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Thermodynamics Notes
Thermodynamics Notes Steven K. Krueger Department of Atmospheric Sciences, University of Utah August 2020 Contents 1 Introduction 1 1.1 What is thermodynamics? . .1 1.2 The atmosphere . .1 2 The Equation of State 1 2.1 State variables . .1 2.2 Charles' Law and absolute temperature . .2 2.3 Boyle's Law . .3 2.4 Equation of state of an ideal gas . .3 2.5 Mixtures of gases . .4 2.6 Ideal gas law: molecular viewpoint . .6 3 Conservation of Energy 8 3.1 Conservation of energy in mechanics . .8 3.2 Conservation of energy: A system of point masses . .8 3.3 Kinetic energy exchange in molecular collisions . .9 3.4 Working and Heating . .9 4 The Principles of Thermodynamics 11 4.1 Conservation of energy and the first law of thermodynamics . 11 4.1.1 Conservation of energy . 11 4.1.2 The first law of thermodynamics . 11 4.1.3 Work . 12 4.1.4 Energy transferred by heating . 13 4.2 Quantity of energy transferred by heating . 14 4.3 The first law of thermodynamics for an ideal gas . 15 4.4 Applications of the first law . 16 4.4.1 Isothermal process . 16 4.4.2 Isobaric process . 17 4.4.3 Isosteric process . 18 4.5 Adiabatic processes . 18 5 The Thermodynamics of Water Vapor and Moist Air 21 5.1 Thermal properties of water substance . 21 5.2 Equation of state of moist air . 21 5.3 Mixing ratio . 22 5.4 Moisture variables . 22 5.5 Changes of phase and latent heats . -
Equations of State and Thermodynamics of Solids Using Empirical Corrections in the Quasiharmonic Approximation
PHYSICAL REVIEW B 84, 184103 (2011) Equations of state and thermodynamics of solids using empirical corrections in the quasiharmonic approximation A. Otero-de-la-Roza* and V´ıctor Luana˜ † Departamento de Qu´ımica F´ısica y Anal´ıtica, Facultad de Qu´ımica, Universidad de Oviedo, ES-33006 Oviedo, Spain (Received 24 May 2011; revised manuscript received 8 October 2011; published 11 November 2011) Current state-of-the-art thermodynamic calculations using approximate density functionals in the quasi- harmonic approximation (QHA) suffer from systematic errors in the prediction of the equation of state and thermodynamic properties of a solid. In this paper, we propose three simple and theoretically sound empirical corrections to the static energy that use one, or at most two, easily accessible experimental parameters: the room-temperature volume and bulk modulus. Coupled with an appropriate numerical fitting technique, we show that experimental results for three model systems (MgO, fcc Al, and diamond) can be reproduced to a very high accuracy in wide ranges of pressure and temperature. In the best available combination of functional and empirical correction, the predictive power of the DFT + QHA approach is restored. The calculation of the volume-dependent phonon density of states required by QHA can be too expensive, and we have explored simplified thermal models in several phases of Fe. The empirical correction works as expected, but the approximate nature of the simplified thermal model limits significantly the range of validity of the results. DOI: 10.1103/PhysRevB.84.184103 PACS number(s): 64.10.+h, 65.40.−b, 63.20.−e, 71.15.Nc I. -
VISCOSITY of a GAS -Dr S P Singh Department of Chemistry, a N College, Patna
Lecture Note on VISCOSITY OF A GAS -Dr S P Singh Department of Chemistry, A N College, Patna A sketchy summary of the main points Viscosity of gases, relation between mean free path and coefficient of viscosity, temperature and pressure dependence of viscosity, calculation of collision diameter from the coefficient of viscosity Viscosity is the property of a fluid which implies resistance to flow. Viscosity arises from jump of molecules from one layer to another in case of a gas. There is a transfer of momentum of molecules from faster layer to slower layer or vice-versa. Let us consider a gas having laminar flow over a horizontal surface OX with a velocity smaller than the thermal velocity of the molecule. The velocity of the gaseous layer in contact with the surface is zero which goes on increasing upon increasing the distance from OX towards OY (the direction perpendicular to OX) at a uniform rate . Suppose a layer ‘B’ of the gas is at a certain distance from the fixed surface OX having velocity ‘v’. Two layers ‘A’ and ‘C’ above and below are taken into consideration at a distance ‘l’ (mean free path of the gaseous molecules) so that the molecules moving vertically up and down can’t collide while moving between the two layers. Thus, the velocity of a gas in the layer ‘A’ ---------- (i) = + Likely, the velocity of the gas in the layer ‘C’ ---------- (ii) The gaseous molecules are moving in all directions due= to −thermal velocity; therefore, it may be supposed that of the gaseous molecules are moving along the three Cartesian coordinates each. -
