Thermodynamic Potentials and Maxwell's Relations
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ENERGY, ENTROPY, and INFORMATION Jean Thoma June
ENERGY, ENTROPY, AND INFORMATION Jean Thoma June 1977 Research Memoranda are interim reports on research being conducted by the International Institute for Applied Systems Analysis, and as such receive only limited scientific review. Views or opinions contained herein do not necessarily represent those of the Institute or of the National Member Organizations supporting the Institute. PREFACE This Research Memorandum contains the work done during the stay of Professor Dr.Sc. Jean Thoma, Zug, Switzerland, at IIASA in November 1976. It is based on extensive discussions with Professor HAfele and other members of the Energy Program. Al- though the content of this report is not yet very uniform because of the different starting points on the subject under consideration, its publication is considered a necessary step in fostering the related discussion at IIASA evolving around th.e problem of energy demand. ABSTRACT Thermodynamical considerations of energy and entropy are being pursued in order to arrive at a general starting point for relating entropy, negentropy, and information. Thus one hopes to ultimately arrive at a common denominator for quanti- ties of a more general nature, including economic parameters. The report closes with the description of various heating appli- cation.~and related efficiencies. Such considerations are important in order to understand in greater depth the nature and composition of energy demand. This may be highlighted by the observation that it is, of course, not the energy that is consumed or demanded for but the informa- tion that goes along with it. TABLE 'OF 'CONTENTS Introduction ..................................... 1 2 . Various Aspects of Entropy ........................2 2.1 i he no me no logical Entropy ........................ -
Lecture 4: 09.16.05 Temperature, Heat, and Entropy
3.012 Fundamentals of Materials Science Fall 2005 Lecture 4: 09.16.05 Temperature, heat, and entropy Today: LAST TIME .........................................................................................................................................................................................2� State functions ..............................................................................................................................................................................2� Path dependent variables: heat and work..................................................................................................................................2� DEFINING TEMPERATURE ...................................................................................................................................................................4� The zeroth law of thermodynamics .............................................................................................................................................4� The absolute temperature scale ..................................................................................................................................................5� CONSEQUENCES OF THE RELATION BETWEEN TEMPERATURE, HEAT, AND ENTROPY: HEAT CAPACITY .......................................6� The difference between heat and temperature ...........................................................................................................................6� Defining heat capacity.................................................................................................................................................................6� -
Chapter 3. Second and Third Law of Thermodynamics
