17.2
Entropy, or S, is a measure of the randomness or disorder of a thermodynamic system, such as the randomness in the arrangement of atoms, molecules, or ions. The greater the disorder in a system, the higher the entropy.
Entropy is a state function, which means that the change in entropy of a process can be calculated by finding the difference between the final state and the initial state, regardless of the path taken.
The entropy of a system can be expressed by Boltzmann’s equation, in which S is equal to Boltzmann’s constant, k, multiplied by the natural log of the number of microstates, W.
Microstates are the distinct energetically equivalent configurations that are possible for the atoms and molecules in a given system.
Consider a system that contains two atoms with a total of two units of energy. This energy can be distributed between the two atoms in three different ways: both units with the first atom, both units with the second atom, or one unit with each atom. Thus, this system has three potential microstates, all of which are energetically equivalent.
It follows that entropy increases in proportion to the number of atoms in a molecule and its molecular weight. For example, under standard conditions of 25 °C and 1 atm, the entropy of 1 mole of sulfuric acid is greater than the entropy of 1 mole of water.
Additionally, the entropy of a mixture is greater than the entropy of its pure components, as increased complexity results in a higher number of possible microstates.
The entropy of a system also increases with temperature. As the temperature increases, so does the kinetic energy resulting in an increase in the number of possible microstates.
The physical state of matter is an indicator of a substance’s relative entropy. The entropy of a given solid is always less than the liquid form of the same substance, and the entropy of the liquid form is always less than that of the gas.
The molecules in a gas are far apart from each other and have many more possible microstates compared to molecules in a liquid or solid. Solids, on the other hand, are much more organized with fewer microstates, thereby resulting in lower entropy.
Salt particles that have dissolved in water never spontaneously come back together in solution to reform solid particles. Moreover, a gas that has exp…
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