Chapter 3 - First Law of Thermodynamics
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1 Chapter 3 - dynamics The ideal gas law is a combination of three intuitive relationships between pressure, volume, temp and moles. David J. Starling Penn State Hazleton Fall 2013
2 When a gas expands, it does work on its surroundings equal to W = F d s = (pa)(ds) = p(a ds) W = Vf V i p dv
3 We can graph p vs. volume the area under the curve is work done.
4 We can graph p vs. volume the area under the curve is work done. Use an inflated balloon to visualize the process.
5 The thermodynamic quantities heat and work alter the energy of a system according to the first law of thermodynamics: E int = Q W (1) de int = dq dw (2)
6 The thermodynamic quantities heat and work alter the energy of a system according to the first law of thermodynamics: E int = Q W (1) de int = dq dw (2) Heat increases the internal energy of the system, but work decreases the internal energy of the system.
7 There are four very important cases involving the first law of thermodynamics.
8 Which one of the following statements is not consistent with the first law of thermodynamics? (a) The internal energy of a finite system must be finite. (b) An engine may be constructed such that the work done by the machine exceeds the energy input to the engine. (c) An isolated system that is thermally insulated cannot do work on its surroundings nor can work be done on the system. (d) The internal energy of a system decreases when it does work on its surroundings and there is no flow of heat. (e) An engine may be constructed that gains energy while heat is transferred to it and work is done on it.
9 When heat is added to a gas at constant volume, its temperature changes according to Q = nc V T (3)
10 When heat is added to a gas at constant volume, its temperature changes according to Q = nc V T (3) C V is the molar specific heat at constant volume From first law E int = Q W = Q = nc V T,
11 When heat is added to a gas at constant volume, its temperature changes according to Q = nc V T (3) C V is the molar specific heat at constant volume From first law E int = Q W = Q = nc V T, C V = E 3 int n T = 2 nrt n T = 3 2 R (4)
12 When heat is added to a gas at constant pressure, its temperature again changes according to Q = nc p T (5)
13 When heat is added to a gas at constant pressure, its temperature again changes according to Q = nc p T (5) W = p V = nr T
14 When heat is added to a gas at constant pressure, its temperature again changes according to Q = nc p T (5) W = p V = nr T E int = nc V T = Q W
15 When heat is added to a gas at constant pressure, its temperature again changes according to Q = nc p T (5) W = p V = nr T E int = nc V T = Q W nc V T = nc p T nr T
16 When heat is added to a gas at constant pressure, its temperature again changes according to Q = nc p T (5) W = p V = nr T E int = nc V T = Q W nc V T = nc p T nr T C V = C p R
17 When heat is added to a gas at constant pressure, its temperature again changes according to Q = nc p T (5) W = p V = nr T E int = nc V T = Q W nc V T = nc p T nr T C V = C p R C p = C V + R
18 Molecules can store energy based upon their geometries, altering their specific heats.
19 Molecules can store energy based upon their geometries, altering their specific heats. Each degree of freedom gets about 1 2kT energy per molecule 1 2RT energy per mole
20 Molecules can also store vibrational energy, but only at higher temperatures.
21 A monatomic gas particle has only 3 degrees of freedom and each particle in the gas has a thermal energy equal to (3/2)kT. How many degrees of freedom does a diatomic gas particle have and how much thermal energy does each molecule have? (a) 2, kt (b) 3, (3/2)kT (c) 4, 2kT (d) 5, (5/2)kT (e) 6, 3kT
22 Adiabatic expansion means that the volume changes while Q = 0; i.e., no heat is transferred. Let s derive the curve in (b) from first principles!
23 There is no heat transfer, Q = 0, so the first law reads: de int = p dv
24 There is no heat transfer, Q = 0, so the first law reads: de int = p dv nc V dt = p dv
25 There is no heat transfer, Q = 0, so the first law reads: de int = p dv nc V dt = p dv n dt = p dv C V
26 There is no heat transfer, Q = 0, so the first law reads: de int = p dv nc V dt = p dv n dt = p dv C V Taking partials of the ideal gas law and using C p = C V + R, p dv + V dp = nr dt
27 There is no heat transfer, Q = 0, so the first law reads: de int = p dv nc V dt = p dv n dt = p dv C V Taking partials of the ideal gas law and using C p = C V + R, p dv + V dp = nr dt n dt = p dv + V dp R
28 There is no heat transfer, Q = 0, so the first law reads: de int = p dv nc V dt = p dv n dt = p dv C V Taking partials of the ideal gas law and using C p = C V + R, p dv + V dp = nr dt n dt = p dv + V dp R = p dv + V dp C p C V
29 There is no heat transfer, Q = 0, so the first law reads: de int = p dv nc V dt = p dv n dt = p dv C V Taking partials of the ideal gas law and using C p = C V + R, p dv + V dp = nr dt n dt = p dv + V dp R = p dv + V dp C p C V p dv p dv + V dp = C V C p C V
30 There is no heat transfer, Q = 0, so the first law reads: de int = p dv nc V dt = p dv n dt = p dv C V Taking partials of the ideal gas law and using C p = C V + R, p dv + V dp = nr dt n dt = p dv + V dp R = p dv + V dp C p C V p dv p dv + V dp = C V C p C V 0 = dp p + C p dv C V V
31 Integrating this equation, we find ln p + C p C V ln V = constant
32 Integrating this equation, we find ln p + C p ln V = constant C ( V ) ln pv Cp/C V = constant
33 Integrating this equation, we find ln p + C p ln V = constant C ( V ) ln pv Cp/C V = constant pv Cp/C V = pv γ = constant
34 Integrating this equation, we find ln p + C p ln V = constant C ( V ) ln pv Cp/C V = constant pv Cp/C V = pv γ = constant This results describes the adiabat in the p V plane.
35 Integrating this equation, we find ln p + C p ln V = constant C ( V ) ln pv Cp/C V = constant pv Cp/C V = pv γ = constant This results describes the adiabat in the p V plane. This also implies (using ideal gas law): p i V γ i = p f V γ f T i V γ 1 i = T f V γ 1 f
36 Consider the following pressure-volume graphs. Which of these graphs represents the behavior of a gas undergoing free expansion? E. None of the graphs represent a gas undergoing free expansion.
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