Chapter 3. Second and third law of thermodynamics Important Concepts Review Entropy; Gibbs Free Energy • Entropy (S) – definitions Law of Corresponding States (ch 1 notes) • Entropy changes in reversible and Reduced pressure, temperatures, volumes irreversible processes • Entropy of mixing of ideal gases • 2nd law of thermodynamics • 3rd law of thermodynamics Math • Free energy Numerical integration by computer • Maxwell relations (Trapezoidal integration • Dependence of free energy on P, V, T https://en.wikipedia.org/wiki/Trapezoidal_rule) • Thermodynamic functions of mixtures Properties of partial differential equations • Partial molar quantities and chemical Rules for inequalities potential Major Concept Review • Adiabats vs. isotherms p1V1 p2V2 • Sign convention for work and heat w done on c=C /R vm system, q supplied to system : + p1V1 p2V2 =Cp/CV w done by system, q removed from system : c c V1T1 V2T2 - • Joule-Thomson expansion (DH=0); • State variables depend on final & initial state; not Joule-Thomson coefficient, inversion path. temperature • Reversible change occurs in series of equilibrium V states T TT V P p • Adiabatic q = 0; Isothermal DT = 0 H CP • Equations of state for enthalpy, H and internal • Formation reaction; enthalpies of energy, U reaction, Hess’s Law; other changes D rxn H iD f Hi i T D rxn H Drxn Href DrxnCpdT Tref • Calorimetry Spontaneous and Nonspontaneous Changes First Law: when one form of energy is converted to another, the total energy in universe is conserved. • Does not give any other restriction on a process • But many processes have a natural direction Examples • gas expands into a vacuum; not the reverse • can burn paper; can't unburn paper • heat never flows spontaneously from cold to hot These changes are called nonspontaneous changes. -
A Simple Method to Estimate Entropy and Free Energy of Atmospheric Gases from Their Action
Article A Simple Method to Estimate Entropy and Free Energy of Atmospheric Gases from Their Action Ivan Kennedy 1,2,*, Harold Geering 2, Michael Rose 3 and Angus Crossan 2 1 Sydney Institute of Agriculture, University of Sydney, NSW 2006, Australia 2 QuickTest Technologies, PO Box 6285 North Ryde, NSW 2113, Australia; [email protected] (H.G.); [email protected] (A.C.) 3 NSW Department of Primary Industries, Wollongbar NSW 2447, Australia; [email protected] * Correspondence: [email protected]; Tel.: + 61-4-0794-9622 Received: 23 March 2019; Accepted: 26 April 2019; Published: 1 May 2019 Abstract: A convenient practical model for accurately estimating the total entropy (ΣSi) of atmospheric gases based on physical action is proposed. This realistic approach is fully consistent with statistical mechanics, but reinterprets its partition functions as measures of translational, rotational, and vibrational action or quantum states, to estimate the entropy. With all kinds of molecular action expressed as logarithmic functions, the total heat required for warming a chemical system from 0 K (ΣSiT) to a given temperature and pressure can be computed, yielding results identical with published experimental third law values of entropy. All thermodynamic properties of gases including entropy, enthalpy, Gibbs energy, and Helmholtz energy are directly estimated using simple algorithms based on simple molecular and physical properties, without resource to tables of standard values; both free energies are measures of quantum field states and of minimal statistical degeneracy, decreasing with temperature and declining density. We propose that this more realistic approach has heuristic value for thermodynamic computation of atmospheric profiles, based on steady state heat flows equilibrating with gravity. -
( ∂U ∂T ) = ∂CV ∂V = 0, Which Shows That CV Is Independent of V . 4
