Thermal equilibrium, a state where an object and its surroundings cease to exchange energy in the form of heat, i.e.

they are at the same temperature.** Mechanical equilibrium, the state in which the sum of the forces, and torque, on each particle of the system is zero Hydrostatic equilibrium, the state of a system in which compression due to gravity is balanced by a pressure gradient force Chemical equilibrium, the state in which the concentrations of the reactants and products have no net change over time Diffusion equilibrium, when the concentrations of the diffusing substance in the two compartments are equal Donnan equilibrium, the distribution of ion species between two ionic solutions separated by a semipermeable membrane or boundary Dynamic equilibrium, the state in which two reversible processes occur at the same rate Equilibrium constant, a quantity characterizing a chemical equilibrium in a chemical reaction Partition equilibrium, a type of chromatography that is typically used in GC Quasistatic equilibrium, the quasi-balanced state of a thermodynamic system near to equilibrium in some sense or degree Schlenk equilibrium, a chemical equilibrium named after its discoverer Wilhelm Schlenk taking place in solutions of Grignard reagents Solubility equilibrium, any chemical equilibrium between solid and dissolved states of a compound at saturation Thermodynamic equilibrium, the state of a thermodynamic system which is in thermal, mechanical, and chemical equilibrium Vapor-liquid equilibrium, where the rates of condensation and vapourization of a material are equal

The four laws of thermodynamics define fundamental physical quantities (temperature, energy, and entropy) that characterize thermodynamic systems. The laws describe how these quantities behave under various circumstances, and forbid certain phenomena (such as perpetual motion). The four laws of thermodynamics are:[1][2][3][4][5][6]

Zeroth law of thermodynamics: If two systems are both in thermal equilibrium with a third system then they are in thermal equilibrium with each other. This law helps to define the notion of temperature.

First law of thermodynamics: Heat and work are forms of energy transfer. Energy is invariably conserved, however the internal energy of a closed system may change as heat is transferred into or out of the system or work is done on or by the system. It is a convention to say that the work that is done by the system has a positive sign and connotes a transfer of energy from the system to its surroundings, while work done on the system has a negative sign. For example, changes in molecular energy (potential energy), are generally considered to remain within the system. Similarly, the rotational and vibrational energies of polyatomic molecules remain within the system. From the above, all the energy associated with a system must be accounted for as heat, work, chemical energy etc., thus perpetual motion machines of the first kind, which would do work without using the energy resources of a system, are impossible.

Second law of thermodynamics: An isolated system, if not already in its state of thermodynamic equilibrium, spontaneously evolves towards it. Thermodynamic equilibrium has the greatest entropy amongst the states accessible to the system. Perpetual motion machines of the second kind are thus impossible. Third law of thermodynamics: The entropy of a system approaches a constant value as the temperature approaches zero. The entropy of a system at absolute zero is typically zero, and in all cases is determined only by the number of different ground states it has. Specifically, the entropy of a pure crystalline substance at absolute zero temperature is zero.

nteractions of thermodynamic systems

Type of system

Mass flow Work Heat

Open

Closed

Thermally isolated

Mechanically isolated

Isolated Overview [edit] The primary objective of chemical thermodynamics is the establishment of a criterion for the determination of the feasibility orspontaneity of a given transformation.[3] In this manner, chemical thermodynamics is typically used to predict the energy exchanges that occur in the following processes: 1. Chemical reactions 2. Phase changes 3. The formation of solutions The following state functions are of primary concern in chemical thermodynamics:

Internal energy (U) Enthalpy (H) Entropy (S) Gibbs free energy (G)

Most identities in chemical thermodynamics arise from application of the first and second laws of thermodynamics, particularly the law of conservation of energy, to these state functions. The 3 laws of thermodynamics: 1. The energy of the universe is constant. 2. In any spontaneous process, there is always an increase in entropy of the universe 3. The entropy of a perfect crystal at 0 kelvins is zero Thermodynamics is the study of relationship between energy and entropy, which deals with heat and work. It is a set of theories that correlate macroscopic properties that we can measure (such as temperature, volume, and pressure) to energy and its capability to deliver work. A thermodynamic system is defined as a quantity of matter of fixed mass and identity. Everything external to the system is the surroundings and the system is separated from the surroundings by boundaries. Some thermodynamics applications include the design of:

