imported>Paul Wormer |
imported>Paul Wormer |
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| The '''second law of thermodynamics''', as formulated in the middle of the 19th century by [[William Thomson]] (Lord Kelvin) and [[Rudolf Clausius]], states that it is impossible to gain mechanical energy from heat flowing from a ''cold'' to a ''hot'' body. Clausius postulated that the opposite is the case, namely, that it always requires input of mechanical energy (work) to transport heat from a low- to a high-temperature body.
| | {{Image|Complex number.png|right|350px| Complex number ''z'' ≡ ''r'' exp(''i''θ) multiplied by ''i'' gives <i>z'</i> <nowiki>=</nowiki> <i>z</i>×''i'' |
| | <nowiki>=</nowiki> ''z'' exp(''i'' π/2) (counter clockwise rotation over 90°). Division of ''z'' by ''i'' gives ''z''". Division by ''i'' is multiplication by −''i'' <nowiki> = </nowiki> exp(−''i''  π/2) (clockwise rotation over 90°).}} |
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| Thomson formulated the principle in a slightly different, but equivalent way. He said that it is impossible to extract work from a single source of heat in a cyclic process. In a cyclic process the heat source ends up in an thermodynamic state that is identical to the state at the beginning of the process; the heat source does not lose any net [[internal energy]]. In order that this cyclic process is in agreement with the [[first law of thermodynamics]] (i.e., conserves energy), it is necessary that the heat generated by the work is returned to the heat source.
| | ==Complex numbers in physics== |
| | ===Classical physics=== |
| | Classical physics consists of [[classical mechanics]], [[Maxwell's equations|electromagnetic theory]], and phenomenological [[thermodynamics]]. One can add Einstein's special and general theory of [[relativity]] to this list, although this theory, being formulated in the 20th century, is usually not referred to as "classical". In these four branches of physics the basic quantities and equations governing the behavior of the quantities are real. |
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| If the second law would not hold, there would be no energy shortage. For example, it would be possible—as already pointed out by Lord Kelvin—to propel ships by energy extracted from sea water. After all, the oceans contain immense amounts of internal energy. When it would be possible to extract a small portion of this energy—whereby a slight cooling of the sea water would occur—and to use this energy to propel a ship (a form of work), then ships could move without any net consumption of energy. It would ''not'' violate the [[first law of thermodynamics]], because the ship's rotating propellers would again heat the water and in total the energy of the supersystem "ship-plus-ocean" would be conserved, in agreement with the first law, and the total process would be cyclic. Unfortunately, it is not possible, no work can be extracted from the water, because it is the single source of heat. Clausius would explain the impossibility by observing that ships are warmer than sea water (or at least they are not colder) and hence it needs work to transport heat from the sea to the ship.
| | Classical mechanics has three different, but equivalent, formulations. The oldest, due to [[Isaac Newton|Newton]], deals with masses and position vectors of particles, which are real, as is time ''t''. The first and second time derivatives of the position vectors enter Newton's equations and these are obviously real, too. The same is true for [[Lagrange formalism|Lagrange's formulation]] of classical mechanics in terms of position vectors and velocities of particles and for [[Hamilton formalism|Hamilton's formulation]] in terms of [[momentum|momenta]] and positions. |
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| A similar setup on land, where energy extracted from the earth, would, say, charge batteries, and heat dissipated by electric currents generated by the batteries would be given back to the earth, is also impossible because of the same fundamental law of physics.
| | Maxwell equations, that constitute the basis of electromagnetic theory, are in terms of real vector operators ([[gradient]], [[divergence]], and [[curl]]) acting on real [[electric field|electric]] and [[magnetic field|magnetic]] fields. |
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| ==Entropy==
| | Thermodynamics is concerned with concepts as [[internal energy]], [[entropy]], and [[work]]. Again, these properties are real. |
| Clausius was able to give a mathematical expression of the second law of thermodynamics. To that end he needed a totally new thermodynamic concept, one that had no mechanical analogy and that had no intuitive meaning like temperature. He called the new thermodynamic property [[entropy]] from the classical Greek έν + τροπη (tropè = change, en = at). Following in his footsteps entropy will be introduced in this section.
