TemperatureTemperature is the physical property of a system which underlies the common notions of "hot" and "cold"; the material with the higher temperature is said to be hotter.
Theoretical foundation of temperatureZeroth-Law definition of temperatureWhile most people have a basic understanding of the concept of temperature, its formal definition is rather complicated. Before jumping to a formal definition, let's consider the concept of thermal equilibrium. If two closed systems with fixed volumes are brought together, so that they are in thermal contact, changes may take place in the properties of both systems. These changes are due to the transfer of heat between the systems. When a state is reached in which no further changes occur, the systems are in thermal equilibrium. Now a basis for the definition of temperature can be obtained from the 'zeroth law of Thermodynamics, which states that if two systems, A and B, are in thermal equilibrium and a third system C is in thermal equilibrium with system A then systems B and C will also be in thermal equilibrium (being in thermal equilibrium is a transitive relation; moreover, it is an equivalence relation). This is an empirical fact, based on observation rather than theory. Since A, B, and C are all in thermal equilibrium, it is reasonable to say each of these systems shares a common value of some property. We call this property temperature. Generally, it is not convenient to place any two arbitrary systems in thermal contact to see if they are in thermal equilibrium and thus have the same temperature. Also, it would only provide an ordinal scale. Therefore, it is useful to establish a temperature scale based on the properties of some reference system. Then, a measuring device can be calibrated based on the properties of the reference system and used to measure the temperature of other systems. One such reference system is a fixed quantity of gas. The ideal gas law indicates that the product of the pressure and volume (P · V) of a gas is directly proportional to the temperature:
Temperature in gasesAs mentioned previously for a monatomic ideal gas the temperature is related to the translational motion or average speed of the atoms. The Kinetic theory of gases uses Statistical mechanics to relate this motion to the average kinetic energy of atoms and molecules in the system. For this case 11300 degrees Celsius corresponds to an average kinetic energy of one electronvolt; to take room temperature (300 kelvin) as an example, the average energy of air molecules is 300/11300 eV, or 0.0273 electronvolts. This average energy is independent of particle mass, which seems counterintuitive to many people. Although the temperature is related to the average kinetic energy of the particles in a gas, each particle has its own energy which may or may not correspond to the average. In a gas the distribution of energy (and thus speeds) of the particles corresponds to the Boltzmann distribution. An electronvolt is a very small unit of energy, on the order of 1.602e-19 joules.Temperature of the vacuum\nA system in a vacuum will radiate its thermal energy, i.e. convert heat into electromagnetic waves. It will do so until an equilibrium with the vacuum is found. This equilibrium will not be at 0 K if the vacuum is filled with electromagnetic waves. Conversely, the system can absorb energy from the vacuum if it contains intense electronic waves. At equilibrium, the radiation's spectrum will be the same as the radiation of a black body at the equilibrium temperature, so that one can say that the vacuum has that temperature. Far from equilibrium, the spectrum usually have very different shapes, and one temperature cannot be assigned to the vacuum anymore. Sometimes, a part of the spectrum follows that shape: for example one can say that the cosmic microwave background radiation, a part of the cosmic radiation, has a temperature of about 3 K.Second-Law definition of temperatureIn the previous section temperature was defined in terms of the Zeroth Law of thermodynamics. It is also possible to define temperature in terms of the second law of thermodynamics, which deals with entropy. Entropy is a measure of the disorder in a system. The second law states that any process will result in either no change or a net increase in the entropy of the universe. This can be understood in terms of probability. Consider a series of coin tosses. A perfectly ordered system would be one in which every coin toss would come up either heads or tails. For any number of coin tosses, there is only one combination of outcomes corresponding to this situation. On the other hand, there are multiple combinations that can result in disordered or mixed systems, where some fraction are heads and the rest tails. As the number of coin tosses increases, the number of combinations corresponding to imperfectly ordered systems increases. For a very large number of coin tosses, the number of combinations corresponding to ~50% heads and ~50% tails