Second Law of Thermodynamics
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1 Second Law of Thermodynamics The First Law of Thermodynamics is a statement of the principle of conservation of energy. The Second Law of Thermodynamics is concerned with the maximum fraction of a quantity of heat that can be converted into work.
2 Second Law of Thermodynamics The First Law of Thermodynamics is a statement of the principle of conservation of energy. The Second Law of Thermodynamics is concerned with the maximum fraction of a quantity of heat that can be converted into work. A discussion of the Carnot cycle can be found in Wallace & Hobbs. It is also described in most standard texts on thermodynamics.
3 Second Law of Thermodynamics The First Law of Thermodynamics is a statement of the principle of conservation of energy. The Second Law of Thermodynamics is concerned with the maximum fraction of a quantity of heat that can be converted into work. A discussion of the Carnot cycle can be found in Wallace & Hobbs. It is also described in most standard texts on thermodynamics. We will provide only an outline here.
4 The Carnot Cycle A cyclic process is a series of operations by which the state of a substance changes but finally returns to its original state. 2
5 The Carnot Cycle A cyclic process is a series of operations by which the state of a substance changes but finally returns to its original state. If the volume of the working substance changes, the substance may do external work, or work may be done on the working substance, during a cyclic process. 2
6 The Carnot Cycle A cyclic process is a series of operations by which the state of a substance changes but finally returns to its original state. If the volume of the working substance changes, the substance may do external work, or work may be done on the working substance, during a cyclic process. Since the initial and final states of the working substance are the same in a cyclic process, and internal energy is a function of state, the internal energy of the working substance is unchanged in a cyclic process. 2
7 The Carnot Cycle A cyclic process is a series of operations by which the state of a substance changes but finally returns to its original state. If the volume of the working substance changes, the substance may do external work, or work may be done on the working substance, during a cyclic process. Since the initial and final states of the working substance are the same in a cyclic process, and internal energy is a function of state, the internal energy of the working substance is unchanged in a cyclic process. Therefore, the net heat absorbed by the working substance is equal to the external work that it does in the cycle. 2
8 A working substance is said to undergo a reversible transformation if each state of the system is in equilibrium, so that a reversal in the direction of an infinitesimal change returns the working substance and the environment to their original states. 3
9 A working substance is said to undergo a reversible transformation if each state of the system is in equilibrium, so that a reversal in the direction of an infinitesimal change returns the working substance and the environment to their original states. A heat engine is a device that does work through the agency of heat. 3
10 A working substance is said to undergo a reversible transformation if each state of the system is in equilibrium, so that a reversal in the direction of an infinitesimal change returns the working substance and the environment to their original states. A heat engine is a device that does work through the agency of heat. If during one cycle of an engine a quantity of heat Q 1 is absorbed and heat Q 2 is rejected, the amount of work done by the engine is Q 1 Q 2 and its efficiency η is defined as η = Work done by the engine Heat absorbed by the working substance = Q 1 Q 2 Q 1 3
11 A working substance is said to undergo a reversible transformation if each state of the system is in equilibrium, so that a reversal in the direction of an infinitesimal change returns the working substance and the environment to their original states. A heat engine is a device that does work through the agency of heat. If during one cycle of an engine a quantity of heat Q 1 is absorbed and heat Q 2 is rejected, the amount of work done by the engine is Q 1 Q 2 and its efficiency η is defined as η = Work done by the engine Heat absorbed by the working substance = Q 1 Q 2 Q 1 Carnot was concerned with the efficiency with which heat engines can do useful mechanical work. He envisaged an ideal heat engine consisting of a working substance contained in a cylinder (figure follows). 3
12 The components of Carnot s ideal heat engine. 4
13 The components of Carnot s ideal heat engine. By means of this contraption, we can induce the working substance to undergo transformations which are either adiabatic or isothermal. 4
14 An infinite warm reservoir of heat (H) at constant temperature T 1, and an infinite cold reservoir for heat (C) at constant temperature T 2 (where T 1 > T 2 ) are available. Also, an insulating stand S to facilitate adiabatic changes. 5
15 An infinite warm reservoir of heat (H) at constant temperature T 1, and an infinite cold reservoir for heat (C) at constant temperature T 2 (where T 1 > T 2 ) are available. Also, an insulating stand S to facilitate adiabatic changes. Heat can be supplied from the warm reservoir to the working substance contained in the cylinder, and heat can be extracted from the working substance by the cold reservoir. 5
16 An infinite warm reservoir of heat (H) at constant temperature T 1, and an infinite cold reservoir for heat (C) at constant temperature T 2 (where T 1 > T 2 ) are available. Also, an insulating stand S to facilitate adiabatic changes. Heat can be supplied from the warm reservoir to the working substance contained in the cylinder, and heat can be extracted from the working substance by the cold reservoir. As the working substance expands, the piston moves outward and external work is done by the working substance. 5
17 An infinite warm reservoir of heat (H) at constant temperature T 1, and an infinite cold reservoir for heat (C) at constant temperature T 2 (where T 1 > T 2 ) are available. Also, an insulating stand S to facilitate adiabatic changes. Heat can be supplied from the warm reservoir to the working substance contained in the cylinder, and heat can be extracted from the working substance by the cold reservoir. As the working substance expands, the piston moves outward and external work is done by the working substance. As the working substance contracts, the piston moves inward and work is done on the working substance. 5