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| The state of a [[thermodynamic system]] (a point in state space) is characterized by a number of variables, such as [[pressure]] ''p'', [[temperature]] ''T'', amount of substance ''n'', volume ''V'', etc. Any thermodynamic parameter can be seen as a function of an arbitrary independent set of other thermodynamic variables, hence the terms "property", "parameter", "variable" and "function" are used interchangeably. The number of ''independent'' thermodynamic variables of a system is equal to the number of energy contacts of the system with its surroundings. | | The special theory of relativity is formulated in [[Minkowski space]]. Although this space is sometimes described as a 3-dimensional [[Euclidean space]] to which the axis ''ict'' (''i'' is the imaginary unit, ''c'' is speed of light, ''t'' is time) is added as a fourth dimension, the role of ''i'' is non-essential. The imaginary unit is introduced as a pedestrian way to the computation of the indefinite, real, inner product that in Lorentz coordinates has the metric |
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| An example of a reversible (quasi-static) energy contact is offered by the prototype thermodynamical system, a gas-filled cylinder with piston. Such a cylinder can perform work on its surroundings,
| |
| :<math> | | :<math> |
| DW = pdV, \quad dV > 0,
| | \begin{pmatrix} |
| </math>
| | -1 & 0 & 0 & 0 \\ |
| where ''dV'' stands for a small increment of the volume ''V'' of the cylinder, ''p'' is the pressure inside the cylinder and ''DW'' stands for a small amount of work. Work by expansion is a form of energy contact between the cylinder and its surroundings. This process can be reverted, the volume of the cylinder can be decreased, the gas is compressed and the surroundings perform work ''DW'' = ''pdV'' ''on'' the cylinder.
| | 0 & 1 & 0 & 0 \\ |
| | | 0 & 0 & 1 & 0 \\ |
| The small amount of work is indicated by ''D'', and not by ''d'', because ''DW'' is not necessarily a differential of a function. However, when we divide ''DW'' by ''p'' the quantity ''DW''/''p'' becomes obviously equal to the differential ''dV'' of the differentiable state function ''V''. State functions depend only on the actual values of the thermodynamic parameters (they are local), and ''not'' on the path along which the state was reached (the history of the state). Mathematically this means that integration from point 1 to point 2 along path I in state space is equal to integration along a different path II,
| | 0 & 0 & 0 & 1 \\ |
| :<math>
| | \end{pmatrix}, |
| V_2 - V_1 = {\int\limits_1\limits^2}_{{\!\!}^{(I)}} dV
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| = {\int\limits_1\limits^2}_{{\!\!}^{(II)}} dV
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| \;\Longrightarrow\; {\int\limits_1\limits^2}_{{\!\!}^{(I)}} \frac{DW}{p} = | |
| {\int\limits_1\limits^2}_{{\!\!}^{(II)}} \frac{DW}{p}
| |
| </math> | | </math> |
| The amount of work (divided by ''p'') performed along path I is equal to the amount of work (divided by ''p'') along path II. This condition is necessary and sufficient that ''DW''/''p'' is a differentiable state function. So, although ''DW'' is not a differential, the quotient ''DW''/''p'' is one. | | which obviously is real. In other words, Minkowski space is a space over the real field ℝ. |
| | The general theory of relativity is formulated over real [[differentiable manifold]]s that are locally Lorentzian. Further, the Einstein field equations contain mass distributions that are real. |
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| Reversible absorption of a small amount of heat ''DQ'' is another energy contact of a system with its surroundings; ''DQ'' is again not a differential of a certain function. In a completely analogous manner to ''DW''/''p'', the following result can be shown for the heat ''DQ'' (divided by ''T'') absorbed by the system along two different paths (along both paths the absorption is reversible):
| | So, although the classical branches of physics do not need complex numbers, this does not mean that these numbers cannot be useful. A very important mathematical technique, especially for those branches of physics where there is flow (of electricity, heat, or mass) is [[Fourier analysis]]. The Fourier series is most conveniently formulated in complex form. Although it would be possible to formulate it in real terms (expansion in terms of sines and cosines) this would be cumbersome, given the fact that the application of the usual trigonometric formulas for the multiplication of sines and cosines is so much more difficult than the corresponding multiplication of complex numbers. Especially electromagnetic theory makes heavy use of complex numbers, but it must be remembered that the final results, that are to be compared with observable quantities, are real. |
