The definition of adiabatic change of state given in the introduction covers many types of thermodynamic processes, including those which are not quasi-static. When reading various textbooks, a different impression can arise, since adiabatic changes of state are often considered there only in connection with quasi-static processes in simple systems.
According to the definition, in the case of an adiabatic change of state, energy may only be added to or removed from the thermodynamic system by means of mechanical, electrical or magnetic work; the system must be insulated against heat flows of any form; ideally, there must be no heat conduction, no convective heat transfer and no heat radiation between the system and the outside world.
In reality, complete thermal isolation is not achievable, but real processes can be adiabatic to a good approximation if
- they take place in a well-insulated container, such as a Dewar vessel or an adiabatic calorimeter,
- the change of state is so rapid that little heat can flow in or out in the short time (e.g. in a combustion engine, in an air pump or in sound propagation) or
- the volume of the system is very large, so that heat flows at its edge play practically no role (e.g. in the case of thermally rising air parcels).
Compression and expansion of gases
The compression of air in an air pump is approximately an adiabatic change of state. The work done on the pump increases the internal energy of the air, and thus the temperature of the air also increases. With rapid repetitive compression, such as when inflating a bicycle tire, the increase in temperature at the pump can be readily felt. The additional internal energy is also colloquially known as compression heat or heat of compression.
With a pneumatic lighter, air is quickly compressed to less than one-twentieth of its original volume. The air becomes so hot that the stored tinder glows and can then be used to start a fire.
Conversely, if internal energy is converted into volume work during an expansion of a volume of air, the temperature of the expanding gas falls. The cooling of air masses during thermal uplift or during ascent at mountain edges is well known. Adiabatic expansion and thus cooling of the air also occurs on the upper surface of wings of commercial aircraft, see Dynamic lift. The cooling becomes visible when the saturation concentration, which decreases with temperature, falls below the existing humidity and cloud or fog formation occurs.
The Gay-Lussac experiment is also an adiabatic change of state. However, during the expansion of the gas, no internal energy is converted into external work. The process is not quasi-static; only at the beginning and end is the system in thermodynamic equilibrium. Ideal gases do not change their temperature during this process.
Friction
It is an adiabatic change of state when frictional work is performed on a thermally isolated system and the system is in thermodynamic equilibrium at the beginning and end of the work process.
The experimental procedure in the classical experiment to determine the heat equivalent by James Prescott Joule is one such process. Joule's system consisted of a copper tank with water and an integrated stirrer. Via the stirrer and a device with weights, a precisely measurable mechanical work was transformed into internal energy of the system (mainly water). Joule measured the temperature before and after the friction work. In his 1850 experimental report, he also discusses his arrangements for thermal insulation of the system.
Instead of a defined amount of mechanical work, a measured amount of electrical work
can also be performed on a system, for example to determine the heat capacity of a substance. The stirrer is replaced by an electric heater; the thermodynamic system consists of a container, the substance and the heater. For thermal isolation, the system is best located in a Dewar vessel or an adiabatic calorimeter. If the system is in thermodynamic equilibrium before and after the introduction of the electrical energy, this is an adiabatic change of state.
Electrochemical cell
An accumulator as a thermodynamic system can deliver energy in the form of electrical work to the outside or energy can be supplied to it by means of electrical work from the outside, depending on the direction of the current in the electrical supply lines. The supply or withdrawal of electrical energy leads to a change in the amounts of material at the electrodes. If the accumulator is thermally insulated by an adiabatic calorimeter in the process, adiabatic changes of state are involved. Since ohmic losses always occur during the process, the system heats up to a greater or lesser extent. Because of these ohmic losses alone, the change of state is not reversible. Such adiabatic changes of state are induced and measured, for example, during safety tests of batteries.
integration of systems
In thermodynamics, adiabatic changes of state are often considered, in which the initial state consists of two systems, each of which is in thermodynamic equilibrium. The two systems are considered as a single composite system. The change of state occurs when the systems are connected to each other without any work and then interact with each other; for example, through a thermal contact or by removing a partition between the systems - e.g. opening a separating valve. The processes involved are irreversible and can be very violent. The change is complete when the entire system no longer changes after the coupling, i.e. has found a new thermodynamic equilibrium.
In order for the change of state to be adiabatic the composite system must be thermally isolated from the environment, Dewar vessels or adiabatic calorimeters are suitable for this purpose. Some examples of such changes of state follow:
- Determination of the heat of solution: One system consists of a known quantity of water and the other of a known quantity of common salt. Both systems have room temperature. Then the salt is added to the water - coupling of the systems. It dissolves in the water, then the temperature of the salt solution is measured.
- Neutralization heat determination: Let one system be an acid and the other an alkali. Then the acid and alkali are carefully stirred together and the temperature of the mixture is followed until it does not change. From the temperature change and the amounts of substance, the heat of neutralization can be determined.
- Chemical reaction: At the beginning a system of two moles of hydrogen and a system with one mole of oxygen are given. If a separating valve is opened between the two systems, an oxyhydrogen mixture is produced, which eventually reacts to form water. In the final state, the system consists of water.
- Phases in equilibrium: One system is water in the liquid phase, the second is water vapour in a container. After a connection of the two systems, an equilibrium is established between the liquid and the gaseous phase.
Heat equalization between two systems
Let A and B be two simple systems, separated at the start of the process and each in thermal equilibrium. A has a higher temperature than B.
- Irreversible heat balance: If the systems are pushed together so that they touch, or if they are thermally connected to each other via a copper wire, heat flows irreversibly from system A to system B until both systems have the same final temperature.
- Reversible heat balance: If the heat energy is transported from the warmer to the colder system by an ideal heat engine - Carnot process - the temperatures of the systems approach each other. In this process, in addition to the heat transfer, work is done by the overall system, i.e. energy is extracted from it. If this process is repeated until the temperatures of the two systems are equal, the final temperature is lower than in the case of irreversible heat exchange, since the energy of the overall system has decreased, but the entropy has remained the same. Conversely, the temperature difference between systems A and B can also be increased again if, with the supply of external work, the machine between the systems is operated as a heat pump.