Thermodynamics systems • A thermodynamic system is any collection of objects that may exchange energy with its surroundings. • The popcorn in the pot is a thermodynamic system. • In the thermodynamic process shown here, heat is added to the system, and the system does work on its surroundings to lift the lid of the pot. © 2016 Pearson Education Inc. Thermodynamics systems • In a thermodynamic process, changes occur in the state of the system. • Careful of signs! • Q is positive when heat flows into a system. • W is the work done by the system, so it is positive for expansion. © 2016 Pearson Education Inc. Ideal-Gas Processes . An ideal-gas process can be represented on a graph of pressure versus volume, called a pV diagram. Knowing p and V, and assuming that n is known for a sealed container, we can find the temperature T by using the ideal-gas law. Here is a pV diagram showing three states of a There are infinitely many system consisting of 1 mol ways to change the gas of gas. from state 1 to state 3. © 2017 Pearson Education, Inc. Slide 18-3 Ideal-Gas Processes . (a) If you slowly pull a piston out, you can reverse the process by slowly pushing the piston in. This is called a quasi-static process. (b) is a sudden process, which cannot be represented on a pV diagram. Quasi-static processes keep the system in thermal equilibrium. © 2017 Pearson Education, Inc. Slide 18-4 Work done during volume changes • We can understand the work done by a gas in a volume change by considering a molecule in the gas. • When one such molecule collides with a surface moving to the right, so the volume of the gas increases, the molecule does positive work on the piston. © 2016 Pearson Education Inc. Work done during volume changes • If the piston moves toward the left as in the figure shown here, so the volume of the gas decreases; positive work is done on the molecule during the collision. • Hence the gas molecules do negative work on the piston. © 2016 Pearson Education Inc. Work done during volume changes • The infinitesimal work done by the system during the small expansion dx is dW = pA dx. • In a finite change of volume from V1 to V2: © 2016 Pearson Education Inc. Work on a pV-diagram • The work done equals the area under the curve on a pV-diagram. • Shown in the graph is a system undergoing an expansion with varying pressure. © 2016 Pearson Education Inc. Work on a pV-diagram • Shown in the graph is a system undergoing a compression with varying pressure. • In this case the work is negative. © 2016 Pearson Education Inc. Work on a pV-diagram • Shown in the graph is a system undergoing an expansion with constant pressure. • In this case, W = p(V2 – V1) © 2016 Pearson Education Inc. Example 1 – As an ideal gas undergoes an isothermal (constant-temperature) expansion at temperature T, its volume changes from V1 to V2. How much work does the gas do? Work depends on the path chosen: Slide 1 of 4 • Consider three different paths on a pV-diagram for getting from state 1 to state 2. © 2016 Pearson Education Inc. Work depends on the path chosen: Slide 2 of 4 • The system does a large amount of work under the path © 2016 Pearson Education Inc. Work depends on the path chosen: Slide 3 of 4 • The system does a small amount of work under the path © 2016 Pearson Education Inc. Work depends on the path chosen: Slide 4 of 4 • Along the smooth curve from 1 to 2, the work done is different from that for either of the other paths. © 2016 Pearson Education Inc. QuickCheck This p-V diagram shows two ways to take a system from state a (at lower left) to state c (at upper right): • via state b (at upper left), or • via state d (at lower right) For which path is W > 0? A. path abc only B. path adc only C. both path abc and path adc D. neither path abc nor path adc First law of thermodynamics • The change in the internal energy U of a system is equal to the heat added minus the work done by the system: • The first law of thermodynamics is just a generalization of the conservation of energy. • Both Q and W depend on the path chosen between states, but is independent of the path. • If the changes are infinitesimal, we write the first law as dU = dQ – dW. © 2016 Pearson Education Inc. First law of thermodynamics • In a thermodynamic process, the internal energy U of a system may increase. • In the system shown below, more heat is added to