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Thermodynamic Potentials and Natural Variables
Revista Brasileira de Ensino de Física, vol. 42, e20190127 (2020) Articles www.scielo.br/rbef cb DOI: http://dx.doi.org/10.1590/1806-9126-RBEF-2019-0127 Licença Creative Commons Thermodynamic Potentials and Natural Variables M. Amaku1,2, F. A. B. Coutinho*1, L. N. Oliveira3 1Universidade de São Paulo, Faculdade de Medicina, São Paulo, SP, Brasil 2Universidade de São Paulo, Faculdade de Medicina Veterinária e Zootecnia, São Paulo, SP, Brasil 3Universidade de São Paulo, Instituto de Física de São Carlos, São Carlos, SP, Brasil Received on May 30, 2019. Revised on September 13, 2018. Accepted on October 4, 2019. Most books on Thermodynamics explain what thermodynamic potentials are and how conveniently they describe the properties of physical systems. Certain books add that, to be useful, the thermodynamic potentials must be expressed in their “natural variables”. Here we show that, given a set of physical variables, an appropriate thermodynamic potential can always be defined, which contains all the thermodynamic information about the system. We adopt various perspectives to discuss this point, which to the best of our knowledge has not been clearly presented in the literature. Keywords: Thermodynamic Potentials, natural variables, Legendre transforms. 1. Introduction same statement cannot be applied to the temperature. In real fluids, even in simple ones, the proportionality Basic concepts are most easily understood when we dis- to T is washed out, and the Internal Energy is more cuss simple systems. Consider an ideal gas in a cylinder. conveniently expressed as a function of the entropy and The cylinder is closed, its walls are conducting, and a volume: U = U(S, V ). -
High Temperature Enthalpies of the Lead Halides
HIGH TEMPERATURE ENTHALPIES OF THE LEAD HALIDES: ENTHALPIES AND ENTROPIES OF FUSION APPROVED: Graduate Committee: Major Professor Committee Member Min fessor Committee Member X Committee Member UJ. Committee Member Committee Member Chairman of the Department of Chemistry Dean or the Graduate School HIGH TEMPERATURE ENTHALPIES OF THE LEAD HALIDES: ENTHALPIES AND ENTROPIES OF FUSION DISSERTATION Presented to the Graduate Council of the North Texas State University in Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY By Clarence W, Linsey, B. S., M. S, Denton, Texas June, 1970 ACKNOWLEDGEMENT This dissertation is based on research conducted at the Oak Ridge National Laboratory, Oak Ridge, Tennessee, which is operated by the Uniofl Carbide Corporation for the U. S. Atomic Energy Commission. The author is also indebted to the Oak Ridge Associated Universities for the Oak Ridge Graduate Fellowship which he held during the laboratory phase. 11 TABLE OF CONTENTS Page LIST OF TABLES iv LIST OF ILLUSTRATIONS v Chapter I. INTRODUCTION . 1 Lead Fluoride Lead Chloride Lead Bromide Lead Iodide II. EXPERIMENTAL 11 Reagents Fusion-Filtration Method Encapsulation of Samples Equipment and Procedure Bunsen Ice Calorimeter Computer Programs Shomate Method Treatment of Data Near the Melting Point Solution Calorimeter Heat of Solution Calculations III. RESULTS AND DISCUSSION 41 Lead Fluoride Variation in Heat Contents of the Nichrome V Capsules Lead Chloride Lead Bromide Lead Iodide Summary BIBLIOGRAPHY ...... 98 in LIST OF TABLES Table Pa8e I. High-Temperature Enthalpy Data for Cubic PbE2 Encapsulated in Gold 42 II. High-Temperature Enthalpy Data for Cubic PbF2 Encapsulated in Molybdenum 48 III. -
Math Background for Thermodynamics ∑
MATH BACKGROUND FOR THERMODYNAMICS A. Partial Derivatives and Total Differentials Partial Derivatives Given a function f(x1,x2,...,xm) of m independent variables, the partial derivative ∂ f of f with respect to x , holding the other m-1 independent variables constant, , is defined by i ∂ xi xj≠i ∂ f fx( , x ,..., x+ ∆ x ,..., x )− fx ( , x ,..., x ,..., x ) = 12ii m 12 i m ∂ lim ∆ xi x →∆ 0 xi xj≠i i nRT Example: If p(n,V,T) = , V ∂ p RT ∂ p nRT ∂ p nR = = − = ∂ n V ∂V 2 ∂T V VT,, nTV nV , Total Differentials Given a function f(x1,x2,...,xm) of m independent variables, the total differential of f, df, is defined by m ∂ f df = ∑ dx ∂ i i=1 xi xji≠ ∂ f ∂ f ∂ f = dx + dx + ... + dx , ∂ 1 ∂ 2 ∂ m x1 x2 xm xx2131,...,mm xxx , ,..., xx ,..., m-1 where dxi is an infinitesimally small but arbitrary change in the variable xi. nRT Example: For p(n,V,T) = , V ∂ p ∂ p ∂ p dp = dn + dV + dT ∂ n ∂ V ∂ T VT,,, nT nV RT nRT nR = dn − dV + dT V V 2 V B. Some Useful Properties of Partial Derivatives 1. The order of differentiation in mixed second derivatives is immaterial; e.g., for a function f(x,y), ∂ ∂ f ∂ ∂ f ∂ 22f ∂ f = or = ∂ y ∂ xx ∂ ∂ y ∂∂yx ∂∂xy y x x y 2 in the commonly used short-hand notation. (This relation can be shown to follow from the definition of partial derivatives.) 2. Given a function f(x,y): ∂ y 1 a. = etc. ∂ f ∂ f x ∂ y x ∂ f ∂ y ∂ x b. -
