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Thermodynamics ------------------------------------- Joseph F. Alward, PhD Department of Physics University of the Pacific Thermodynamics: "thermo": Greek therme heat "dynamics": Greek dynamikos powerful Physics that deals with the mechanical action or relations between heat and work Example 1: Heat to work Heat Q from flame provides energy to do work ---------------------------------------------------------Example 2: Work to heat. Work done by person is converted to heat energy via friction. Internal Energy U: (measured in joules) Sum of random translational, rotational, and vibrational kinetic energies U: change in U U > 0 is a gain of internal energy U < 0 is a loss of internal energy ---------------------------------------- Thermal Energy: Vibrational kinetic energy in solids The hotter the object, the larger the vibrational kinetic energy same as internal energy Ideal Gases Molecules are point-size. Gas is low-density. Elastic collisions are the only interactions. ----------------------------------------------------------------Average kinetic energy per molecule = (3/2)kT k = Boltzmann's constant = 1.38 x 10-23 J/K U = (3/2) NkT N = number of molecules In an ideal gas, internal energy is proportional to the absolute (Kelvin) temperature. Motions of a diatomic molecule in a fluiid Heat ... is the amount of internal energy entering or leaving a system ... occurs by conduction, convection, or radiation. ... causes a substance's temperature to change ... is not the same as the internal energy of a substance ... is positive if thermal energy flows into the substance ... is negative if thermal energy flows out of the substance ... is measured in joules ------------------------------------------------------------------------------------improper: "heat flow" is redundant Thermal Equilibrium: Systems (or objects) are said to be in thermal equilibrium if there is no net flow of thermal energy from one to the other. A thermometer is in thermal equilibrium with the medium whose temperature it measures, for example. If two objects are in thermal equilibrium, they are at the same temperature. Are you now in thermal equilibrium with your environment? Positive and Negative Work W is positive if work is done by system. (Recall: Work = Fcos W is negative if work is done on the system. Air does work on the environment: W > 0. Environment (man) does work on system: W < 0 (Alternative: system does negative work because force by air pressure on thumb is opposite to the direction of motion of the thumb.) The First Law of Thermodynamics (Conservation of Energy) "Energy can neither be created nor destroyed, but only transferred from one system to another and transformed from one form to another." or "The internal energy of an isolated system is constant (even though that energy may be transformed from one type to another)." For thermodynamic systems, the 1st Law is: U = Q - W Types of Thermodynamic Processes Greek isos: equal baros: weight adiabatos: not passable ----------------------------------------------------Isothermal: Isobaric: Isochoric: Adiabatic: Same temperature Same pressure Same volume Zero heat flow (Q = 0) First Law Example Example: 1000 J of thermal energy flows into a system (Q = 1000 J). At the same time, 400 J of work is done by the system (W = 400 J). What is the change in the system's internal energy U? ---------------------------------------------------------Solution: U = Q - W = 1000 J - 400 J = 600 J First Law Example Example: 800 J of work is done on a system (W = -800 J) as 500 J of thermal energy is removed from the system (Q = -500 J). What is the change in the system's internal energy U? -------------------------------------------------------------Solution: U = Q - W = -500 J - (-800 J) = -500 J + 800 J = 300 J Work Done by an Expanding Gas W = Fs = (PA) s = PV V = Vf - Vi W = P (Vf - Vi) Area under pressure-volume curve is the work done ---------------------------------------------------Isobaric Process: "same pressure" Greek: barys, heavy Work and the Pressure-Volume Curve (Related to Problems 10 and 14) Work Done = Area Under PV curve ------------------------------------How much work is done by the system when the system is taken from: (a) A to B (900 J) (b) B to C (0 J) (c) C to A (-1500 J) ------------------------------------Each "rectangle" has an area of 100 Pa-m3 = 100 (N/m2)-m3 = 100 N-m = 100 Joules Expanding Gas (First Law) 10 grams of steam at 100 C at constant pressure rises to 110 C: P = 4 x 105 Pa T = 10 C V = 30.0 x 10-6 m3 c = 0.48 cal/g Example: If a gas expands at a constant pressure, the work done by the gas What is the change in internal energy? U = Q - W -----------------------------------------------------W = (4 x 105)(30.0 x 10-6) = 12 J Q = mcT = (10)(.48)(10) = 48 cal = (48 cal)(4.186 J/cal) = 201 J U = Q - W = 201 J - 12 J = 189 J ------------------------------------------------------ is: W = Fs = (PA)s = P(As) = PV What if the steam were compressed while it was absorbing heat? First Law Example Key Ideas: Example: Aluminum cube of side L is heated in a chamber at atmospheric pressure. What is the change in the cube's internal energy? 1. U = Q - W 2. Q = mcT 3. m = V0 4. V0 = L3 5. W = PV 6. V = V0T U = Q - W Go to Solution First Law Example U = Q - W W is positive U = Q - W Q is zero. W = -0.03 J U = 0 - (-0.03 J) = 0.03 J (positive) Assuming ideal gas: U = (3 / 2) N k T Q is zero U is negative Temperature drops from 41F to - 31 F causing vapor to condense into a cloud of tiny droplets. T is positive since U is positive First Law Examples U = Q - W W is positive Q is zero U is negative Steam temperature drops and is cool to the touch. U = Q - W Q is zero. W is negative Why does paper catch on fire? Work, Rubber Bands, and Internal Energy U = Q - W Expand rubber band: W < 0, Q = 0 U > 0 temperature increases --------------------------------------------------------Press thick rubber band to lip and expand it rapidly. The warming should be obvious. Now allow the band to contract quickly; cooling will also be evident. Heating a Gas at Constant Volume Isochoric Process "same volume" U = Q - W = Q Conceptual Questions 1. 100 Joules of heat is added to a gas, and the gas expands at constant pressure. Is it possible that the internal energy increases by 200 J? No. 2. A gas is compressed isothermally, and its internal energy increases. Is the gas an ideal gas? No. For an ideal gas, U = (3 / 2) N k T. 3. State how U changes in each of the following processes (U = Q - W) (a) 500 J (b) 200 J (c) (d) (e) W = -500 J W=0 and and Q= 0 ................. U = 0 - (- 500 J) = Q = -200 J ................. U = - 200 J - 0 = - W = 100 J and Q = 100 J W = -100 J and Q = -100 J W = 300 J and Q = 500 J Adiabatic Expansion of a Ideal Gas Key Idea #1: For an ideal gas, U depends only on the absolute temperature T. Key Idea #2: If there's nothing to push against, an expanding gas does zero work. Gas in Chamber A suddenly rushes into Chamber B. How does the final temperature of gas compare to its initial temperature? ---------------------------------------U = Q - W Q =0 W =0 U = (3 / 2) N k T = 0 T = 0 Second Law of Thermodynamics Heat flows naturally from a region at high temperature to a region at low temperature. By itself, heat will not flow from a cold to a hot body. When an isolated system undergoes a change, passing from one state to another, it will do so in such a way that its entropy (disorder) will increase, or at best remain the same. The 2d Law applied to creationism: "The earth must have been created supernaturally, since it is a highly-ordered system." Rebuttal: The earth is not isolated; the sun provides the energy to create the order. Appendix: Example: Aluminum cube of side L is heated in a chamber at atmospheric pressure. What is the change in the cube's internal energy? --------------------------------------------------------------------------U = Q - W = mcT - PV = ( V0 ) cT - P ( V0T ) = ( c - PV0T --------------------------------------------------------------------------L = 20 cm P = 1.01 x 105 Pa = 2.7 x 103 kg/m3 T = 100 C c = 0.90 x 103 J/kg-C = 72 x 10-6 C-1 (coefficient of volume expansion) U = ( c - PV0T = [( 2.7 x 103 )( .48 ) - (1.01 x 105) (72 x 10-6) ] (0.20)3 (100)