical and physical processes have a natural tendency to occur in one direction under certain conditions. A spontaneous process occurs without the need for a continual input of energy from some external source, while a nonspontaneous process requires such. Systems undergoing a spontaneous process may or may not experience a gain or loss of energy, but they will experience a change in the way matter and/or energy is distributed within the system.
• 3.6: Entropy
Entropy (S) is a state function that can be related to the number of microstates for a system (the number of ways the system can be arranged) and to the ratio of reversible heat to kelvin temperature. It may be interpreted as a measure of the dispersal or distribution of matter and/or energy in a system, and it is often described as representing the “disorder” of the system. For a given substance, $$S_{solid} < S_{liquid} < S_{gas}$$ in a given physical state at a given temperature.
• 3.7: The Second and Third Laws of Thermodynamics
The second law of thermodynamics states spontaneous processes increases the entropy of the universe. If not, then the process is nonspontaneous, and if no change occurs, the system is at equilibrium. The third law of thermodynamics establishes the zero for entropy at 0 for a perfect, pure crystalline solid at 0 K with only one possible microstate. The standard entropy change for a process is computed standard entropy values for the species involv
• 3.8: Gibbs Energy
Gibbs free energy (G) is a state function defined with regard to system quantities only and may be used to predict the spontaneity of a process. A negative value for ΔG indicates a spontaneous process; a positive ΔG indicates a nonspontaneous process; and a ΔG of zero indicates that the system is at equilibrium. A number of approaches to the computation of free energy changes are possible.