Archive for May, 2015


Reversible change is a key concept in classical thermodynamics. It is important to understand what is meant by the term as it is closely allied to other important concepts such as equilibrium and entropy. But reversible change is not an easy idea to grasp – it helps to be able to visualize it.

Reversibility and mechanical systems

The simple mechanical system pictured above provides a useful starting point. The aim of the experiment is to see how much weight can be lifted by the fixed weight M1. Experience tells us that if a small weight M2 is attached – as shown on the left – then M1 will fall fast while M2 is pulled upwards at the same speed.

Experience also tells us that as the weight of M2 is increased, the lifting speed will decrease until a limit is reached when the weight difference between M2 and M1 becomes vanishingly small and the pulley moves infinitely slowly, as shown on the right.

We now ask the question – Under what circumstances does M1 do the maximum lifting work? Clearly the answer is visualized on the right, where the lifted weight M2 is as close as we can imagine to the weight of M1. In this situation the pulley moves infinitely slowly (like a nanometer in a zillion years!) and is indistinguishable from being at rest.

This state of being as close to equilibrium as we can possibly imagine is the condition of reversible change, where the infinitely slow lifting motion could be reversed by an infinitely small nudge in the opposite direction.

From this simple mechanical experiment we can draw an important conclusion: the work done under reversible conditions is the maximum work that the system can do.

Any other conditions i.e. when the pulley moves with finite, observable speed, are irreversible and the work done is less than the maximum work.

The irreversibility is explained by the fact that observable change inevitably involves some dissipation of energy, making it impossible to reverse the change and exactly restore the initial state of the system and surroundings.

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Reversibility and thermodynamic systems

The work-producing system so far considered has been purely mechanical – a pulley and weights. Thermodynamic systems produce work through different means such as temperature and pressure differences, but however the work is produced, the work done under reversible conditions is always the maximum work that a system can do.

In thermodynamic systems, heat q and work w are connected by the first law relationship


What this equation tells us is that for a given change in internal energy (ΔU), both the heat absorbed and the work done in a reversible change are the maximum possible. The corresponding irreversible process absorbs less heat and does less work.

It helps to think of this in simple numbers. U is a state function and therefore ΔU is a fixed amount regardless of the way the change is carried out. Say ΔU = 2 units and the reversible work w = 4 units. The heat q absorbed in this reversible change is therefore 6 units. These must be the maximum values of w and q, because ΔU is fixed at 2; for any other change than reversible change, w is less than 4 and so q is less than 6.

For an infinitesimal change, the inequality in relation to q can be written


and so for a change at temperature T


The term on the left defines the change in the state function entropy


Since reversible conditions equate to equilibrium and irreversible conditions equate to observable change, it follows that


These criteria are fundamental. They are true for all thermodynamic processes, subject only to the restriction that the system is a closed one i.e. there is no mass transfer between system and surroundings. It is from these expressions that the conclusion can be drawn – as famously stated by Clausius – that entropy increases towards a maximum in isolated systems.

Rudolf Clausius (1822-1888)

Rudolf Clausius (1822-1888)

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Die Entropie der Welt strebt einem Maximum zu

Consider an adiabatic change in a closed system: dq = 0 so the above criteria for equilibrium and observable change become dS = 0 and dS > 0 respectively. If the volume is also kept constant during the change, it follows from the first law that dU = 0. In other words the volume and internal energy of the system are constant and so the system is isolated, with no energy or mass transfer between system and surroundings.

Under these circumstances the direction of observable change is such that entropy increases towards a maximum; when there is equilibrium, the entropy is constant. The criteria for these conditions may be expressed as follows


The assertion that entropy increases towards a maximum is true only under the restricted conditions of constant U and V. Such statements as “the entropy of the universe tends to a maximum” therefore depend on assumptions, such as a non-expanding universe, that are not known to be fulfilled.

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