| | | ===Quantum physics=== |
| <div style="text-align: right;" >
| | In quantum physics complex numbers are essential. In the oldest formulation, due to [[Heisenberg]] the imaginary unit appears in an essential way through the canonical commutation relation |
| <div style="float: left; margin-left: 35px;" >
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| <math>{\int\limits_1\limits^2}_{{\!\!}^{(I)}}\frac{DQ}{T} = {\int\limits_1\limits^2}_{{\!\!}^{(II)}} \frac{DQ}{T} .
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| </math>
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| </div>
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| <span id="(1)" style="margin-right: 200px; vertical-align: -40px; ">(1)</span>
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| </div>
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| <br><br>
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| Hence the quantity ''dS'' defined by
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| :<math>
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| dS \;\stackrel{\mathrm{def}}{=}\; \frac{DQ}{T}
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| </math>
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| is the differential of a state variable ''S'', the ''entropy'' of the system. In a later subsection equation (1) will be proved from the Clausius/Kelvin principle. Observe that this definition of entropy only fixes entropy differences:
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| :<math>
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| S_2-S_1 \equiv \int_1^2 dS = \int_1^2 \frac{DQ}{T}
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| </math>
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| Note further that entropy has the dimension energy per degree temperature (joule per degree kelvin) and recalling the [[first law of thermodynamics]] (the differential ''dU'' of the [[internal energy]] satisfies ''dU'' = ''DQ'' − ''DW''), it follows that
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| :<math> | | :<math> |
| dU = TdS - pdV.\,
| | [p_i,q_j] \equiv p_i q_j - q_j p_i = -i\hbar \delta_{ij}, |
| </math> | | </math> |
| (For convenience sake only a single work term was considered here, namely ''DW'' = ''pdV'', work done ''by'' the system).
| | ''p''<sub>''i''</sub> and ''q''<sub>''j''</sub> are linear operators (matrices) representing the ''i''th and ''j''th component of the momentum and position of a particle, respectively,. |
| The internal energy is an extensive quantity, that is, when the system is doubled, ''U'' is doubled too. The temperature ''T'' is an intensive property, independent of the size of the system. The entropy ''S'', then, is an extensive property. In that sense the entropy resembles the volume of the system.
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| An important difference between ''V'' and ''S'' is that the former is a state function with a well-defined mechanical meaning, whereas entropy is introduced by analogy and is not easily visualized. Indeed, as is shown in the next subsection, it requires a fairly elaborate reasoning to prove that ''S'' is a state function, i.e., equation [[#(1)|(1)]] to hold.
| | The time-dependent [[Schrödinger equation]] also contains ''i'' in an essential manner. For a free particle of mass ''m'' the equation reads |
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| ===Proof that entropy is a state function===
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| When equation [[#(1)|(1)]] has been proven, the entropy ''S'' is shown to be a state function. The standard proof, as given now, is physical, by means of [[Carnot cycle]]s, and is based on the Clausius/Kelvin formulation of the second law given in the introduction.
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| {{Image|Entropy.png|right|350px|Fig. 1. ''T'' > ''T''<sub>0</sub>. (I): Carnot engine E moves heat from heat reservoir R to "condensor" C and needs input of work DW<sub>in</sub>. (II): E generates work DW<sub>out</sub> from the heat flow from C to R. }} An alternative, more mathematical proof, postulates the existence of a state variable ''S'' with certain properties and derives the existence of [[thermodynamical temperature]] and the second law from these properties.
