Chemical thermodynamics

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  1. Chemical thermodynamics is the study of the interrelation of heat and work with chemical reactions or with physical changes of state within the confines of the laws of thermodynamics. Chemical thermodynamics involves not only laboratory measurements of various thermodynamic properties, but also the application of mathematical methods to the study of chemical questions and the spontaneity of processes.

The structure of chemical thermodynamics is based on the first two laws of thermodynamics. Starting from the first and second laws of thermodynamics, four equations called the "fundamental equations of Gibbs" can be derived. From these four, a multitude of equations, relating the thermodynamic properties of the thermodynamic system can be derived using relatively simple mathematics. This outlines the mathematical framework of chemical thermodynamics

  1. Thermodynamics, science of the relationship between heatworktemperature, 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 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.

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.

  1. For thermodynamics, a thermodynamic state of a system is its condition at a specific time, that is fully identified by values of a suitable set of parameters known as state variables, state parameters or thermodynamic variables. Once such a set of values of thermodynamic variables has been specified for a system, the values of all thermodynamic properties of the system are uniquely determined. Usually, by default, a thermodynamic state is taken to be one of thermodynamic equilibrium. This means that the state is not merely the condition of the system at a specific time, but that the condition is the same, unchanging, over an indefinitely long duration of time.

Thermodynamics sets up an idealized formalism that can be summarized by a system of postulates of thermodynamics. Thermodynamic states are amongst the fundamental or primitive objects or notions of the formalism, in which their existence is formally postulated, rather than being derived or constructed from other concepts.

  1. The central concept of thermodynamics is that of energy, the ability to do work. As stipulated by the first law, the total energy of the system and its surroundings is conserved. It may be transferred into a body by heating, compression, or addition of matter, and extracted from a body either by cooling, expansion, or extraction of matter. For comparison, in mechanics, energy transfer results from a force which causes displacement, the product of the two being the amount of energy transferred. In a similar way, thermodynamic systems can be thought of as transferring energy as the result of a generalized force causing a generalized displacement, with the product of the two being the amount of energy transferred. These thermodynamic force-displacement pairs are known as conjugate variables. The most common conjugate thermodynamic variables are pressure-volume (mechanical parameters), temperature-entropy (thermal parameters), and chemical potential-particle number (material parameters).

  1. Classical thermodynamics considers three main kinds of thermodynamic process by change in a system, cycles in a system, and flow processes.

Defined by change in a system, a thermodynamic process is a passage of a thermodynamic system from an initial to a final state of thermodynamic equilibrium. The initial and final states are the defining elements of the process. The actual course of the process is not the primary concern, and thus often is ignored. This is the customary default meaning of the term 'thermodynamic process'. In general, during the actual course of a thermodynamic process, the system passes through physical states which are not describable as thermodynamic states, because they are far from internal thermodynamic equilibrium. Such processes are useful for thermodynamic theory.

Defined by a cycle of transfers into and out of a system, a cyclic process is described bythe quantities transferred in the several stages of the cycle, which recur unchangingly. The descriptions of the staged states of the system are not the primary concern. Cyclic processes were important conceptual devices in the early days of thermodynamical investigation, while the concept of the thermodynamic state variable was being developed.

Defined by flows through a system, a flow process is a steady state of flows into and out of a vessel with definite wall properties. The internal state of the vessel contents is not the primary concern. The quantities of primary concern describe the states of the inflow and the outflow materials, and, on the side, the transfers of heat, work, and kinetic and potential energies for the vessel. Flow processes are of interest in engineering.

  1. In thermodynamics, a state functionfunction of state, or point function is a function defined for a system relating several state variables or state quantities that depends only on the current equilibrium thermodynamic state of the system[1] (e.g. gas, liquid, solid, crystal, or emulsion), not the path which the system took to reach its present state. A state function describes the equilibrium state of a system, thus also describing the type of system. For example, a state function could describe an atom or molecule in a gaseous, liquid, or solid form; a heterogeneous or homogeneous mixture; and the amounts of energy required to create such systems or change them into a different equilibrium state.

Internal energyenthalpy, and entropy are examples of state quantities because they quantitatively describe an equilibrium state of a thermodynamic system, regardless of how the system arrived in that state. In contrast, mechanical work and heat are process quantities or path functions because their values depend on the specific "transition" (or "path") between two equilibrium states. Heat (in certain discrete amounts) can describe a state function such as enthalpy, but in general does not truly describe the system unless it is defined as the state function of a certain system, and thus enthalpy is described by an amount of heat. This can also apply to entropy when heat is compared to temperature. The description breaks down for quantities exhibiting hysteresis.

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