Laws of thermodynamics From Wikipedia, the free encyclopedia ‘The four laws of thermodynamics summarize its most important facts. They define findamental physical ‘quantities, such as temperature, energy, and entropy, in order to describe thermodynamic systems, They also describe the transfer of energy as heat and work in thermodynamic processes. The experimentally reproducible distinction between heat and work is at the heart of thermodynamics; thermodynamics has nothing to say about processes in which ths distinction cannot be made. The four principle are! EIETAISIS) or laws, of thermodynamics = The zeroth law of thermodynamics recognizes that iftwo systems are in thermal equilibrium with a third, they are also in thermal equilibrium with each other, thus supporting the notions of ‘temperature and heat. The first law of thermodynamics distinguishes between two kinds of physical processes, namely energy transfer as work, and energy transfer as heat. It tells how this shows the existence ofa mathematical quantity called the intemal energy of a system. The intemal energy ‘obeys the principle of conservation of energy bbut work and heat are not defined as separately conserved quantities. Equivalently, the frst law of thermodynamics states that perpetual motion machines of the first kind are impossible = The second law of thermodynamics distinguishes between reversible and irreversible physical processes. It tells how this shows the existence of'a mathematical quantity called the entropy ofa system, and thus it expresses the irreversibility of actual physical processes by the statement that the entropy of an isolated macroscopic system never decreases. Equivalently, perpetual motion ‘machines of the second kind are impossible, "= The third law of thermodynamics concems the Thermodynamics o™ Branches Classical - Statistical - Chemical Equilibrium / Non-equilibrium Thermofluids Laws Zeroth * First + Second + Third Systems State: Equation of state Teal gas + Real gas Phase of matter * Equilibrium Control volume - Instruments Processes Isobarie « Isochoric « Isothermal Adiabatic - Isentropie + Isenthalpic Quasistatic - Poivtropic Free expansion Reversibility - nreversbilty Endoreversibiliy Cycles: Heat engines - Heat pumps ‘Thermal efficiency System properties Property diagrams Intensive and extensive properties State functions: Temperature / Entropy (intro,) + Pressure / Volume + Chemical potential / Particle no. ¢ Conjugate variables) ‘Vapor quality Reduced propertiesentropy ofa perfect erystal at absolute zero ‘temperature, and implies that it is impossible to cool a system to exactly absolute zero, or, ‘equivalently, that perpetual motion machines of the third kind are impossible.|71 Classical thermodynamics describes the exchange of work and heat between systems. It has a special interest in systems that are individually in states of thermodynamic equilibrium. Thermodynamic equilibrium is a condition of systems which are adequately described by only macroscopic variables. Every physical system, however, ‘when microscopically examined, shows apparently random microscopic statistical flatuations in its thermodynamic variables of state (entropy, temperature, pressure, etc.). These microscopic fluctuations are negligible for systems which are nearly in thermodynamic equilibrium and which are only macroscopically examined. ‘They become important, however, for systems which are nearly in thermodynamic equilibrium when they are microscopically examined, and, exceptionally, for macroscopically examined systems that are in critical states!*l, and for macroscopically examined systems that are far from thermodynamic equilibrium, ‘There have been suggestions of additional laws, but none of them achieve the generality of the four accepted laws, and they are not mentioned in standard textbooks, 1211115191110) ‘The laws of thermodynamics are important fimdamental laws in physics and they are applicable in other natural sciences. Contents = 1 Zeroth law = 2 First law = 3 Second law = 4 Third law = 5 History = 6 See abo = 7 References "8 Further reading Zeroth law Process functions: Work » Heat ‘Material properties Compressibilty B = oe Property database Equations Carnot’s theorem (Clausius theorem Fundamental relation Ideal gas law Maxwell relations ‘Table of thermodynamic equations Potentials Free energy - Free entropy Intemalenergy —-U(S,)) Enthalpy. A(Sp)=U+ pV Helmholtz free energy A(I,V) = U- TS Gibbs free energy G(Tip) = H~ TS History and culture Philosophy: Entropy and time + Entropy and life Brownian ratchet Maxwell's demon Heat death paradox Loschmiat's paradox Synergeties History General Heat - Entropy + Gas laws Perpetual motion Theories Caloric theory + Vis viva Theory of heat ‘Mechanical equivalent of heat Motive power Publications: "An Experimental Enquiry Concerning ... Heat” “On the Equilibrium of Heterogeneous Substances" "Re ections on the‘The zeroth law of thermodynamics may be stated as follows: Isystem 4 and system B are individually in thermal ‘equilibrium with system C, then system A is in thermal equilibrium with system B ‘The zeroth law implies that thermal equilibrium, viewed as a binary relation, is a Euclidean relation. Ifwe assume that the binary relationship is also reflexive, then it follows that thermal equilibrium is an equivalence relation. Equivalence relations are also transitive and symmetric. The symmetric relationship allows one to speak of two systems being "in thermal equilibrium with each other", which gives rise to a simpler statement of the zeroth law: ‘ftwo systems are in thermal equilibrium with a third, they are in thermal equilibrium with each other However, this statement requires the implicit assumption ofboth symmetry and reflexivity, rather than reflexivity alone. ‘The law is also a statement about measurability. To this effect the law allows the establishment of an empirical parameter, the temperature, as a property ofa system such that systems in equilibrium with each other have the same temperature. The notion of transitivity permits a system, for example a gas thermometer, to be used as a device to measure the temperature of another system, Motive Power of Fire’ ‘Timelines of: ‘Thermodynamics + Heat engines Art Maxwell's thermodynamic surface Education: Entropy as energy dispersal Scientists Daniel Bernoulli Sadi Carnot Benoit Paul Emile Clapeyron Rudolf Clausius Hermann von Helmholtz Constantin Carathéodory Pierre Duhem Josiah Willard Gibbs James Prescott Joule James Clerk Maxwell Julius Robert von Mayer William Rankine John Smeaton Georg Emst Stahl Benjamin Thompson William Thomson, Ist Baron Kelvin John James Waterston Although the concept of thermodynamic equilibrium is findamental to thermodynamics, the need to state it explicitly as a law was not widely perceived until Fowler and Planck stated it in the 1930s, long afier the first, second, and third law were already widely understood and recognized. Hence it was numbered the zeroth law. ‘The importance of the law as a foundation to the earlier ws is that it allows the definition of temperature in a non-circular way without reference to entropy, its conjugate variable. First law ‘The fist law of thermodynamics may be expressed by several forms of the fimdamental thermodynamic relation for a closed system: Increase in internal energy of a system = heat supplied to the system - work done by the system. For a thermodynamic eycle, the net heat supplied to the system equals the net work done by the system. More specifically, the First Law encompasses the following three principles: = The law of conservation of energy This states that energy can be neither created nor destroyed. However, energy can change