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1 Halesworth U3A Science Group Thermodynamics Or Why Things are How They Are Or Why You Can t Get Something For Nothing Ken Derham Includes quotations from publicly available internet sources Halesworth U3A Science Study Group

2 What is Thermodynamics Thermodynamics is the branch of physics concerned with heat and temperature and their relation to energy and work. It defines macroscopic variables, such as internal energy, entropy, and pressure, that describe a body of matter or radiation. Thermodynamics applies to a wide range of topics in science and engineering, including: Physical chemistry Chemical engineering Mechanical engineering

3 Thermodynamics in a nutshell Energy is conserved It tends to disperse Things become more random

4 History 1650s-1670s Hooke & Boyle Boyle s Law PV/T=c or P 1 V 1 = P 2 V 2 T 1 T 2 Halesworth U3A Science Study Group

5 History - 18 th & early 19 th c 1750s-Joseph Black -Distinction between heat and temperature 1820s Sadi Carnot - worked on efficiency of heat engines

6 History later 19 th c 1850s William Thompson (Lord Kelvin) coined the term thermo-dynamics, linking heat and power, and was first to formulate concise definitions of thermodynamics 1870s J Willard Gibbs developed analysis of energy, entropy, volume, chemical energy, etc to determine whether a process would occur spontaneously

7 What is Heat? Until the mid-19 th century heat was thought of as a caloric fluid. The Scot, James Clerk Maxwell & the Austrian Ludwig Boltzmann understood that a hot substance one in which its atoms move quickly. The heatof an object is the total energy of all the molecular motion inside that object. Temperature, on the other hand, is a measure of the average heator thermal energy of the molecules in a substance

8 Equilibrium Many important practical engineering applications, such as heat engines, refrigerators etccan be approximated as systems consisting of several subsystems at different temperatures and pressures but in equilibrium. If two systems are each in thermal equilibrium with a third, then they are also in thermal equilibrium with each other

9 First Law of Thermodynamics The increase in internal energy of a closed system is equal to the difference of the heat supplied to the system and the work done by the system: ΔU = Q W The internal energy of an isolated system obeys the principle of conservation of energy; i.e. Energy can be transformed (changed from one form to another) but cannot be created or destroyed

10 Enthalpy Enthalpyis a measurement of energy It includes the internal energy (U), which is the energy required to create a system, and the amount of energy required to make room for it by displacing its environment and establishing its volume and pressure The enthalpy of a homogeneous system is defined as: where H = U + pv His the enthalpy of the system, Uis the internal energyof the system, pis the pressureof the system, Vis the volumeof the system

11 Second Law of Thermodynamics Heat flows from a hotter location to a colder location. There are many versions of the second law, but they all have the same effect, which is to explain the phenomenon of irreversibility of nature.

12 Second Law of Thermodynamics Kelvin s research into the nature of heat led to his formulation of the second law of thermodynamics, which states that that Heat will not flow from a colder body to a hotter body. It was first formulated to explain how a steam engine works.

13 Second Law of Thermodynamics Kelvin's statement of the law says that heat from a high-temperature energy source cannot be entirely converted to 'work'. Some of the heat will be reduced to low-quality energy and 'lost' to the process. This proved that it is impossible to have a heat engine that is 100% efficient.

14 Entropy A measure of the energy that is not available for work during a thermodynamic process.

15 Entropy A measure of the randomness of the microscopic constituents of a thermodynamic system. Symbol: S

16 The Second Law & Entropy Entropy is a measure of the level of disorder of a system. Although it's difficult to measure the total entropy (S) of a system, it is fairly easy to measure changes in entropy (ΔS). For a thermodynamic system involved in a heat transfer of size Q at a temperature T, a change in entropy can be measured by: ΔS = Q / T

17 The Second Law & Entropy The second law of thermodynamics can be stated in terms of entropy. If a reversible process occurs, there is no net change in entropy. In an irreversible process, entropy always increases, so the change in entropy is positive. The total entropy of the universe is continually increasing.

18 The Second Law & Entropy Mathematically: ΔS 0 I.e. the change in entropy is always greater than or equal to zero

19 Entropy (in cosmology) a tendency for the universe to attain a state of maximum homogeneity in which all matter is at a uniform temperature (heat death)

20 Time In any process in which heat exchange does not occur (or when the heat exchanged is negligible) we see that the future behaves exactly like the past. E.g. In the motion of the planets in the solar system heat is almost irrelevant. The same motion could equally take place in reverse without any law of physics being infringed. As soon as there is any transfer of heat, the future is different from the past.