Equation of State for the Lennard-Jones Fluid
Equation of State for the Lennard-Jones Fluid Monika Thol1*, Gabor Rutkai2, Andreas Köster2, Rolf Lustig3, Roland Span1, Jadran Vrabec2 1Lehrstuhl für Thermodynamik, Ruhr-Universität Bochum, Universitätsstraße 150, 44801 Bochum, Germany 2Lehrstuhl für Thermodynamik und Energietechnik, Universität Paderborn, Warburger Straße 100, 33098 Paderborn, Germany 3Department of Chemical and Biomedical Engineering, Cleveland State University, Cleveland, Ohio 44115, USA Abstract An empirical equation of state correlation is proposed for the Lennard-Jones model fluid. The equation in terms of the Helmholtz energy is based on a large molecular simulation data set and thermal virial coefficients. The underlying data set consists of directly simulated residual Helmholtz energy derivatives with respect to temperature and density in the canonical ensemble. Using these data introduces a new methodology for developing equations of state from molecular simulation data. The correlation is valid for temperatures 0.5 < T/Tc < 7 and pressures up to p/pc = 500. Extensive comparisons to simulation data from the literature are made. The accuracy and extrapolation behavior is better than for existing equations of state. Key words: equation of state, Helmholtz energy, Lennard-Jones model fluid, molecular simulation, thermodynamic properties _____________ *E-mail: [email protected] Content Content ....................................................................................................................................... 2 List of Tables ............................................................................................................................. -
Viscosity of Gases References
VISCOSITY OF GASES Marcia L. Huber and Allan H. Harvey The following table gives the viscosity of some common gases generally less than 2% . Uncertainties for the viscosities of gases in as a function of temperature . Unless otherwise noted, the viscosity this table are generally less than 3%; uncertainty information on values refer to a pressure of 100 kPa (1 bar) . The notation P = 0 specific fluids can be found in the references . Viscosity is given in indicates that the low-pressure limiting value is given . The dif- units of μPa s; note that 1 μPa s = 10–5 poise . Substances are listed ference between the viscosity at 100 kPa and the limiting value is in the modified Hill order (see Introduction) . Viscosity in μPa s 100 K 200 K 300 K 400 K 500 K 600 K Ref. Air 7 .1 13 .3 18 .5 23 .1 27 .1 30 .8 1 Ar Argon (P = 0) 8 .1 15 .9 22 .7 28 .6 33 .9 38 .8 2, 3*, 4* BF3 Boron trifluoride 12 .3 17 .1 21 .7 26 .1 30 .2 5 ClH Hydrogen chloride 14 .6 19 .7 24 .3 5 F6S Sulfur hexafluoride (P = 0) 15 .3 19 .7 23 .8 27 .6 6 H2 Normal hydrogen (P = 0) 4 .1 6 .8 8 .9 10 .9 12 .8 14 .5 3*, 7 D2 Deuterium (P = 0) 5 .9 9 .6 12 .6 15 .4 17 .9 20 .3 8 H2O Water (P = 0) 9 .8 13 .4 17 .3 21 .4 9 D2O Deuterium oxide (P = 0) 10 .2 13 .7 17 .8 22 .0 10 H2S Hydrogen sulfide 12 .5 16 .9 21 .2 25 .4 11 H3N Ammonia 10 .2 14 .0 17 .9 21 .7 12 He Helium (P = 0) 9 .6 15 .1 19 .9 24 .3 28 .3 32 .2 13 Kr Krypton (P = 0) 17 .4 25 .5 32 .9 39 .6 45 .8 14 NO Nitric oxide 13 .8 19 .2 23 .8 28 .0 31 .9 5 N2 Nitrogen 7 .0 12 .9 17 .9 22 .2 26 .1 29 .6 1, 15* N2O Nitrous -
States of Matter Lesson
National Aeronautics and Space Administration STATES OF MATTER NASA SUMMER OF INNOVATION LESSON DESCRIPTION UNIT This lesson explores the states of matter Physical Science—States of Matter and their properties. GRADE LEVELS OBJECTIVES 4 – 6 Students will CONNECTION TO CURRICULUM • Simulate the movement of atoms and molecules in solids, liquids, Science and gases TEACHER PREPARATION TIME • Demonstrate the properties of 2 hours liquids including density and buoyancy LESSON TIME NEEDED • Investigate how the density of a 4 hours Complexity: Moderate solid behaves in varying densities of liquids • Construct a rocket powered by pressurized gas created from a chemical reaction between a solid and a liquid NATIONAL STANDARDS National Science Education Standards (NSTA) Science and Technology • Abilities of technological design • Understanding science and technology Physical Science • Position and movement of objects • Properties and changes in properties of matter • Transfer of energy MANAGEMENT For the first activity you may need to enhance prior knowledge about matter and energy from a supplemental handout called “Diagramming Atoms and Molecules in Motion.” At the middle school level, this information about the invisible world of the atom is often presented as a story which we ask them to accept without much ready evidence. Since so many middle school students have not had science experience at the concrete operational level, they are poorly equipped to work at an abstract level. However, in this activity students can begin to see evidence that supports the abstract information you are sharing with them. They can take notes on the first two descriptions as you present on the overhead. Emphasize the spacing of the particles, rather than the number. -
