1 A Workbook in CBE Thermodynamics J. Richard Elliott Chemical and Biomolecular Engineering Dept. The University of Akron, Akron, OH 44325-3906 Introduction ‘These notes are intended to facilitate the discussion of Chemical Engineering Thermodynamics. They supplement the text of Elliott and Lira with a few brief examples and equations for convenient reference and with ConcepTests for checking your understanding 1 INTRODUCTORY CONCEPTS. ENERGY BALANCES 3. ENERGY BALANCES FOR COMPOSITE SYSTEMS 4 ENTROPY BALANCES.. 3 THERMODYNAMICS OF COMMON PROCESSES... 6 CLASSICAL THERMODYNAMICS... 1 8 9 ENGINEERING EQUATIONS OF STATE (E0S'S) DEPARTURE FUNCTIONS. PHASE EQUILIBRIUM IN A PURE FLUID 10 INTRODUCTION TO MULTICOMPONENT SYSTEMS... 11 EMPIRICAL ACTIVITY MODELS. 12 VDWACTIVITY MODELS 13 LOCAL COMPOSITION ACTIVITY MODELS. MM LLEANDSLE. 15 EOS'S FOR MIXTURES 16 COMPLEX PHASE BEHAVIOR.. 17 REACTION EQUILIBRIA 18 ELECTROLYTES.1 Introductory Concepts Interual Energy. tanslational, vibrational, potential U*=Z mtv = (3/2 (NED) =[C/"aT Kinetic energy of translational movement in space Prot = (mn/L? 4S v2) = (nNaniD<7> = (MIF) , Ideal gas pressure in 3D T=Smv2/3nR = Namev2>/3R = Miav2=/3R Ideal gas 3D temperature u(r) =[F(n dr potential energy (work=F*c) of bringing tvo atoms from infinite distance tor. Workbook submissions: Feel free to copy/paste sections of this document into MsWord and obtain whatever spacing that you need to fill in your solutions. Iti fine for your solutions to be handwritten as long as they are neatly documented. At the end of the course, the workbook will bbe compiled and should serve as a neat and convenient reference to all your work throughout the semester 1.1. Which of the following represents an ideal gas? Explain, 10 » es = oft Ls s 5 a0 10 0 02 04 06 08 002, gy 08 0s (sin) wo ® 7 * 5 @2 “ fo 20 . 40 © ©) 1.2 Explain temperature from a molecular perspective (in a complete sentence or two). What do you need to know about the molecules in order to calculate the temperature, and how do you calculate it?1.3 Which is characteristic of a liquid in equilibrium with its vapor? Explain. A. Liquid molecules move slower. B. Liquid has a higher pressure. C. Liquid molecules collide more. D. The liquid has more energy Explanation: 1.4 For water at 375°C and 10 MPa, find the internal energy (ki/ke) 1.5 The outlet from a turbine consists of steam at 100°C and entropy (5) of 7 ki/kg-K. What is its quality? Show your work. 1.6 Two molecules are bouncing in 2D with molecular weight of 16g/mole. Their velocities (a's) are given by: <555, -432>, < -555,432>. Estimate the temperature in the box (K). 1.7 Estimate the average velocity (mph) of hydrogen molecules in a (3D) tank at 300K and 10 bars, (Hint: check your units. 1J=1kg-m2/s2) 1.8 Estimate the change in intemal energy (J/mol) of argon molecules in a tank going fom 300K and 10 bars to 400K and 5 bars assuming the ideal gas model14 19 Derive the expression for the force between two molecules characterized by the Yukawa potential (given below) uO)=|_ em-BG/)-D 5 Cie) 1.10 Molecules 4 and B can be represented by the square-well potential. For molecule 4, o= 0.3 nm and e= 10e-22 J.For molecule B, o= 0.5 nm and e= 30e-22 J. Which molecule would you expect to have the higher boiling temperature? Explain. 1.11 Molecules 4 and B can be represented by the square-well potential. For molecule 4, 0= 0.3 nm and é= 10e-22 J. For molecule B, 7= 0.5 nm and ¢= 30e-22 J. Sketch the SW potential models (J=1.5) for the two molecules on the same pair of axes clearly indicating o's and ¢'s of each species. Make molecule 4 a solid line and B a dashed line. Make sure that the relative distances and depths are qualitatively correct. 1.12 Saturation pressure (P) can be estimated using logo(P*") = A —B/(T+C) with A= logio(P.) + 70+w)/3, B= Te*7(1+w)/3, C= 273.15, where P*"[=] MPa, Pc [=] MPa, T [=] °C, and Tz [=] K. We refer to this as the shortcut vapor pressure model (SCVP). Estimate the saturation pressure (MPa) of methane at 111K. Assume the SCVP model, 1.13 How many degrees of freedom are applicable to superheated steam?1.14 Steam Table Practice Performing computations using tables and graphs is a common part of engineering practice. This necessary skill is often taken for granted, but may be demanded when least expected. A skilled engineer should be able to extract ‘meaningfil numbers from tables in graphs as naturally (and quickly) as drinking a glass of water. The following exercises are intended to give you the practice you need to raise your skill to a reasonable level. The problems are posed below with reasonable times (sec) listed for each case. The answers are given on the next page so you can check yourself. Keep exercising until you "get in shape" for sufficiently quick steam table computations. Maybe it seems mundane and tedious (because itis), but doing it badly and slowly does not make it les tedious. Practice!!! Tabulate the T, P, V; q, U, H, Sof steam at the following conditions: (2) 325°C, 3MPa (b) 150°C, 1.5 bars (c) saturated liquid at Ibar (d saturated liquid at O°C (e) saturated steam at Tar ( 200°C, H = 2600 Jig (g) 1.7243MPa, U = 2596.4 () 1.2 MPa, H=2816.1 J/g (i) IMPa, S=60/g [PC [POPs | Vensikg) Tq Uigy THO) [SOEK) [tiecs) [tauls) [Notes 155 175 4 44 oy 120 120 55 88