6CCP3212 Statistical Mechanics Homework 1
6CCP3212 Statistical Mechanics Homework 1 Lecturer: Dr. Eugene A. Lim 2018-19 Year 3 Semester 1 https://nms.kcl.ac.uk/eugene.lim/teach/statmech/sm.html 1) (i) For the following differentials with α and β non-zero real constants, which are exact and which are inexact? Integrate the equation if it is exact. (a) x dG = αdx + β dy (1) y (b) α dG = dx + βdy (2) x (c) x2 dG = (x + y)dx + dy (3) 2 (ii) Show that the work done on the system at pressure P d¯W = −P dV (4) where dV is the change in volume is an inexact differential by showing that there exists no possible function of state for W (P; V ). (iii) Consider the differential dF = (x2 − y)dx + xdy : (5) (a) Show that this is not an exact differential. And hence integrate this equation in two different straight paths from (1; 1) ! (2; 2) and from (1; 1) ! (1; 2) ! (2; 2), where (x; y) indicates the locations. Compare the results { are they identical? (b) Define a new differential with dF y 1 dG ≡ = 1 − dx + dy : (6) x2 x2 x Show that dG is exact, and find G(x; y). 2) This problem asks you to derive some derivative identities of a system with three variables x, y and z, with a single constraint x(y; z). This kind of system is central to thermodynamics as we often use three state variables P , V and T , with an equation of state P (V; T ) (i.e. the constraint) to describe a system. -
3 More Applications of Derivatives
3 More applications of derivatives 3.1 Exact & inexact di®erentials in thermodynamics So far we have been discussing total or \exact" di®erentials µ ¶ µ ¶ @u @u du = dx + dy; (1) @x y @y x but we could imagine a more general situation du = M(x; y)dx + N(x; y)dy: (2) ¡ ¢ ³ ´ If the di®erential is exact, M = @u and N = @u . By the identity of mixed @x y @y x partial derivatives, we have µ ¶ µ ¶ µ ¶ @M @2u @N = = (3) @y x @x@y @x y Ex: Ideal gas pV = RT (for 1 mole), take V = V (T; p), so µ ¶ µ ¶ @V @V R RT dV = dT + dp = dT ¡ 2 dp (4) @T p @p T p p Now the work done in changing the volume of a gas is RT dW = pdV = RdT ¡ dp: (5) p Let's calculate the total change in volume and work done in changing the system between two points A and C in p; T space, along paths AC or ABC. 1. Path AC: dT T ¡ T ¢T ¢T = 2 1 ´ so dT = dp (6) dp p2 ¡ p1 ¢p ¢p T ¡ T1 ¢T ¢T & = ) T ¡ T1 = (p ¡ p1) (7) p ¡ p1 ¢p ¢p so (8) R ¢T R ¢T R ¢T dV = dp ¡ [T + (p ¡ p )]dp = ¡ (T ¡ p )dp (9) p ¢p p2 1 ¢p 1 p2 1 ¢p 1 R ¢T dW = ¡ (T ¡ p )dp (10) p 1 ¢p 1 1 T (p ,T ) 2 2 C (p,T) (p1,T1) A B p Figure 1: Path in p; T plane for thermodynamic process. -
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). -
Chapter 11 Liquids, Solids, and Phase Changes
Lecture Presentation Chapter 11 Liquids, Solids, and Phase Changes 11.1, 11.2, 11.3, 11.4, 11.15, 11.17, 11.26, 11.30, 11.32, 11.40, 11.42, 11.60, 11.82, 11.116 John E. McMurry Robert C. Fay Properties of Liquids Viscosity: The measure of a liquid’s resistance to flow (higher intermolecular force, higher viscosity) Surface Tension: The resistance of a liquid to spread out and increase its surface area (forms beads) (higher intermolecular force, higher surface tension) Properties of Liquids low intermolecular force – low viscosity, low surface tension high intermolecular force – high viscosity, high surface tension HW 11.1 Properties of Liquids high intermolecular force – high viscosity, high surface tension For the following molecules which has the higher intermolecular force, viscosity and surface tension ? (LD structure, VSEPRT, dipole of molecule) (if the molecules are in the liquid state) a. CHCl3 vs CH4 b. H2O vs H2 (changed from handout) c. N Cl3 vs N H Cl2 Phase Changes between Solids, Liquids, and Gases Phase Change (State Change): A change in the physical state but not the chemical identity of a substance Fusion (melting): solid to liquid Freezing: liquid to solid Vaporization: liquid to gas Condensation: gas to liquid Sublimation: solid to gas Deposition: gas to solid Phase Changes between Solids, Liquids, and Gases Enthalpy – add heat to system Entropy – add randomness to system Phase Changes between Solids, Liquids, and Gases Heat (Enthalpy) of Fusion (DHfusion ): The amount of energy required to overcome enough intermolecular forces to convert a solid to a liquid Heat (Enthalpy) of Vaporization (DHvap): The amount of energy required to overcome enough intermolecular forces to convert a liquid to a gas HW 11.2: Phase Changes between Solids, Liquids, & Gases DHfusion solid to a liquid DHvap liquid to a gas At phase change (melting, boiling, etc) : DG = DH – TDS & D G = zero (bc 2 phases in equilibrium) DH = TDS o a. -