21 Time As soon as there is any transfer of heat, the future is different from the past. E.g. If there were no friction a pendulum can swing forever. If we filmed it and ran the film in reverse we would see no difference. But there is friction, so the pendulum heats its supports and surroundings slightly, loses energy and slows down. Immediately we are able to distinguish the future (towards which the pendulum slows) from the past.

22 Heat and Time The difference between the past and the future only exists when there is heat. The fundamental phenomenon that distinguishes the future from the past is that heat passes from things that are hotter to things that are colder.

23 Why does heat move from hot things to cold things and not the other way? It is sheer chance! Boltzmann showed that it is statistically more probable that a quickly moving atom of a hot substance collides with a cold one and passes on a little of its energy. Energy is conserved in collisions, but tends to get distributed in more or less equal parts when there are many collisions.

24 Why does heat move from hot things to cold things and not the other way? In this way the temperature of objects in contact with each other tends to equalise. It is not actually impossiblefor a hot body to become hotter through contact with a cooler one, it is just extremely improbable.

25 The Kelvin temperature scale Kelvin realised that it would be useful to be able to define extremely low temperatures precisely. He noted that molecules stop moving at absolute zero. In 1848, he proposed an absolute temperature scale now called the 'Kelvin scale' where absolute zero is 0 kelvin (0 K). Absolute zero on the Kelvin scale = minus degrees on the Celsius scale. On the Celsius scale, water freezes at 0 degrees. On the Kelvin scale, it freezes at kelvin.

26 Third Law of Thermodynamics As a system approaches absolute zero, the entropy of the system approaches a minimum value or The entropy of all systems and of all states of a system is the smallest at absolute zero Or equivalently: It is impossible to reach the absolute zero of temperature by any finite number of processes

27 Gibbs Free Energy Willard Gibbs, 1873, defined a thermodynamic quantity equal to the enthalpy (H) of a system or process, minus the product of the entropy (S) and the absolute temperature (T) G = H TS G is known as the Gibbs Free Energy or Gibbs Energy

28 Gibbs Free Energy In chemical reactions the change in free energy (at constant temperature) is expressed as ΔG = ΔH T ΔS change in free energy change in enthalpy (temperature x) change in entropy If ΔG<0 reaction will be spontaneous If ΔG=0 the system is at equilibrium (reversible) If ΔG>0 the process will not be spontaneous and would require an input of energy to occur

29 How does thermodynamics help us in our daily lives? Because refrigerators, car engines and power plants are thermodynamic machines." That s true, but you don't have to understand thermodynamics in order to know those things. You can simply accept them and that's that. Thermodynamics is so much more than that.

30 How does thermodynamics help us in our daily lives? Thermodynamics provides a framework in which the universe operates. In other words, anything you are likely to encounter in your daily experience can be broken down to thermodynamics. Anything. Therefore, understanding the fundamental laws of thermodynamics is a fundamental part of being a rational being.

31 How does thermodynamics help us in our daily lives? Conservation of energy is everywhere. This law can (almost) never be broken. Anything that happens around you, happens for a reason, and that energy is not simply created. The way the universe operates is easier to grasp if you search for answers under the first law of thermodynamics.

32 How does thermodynamics help us in our daily lives? In fact, you can't even break even. If you have a limited amount of energy, its availability will decrease with time. This is the second law of thermodynamics. This means that natural systems are inherently inefficient, and there is no easy way to overcome this problem (we can't just simply make a 100% efficient engine).

33 How does thermodynamics help us in our daily lives? If people reason based on the laws of thermodynamics, misinformation would not be as widespread as it is today. I.e. misinformation from economics, to politics, to engineering, to science in general. People tend to believe in the most absurd things, some of which are easily proven wrong if people knew the laws of thermodynamics.

34 Application to Pharmacy & Pharmacology Every aspect of how a drug behaves in solution and (more importantly) within the body is governed by the simple (?) principles of thermodynamics. Drug solubility, partitioning between immiscible solvents and drug receptor binding can all be understood based upon the description of such systems according to thermodynamic terms. In fact, our understanding of these properties is critically dependent upon a basic understanding of the three fundamental laws of thermodynamics.

35 8 minute video by a professional Professor Dave

36 All you need to remember: Energy is conserved (Energy cannot be created or destroyed) Energy becomes more dispersed (High temperature/high concentration of energy tends towards lower temperature/dispersed energy) Things become more random (Increase in disorder)

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