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| In figure 1 a finite heat bath C ("condensor")<ref>Because of a certain similarity of C with the condensor of a steam engine C is referred as "condensor". The quotes are used to remind us that nothing condenses, unlike the steam engine where steam condenses to water</ref> of constant volume and variable temperature ''T'' is shown. It is connected to an infinite heat reservoir R through a reversible Carnot engine E. Because R is infinite its temperature ''T''<sub>0</sub> is constant, addition or extraction of heat does not change ''T''<sub>0</sub>. It is assumed that always ''T'' ≥ ''T''<sub>0</sub>. One may think of the system E-plus-C as a ship and the heat reservoir R as the sea. The following argument then deals with an attempt of extracting energy from the sea in order to move the ship, i.e., with an attempt to let E perform net outgoing work in a cyclic (i.e., along a closed path in the state space of C) process.
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| A Carnot engine performs reversible cycles (in the state space of E, not be confused with cycles in the state space of C) and per cycle either generates work ''DW''<sub>out</sub> when heat is transported from high temperature to low temperature (II), or needs work ''DW''<sub>in</sub> when heat is transported from low to high temperature (I), in accordance with the Clausius/Kelvin formulation of the second law.
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| The definition of [[thermodynamical temperature]] (a positive quantity) is such that for II,
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| :<math> | | :<math> |
| \frac{DW_\mathrm{out}}{DQ} = \frac{T-T_0}{T}, | | \frac{\hbar}{2m} \nabla^2 \Psi(\mathbf{r},t) = -i \frac{\partial}{\partial t} \Psi(\mathbf{r},t) . |
| </math> | | </math> |
| while for I
| | This equation may be compared to the [[wave equation]] that appears in several branches of classical physics |
| :<math> | | :<math> |
| \frac{DW_\mathrm{in}}{DQ_0} = \frac{T-T_0}{T_0}. | | v^2 \nabla^2 \Psi(\mathbf{r},t) = \frac{\partial^2}{\partial t^2} \Psi(\mathbf{r},t), |
| </math> | | </math> |
| | where ''v'' is the [[phase velocity|velocity]] of the wave. It is clear from this similarity why |
| | Schrödinger's equation is sometimes called the wave equation of quantum mechanics. It is also clear that the essential difference between quantum physics and classical physics is the first-order time derivative including the imaginary unit. The classical equation is real and has on the right hand side a second derivative with respect to time. |
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| The first law of thermodynamics states for I and II, respectively, | | The more general form of the Schrödinger equation is |
| :<math> | | :<math> |
| -DW_\mathrm{in} -DQ_0 + DQ=0\quad\hbox{and}\quad DW_\mathrm{out} + DQ_0-DQ=0
| | H \Psi(t) = i \hbar \frac{\partial}{\partial t} \Psi(t) , |
| </math> | | </math> |
| {{Image|Cycle entropy.png|right|150px|Fig. 2. Two paths in the state space of the "condensor" C.}}
| | where ''H'' is the operator representing the energy of the quantum system under consideration. If this energy is time-independent (no time-dependent external fields interact with the system), the equation can be separated, and the imaginary unit enters fairly trivially through a so-called phase factor, |
| For I,
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| :<math> | | :<math> |
| \begin{align} | | \Psi(t) = e^{-iEt/\hbar} \Phi\quad\hbox{with}\quad H\Phi = E\Phi. |
| \frac{DW_\mathrm{in}}{DQ_0} &= \frac{DQ- DQ_0}{DQ_0} = \frac{DQ}{DQ_0} -1 \\
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| &=\frac{T-T_0}{T_0} = \frac{T}{T_0} - 1 \;
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| \Longrightarrow DQ_0 = T_0 \left(\frac{DQ}{T}\right)
| |
| \end{align}
| |
| </math> | | </math> |
