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Biological Thermodynamics~Tqw~ Darksiderg Chapter 2 The First Law of Thermodynamics A. Introduction To gain a good understanding of the laws of thermodynamics, it will help to develop an appreciation of the meaning of the words law and thermodynamics. Let’s take a moment to think about these words before launching into a detailed discussion of how we might unpack the content of how the laws can be formulated. We are aided in this quest by the nature of science itself, which unlike ordinary prose and poetry aims to give words a more or less precise definition. We are familiar with the concept of law from our everyday experience. Laws are rules that we are not supposed to break; they exist to protect someone’s interests, possibly our own, and there may be a penalty to pay if the one who breaks a law gets caught. Such are civil and criminal laws. Physical laws are similar but dif- ferent. They are similar in that they regulate something, namely how matter behaves under given circumstances. They are different in that violations are not known to have occurred, and they describe what is considered to be a basic property of nature. If a violation of a physical law should ever seem to have occurred, you will think first that the experiment has gone wrong at some stage, and second that maybe the “law” isn’t a law after all. Here’s an example. Galileo,1 like Copernicus,2 believed that the orbits of the known planets were circles; the circle being the shaper of perfection and perfection being of the heavens. This view was inherited from Aristotle. Galileo also thought that the motion of 1 Galileo Galilei, Italian astronomer and physicist, lived 1564–1642. His model of the Earth, the Moon, the Sun and planets was based on that of Copernicus, who had proposed a Sun-centered planetary system in his De Revolutionibus Orbium Coelestium (1543). Galileo is widely considered the father of modern science, because he emphasized the role of observations and experimentation in the discovery of new aspects of nature. 2 Nicolaus Copernicus (1473 –1543) held an ecclesiastical position in a church in Poland and was fascinated by astronomy. 26 THEFIRST LAWOF THERMODYNAMICS celestial objects like planets was qualitatively different from the motion of terrestrial objects like cannonballs and feathers. But in fact, the orbits of planets are ellipses, not circles,3 and the mechanical laws of planetary motion are fundamentally the same as those of a missile flying through the air on a battlefield, an object rolling down an inclined plane, and an apple falling to the ground in an orchard.4 The point is not that Galileo was poor at science: his contributions to science have played an extremely important role in its development. Rather, the point is that what was considered a “law” was later shown not to be a law. (We can also see that at times a great does not get it quite right, in the best cases not through an inherent unwillingness to give all due consideration to available evidence, but because the evidence needed to change a perspective simply did not exist and was not yet sufficiently compelling.) There are many related examples one could cite from the history of sci- ence. It is the nature of human awareness of the physical world to develop in this way. It borders on the inhumane to assess the sci- entific ability of people who lived in a previous age by the standards and knowledge of today. Whereas a human can break a law intentionally or unwittingly, a basic assumption of science is that a particle cannot break a law of physics. Particle motion is governed by the laws of physics (even if we don’t know what those laws are). An important fact for us is that no violation of a law of thermodynamics is known to have occurred in nearly two hundred years of research in this area. Because of this many scientists, for example, Einstein, consider the laws of ther- modynamics to be the laws of physics least likely to be overturned or superseded by further research. The laws of thermodynamics are generally described as the most general concepts of all of modern science. It behoves the biologist to be familiar with the basic prin- ciples of thermodynamics because they are of such basic impor- tance. In view of all this, we might begin to suspect that the concepts we shall discuss are very deep and that considerable study and thought will be the price to pay for mastery of them. Thus has it ever been with basic things. Energy has been around, well, since “the beginning,” but the word thermodynamics was not coined until 1840, from the Greek roots therme, heat, and dynamis, power. The same roots appear in thermometer (a device to measure temperature, or heat) and dynamite (a powerful explosive). We can guess, then, that thermodynamics 3 This was demonstrated by the German astronomer Johannes Kepler (1571– 1630). In fact, though, the orbit of Earth is remarkably close to circular. 4 As shown by the English mathematician, natural philosopher, and alchemist Isaac Newton (1642–1727). Sir Isaac is perhaps the greatest scientist of all time. His voluminous writings show that he was apparently as interested in theology and alchemy as in mathematics and natural philosophy, i.e. science. Thomas Jefferson, principal author of the Declaration of Independence and third president of the USA, owned a copy of one of Newton’s lesser known works, Observations upon the Prophecies of Daniel. INTRODUCTION 27 will have to do with heat energy and power or movement. In fact, this branch of physics is concerned with energy storage, transfor- mation, and dissipation. Thermodynamics aims to describe and relate – in relatively simple mathematical terms – the physical properties of systems of energy and matter. Thermodynamics has very much to do with molecular motion. You might not think so, but you will certainly know something about thermodynamics. If not from having studied physics before starting university, then from having seen what happens when a pan of water is heated on the stove! At first, when the temperature of still water is about 25 C, nothing seems to be happening; the eye does not detect any motion. But when heat is applied, motion becomes more significant and indeed readily apparent, so that by the time the boiling point is reached the water is moving about rather violently! So you do know something about thermodynamics, even if you don’t normally think about it in the framework of today’s physics, and a lot was known about thermodynamics well before the word was invented. There is not space to say much about the history of thermodynamics here, but it is worth mentioning that the principles of this science grew out of practical attempts in the nineteenth century to understand how to make a steam engine work as efficiently as possible and why heat is generated when one drills the bore of cannon, not academic speculation on universal law. This suggests that there may be value in avoiding being too prescriptive about how scientific knowledge should develop. Like Kepler’s laws of planetary motion and Newton’s laws of mechanics, there are three laws of thermodynamics (plus one). There is a good deal about the first two of them here and in Chapter 3; they form the core of classical thermodynamics. Discussion of the First and Second Laws also provides the necessary context for introducing concepts that underlie the concept of free energy, a useful tool in the biological sciences (Chapters 4 and 5). The Third Law of Thermodynamics is of less immediate importance to biolo- gists, but we’ll touch on it at the end of Chapter 3, showing how it raises some very interesting questions about the nature of living organisms. For the purposes of our present subject, the chief prac- tical value of studying the laws of thermodynamics is that they provide insight into how biological systems work and a framework for designing experiments, testing hypotheses, and explaining results. We’re ready for the First Law of Thermodynamics. But before investigating it, let’s take one minute to go over the so-called Zeroth Law. The function of the Zeroth Law is to justify the concept of temperature and the use of thermometers (two things most of us are accustomed to take for granted!), and it is included here to provide a broader conceptual foundation to our subject. The form of the Zeroth Law is identical to that of a famous logical argument known at least as early as the ancient Greeks. It goes like this: if fi fl (one premise), and fl ° (another premise), then ° fi ¼ ¼ ¼ 28 THEFIRST LAWOF THERMODYNAMICS (conclusion). The Zeroth Law is built on this syllogism, or logical argument consisting of three propositions. It involves the concept of thermal equilibrium, that two objects A and B are in contact and at the same temperature.5 The Zeroth Law states that if A is in thermal equilibrium with B, and B is in equilibrium with object C, then C is Fig. 2.1 The Zeroth Law of also in thermal equilibrium with A (Fig. 2.1). Simple! In Chapter 1 we Thermodynamics. If three systems, touched on how temperature is a measure of the average speed of A, B and C, are in physical contact, molecules in a gas. And now that we have the Zeroth Law, we are at equilibrium all three will have the free to use the concept of temperature as much as we like.
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