1 Fluid Flow Outline Fundamentals of Rheology
Fluid Flow Outline • Fundamentals and applications of rheology • Shear stress and shear rate • Viscosity and types of viscometers • Rheological classification of fluids • Apparent viscosity • Effect of temperature on viscosity • Reynolds number and types of flow • Flow in a pipe • Volumetric and mass flow rate • Friction factor (in straight pipe), friction coefficient (for fittings, expansion, contraction), pressure drop, energy loss • Pumping requirements (overcoming friction, potential energy, kinetic energy, pressure energy differences) 2 Fundamentals of Rheology • Rheology is the science of deformation and flow – The forces involved could be tensile, compressive, shear or bulk (uniform external pressure) • Food rheology is the material science of food – This can involve fluid or semi-solid foods • A rheometer is used to determine rheological properties (how a material flows under different conditions) – Viscometers are a sub-set of rheometers 3 1 Applications of Rheology • Process engineering calculations – Pumping requirements, extrusion, mixing, heat transfer, homogenization, spray coating • Determination of ingredient functionality – Consistency, stickiness etc. • Quality control of ingredients or final product – By measurement of viscosity, compressive strength etc. • Determination of shelf life – By determining changes in texture • Correlations to sensory tests – Mouthfeel 4 Stress and Strain • Stress: Force per unit area (Units: N/m2 or Pa) • Strain: (Change in dimension)/(Original dimension) (Units: None) • Strain rate: Rate -
Ionic Liquid and Supercritical Fluid Hyphenated Techniques for Dissolution and Separation of Lanthanides, Actinides, and Fission Products
Project No. 09-805 Ionic Liquid and Supercritical Fluid Hyphenated Techniques for Dissolution and Separation of Lanthanides, Actinides, and Fission Products ItIntegrat tdUied Universit itPy Programs Dr. Chien Wai University of Idaho In collaboration with: Idaho National Laboratory Jack Law, Technical POC James Bresee, Federal POC 1 Ionic Liquid and Supercritical Fluid Hyphenated Techniques For Dissolution and Separation of Lanthanides and Actinides DOE-NEUP Project (TO 00058) Final Technical Report Principal Investigator: Chien M. Wai Department of Chemistry, University of Idaho, Moscow, Idaho 83844 Date: December 1, 2012 2 Table of Contents Project Summary 3 Publications Derived from the Project 5 Chapter I. Introduction 6 Chapter II. Uranium Dioxide in Ionic Liquid with a TP-HNO3 Complex – Dissolution and Coordination Environment 9 1. Dissolution of UO2 in Ionic Liquid with TBP(HNO3)1.8(H2O)0.6 2. Raman Spectra of Dissolved Uranyl Species in IL 13 3. Transferring Uranium from IL Phase to sc-CO2 15 Chapter III. Kinetic Study on Dissolution of Uranium Dioxide and Neodymium Sesquioxide in Ionic Liquid 19 1. Rate of Dissolution of UO2 and Nd2O3 in RTIL 19 2. Temperature Effect on Dissolution of UO2 and Nd2O3 24 3. Viscosity Effect on Dissolution of UO2 in IL with TBP(HNO3)1.8(H2O)0.6 Chapter IV. Separation of UO2(NO3)2(TBP)2 and Nd(NO3)3(TBP)3 in Ionic Liquid Using Diglycolamide and Supercritical CO2 Extraction 30 1. Complexation of Uranyl with Diglycolamide TBDGA in Ionic Liquid 31 2. Complexation of Neodymium(III) with TBDGA in Ionic Liquid 35 3. Solubility and Distribution Ratio of UO2(NO3)2(TBP)2 and Nd(NO3)3(TBP)3 in Supercritical CO2 Phase 38 4. -
Chapter 3 Equations of State