| | | The second equation has the form of an operator [[eigenvalue equation]]. The eigenvalue ''E'' (one of the possible observable values of the energy) is real, which is a fairly deep consequence of the quantum laws.<ref>If ''E'' were complex, two separate measurements would be necessary to determine it. One for its real and one for its imaginary part. Since quantum physics states that a measurement gives a collapse of the wave function to an undetermined state, the measurements, even if they would be made in quick succession, would interfere with each other and energy would be unobservable.</ref> The time-independent function Φ can very often be chosen to be real. The exception being the case that ''H'' is not invariant under [[time-reversal]]. Indeed, since the time-reversal operator θ is [[anti-unitary]], it follows that |
| For II we find the same result,
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| :<math> | | :<math> |
| \begin{align} | | \theta H \theta^\dagger \bar{\Phi} = E \bar{\Phi} |
| \frac{DW_\mathrm{out}}{DQ} &= \frac{DQ- DQ_0}{DQ} = 1- \frac{DQ_0}{DQ} \\ | |
| &=\frac{T-T_0}{T} = 1- \frac{T_0}{T}
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| \;\Longrightarrow DQ_0 = T_0 \left(\frac{DQ}{T}\right) | |
| \end{align}
| |
| </math> | | </math> |
| In figure 2 the state diagram of the "condensor" C is shown. Along path I the Carnot engine needs input of work to transport heat from the colder reservoir R to the hotter C and the absorption of heat by C raises its temperature and pressure. Integration of ''DW''<sub>in</sub> = ''DQ'' − ''DQ''<sub>0</sub> (that is, summation over many cycles of the engine E) along path I gives
| | where the bar indicates [[complex conjugation]]. Now, if ''H'' is invariant, |
| :<math> | | :<math> |
| W_\mathrm{in} = Q_\mathrm{in} - T_0 {\int\limits_1\limits^2}_{{\!\!}^{(I)}} \frac{DQ}{T} \quad\hbox{with}\quad Q_\mathrm{in} \equiv {\int\limits_1\limits^2}_{{\!\!}^{(I)}} DQ.
| | \theta H \theta^\dagger = H \Longrightarrow H\bar{\Phi} = E\bar{\Phi}\quad\hbox{and}\quad |
| | H\Phi = E\Phi, |
| </math> | | </math> |
| Along path II the Carnot engine delivers work while transporting heat from C to R. Integration of ''DW''<sub>out</sub> = ''DQ'' − ''DQ''<sub>0</sub> along path II gives
| | then also the real linear combination <math>\Phi+\bar{\Phi}</math> is an eigenfunction belonging to ''E'', which means that the wave function may be chosen real. If ''H'' is not invariant, it usually is transformed into minus itself. Then <math>\Phi\;</math> and <math>\bar{\Phi}</math> belong to ''E'' and −''E'', respectively, so that they are essentially different and cannot be combined to real form. Time-reversal symmetry is usually broken by magnetic fields, which give rise to interactions linear in spin or orbital [[angular momentum]]. |
| :<math>
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| W_\mathrm{out} = Q_\mathrm{out} - T_0 {\int\limits_2\limits^1}_{{\!\!}^{(II)}} \frac{DQ}{T}
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| \quad\hbox{with}\quad Q_\mathrm{out} \equiv {\int\limits_2\limits^1}_{{\!\!}^{(II)}} DQ
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| </math> | |
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| Assume now that the amount of heat ''Q''<sub>out</sub> extracted (along path II) from C and the heat ''Q''<sub>in</sub> delivered (along I) to C are the same in absolute value. In other words, after having gone along a closed path in the state diagram of figure 2, the condensor C has not gained or lost heat. That is,
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| :<math>
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| Q_\mathrm{in} + Q_\mathrm{out} = 0, \,
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| </math>
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| then
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| :<math>
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| W_\mathrm{in} + W_\mathrm{out} = - T_0 {\int\limits_1\limits^2}_{{\!\!}^{(I)}} \frac{DQ}{T}
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| - T_0 {\int\limits_2\limits^1}_{{\!\!}^{(II)}} \frac{DQ}{T}.
