Heat capacity
Also see Specific heat capacity.
Temperature is related to the amount of thermal energy or heat in a system. As heat is added to the system, the temperature increases by an amount proportional to the amount of heat being added. The constant of proportionality is called the heat capacity and reflects the ability of the material to store heat.
The heat is stored in a variety of modes, corresponding to the various quantum states accessible to the system. As the temperature increases more quantum states become accessible, resulting in an increase in heat capacity. For a monatomic gas at low temperatures, the only accessible modes correspond to the translational motion of the atoms, so all of the energy is due to movement of the atoms (Actually, a small amount of energy, called the Zero Point Energy arises due to the confinement of the gas into a fixed volume, this energy is present even at 0 K). Since the kinetic energy is related to the motion of the atoms, 0 K corresponds to the point at which all atoms are motionless. For such a system, a temperature below 0 K is not possible, since it is not possible for the atoms to move slower than to be motionless.
At higher temperatures, electronic transitions become accessible, further increasing the heat capacity. For most materials these transitions are not important below 104 K, however for a few common molecules, such transitions are important even at room temperature. At extremely high temperatures (>108 K) nuclear transitions become accessible. In addition to translational, electronic, and nuclear modes, polyatomic molecules also have modes associated with rotation and vibrations along the molecular bonds, which are accessible even at low temperatures. In solids most of the stored heat corresponds to atomic vibrations.
Negative Temperatures
At 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
it 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. For additional information see [1].
Temperature in gases
As 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 Measurement
Many methods have been developed for measuring temperature. Most of these rely on measuring some physical property of a working material that varies with temperature. One of the most common devices for measuring temperature is the glass thermometer. This consists of a glass tube filled with mercury or some other liquid, which acts as the working fluid. Temperature increases cause the fluid to expand, so the temperature can be determined by measuring the volume of the fluid. Such thermometers are usually calibrated, so that one can read the temperature, simply by observing the level of the fluid in the thermometer. Another type of thermometer that is not really used much in practice, but is important from a theoretical standpoint is the gas thermometer mentioned previously.
Other important devices for measuring temperature include:
One must be careful when measuring temperature to ensure that the measuring instrument (thermometer, thermocouple, etc) is really the same temperature as the material that is being measured. Under some conditions heat from the measuring instrument can cause a temperature gradient, so the measured temperature is different from the actual temperature of the system. In such a case the measured temperature will vary not only with the temperature of the system, but also with the heat transfer properties of the system. An extreme case of this effect gives rise to the wind chill factor, where the weather feels colder under windy conditions than calm conditions even though the temperature is the same. What is happening is that the wind increases the rate of heat transfer from the body, resulting in a larger reduction in body temperature for the same ambient temperature.
See also: color temperature, Timeline of temperature and pressure measurement technology, Planck temperature
Articles about temperature ranges:
External links