DIRECTION OF THERMODYNAMIC PROCESSES

Thermodynamic processes that occur in nature are all irreversible processes.

Irreversible Process

An irreversible process is a process that is not reversible. All real processes are irreversible. Irreversible processes occur because of the following: a. Friction b. Unrestrained expansion of gases c. Heat transfer through a finite temperature difference d. Mixing of two different substances e. I 2R losses in electrical circuits f. Any deviation from a quasi-equlibrium process

Irreversibility:

Once a system creates thermal energy, that system will never by itself (spontaneously) be able to return to its previous condition. There is an irreversibility about any process that creates thermal energy.

Reversible Processes A reversible process is a quasi-equilibrium, or quasi-static, process with a more restrictive requirement. (equilibrium process - the system is always in thermodynamic equilibrium) Internally reversible process The internally reversible process is a quasi-equilibrium process, which, once having taken place, can be reversed and in so doing leave no change in the system. This says nothing about what happens to the surroundings about the system.

Totally or externally reversible process

The externally reversible process is a quasi-equilibrium process, which, once having taken place, can be reversed and in so doing leave no change in the system or surroundings.

DISORDER and THERMODYNAMIC PROCESSES

 heat transfer involves changes in energy towards a random, disordered molecular motion.
conversion of mechanical energy to heat involves an increase of randomness or disorder.

SECOND LAW OF THERMODYNAMICS

ENGINE STATEMENT of the SECOND LAW OF THERMODYNAMICS (KELVIN PLANCK STATEMENT)

It is impossible for any system to undergo a process in which it absorbs heat from a reservoir at a single temperature and converts the heat completely into mechanical work, with the system ending in the same state in which it began.

Heat engines use a portion of the thermal energy that flows naturally from a high to a low temperature and convert it to work. ====>

A schematic representation of a heat engine. Heat is taken in at high temperatures, TH. Some heat is converted to work, and the remainder is released at a lower temperature, TC.

 The basis of this is the difference between the nature of internal energy and that of macroscopic mechanical energy. Since we cannot control the motions of molecules, we cannot convert this random motion COMPLETELY back to organized motion. We can convert PART of it, and this is what a heat engine does.

 The first law denies the possibility of creating or destroying energy; the second law limits the availability of energy and the ways in which it can be used and converted.

REFRIGERATOR STATEMENT of the SECOND LAW OF THERMODYNAMICS

(CLAUSIUS STATEMENT)

It is impossible for any process to have as its sole result the transfer of heat from a cooler to a hotter body.

 Heat will not flow spontaneously from a cold to a hot body. Thermal energy flows spontaneously (without external assistance) from a higher temperature object to a lowertemperature object. * It will not spontaneously flow the other way!

Perpetual-Motion Machines
Any device that violates the first or second law of thermodynamics is called a perpetual-motion machine. If the device violates the first law, it is a perpetualmotion machine of the first kind. If the device violates the second law, it is a perpetual-motion machine of the second kind.

ENTROPY STATEMENT of the SECOND LAW OF THERMODYNAMICS

The entropy of an isolated system can only increase (irreversible) or remain constant (reversible process) . Its entropy cannot decrease.

When a box of hot gas & cold gas are allowed to mix . ..
. . . eventually the faster molecules striking the slower molecules spread out some of their energy to the slower molecules . . .

However, the molecules will NOT spontaneously re arrange . . . .leading to a wider range of re-themselves into a hot cold speed and an intermediate temperature in the box.

The Second Law of Thermodynamics The total entropy of the universe increases if a process is spontaneous. For a phase change at the transition temperature (ice melting/freezing at 0 C) the system is in equilibrium. At equilibrium there is no entropy created. The entropy created is always a positive number.

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