Chapter 3 Equations of State The simplest way to derive the Helmholtz function of a fluid is to directly integrate the equation of state with respect to volume (Sadus, 1992a, 1994). An equation of state can be applied to either vapour-liquid or supercritical phenomena without any conceptual difficulties. Therefore, in addition to liquid-liquid and vapour -liquid properties, it is also possible to determine transitions between these phenomena from the same inputs. All of the physical properties of the fluid except ideal gas are also simultaneously calculated. Many equations of state have been proposed in the literature with either an empirical, semi- empirical or theoretical basis. Comprehensive reviews can be found in the works of Martin (1979), Gubbins (1983), Anderko (1990), Sandler (1994), Economou and Donohue (1996), Wei and Sadus (2000) and Sengers et al. (2000). The van der Waals equation of state (1873) was the first equation to predict vapour-liquid coexistence. Later, the Redlich-Kwong equation of state (Redlich and Kwong, 1949) improved the accuracy of the van der Waals equation by proposing a temperature dependence for the attractive term. Soave (1972) and Peng and Robinson (1976) proposed additional modifications of the Redlich-Kwong equation to more accurately predict the vapour pressure, liquid density, and equilibria ratios. Guggenheim (1965) and Carnahan and Starling (1969) modified the repulsive term of van der Waals equation of state and obtained more accurate expressions for hard sphere systems. Christoforakos and Franck (1986) modified both the attractive and repulsive terms of van der Waals equation of state. Boublik (1981) extended the Carnahan-Starling hard sphere term to obtain an accurate equation for hard convex geometries. -
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). -
Sounds of a Supersolid A
NEWS & VIEWS RESEARCH hypothesis came from extensive population humans, implying possible mosquito exposure long-distance spread of insecticide-resistant time-series analysis from that earlier study5, to malaria parasites and the potential to spread mosquitoes, worsening an already dire situ- which showed beyond reasonable doubt that infection over great distances. ation, given the current spread of insecticide a mosquito vector species called Anopheles However, the authors failed to detect resistance in mosquito populations. This would coluzzii persists locally in the dry season in parasite infections in their aerially sampled be a matter of great concern because insecticides as-yet-undiscovered places. However, the malaria vectors, a result that they assert is to be are the best means of malaria control currently data were not consistent with this outcome for expected given the small sample size and the low available8. However, long-distance migration other malaria vectors in the study area — the parasite-infection rates typical of populations of could facilitate the desirable spread of mosqui- species Anopheles gambiae and Anopheles ara- malaria vectors. A problem with this argument toes for gene-based methods of malaria-vector biensis — leaving wind-powered long-distance is that the typical infection rates they mention control. One thing is certain, Huestis and col- migration as the only remaining possibility to are based on one specific mosquito body part leagues have permanently transformed our explain the data5. (salivary glands), rather than the unknown but understanding of African malaria vectors and Both modelling6 and genetic studies7 undoubtedly much higher infection rates that what it will take to conquer malaria. -
Current Status of Equation of State in Nuclear Matter and Neutron Stars
Open Issues in Understanding Core Collapse Supernovae June 22-24, 2004 Current Status of Equation of State in Nuclear Matter and Neutron Stars J.R.Stone1,2, J.C. Miller1,3 and W.G.Newton1 1 Oxford University, Oxford, UK 2Physics Division, ORNL, Oak Ridge, TN 3 SISSA, Trieste, Italy Outline 1. General properties of EOS in nuclear matter 2. Classification according to models of N-N interaction 3. Examples of EOS – sensitivity to the choice of N-N interaction 4. Consequences for supernova simulations 5. Constraints on EOS 6. High density nuclear matter (HDNM) 7. New developments Equation of State is derived from a known dependence of energy per particle of a system on particle number density: EA/(==En) or F/AF(n) I. E ( or Boltzman free energy F = E-TS for system at finite temperature) is constructed in a form of effective energy functional (Hamiltonian, Lagrangian, DFT/EFT functional or an empirical form) II. An equilibrium state of matter is found at each density n by minimization of E (n) or F (n) III. All other related quantities like e.g. pressure P, incompressibility K or entropy s are calculated as derivatives of E or F at equilibrium: 2 ∂E ()n ∂F ()n Pn()= n sn()=− | ∂n ∂T nY, p ∂∂P()nnEE() ∂2 ()n Kn()==9 18n +9n2 ∂∂nn∂n2 IV. Use as input for model simulations (Very) schematic sequence of equilibrium phases of nuclear matter as a function of density: <~2x10-4fm-3 ~2x10-4 fm-3 ~0.06 fm-3 Nuclei in Nuclei in Neutron electron gas + ‘Pasta phase’ Electron gas ~0.1 fm-3 0.3-0.5 fm-3 >0.5 fm-3 Nucleons + n,p,e,µ heavy baryons Quarks ???