1 Introduction

1.1 What is thermodynamics?

1.1.1 Historical perspective There was a time, not so long ago, when a new technology was in the process of changing the world: the way business and human interactions were being fundamentally changed. Vast national networks were being constructed at great expense to take advantage of this new technology. Fortunes were won and lost and a new wealthy elite was formed due to the success of this new technology and scientists and engineers at the worlds most prestigious institutions were scrambling to study this new technology in order to harness, understand, and improve this new technology. The world would never the same. What am I talking about? The internet perhaps? Well, no, Im talking about the steam engine in the late 1800s. With steam engines came railroads, the ability to go from New York to San Francisco without passing Antartica, and the onset of the industrial revolution. Clearly life was never the same. Clearly steam engines were the heart of this revolution, and it took a principle place in this advance. Thus, understanding steam engines was the biotechnology or nanotechnology of its day. And like these elds, there were numerous surprises in our study of this new eld. While steam engines may seem to be common place, there were fundamental physical insights missing at that time. These fundamental insights arose from understanding how heat moves and this eld in general is thus called thermodynamics. However, if thermodynamics was only relevant for steam engines, none of us would be studying it today. As we will see, thermodynamics is at the heart of many important areas of modern science, including biotechnology and nanotechnology and the mysteries rst seen with steam engines are as important, relevant, and as counter intuitive now as they were then. 1.1.2 What can thermodynamics tell us? Thermodynamics is a theory which gives us a set of relations between macroscopic properties we can measure (temperature, volume, pressure, length). Whats really remarkable about it is that it requires no assumptions about the nature of the underlying molecules (or even that molecules exist!). Thus, it is really very powerful, especially in cases where one does not know the molecular nature of the system of interest or if this nature is very complicated. Traditional (boring?) examples: Modern examples:

air conditioners, refrigerators gases, liquids pressure cookers

Many of these questions revolve around understanding the nature of a reaction, i.e.

which could be

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or etc.

What is the nal result of the reaction (do we get products or reactants and in what concentrations)? How can we drive the reaction in the direction we want? How do these reactions depend on external conditions, such as temperature, pressure, pH, ionic concentrations, etc? How can we quantitatively understand these systems and potentially improve upon them? These are some of the questions that thermodynamics answers. However, thermodynamics does not say anything about time. Thermodynamics will tell us what the eventual result will be, but cannot say how long the reaction will take. However, for the question above, we care more about the nal state than how we get there. In this case, thermodyanmics can yield some very powerful tools to answer these questions.

1.2 An analogy to mechanical systems

We make an analogy to mechanical systems because we have some physical intuition for these systems, and there are many concepts which carry over. Moreover, in the cases where our intuition does not carry over, that will be even more interesting and important. 1.2.1 Types of energy For example, consider someone sledding on a hill. What he cares about is that there are some forces which bring him down (and that there is a certain amount of work he has to do to climb up the hill to go again). Thus, there are three important quantities/aspects: 1. Force: In this case gravity 2. Distance: In this case how high he has to climb up in order to go sledding again 3. Work: How much work he has to do to climb up again So whats going on here? Lets consider the case of downhill and then going back up. When going down hill, potential energy is turned into kinetic energy (i.e. sledding), which is then turned into friction (heat created when the sled stops). When going up the hill, some chemical energy (breakfast) is turned into potential energy (climbing the hill). Lets use this example to review the different types of energy. Potential energy energy can be turned into some other form; it is in a sense stored energy. For the case of the sleding example, , where is the potential energy, is the mass, is the gravitational acceleration, and is the height of the hill. Kinetic energy is energy associated with motion, for example ( per degree of freedom). Heat is a third type of energy. Well talk about this in much more detail. Actually, in sense a course on thermodynamics is all about heat. In this example, we see that heat is the nal form of energy. As in mechanics, equilibrium is an important concept in thermodynamics as well. There are several, equivalent ways of understanding it. 1. point where the forces are balanced

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(a) mg

(Vi,Ti)

T
(Vf,Tf)

(b)
HEAT

V
space. In Figure 1.2: Different paths in both cases, the energy is the same, i.e. independent of path. Path independence is a hallmark property of state functions.

Figure 1.1: Different paths for lowering a block.

2. state at which the system has minimized its potential energy 3. small changes require the maximum amount of work 4. state at which the system will remain if we wait for a long time To illustrate this, consider a pendulum which has some friction at the pivot point. It will swing for a while, but eventually it will stop swinging and simply rest at the bottom. This is the equilibrium state, since it agrees with the denition above. 1.2.2 Reversibility Reversibility is a very important another concept in thermodynamics which has analogies in mechanical systems. Most processes in life are irreversible, i.e. once changed, the system does not return back to the initial condition. For example When a drop of dye is placed in a bucket of water, it spreads throughout the bucket: it rarely spontaneously comes together to form the initial droplet

If you start out with a deck of cards which is ordered (say by suite and card value) and then shufe the deck, it never (on time scales we live in) comes back to the original order

An example of a reversible system is a pendulum with no friction. In this case, the pendulum will swing back and forth forever. At the top of its swing, the pendulum has the maximum potential

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energy and no kinetic energy. At the bottom, it has the reverse: all of its potential energy has been turned into kinetic energy. The reason why this process is reversible is that there is no wasted energy: all the potential energy is turned into kinetic energy and thats precisely the amount of energy needed to bring it back to the top level. A more mathematical way to think about it is the following. One can imagine an irreversible process as follows. Lets say we have two masses and on a pulley. If the masses are equal , then the system is in equilibrium. If one mass is larger by some signicant amount, eg , then the system would quickly change (mass 1 would fall). As the mass falls a distance , this work will be (note that while mass 1 is going down, mass 2 is being pulled up!). However, we could make only a small change in , i.e. , where , then only an innitesimal quantity of work would be required to restore the system. Also, at every point during the reversible process, which is virtually indistinguishable from the equilibrium (since is so small). Thus, to summarize, reversible systems occur in situations when the system is essentially in equilibrium during the transition and at each step, only an innitesimal amount of work would be necessary to truly restore equilibrium. 1.2.3 A mystery unfolds: watching energy isnt enough! Our analogy of a sled sliding down a hill is a good one in many ways, but does seem to break down in certain situations. It is an example of an exothermic reaction, i.e. heat is given off. This occurs in the sled case since the potential energy of the sled is turned into heat by friction. This heat raises the temperature of the surroundings. However, there are endothermic reactions too. In these cases, heat is absorbed (and the temperature goes down) and the total energy goes up. In the sled example, this would be like the sled spontaneously going up hill! Clearly there is something shy here. In mechanical systems, looking for the energy minimum is enough to tell the equilibrium state of the system. Thats not the case in thermodynamic systems. Theres clearly something missing here some concept we need to add in order to explain thermodynamic systems. Thermodynamics has new ways to look at energies which clear up this seeming contradiction. However, the intuition of mechanical systems will still be with us in many ways. In particular, our rst goal is to nd some quantity analogous to the energy whose minimum, in thermodynamic systems, will be the equilibrium state.

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