the system than the system does work. • So the internal energy of the system increases. © 2016 Pearson Education Inc. First law of thermodynamics • In a thermodynamic process, the internal energy U of a system may decrease. • In the system shown below, more heat flows out of the system than work is done. • So the internal energy of the system decreases. © 2016 Pearson Education Inc. First law of thermodynamics • In a thermodynamic process, the internal energy U of a system may remain the same. • In the system shown below, the heat added to the system equals the work done by the system. • So the internal energy of the system is unchanged. © 2016 Pearson Education Inc. QuickCheck You put a flame under a piece of metal, raising the temperature of the metal and making the metal expand. The metal is surrounded by air. What are the signs of ∆U, Q, and W for the metal in this process? A. ∆U > 0, Q > 0, W > 0 B. ∆U < 0, Q > 0, W > 0 C. ∆U > 0, Q > 0, W < 0 D. ∆U < 0, Q > 0, W < 0 © 2016 Pearson Education, Inc. The First Law of Thermodynamics . An isothermal process is one for which the temperature of a specific amount of gas is held constant (no change in total thermal energy). An isochoric process is one for which the volume of the gas is held constant. An adiabatic process is one in which no heat energy is transferred. ∆퐸푡ℎ= 푄 − 푊 © 2017 Pearson Education, Inc. Slide 18-22 QuickCheck A cylinder of gas has a frictionless but tightly sealed piston of mass M. Small masses are placed onto the top of the piston, causing it to slowly move downward. A water bath keeps the temperature constant. In this process: A. Q > 0 B. Q = 0 C. Q < 0 D. There’s not enough information to say anything about the heat. © 2017 Pearson Education, Inc. Slide 18-23 QuickCheck A system can be taken from state a to state b along any of the three paths shown in the p-V diagram. If state b has greater internal energy than state a, along which path is the absolute value |Q| of the heat transfer the greatest? A. path 1 B. path 2 C. path 3 D. |Q| is the same for all three paths. © 2016 Pearson Education, Inc. QuickCheck A system can be taken from state a to state b along any of the three paths shown in the p-V diagram. If state b has greater internal energy than state a, along which path is there a net flow of heat out of the system? A. path 1 B. path 3 C. all of paths 1, 2, and 3 D. none of paths 1, 2, or 3 © 2016 Pearson Education, Inc. Example 2 – You propose to climb several flights of stairs to work off the energy you took in by eating a 900-calorie hot fudge sundae. How high must you climb? Assume your mass is 80.0 kg and a 25% efficiency of converting food energy to mechanical energy. Example 3 – One gram of water (1 cm3) becomes 1671 cm3 of steam when boiled at a constant pressure of 1 atm. Compute the work done by the water when it vaporizes and its increase in internal energy Note: The increase in internal energy is used to dissociate the water molecules as it turns to steam. It will not increase the temperature of the steam. Example 4 – The figure below shows a pV-diagram for a cyclic process in which the initial and final states of some thermodynamic system are the same. The state of the system starts at point a and proceeds counterclockwise in the diagram to point b, then back to a; the total work is W = -500J. Why is the work negative? Also, Find the change in internal energy and the heat added during this process. In-class Activity #1 – The pV-diagram below shows a series of thermodynamic processes. In process ab, 150 J of heat is added to the system; in process bd, 600 J heat is added. Find (a) the internal energy change in process ab; (b) the internal energy change in process abd; and (c) the total heat added in process acd. Special Ideal-Gas Processes . There are three ideal-gas processes in which one of the three terms in the first law—∆Eth, W, or Q—is zero: • Isothermal process (∆ Eth = 0): If the temperature of a gas doesn’t change, neither does its thermal energy. So, the first law is W = Q. • Isochoric process (W = 0): Work is done on (or by) a gas when its volume changes. An isochoric process has ∆V = 0; thus no work is done and the first law can be written ∆Eth = Q. • Adiabatic process (Q = 0): A process in which no heat is transferred— perhaps the system is extremely well insulated—is called an adiabatic process.