air conditioners and refrigerators turbo chargers and superchargers in automobile engines steam turbines in power generation plants jet engines used in aircraft Zeroth Law of Thermodynamics The zeroth law of thermodynamics states that when two bodies have equality of temperature with a third body, they in turn have equality of temperature with each other. All three bodies share a common property, which is the temperature. For example: one block of copper is brought into contact with a thermometer until equality of temperature is established, and is then removed. A second block of copper is brought into contact with the same thermometer. If there is no change in the mercury level of the thermometer during this process, it can be said that both blocks are in thermal equilibrium with the given thermometer. First Law of Thermodynamics The first law of thermodynamics states that, as a system undergoes a change of state, energy may cross the boundary as either heat or work, and each may be positive or negative. The net change in the energy of the system will be equal to the net energy that crosses the boundary of the system, which may change in the form of internal energy, kinetic energy, or potential energy. The first law of thermodynamics can be summarized in the equation:

Where: is the heat transferred to the system during the process is the change in internal energy is the change in kinetic energy is the change in potential energy is the work done by the system during the process

Second Law of Thermodynamics The second law defines the direction in which a specific thermal process can take place. The second law of thermodynamics states that it impossible to construct a device that operates in a cycle and produces no effect other than the transfer of heat from a cooler body to a hotter body. The second law of thermodynamics is sometimes called the law of entropy, as it introduces the important property called entropy. Entropy can be thought of as a measure of how close a system is to equilibrium; it can also be thought of as a measure of the disorder in the system.

Vapor Compression Refrigeration Cycle One of the applications that involves thermodynamic principles is the refrigerator. The figure below is a schematic diagram of the components found in a typical refrigerator. The refrigerant enters the compressor as a slightly superheated vapor at a low pressure. It then leaves the compressor and enters the condenser as a vapor at some elevated pressure, where the refrigerant is condensed as a result of heat transfer to cooling water or to the surroundings. The refrigerant then leaves the condenser as a high-pressure liquid. The pressure of the liquid is decreased as it flows through the expansion valve and, as a result, some of the liquid flashes into vapor. The remaining liquid, now at a lower pressure, is vaporized in the evaporator as a result of heat transfer from the refrigerated space. This vapor then enters the compressor.

Reversibility A reversible process for a system is defined as a process that, once having taken place, can be reversed and leaves no change in either system or surroundings. The difference between a reversible and an irreversible process can be illustrated with the example below. Suppose a gas under pressure is contained in a cylinder fitted with a piston. The piston is locked in place with a pin. If the pin is removed, the piston is raised and forced abruptly against the stopper. Work is done by the system during this process because the piston has been raised by a certain amount. If the system has to be restored to its initial state, force has to be exerted on the piston until the pin can be reinserted. Since the pressure on the face of the piston is greater on the return stroke than on the initial stroke, the work done on the gas is greater on the return stroke than the work done by the gas in the initial process. This caused an amount of heat to be transferred from the gas to the surroundings in order that the system have the same internal energy. The fact that work was required to force the piston down and that heat was transferred to the surroundings during the reverse process makes the system an irreversible process.

Another system has a number of weights loaded on the piston at the initial state. The weights are removed from the piston one at a time, allowing gas to expand and do work in raising the weight remaining. If the process is reversed, the weight can be placed back onto the piston without any work requirement, as for each level of the piston there will be a small weight that is exactly at the level of the platform. Such a process is a reversible process. There are many factors that render a process irreversible, such as friction and unrestrained expansion. Thus, to summarize, reversible systems occur in situations when the system is essentially in equilibrium during the transition and at each step, and only an infinitesimal amount of work would be necessary to truly restore equilibrium.

Question: What is a Thermodynamic Process? What is a thermodynamic process? How do they relate to the laws of thermodynamics? Can you use them to determine the work done by a system? Answer: A system undergoes a thermodynamic process when there is some sort of energetic change within the system, generally associated with changes in pressure, volume, internal energy, temperature, or any sort of heat transfer. Major Types of Thermodynamic Processes There are several specific types of thermodynamic processes that happen frequently enough (and in practical situations) that they are commonly treated in the study of thermodynamics. Each has a unique trait that identifies it, and which is useful in analyzing the energy and work changes related to the process.