Vector Calculus and Differential Forms with Applications To
Vector Calculus and Differential Forms with Applications to Electromagnetism Sean Roberson May 7, 2015 PREFACE This paper is written as a final project for a course in vector analysis, taught at Texas A&M University - San Antonio in the spring of 2015 as an independent study course. Students in mathematics, physics, engineering, and the sciences usually go through a sequence of three calculus courses before go- ing on to differential equations, real analysis, and linear algebra. In the third course, traditionally reserved for multivariable calculus, stu- dents usually learn how to differentiate functions of several variable and integrate over general domains in space. Very rarely, as was my case, will professors have time to cover the important integral theo- rems using vector functions: Green’s Theorem, Stokes’ Theorem, etc. In some universities, such as UCSD and Cornell, honors students are able to take an accelerated calculus sequence using the text Vector Cal- culus, Linear Algebra, and Differential Forms by John Hamal Hubbard and Barbara Burke Hubbard. Here, students learn multivariable cal- culus using linear algebra and real analysis, and then they generalize familiar integral theorems using the language of differential forms. This paper was written over the course of one semester, where the majority of the book was covered. Some details, such as orientation of manifolds, topology, and the foundation of the integral were skipped to save length. The paper should still be readable by a student with at least three semesters of calculus, one course in linear algebra, and one course in real analysis - all at the undergraduate level. -
Notes on the Calculus of Thermodynamics
Supplementary Notes for Chapter 5 The Calculus of Thermodynamics Objectives of Chapter 5 1. to understand the framework of the Fundamental Equation – including the geometric and mathematical relationships among derived properties (U, S, H, A, and G) 2. to describe methods of derivative manipulation that are useful for computing changes in derived property values using measurable, experimentally accessible properties like T, P, V, Ni, xi, and ρ . 3. to introduce the use of Legendre Transformations as a way of alternating the Fundamental Equation without losing information content Starting with the combined 1st and 2nd Laws and Euler’s theorem we can generate the Fundamental Equation: Recall for the combined 1st and 2nd Laws: • Reversible, quasi-static • Only PdV work • Simple, open system (no KE, PE effects) • For an n component system n dU = Td S − PdV + ∑()H − TS i dNi i=1 n dU = Td S − PdV + ∑µidNi i=1 and Euler’s Theorem: • Applies to all smoothly-varying homogeneous functions f, f(a,b,…, x,y, … ) where a,b, … intensive variables are homogenous to zero order in mass and x,y, extensive variables are homogeneous to the 1st degree in mass or moles (N). • df is an exact differential (not path dependent) and can be integrated directly if Y = ky and X = kx then Modified: 11/19/03 1 f(a,b, …, X,Y, …) = k f(a,b, …, x,y, …) and ⎛ ∂f ⎞ ⎛ ∂f ⎞ x⎜ ⎟ + y⎜ ⎟ + ... = ()1 f (a,b,...x, y,...) ⎝ ∂x ⎠a,b,...,y,.. ⎝ ∂y ⎠a,b,..,x,.. Fundamental Equation: • Can be obtained via Euler integration of combined 1st and 2nd Laws • Expressed in Energy (U) or Entropy (S) representation n U = fu []S,V , N1, N2 ,..., Nn = T S − PV + ∑µi Ni i=1 or n U P µi S = f s []U,V , N1, N2 ,..., Nn = + V − ∑ Ni T T i=1 T The following section summarizes a number of useful techniques for manipulating thermodynamic derivative relationships Consider a general function of n + 2 variables F ( x, y,z32,...,zn+ ) where x ≡ z1, y ≡ z2. -
Physical Chemistry II “The Mistress of the World and Her Shadow” Chemistry 402