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| </math>
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| If the total net work ''W''<sub>in</sub> + ''W''<sub>out</sub> is positive (outgoing), this work is done by heat obtained from R, which is not possible because of the Clausius/Kelvin principle. If the total net work ''W''<sub>in</sub> + ''W''<sub>out</sub> is negative, then by inverting all reversible processes, i.e., by going down path I and going up along II, the net work changes sign and becomes positive (outgoing). Again the Clausius/Kelvin principle is violated. The conclusion is that the net work is zero and that
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| :<math>
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| T_0 {\int\limits_1\limits^2}_{{\!\!}^{(I)}} \frac{DQ}{T} +
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| T_0 {\int\limits_2\limits^1}_{{\!\!}^{(II)}} \frac{DQ}{T} = 0
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| \;\Longrightarrow\; {\int\limits_1\limits^2}_{{\!\!}^{(I)}} \frac{DQ}{T} = {\int\limits_1\limits^2}_{{\!\!}^{(II)}} \frac{DQ}{T}.
| |
| </math> | |
| From this independence of path it is concluded that
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| :<math>
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| dS \equiv \frac{DQ}{T}
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| </math>
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| is a state (local) variable.
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| ==Mathematical expression of the second law==
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| Recall the following property of path integrals,
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| :<math>
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| {\int\limits_1\limits^2} f(s) ds = - {\int\limits_2\limits^1} f(s) ds. | |
| </math> | |
| Using this one finds immediately from equation [[#(1)|(1)]] the second law for a ''reversible'' cyclic (a closed path in state space) process, where the suffix "rev" is added to stress that this law holds only for reversible processes,
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| :<math>
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| \oint \frac{DQ_\mathrm{rev}}{T} \equiv {\int\limits_1\limits^2}_{{\!\!}^{(I)}}\frac{DQ_\mathrm{rev}}{T} + {\int\limits_2\limits^1}_{{\!\!}^{(II)}} \frac{DQ_\mathrm{rev}}{T} = \oint dS_\mathrm{rev} = 0 .
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| </math>
| |
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| Many, in fact most, thermodynamic processes are spontaneous and irreversible. A well-known spontaneous process is the flow of heat from a hot to a cold body. The opposite process—the transport of heat from a cold to a hot body—needs work (by the Clausius principle), the process is not spontaneous and accordingly not the reverse of the spontaneous flow of heat from hot to cold bodies. Another example of an irreversible process is [[Count Rumford]]'s seminal cannon boring experiment where work is converted by friction into heat. It is impossible to revert this process, which is intuitively clear, but also contradicts the Kelvin principle, the impossibility of obtaining work from a single source of heat. The [[Joule-Thomson effect]] is yet another example of an irreversible process.
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| ==References==
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| C. S. Helrich, ''Modern Thermodynamics with Statistical Mechanics'', Springer (2009).
| |
| [http://books.google.nl/books?id=RpwpYdYmnXMC&printsec=frontcover&source=gbs_navlinks_s#v=onepage&q=&f=false Google books]
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|
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|
| | ==Note== |
| <references /> | | <references /> |
PD Image Complex number
z ≡
r exp(
iθ) multiplied by
i gives
z' =
z×
i =
z exp(
i π/2) (counter clockwise rotation over 90°). Division of
z by
i gives
z". Division by
i is multiplication by −
i = exp(−
i π/2) (clockwise rotation over 90°).
Complex numbers in physics
Classical physics
Classical physics consists of classical mechanics, electromagnetic theory, and phenomenological thermodynamics. One can add Einstein's special and general theory of relativity to this list, although this theory, being formulated in the 20th century, is usually not referred to as "classical". In these four branches of physics the basic quantities and equations governing the behavior of the quantities are real.
