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First Law of Thermodynamics A series of Experiments carried out by Joule between 1843 and 1848 from the basis for the First Law of Thermodynamics The following are the observations during the Paddle Wheel experiment shown in Fig. 6.1.

Work done on the system by lowering the mass m through Temperature of the system was found to increase System was brought into contact with a water bath System was allowed to come back to initial state Energy is transferred as heat from the system to the bath

= change in PE of m

The system thus executes a cycle which consists of work input to the system followed by the transfer of heat from the system.

Whenever a system undergoes a cyclic change, however complex the cycle may be, the algebraic sum of the work transfer is equal to the algebraic sum of the energy transfer as heat (FIRST LAW OF THERMODYNAMICS).

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Work done by a system on its surroundings is treated as a positive quantity. Energy transfer as heat to a system from its surroundings is treated as a positive quantity

or,

Heat is Path Function Lets us consider following two cycles: 1a2b1 and la2cl and apply the first law of thermodynamics Eq to get

or,

Subtracting Eq. (6.4) from Eq. (6.3)

Since, work depends on the path

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Therefore,

Energy transfer as heat is not a point function, neither is it a property of the system. Heat interaction is a path function. Energy is a Property of the System Refer to Figure 6.2 again and consider Eq. (6.5)

and the processes

depend on path function followed by the system. The quantity and connecting the states 2 and 1. The quantity

is the same for both does not depend on path is an exact differential.

followed by the system, depends on the initial and final states. Hence

Differential of property of the system This property is the internal energy of system, E

Energy of an Isolated System An isolated system is one in which there is no interaction of the system with the surroundings. For an isolated system

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A Perpetual Motion Machine of First Kind Thermodynamics originated as a result of man's endeavour to convert the disorganized form of energy (internal energy) into organized form of energy (work). (6.11) An imaginary device which would produce work continuously without absorbing any energy from its surroundings is called a Perpetual Motion Machine of the First kind, (PMMFK). A PMMFK is a device which violates the first law of thermodynamics. It is impossible to devise a PMMFK (Figure 6.3)

The converse of the above statement is also true, i.e., there can be no machine which would continuously consume work without some other form of energy appearing simultaneously. Analysis of Closed System Let us consider a system that refers to a definite quantity of matter which remains constant while the system undergoes a change of state. We shall discuss the following elementary processes involving the closed systems.

Constant Volume Process Our system is a gas confined in a rigid container of volume V (Refer to Figure)

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Let the system be brought into contact with a heat source. The energy is exchanged reversibly. The expansion work done (PdV) by the system is zero. Applying the first law of thermodynamics, we get

or,

Hence the heat interaction is equal to the change in the internal energy of the system.

Constant Volume Adiabatic Process Refer to Figure where a change in the state of the system is brought about by performing paddle wheel work on the system.

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The process is irreversible. However, the first law gives

or

Interaction of heat and irreversible work with the system is same in nature. (-W) represents the work done on the system by the surroundings Specific Heat at Constant Volume By definition it is the amount of energy required to change the temperature of a unit mass of the substance by one degree.

While the volume is held constant. For a constant volume process, first law of thermodynamics gives

Therefore,

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Where is the specific internal energy of the system. If heat at constant volume

varies with temperature, one can use mean specific

The total quantity of energy transferred during a constant volume process when the system temperature changes from

The unit for

is kJ/kgK. The unit of molar specific heat is kJ/kmolK.