so we have ∂ ∂U ∂ ∂U ∂C =0 = = V =0, ∂T ∂V ⇒ ∂V ∂T ∂V which shows that CV is independent of V . 4. Using Maxwell’s relations. Show that (∂H/∂p) = V T (∂V/∂T ) . T − p Start with dH = TdS+ Vdp. Now divide by dp, holding T constant: dH ∂H ∂S [at constant T ]= = T + V. dp ∂p ∂p T T Use the Maxwell relation (Table 9.1 of the text), ∂S ∂V = ∂p − ∂T T p to get the result ∂H ∂V = T + V. ∂p − ∂T T p 97 5. Pressure dependence of the heat capacity. (a) Show that, in general, for quasi-static processes, ∂C ∂2V p = T . ∂p − ∂T2 T p (b) Based on (a), show that (∂Cp/∂p)T = 0 for an ideal gas. (a) Begin with the definition of the heat capacity, δq dS C = = T , p dT dT for a quasi-static process. Take the derivative: ∂C ∂2S ∂2S p = T = T (1) ∂p ∂p∂T ∂T∂p T since S is a state function. Substitute the Maxwell relation ∂S ∂V = ∂p − ∂T T p into Equation (1) to get ∂C ∂2V p = T . ∂p − ∂T2 T p (b) For an ideal gas, V (T )=NkT/p,so ∂V Nk = , ∂T p p ∂2V =0, ∂T2 p and therefore, from part (a), ∂C p =0. ∂p T 98 (a) dU = TdS+ PdV + μdN + Fdx, dG = SdT + VdP+ Fdx, − ∂G F = , ∂x T,P 1 2 G(x)= (aT + b)xdx= 2 (aT + b)x . ∂S ∂F (b) = , ∂x − ∂T T,P x,P ∂S ∂F (c) = = ax, ∂x − ∂T − T,P x,P S(x)= ax dx = 1 ax2. -
Thermodynamics
ME346A Introduction to Statistical Mechanics { Wei Cai { Stanford University { Win 2011 Handout 6. Thermodynamics January 26, 2011 Contents 1 Laws of thermodynamics 2 1.1 The zeroth law . .3 1.2 The first law . .4 1.3 The second law . .5 1.3.1 Efficiency of Carnot engine . .5 1.3.2 Alternative statements of the second law . .7 1.4 The third law . .8 2 Mathematics of thermodynamics 9 2.1 Equation of state . .9 2.2 Gibbs-Duhem relation . 11 2.2.1 Homogeneous function . 11 2.2.2 Virial theorem / Euler theorem . 12 2.3 Maxwell relations . 13 2.4 Legendre transform . 15 2.5 Thermodynamic potentials . 16 3 Worked examples 21 3.1 Thermodynamic potentials and Maxwell's relation . 21 3.2 Properties of ideal gas . 24 3.3 Gas expansion . 28 4 Irreversible processes 32 4.1 Entropy and irreversibility . 32 4.2 Variational statement of second law . 32 1 In the 1st lecture, we will discuss the concepts of thermodynamics, namely its 4 laws. The most important concepts are the second law and the notion of Entropy. (reading assignment: Reif x 3.10, 3.11) In the 2nd lecture, We will discuss the mathematics of thermodynamics, i.e. the machinery to make quantitative predictions. We will deal with partial derivatives and Legendre transforms. (reading assignment: Reif x 4.1-4.7, 5.1-5.12) 1 Laws of thermodynamics Thermodynamics is a branch of science connected with the nature of heat and its conver- sion to mechanical, electrical and chemical energy. (The Webster pocket dictionary defines, Thermodynamics: physics of heat.) Historically, it grew out of efforts to construct more efficient heat engines | devices for ex- tracting useful work from expanding hot gases (http://www.answers.com/thermodynamics). -
7 Apr 2021 Thermodynamic Response Functions . L03–1 Review Of
7 apr 2021 thermodynamic response functions . L03{1 Review of Thermodynamics. 3: Second-Order Quantities and Relationships Maxwell Relations • Idea: Each thermodynamic potential gives rise to several identities among its second derivatives, known as Maxwell relations, which express the integrability of the fundamental identity of thermodynamics for that potential, or equivalently the fact that the potential really is a thermodynamical state function. • Example: From the fundamental identity of thermodynamics written in terms of the Helmholtz free energy, dF = −S dT − p dV + :::, the fact that dF really is the differential of a state function implies that @ @F @ @F @S @p = ; or = : @V @T @T @V @V T;N @T V;N • Other Maxwell relations: From the same identity, if F = F (T; V; N) we get two more relations. Other potentials and/or pairs of variables can be used to obtain additional relations. For example, from the Gibbs free energy and the identity dG = −S dT + V dp + µ dN, we get three relations, including @ @G @ @G @S @V = ; or = − : @p @T @T @p @p T;N @T p;N • Applications: Some measurable quantities, response functions such as heat capacities and compressibilities, are second-order thermodynamical quantities (i.e., their definitions contain derivatives up to second order of thermodynamic potentials), and the Maxwell relations provide useful equations among them. Heat Capacities • Definitions: A heat capacity is a response function expressing how much a system's temperature changes when heat is transferred to it, or equivalently how much δQ is needed to obtain a given dT . The general definition is C = δQ=dT , where for any reversible transformation δQ = T dS, but the value of this quantity depends on the details of the transformation. -