Classical mechanics has three different, but equivalent, formulations. The oldest, due to Newton, deals with masses and position vectors of particles, which are real, as is time t. The first and second time derivatives of the position vectors enter Newton's equations and these are obviously real, too. The same is true for Lagrange's formulation of classical mechanics in terms of position vectors and velocities of particles and for Hamilton's formulation in terms of momenta and positions.
Maxwell equations, that constitute the basis of electromagnetic theory, are in terms of real vector operators (gradient, divergence, and curl) acting on real electric and magnetic fields.
Thermodynamics is concerned with concepts as internal energy, entropy, and work. Again, these properties are real.
The special theory of relativity is formulated in Minkowski space. Although this space is sometimes described as a 3-dimensional Euclidean space to which the axis ict (i is the imaginary unit, c is speed of light, t is time) is added as a fourth dimension, the role of i is non-essential. The imaginary unit is introduced as a pedestrian way to the computation of the indefinite, real, inner product that in Lorentz coordinates has the metric
which obviously is real. In other words, Minkowski space is a space over the real field ℝ.
The general theory of relativity is formulated over real differentiable manifolds that are locally Lorentzian. Further, the Einstein field equations contain mass distributions that are real.
So, although the classical branches of physics do not need complex numbers, this does not mean that these numbers cannot be useful. A very important mathematical technique, especially for those branches of physics where there is flow (of electricity, heat, or mass) is Fourier analysis. The Fourier series is most conveniently formulated in complex form. Although it would be possible to formulate it in real terms (expansion in terms of sines and cosines) this would be cumbersome, given the fact that the application of the usual trigonometric formulas for the multiplication of sines and cosines is so much more difficult than the corresponding multiplication of complex numbers. Especially electromagnetic theory makes heavy use of complex numbers, but it must be remembered that the final results, that are to be compared with observable quantities, are real.
Quantum physics
In quantum physics complex numbers are essential. In the oldest formulation, due to Heisenberg the imaginary unit appears in an essential way through the canonical commutation relation
pi and qj are linear operators (matrices) representing the ith and jth component of the momentum and position of a particle, respectively,.
The time-dependent Schrödinger equation also contains i in an essential manner. For a free particle of mass m the equation reads
This equation may be compared to the wave equation that appears in several branches of classical physics
where v is the velocity of the wave. It is clear from this similarity why
Schrödinger's equation is sometimes called the wave equation of quantum mechanics. It is also clear that the essential difference between quantum physics and classical physics is the first-order time derivative including the imaginary unit. The classical equation is real and has on the right hand side a second derivative with respect to time.
The more general form of the Schrödinger equation is
where H is the operator representing the energy of the quantum system under consideration. If this energy is time-independent (no time-dependent external fields interact with the system), the equation can be separated, and the imaginary unit enters fairly trivially through a so-called phase factor,
The second equation has the form of an operator eigenvalue equation. The eigenvalue E (one of the possible observable values of the energy) is real, which is a fairly deep consequence of the quantum laws.[1] The time-independent function Φ can very often be chosen to be real. The exception being the case that H is not invariant under time-reversal. Indeed, since the time-reversal operator θ is anti-unitary, it follows that
where the bar indicates complex conjugation. Now, if H is invariant,
then also the real linear combination is an eigenfunction belonging to E, which means that the wave function may be chosen real. If H is not invariant, it usually is transformed into minus itself. Then and belong to E and −E, respectively, so that they are essentially different and cannot be combined to real form. Time-reversal symmetry is usually broken by magnetic fields, which give rise to interactions linear in spin or orbital angular momentum.
Note
- ↑ If E were complex, two separate measurements would be necessary to determine it. One for its real and one for its imaginary part. Since quantum physics states that a measurement gives a collapse of the wave function to an undetermined state, the measurements, even if they would be made in quick succession, would interfere with each other and energy would be unobservable.