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The Laws of Thermodynamics

The Zeroth Law when two bodies have equality of temperature with a third body, they in turn have equality of temperature with each other True and seemingly intuitive, but it cannot be derived from other laws. As it precedes the First and Second Law it is calledthe Zeroth Law. The First Law Commonly known as the Law of Conservation of Energy, this Law can be stated crudely as energy can neither be created nor destroyed but only changed from one form to another. However, when expressed thus it is not strictly true, a well known exception being the equivalence of matter and energy: As shown by Einstein, mass has an energy equivalent given by E = MC2. More rigorous treatment of the First Law is facilitated by defining a system (a fixed quantity of matter) or a control volume (a fixed volume in space) to which to apply the Law. There are two distinct types of process considered in thermodynamic analysis of systems cycles, in which the system is returned to its initial state at the end of the cycle; and state changes in which a system undergoes a specified change in its thermodynamic state.

The First Law Applied to a System Undergoing a cycle: The first Law states, during any cycle a system undergoes the cyclic integral (sum) of the heat is equal to the cyclic integral of the work. Note that the equality depends upon using the same units for heat and work, as is done in the SI system. The first Law as applied to a cycle can thus be written:

Q = W

(1)

The First Law Applied to a Change in State of a System Applying the first law to a change in state is considerably more involved as it becomes necessary to account for different forms of energy. The first step is to establish the existence of a thermodynamic property E the energy of a system.

1 A B

2 V

Figure 1. Processes undergone by a system This is most easily done by formally analysing the system depicted in Fig. 1. The system changes between states 1 and 2 by three different paths, which can be linked to form two different cyclic systems (A followed by B or C followed by B). Each cyclic system must obey the First Law as defined above, giving:

Q A + Q B = W A + W B
1 2 1 2

(2) A followed by B

Q + Q
C 1 2

= W C + W B
1 2

(3) C followed by B

Subtracting the second equation (2) from the first (3) we have:

QC Q A = WC + W A
1 2 1 2

(4)

Which rearranges to give:

(Q W )
1

= (Q W ) A
1

(5)

As both sides of equation (5) describe cyclic systems around the same two end states by different thermodynamic paths, we can conclude that the quantity (Q W ) is a property of the end state, independent of path, and hence the differential of a property of the system. Thus the thermodynamic property E can be defined:
E = Q W

Integrating up to a given state from a reference state (not generally important as we typically deal with changes between specified states, but the topic of the Third Law), hence gives the sum of all the energy of the system in that state.

The system energy is usually split into three terms as follows: E = Internal Energy + Kinetic Energy + Potential Energy The latter two terms are associated with the choice of coordinate system and are specified by the macroscopic parameters mass, velocity and elevation. The internal energy includes all other forms of energy and is associated with the thermodynamic state of the system. It is in the definition of System Energy that rigorous consideration of all phenomena can be performed (i.e. including nuclear mass changes, magnetic effects, etc), but for most thermodynamic analyses these are not significant. Hence the First Law of Thermodynamics for a change of state may be written:

Q = U + ( KE ) + ( PE ) + W
Where indicates a change in a system property and a change in a transferred quantity. Q represents heat, U internal energy, KE Kinetic Energy, PE potential Energy and W work.

The First Law Applied to a Control Volume In order to apply the First Law to a control volume we must consider variation of a system with time. Consider the system shown in Fig. 2 at time (t) and time (t+t).
pi
mi

Wx me mcv Ecv Mcv+mcv Ecv+Ecv

pe

(vi, ei)

(ve, ee)

Time (t)

Time (t+t) Control Volume System Boundary

Figure 2. System and Control Volume At time (t) the control volume contains mass mcv and energy Ecv and, at time (t+t), these have increased to (m+mcv) and (E+Ecv). Note that properties are not necessarily constant throughout the control volume and that the energy includes contributions from internal, potential and kinetic sources.

To be continued.

Reference: [1] R.E. Sonntag & G.J. Van Wylen, Introduction to Thermodynamics, John Wiley & Sons, Inc, 1991.

Ben Todd 2002 Last Updated: December 3, 2002