In a closed system, no mass may be transferred in or out of the system boundaries. The system will always contain the same amount of matter, but heat and work can be exchanged across the boundary of the system. Whether a system can exchange heat, work, or both is dependent on the property of its boundary.
- Adiabatic boundary – not allowing any heat exchange
- Rigid boundary – not allowing exchange of work
One example is fluid being compressed by a piston in a cylinder. Another example of a closed system is a bomb calorimeter, a type of constant-volume calorimeter used in measuring the heat of combustion of a particular reaction. Electrical energy travels across the boundary to produce a spark between the electrodes and initiates combustion. Heat transfer occurs across the boundary after combustion but no mass transfer takes place either way.
Beginning with the first law of thermodynamics for an open system, this is expressed as:
where U is internal energy, Q is heat transfer, W is work, and since no mass is transferred in or out of the system, both expressions involving mass flow, , zeroes, and the first law of thermodynamics for a closed system is derived. The first law of thermodynamics for a closed system states that the amount of internal energy within the system equals the difference between the amount of heat added to or extracted from the system and the work done by or to the system. The first law for closed systems is stated by:
- dU = δQ − δW
where U is the average internal energy within the system, Q is the heat added to or extracted from the system and W is the work done by or to the system.
Substituting the amount of work needed to accomplish a reversible process, which is stated by:
- δW = PdV
where P is the measured pressure and V is the volume, and the heat required to accomplish a reversible process stated by the second law of thermodynamics, the universal principle of entropy, stated by:
- δQ = TdS
where T is the absolute temperature and S is the entropy of the system, derives the fundamental thermodynamic relationship used to compute changes in internal energy, which is expressed as:
- δU = TdS − PdV
For a simple system, with only one type of particle (atom or molecule), a closed system amounts to a constant number of particles. However, for systems which are undergoing a chemical reaction, there may be all sorts of molecules being generated and destroyed by the reaction process. In this case, the fact that the system is closed is expressed by stating that the total number of each elemental atom is conserved, no matter what kind of molecule it may be a part of. Mathematically:
where Nj is the number of j-type molecules, aij is the number of atoms of element i in molecule j and bi0 is the total number of atoms of element i in the system, which remains constant, since the system is closed. There will be one such equation for each different element in the system.
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