Thermodynamics
thermodynamics, science of the relationship between heat, work, temperature, and energy. In broad terms, thermodynamics deals with the transfer of energy from one place to another and from one form to another. The key concept is that heat is a form of energy corresponding to a definite amount of mechanical work.The most important laws of thermodynamics are:
- The zeroth law of thermodynamics. When two systems are each in thermal equilibrium with a third system, the first two systems are in thermal equilibrium with each other. This property makes it meaningful to use thermometers as the “third system” and to define a temperature scale.
- The first law of thermodynamics, or the law of conservation of energy. The change in a system’s internal energy is equal to the difference between heat added to the system from its surroundings and work done by the system on its surroundings.
- The second law of thermodynamics. Heat does not flow spontaneously from a colder region to a hotter region, or, equivalently, heat at a given temperature cannot be converted entirely into work. Consequently, the entropy of a closed system, or heat energy per unit temperature, increases over time toward some maximum value. Thus, all closed systems tend toward an equilibrium state in which entropy is at a maximum and no energy is available to do useful work. This asymmetry between forward and backward processes gives rise to what is known as the “arrow of time.”
- The third law of thermodynamics. The entropy of a perfect crystal of an element in its most stable form tends to zero as the temperature approaches absolute zero. This allows an absolute scale for entropy to be established that, from a statistical point of view, determines the degree of randomness or disorder in a system.
This article covers classical thermodynamics, which does not involve the consideration of individual atoms or molecules. Such concerns are the focus of the branch of thermodynamics known as statistical thermodynamics, or statistical mechanics, which expresses macroscopic thermodynamic properties in terms of the behaviour of individual particles and their interactions. It has its roots in the latter part of the 19th century, when atomic and molecular theories of matter began to be generally accepted.
Fundamental concepts
Thermodynamic states
The application of thermodynamic principles begins by defining a system that is in some sense distinct from its surroundings. For example, the system could be a sample of gas inside a cylinder with a movable piston, an entire steam engine, a marathon runner, the planet Earth, a neutron star, a black hole, or even the entire universe. In general, systems are free to exchange heat, work, and other forms of energy with their surroundings.A system’s condition at any given time is called its thermodynamic state. For a gas in a cylinder with a movable piston, the state of the system is identified by the temperature, pressure, and volume of the gas. These properties are characteristic parameters that have definite values at each state and are independent of the way in which the system arrived at that state. In other words, any change in value of a property depends only on the initial and final states of the system, not on the path followed by the system from one state to another. Such properties are called state functions. In contrast, the work done as the piston moves and the gas expands and the heat the gas absorbs from its surroundings depend on the detailed way in which the expansion occurs.
The behaviour of a complex thermodynamic system, such as Earth’s atmosphere, can be understood by first applying the principles of states and properties to its component parts—in this case, water, water vapour, and the various gases making up the atmosphere. By isolating samples of material whose states and properties can be controlled and manipulated, properties and their interrelations can be studied as the system changes from state to state.
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