Physical Chemistry II “The mistress of the world and her shadow” Chemistry 402 L. G. Sobotka Department of Chemistry Washington University, St Louis, MO, 63130 January 3, 2012 Contents IIntroduction 7 1 Physical Chemistry II - 402 -Thermodynamics (mostly) 8 1.1Who,when,where.............................................. 8 1.2CourseContent/Logistics.......................................... 8 1.3Grading.................................................... 8 1.3.1 Exams................................................. 8 1.3.2 Quizzes................................................ 8 1.3.3 ProblemSets............................................. 8 1.3.4 Grading................................................ 8 2Constants 9 3 The Structure of Physical Science 10 3.1ClassicalMechanics.............................................. 10 3.2QuantumMechanics............................................. 11 3.3StatisticalMechanics............................................. 11 3.4Thermodynamics............................................... 12 3.5Kinetics.................................................... 13 4RequisiteMath 15 4.1 Exact differentials.............................................. 15 4.2Euler’sReciprocityrelation......................................... 15 4.2.1 Example................................................ 16 4.3Euler’sCyclicrelation............................................ 16 4.3.1 Example................................................ 16 4.4Integratingfactors.............................................. 17 4.5LegendreTransformations......................................... -
Exact and Inexact Differentials in the Early Development of Mechanics
Revista Brasileira de Ensino de Física, vol. 42, e20190192 (2020) Articles www.scielo.br/rbef cb DOI: http://dx.doi.org/10.1590/1806-9126-RBEF-2019-0192 Licença Creative Commons Exact and inexact differentials in the early development of mechanics and thermodynamics Mário J. de Oliveira*1 1Universidade de São Paulo, Instituto de Física, São Paulo, SP, Brasil Received on July 31, 2019. Revised on October 8, 2019. Accepted on October 13, 2019. We give an account and a critical analysis of the use of exact and inexact differentials in the early development of mechanics and thermodynamics, and the emergence of differential calculus and how it was applied to solve some mechanical problems, such as those related to the cycloidal pendulum. The Lagrange equations of motions are presented in the form they were originally obtained in terms of differentials from the principle of virtual work. The derivation of the conservation of energy in differential form as obtained originally by Clausius from the equivalence of heat and work is also examined. Keywords: differential, differential calculus, analytical mechanics, thermodynamics. 1. Introduction variable x. If another variable y depends on the indepen- dent variable x, then the resulting increment dy of y is It is usual to formulate the basic equations of thermo- its differential. The quotient of these two differentials, dynamics in terms of differentials. The conservation of dy/dx, was interpreted geometrically by Leibniz as the energy is written as ratio of the ordinate y of a point on a curve and the length of the subtangent associated to this point. -
Cryometric Determination of the Enthalpy of Fusion of Sodium Cryolite
Cryometric determination of the enthalpy of fusion of sodium cryolite M. MALINOVSKÝ Department of Chemical Technology of Inorganic Substances, Slovak Technical University, CS-812 37Bratislava Received 30 July 1982 Accepted for publication 22 August 1983 Using the method of classical thermal analysis a part of the liquidus of sodium cryolite in the system Na3AlF6—Na3FS04 was measured in the compo sition range 0—5 mole % Na3FS04. On the basis of these results the molar enthalpy of fusion of cryolite was calculated. It was found that AHf(Na3AlFft) = = 115.4 kJ mol"1; error in this result was estimated to be ±4.9 %. Методом классического термического анализа измерена часть ликви дуса натриевого криолита в системе Na3AlF6—Na3FS04 в интервале кон центраций 0—5 мол. % Na3FS04. На основании этих результатов рассчи тана мольная энтальпия плавления криолита. Найдено, что 1 AH,(Na3AlF6) = 115,4 кДж моль" ; точность этого результата ±4,9 %. Literature survey and theoretical Knowledge of the enthalpy of fusion of sodium hexafluoroaluminate Na3AlF6 (cryolite) is important both from theoretical and practical points of view. For example, it is needed at calculation of the thermal and energy balance and/or the thermal inertia of aluminium cells (the electrolyte contains about 90 mass % of Na3AlF6). The most precise values of the molar enthalpy of fusion AHf(i) of chemical substances can be generally obtained from calorimetric measurements. However, when we deal with substances having higher melting temperature and which are also unstable and very corrosive the calorimetric determination of the quantity AHf(i) can be less reliable. In the case of cryolite Roth and Bertram [1] found from the calorimetric 1 1 measurements ÄH,(Na3 A1F6) = 16.64 kcal mol" = 69.62 kJ mol" .