dominates and obtaining an outcome significantly different than 50/50 becomes extremely unlikely. Thus the system naturally progresses to a state of maximum disorder or entropy. Now, we have stated previously that temperature controls the flow of heat between two systems and we have just shown that the universe, and we would expect any natural system, tends to progress so as to maximize entropy. Thus, we would expect there to be some relationship between temperature and entropy. In order to find this relationship let's first consider the relationship between heat, work and temperature. A Heat engine is a device for converting heat into mechanical work and analysis of the Carnot heat engine provides the necessary relationships we seek. The work from a heat engine corresponds to the difference between the heat put into the system at the high temperature, qH and the heat ejected at the low temperature, qC. The efficiency is the work divided by the heat put into the system or:
Negative temperaturesAt low temperatures, particles tend to move to their lowest energy states. As you increase the temperature, particles move into higher and higher energy states. As the temperature becomes infinite, the number of particles in the lower energy states and the higher energy states becomes equal. In some situations, it is possible to create a system in which there are more particles in the higher energy states than in the lower ones. This situation can be described with a negative temperature. A negative temperature is not colder than absolute zero, but rather\nit is hotter than infinite temperature. The previous section described how heat is stored in the various translational, vibrational, rotational, electronic, and nuclear modes of a system. The macroscopic temperature of a system is related to the total heat stored in all of these modes and in a normal system thermal energy is constantly being exchanged between the various modes. However, for some cases it is possible to isolate one or more of the modes. In practice the isolated modes still exchange energy with the other modes, but the time scale of this exchange is much slower than for the exchanges within the isolated mode. One example is the case of nuclear spins in a strong external magnetic field. In this case energy flows fairly rapidly among the spin states of interacting atoms, but energy transfer between the nuclear spins and other modes is relatively slow. Since the energy flow is predominantly within the spin system, it makes sense to think of a spin temperature that is distinct from the temperature due to other modes. Based on Equation 7, we can say a positive temperature corresponds to the condition where entropy increases as thermal energy is added to the system. This is the normal condition in the macroscopic world and is always the case for the translational, vibrational, rotational, and non-spin related electronic and nuclear modes. The reason for this is that there are an infinite number of these types of modes and adding more heat to the system increases the number of modes that are energetically accessible, and thus the entropy. However, for the case of electronic and nuclear spin systems there are only a finite number of modes available (often just 2, corresponding to spin up and spin down). In the absence of a magnetic field, these spin states are degenerate, meaning that they correspond to the same energy. When an external magnetic field is applied, the energy levels are split, since those spin states that are aligned with the magnetic field will have a different energy than those that are anti-parallel to it. In the absence of a magnetic field, one would expect such a two-spin system to have roughly half the atoms in the spin-up state and half in the spin-down state, since this maximizes entropy. Upon application of a magnetic field, some of the atoms will tend to align so as to minimize the energy of the system, thus slightly more atoms should be in the lower-energy state (for the purposes of this example we'll assume the spin-down state is the lower-energy state). It is possible to add energy to the spin system using radio frequency (RF) techniques. This causes atoms to flip from spin-down to spin-up. Since we started with over half the atoms in the spin-down state, initially this drives the system towards a 50/50 mixture, so the entropy is increasing, corresponding to a positive temperature. However, at some point more than half of the spins are in the spin-up position. In this case adding additional energy, reduces the entropy since it moves the system further from a 50/50 mixture. This reduction in entropy with the addition of energy corresponds to a negative temperature.See also\n*Maxwell's demonExternal linksCategory:Thermodynamics\nCategory:Meteorology\nCategory:Physical quantity \n \n\n \n \n \n \n \n \n \n\n\n \n\n |
||
"I don't know why we are here, but I'm pretty sure that it is not in order to enjoy ourselves." - Ludwig Wittgenstein (1889-1951) |