Grand-Canonical Ensemble
PHYS4006: Thermal and Statistical Physics Lecture Notes (Unit - IV) Open System: Grand-canonical Ensemble Dr. Neelabh Srivastava (Assistant Professor) Department of Physics Programme: M.Sc. Physics Mahatma Gandhi Central University Semester: 2nd Motihari-845401, Bihar E-mail: [email protected] • In microcanonical ensemble, each system contains same fixed energy as well as same number of particles. Hence, the system dealt within this ensemble is a closed isolated system. • With microcanonical ensemble, we can not deal with the systems that are kept in contact with a heat reservoir at a given temperature. 2 • In canonical ensemble, the condition of constant energy is relaxed and the system is allowed to exchange energy but not the particles with the system, i.e. those systems which are not isolated but are in contact with a heat reservoir. • This model could not be applied to those processes in which number of particle varies, i.e. chemical process, nuclear reactions (where particles are created and destroyed) and quantum process. 3 • So, for the method of ensemble to be applicable to such processes where number of particles as well as energy of the system changes, it is necessary to relax the condition of fixed number of particles. 4 • Such an ensemble where both the energy as well as number of particles can be exchanged with the heat reservoir is called Grand Canonical Ensemble. • In canonical ensemble, T, V and N are independent variables. Whereas, in grand canonical ensemble, the system is described by its temperature (T),volume (V) and chemical potential (μ). 5 • Since, the system is not isolated, its microstates are not equally probable. -
The Grand Canonical Ensemble
University of Central Arkansas The Grand Canonical Ensemble Stephen R. Addison Directory ² Table of Contents ² Begin Article Copyright °c 2001 [email protected] Last Revision Date: April 10, 2001 Version 0.1 Table of Contents 1. Systems with Variable Particle Numbers 2. Review of the Ensembles 2.1. Microcanonical Ensemble 2.2. Canonical Ensemble 2.3. Grand Canonical Ensemble 3. Average Values on the Grand Canonical Ensemble 3.1. Average Number of Particles in a System 4. The Grand Canonical Ensemble and Thermodynamics 5. Legendre Transforms 5.1. Legendre Transforms for two variables 5.2. Helmholtz Free Energy as a Legendre Transform 6. Legendre Transforms and the Grand Canonical Ensem- ble 7. Solving Problems on the Grand Canonical Ensemble Section 1: Systems with Variable Particle Numbers 3 1. Systems with Variable Particle Numbers We have developed an expression for the partition function of an ideal gas. Toc JJ II J I Back J Doc Doc I Section 2: Review of the Ensembles 4 2. Review of the Ensembles 2.1. Microcanonical Ensemble The system is isolated. This is the ¯rst bridge or route between mechanics and thermodynamics, it is called the adiabatic bridge. E; V; N are ¯xed S = k ln (E; V; N) Toc JJ II J I Back J Doc Doc I Section 2: Review of the Ensembles 5 2.2. Canonical Ensemble System in contact with a heat bath. This is the second bridge between mechanics and thermodynamics, it is called the isothermal bridge. This bridge is more elegant and more easily crossed. T; V; N ¯xed, E fluctuates. -
Standard Thermodynamic Values
Standard Thermodynamic Values Enthalpy Entropy (J Gibbs Free Energy Formula State of Matter (kJ/mol) mol/K) (kJ/mol) (NH4)2O (l) -430.70096 267.52496 -267.10656 (NH4)2SiF6 (s hexagonal) -2681.69296 280.24432 -2365.54992 (NH4)2SO4 (s) -1180.85032 220.0784 -901.90304 Ag (s) 0 42.55128 0 Ag (g) 284.55384 172.887064 245.68448 Ag+1 (aq) 105.579056 72.67608 77.123672 Ag2 (g) 409.99016 257.02312 358.778 Ag2C2O4 (s) -673.2056 209.2 -584.0864 Ag2CO3 (s) -505.8456 167.36 -436.8096 Ag2CrO4 (s) -731.73976 217.568 -641.8256 Ag2MoO4 (s) -840.5656 213.384 -748.0992 Ag2O (s) -31.04528 121.336 -11.21312 Ag2O2 (s) -24.2672 117.152 27.6144 Ag2O3 (s) 33.8904 100.416 121.336 Ag2S (s beta) -29.41352 150.624 -39.45512 Ag2S (s alpha orthorhombic) -32.59336 144.01328 -40.66848 Ag2Se (s) -37.656 150.70768 -44.3504 Ag2SeO3 (s) -365.2632 230.12 -304.1768 Ag2SeO4 (s) -420.492 248.5296 -334.3016 Ag2SO3 (s) -490.7832 158.1552 -411.2872 Ag2SO4 (s) -715.8824 200.4136 -618.47888 Ag2Te (s) -37.2376 154.808 43.0952 AgBr (s) -100.37416 107.1104 -96.90144 AgBrO3 (s) -27.196 152.716 54.392 AgCl (s) -127.06808 96.232 -109.804896 AgClO2 (s) 8.7864 134.55744 75.7304 AgCN (s) 146.0216 107.19408 156.9 AgF•2H2O (s) -800.8176 174.8912 -671.1136 AgI (s) -61.83952 115.4784 -66.19088 AgIO3 (s) -171.1256 149.3688 -93.7216 AgN3 (s) 308.7792 104.1816 376.1416 AgNO2 (s) -45.06168 128.19776 19.07904 AgNO3 (s) -124.39032 140.91712 -33.472 AgO (s) -11.42232 57.78104 14.2256 AgOCN (s) -95.3952 121.336 -58.1576 AgReO4 (s) -736.384 153.1344 -635.5496 AgSCN (s) 87.864 130.9592 101.37832 Al (s) -
Lecture 6: Entropy
Matthew Schwartz Statistical Mechanics, Spring 2019 Lecture 6: Entropy 1 Introduction In this lecture, we discuss many ways to think about entropy. The most important and most famous property of entropy is that it never decreases Stot > 0 (1) Here, Stot means the change in entropy of a system plus the change in entropy of the surroundings. This is the second law of thermodynamics that we met in the previous lecture. There's a great quote from Sir Arthur Eddington from 1927 summarizing the importance of the second law: If someone points out to you that your pet theory of the universe is in disagreement with Maxwell's equationsthen so much the worse for Maxwell's equations. If it is found to be contradicted by observationwell these experimentalists do bungle things sometimes. But if your theory is found to be against the second law of ther- modynamics I can give you no hope; there is nothing for it but to collapse in deepest humiliation. Another possibly relevant quote, from the introduction to the statistical mechanics book by David Goodstein: Ludwig Boltzmann who spent much of his life studying statistical mechanics, died in 1906, by his own hand. Paul Ehrenfest, carrying on the work, died similarly in 1933. Now it is our turn to study statistical mechanics. There are many ways to dene entropy. All of them are equivalent, although it can be hard to see. In this lecture we will compare and contrast dierent denitions, building up intuition for how to think about entropy in dierent contexts. The original denition of entropy, due to Clausius, was thermodynamic. -
Energy and Enthalpy Thermodynamics
Energy and Energy and Enthalpy Thermodynamics The internal energy (E) of a system consists of The energy change of a reaction the kinetic energy of all the particles (related to is measured at constant temperature) plus the potential energy of volume (in a bomb interaction between the particles and within the calorimeter). particles (eg bonding). We can only measure the change in energy of the system (units = J or Nm). More conveniently reactions are performed at constant Energy pressure which measures enthalpy change, ∆H. initial state final state ∆H ~ ∆E for most reactions we study. final state initial state ∆H < 0 exothermic reaction Energy "lost" to surroundings Energy "gained" from surroundings ∆H > 0 endothermic reaction < 0 > 0 2 o Enthalpy of formation, fH Hess’s Law o Hess's Law: The heat change in any reaction is the The standard enthalpy of formation, fH , is the change in enthalpy when one mole of a substance is formed from same whether the reaction takes place in one step or its elements under a standard pressure of 1 atm. several steps, i.e. the overall energy change of a reaction is independent of the route taken. The heat of formation of any element in its standard state is defined as zero. o The standard enthalpy of reaction, H , is the sum of the enthalpy of the products minus the sum of the enthalpy of the reactants. Start End o o o H = prod nfH - react nfH 3 4 Example Application – energy foods! Calculate Ho for CH (g) + 2O (g) CO (g) + 2H O(l) Do you get more energy from the metabolism of 1.0 g of sugar or