Adiabatic process - a process with no heat transfer into or out of the system. Isochoric process - a process with no change in volume, in which case the system does no work. Isobaric process - a process with no change in pressure. Isothermal process - a process with no change in temperature. It is possible to have multiple processes within a single process. The most obvious example would be a case where volume and pressure change, resulting in no change in temperature or heat transfer - such a process would be both adiabatic & isothermal. The First Law of Thermodynamics In mathematical terms, the first law of thermodynamics can be written as: delta-U = Q - W or Q = delta-U + W where

delta-U = system's change in internal energy Q = heat transferred into or out of the system. W = work done by or on the system. When analyzing one of the special thermodynamic processes described above, we frequently (though not always) find a very fortunate outcome - one of these quantities reduces to zero! For example, in an adiabatic process there is no heat transfer, so Q = 0, resulting in a very straightforward relationship between the internal energy and work: delta-Q = -W. See the individual definitions of these processes for more specific details about their unique properties. Reversible Processes Most thermodynamic processes proceed naturally from one direction to another. In other words, they have a preferred direction. Heat flows from a hotter object to a colder one. Gases expand to fill a room, but will not spontaneously contract to fill a smaller space. Mechanical energy can be converted completely to heat, but it's virtually impossible to convert heat completely into mechanical energy. However, some systems do go through a reversible process. Generally, this happens when the system is always close to thermal equilibrium, both inside the system itself and with any surroundings. In this case, infinitesimal changes to the conditions of the system can cause the process to go the other way. As such, a reversible process is also known as an equilibrium process. Example 1: Two metals (A & B) are in thermal contact and thermal equilibrium. Metal A is heated an infinitesimal amount, so that heat flows from it to metal B. This process can be

reversed by cooling A an infinitesimal amount, at which point heat will begin to flow from B to A until they are once again in thermal equilibrium. Example 2: A gas is expanded slowly and adiabatically in a reversible process. By increasing the pressure by an infinitesimal amount, the same gas can compress slowly and adiabatically back to the initial state. It should be noted that these are somewhat idealized examples. For practical purposes, a system that is in thermal equilibrium ceases to be in thermal equilibrium once one of these changes is introduced ... thus the process is not actually completely reversible. It is anidealized model of how such a situation would take place, though with careful control of experimental conditions a process can be carried out which is extremely close to being fully reversible. Irreversible Processes & The Second Law of Thermodynamics Most processes, of course, are irreversible processes (or nonequilibrium processes). Using the friction of your brakes do work on your car is an irreversible process. Letting air from a balloon release into the room is an irreversible process. Placing a block of ice onto a hot cement walkway is an irreversible process. Overall, these irreversible processes are a consequence of the second law of thermodynamics, which is frequently defined in terms of the entropy, or disorder, of a system. There are several ways to phrase the second law of thermodynamics, but basically it places a limitation on how efficient any transfer of heat can be. According to the second law of thermodynamics, some heat will always be lost in the process, which is why it is not possible to have a completely reversible process in the real world. Heat Engines, Heat Pumps, & Other Devices We call any device which transforms heat partly into work or mechanical energy a heat engine. A heat engine does this by transferring heat from one place to another, getting some work done along the way. Using thermodynamics, it is possible to analyze the thermal efficiency of a heat engine, and that is a topic covered in most introductory physics courses. Here are some heat engines which are frequently analyzed in physics courses:

Internal-Combusion Engine - A fuel-powered engine such as those used in automobiles. The "Otto cycle" defines the thermodynamic process of a regular gasoline engine. The "Diesel cycle" refers to Diesel powered engines. Refrigerator - A heat engine in reverse, the refrigerator takes heat from a cold place (inside the refrigerator) and transfers it to a warm place (outside the refrigerator). Heat Pump - A heat pump is a type of heat engine, similar to a refrigerator, which is used to heat buildings by cooling the outside air.

The Carnot Cycle In 1924, French engineer Sadi Carnot created an idealized, hypothetical engine which had the maximum possible efficiency consistent with the second law of thermodynamics. He arrived at the following equation for his efficiency, eCarnot: eCarnot = ( TH - TC) / TH TH and TC are the temperatures of the hot and cold reservoirs, respectively. With a very large temperature difference, you get a high efficiency. A low efficiency comes if the temperature difference is low. You only get an efficiency of 1 (100% efficiency) if TC = 0 (i.e. absolute value) which is impossible.