18 Representations of a Carnot cycle on a p V diagram. The red lines are isotherms and the blue lines adiabats. 6
19 Carnot s cycle consists of taking the working substance in the cylinder through the following four operations that together constitute a reversible, cyclic transformation 7
20 Carnot s cycle consists of taking the working substance in the cylinder through the following four operations that together constitute a reversible, cyclic transformation 1. The substance starts at point A with temperature T 2. The working substance is compressed adiabatically to state B. Its temperature rises to T 1. 7
21 Carnot s cycle consists of taking the working substance in the cylinder through the following four operations that together constitute a reversible, cyclic transformation 1. The substance starts at point A with temperature T 2. The working substance is compressed adiabatically to state B. Its temperature rises to T The cylinder is now placed on the warm reservoir H, from which it extracts a quantity of heat Q 1. The working substance expands isothermally at temperature T 1 to point C. During this process the working substance does work. 7
22 Carnot s cycle consists of taking the working substance in the cylinder through the following four operations that together constitute a reversible, cyclic transformation 1. The substance starts at point A with temperature T 2. The working substance is compressed adiabatically to state B. Its temperature rises to T The cylinder is now placed on the warm reservoir H, from which it extracts a quantity of heat Q 1. The working substance expands isothermally at temperature T 1 to point C. During this process the working substance does work. 3. The working substance undergoes an adiabatic expansion to point D and its temperature falls to T 2. Again the working substance does work against the force applied to the piston. 7
23 Carnot s cycle consists of taking the working substance in the cylinder through the following four operations that together constitute a reversible, cyclic transformation 1. The substance starts at point A with temperature T 2. The working substance is compressed adiabatically to state B. Its temperature rises to T The cylinder is now placed on the warm reservoir H, from which it extracts a quantity of heat Q 1. The working substance expands isothermally at temperature T 1 to point C. During this process the working substance does work. 3. The working substance undergoes an adiabatic expansion to point D and its temperature falls to T 2. Again the working substance does work against the force applied to the piston. 4. Finally, the working substance is compressed isothermally back to its original state A. In this transformation the working substance gives up a quantity of heat Q 2 to the cold reservoir. 7
24 The net amount of work done by the working substance during the Carnot cycle is equal to the area contained within the figure ABCD. This can be written W = p dv C 8
25 The net amount of work done by the working substance during the Carnot cycle is equal to the area contained within the figure ABCD. This can be written W = p dv Since the working substance is returned to its original state, the net work done is equal to Q 1 Q 2 and the efficiency of the engine is given by C η = Q 1 Q 2 Q 1 8
26 The net amount of work done by the working substance during the Carnot cycle is equal to the area contained within the figure ABCD. This can be written W = p dv Since the working substance is returned to its original state, the net work done is equal to Q 1 Q 2 and the efficiency of the engine is given by C η = Q 1 Q 2 Q 1 In this cyclic operation the engine has done work by transferring a certain quantity of heat from a warmer (H) to a cooler (C) body. 8
27 One way of stating the Second Law of Thermodynamics is: only by transferring heat from a warmer to a colder body can heat can be converted into work in a cyclic process. 9
28 One way of stating the Second Law of Thermodynamics is: only by transferring heat from a warmer to a colder body can heat can be converted into work in a cyclic process. It can be shown that no engine can be more efficient than a reversible engine working between the same limits of temperature, and that all reversible engines working between the same temperature limits have the same efficiency. 9
29 One way of stating the Second Law of Thermodynamics is: only by transferring heat from a warmer to a colder body can heat can be converted into work in a cyclic process. It can be shown that no engine can be more efficient than a reversible engine working between the same limits of temperature, and that all reversible engines working between the same temperature limits have the same efficiency. The validity of these two statements, which are known as Carnot s Theorems, depends on the truth of the Second Law of Thermodynamics. 9
30 One way of stating the Second Law of Thermodynamics is: only by transferring heat from a warmer to a colder body can heat can be converted into work in a cyclic process. It can be shown that no engine can be more efficient than a reversible engine working between the same limits of temperature, and that all reversible engines working between the same temperature limits have the same efficiency. The validity of these two statements, which are known as Carnot s Theorems, depends on the truth of the Second Law of Thermodynamics. Exercise: Show that in a Carnot cycle the ratio of the heat Q! absorbed from the warm reservoir at temperature T 1 to the heat Q 2 rejected to the cold reservoir at temperature T 2 is equal to T 1 /T 2. Solution: See Wallace & Hobbs. 9
31 Heat Engines A heat engine is a device that does work through the agency of heat. 10
32 Heat Engines A heat engine is a device that does work through the agency of heat. Examples of real heat engines are the steam engine and a nuclear power plant. 10
33 Heat Engines A heat engine is a device that does work through the agency of heat. Examples of real heat engines are the steam engine and a nuclear power plant. The warm and cold reservoirs for a steam engine are the boiler and the condenser. The warm and cold reservoirs for a nuclear power plant are the nuclear reactor and the cooling tower. 10
34 Heat Engines A heat engine is a device that does work through the agency of heat. Examples of real heat engines are the steam engine and a nuclear power plant. The warm and cold reservoirs for a steam engine are the boiler and the condenser. The warm and cold reservoirs for a nuclear power plant are the nuclear reactor and the cooling tower. In both cases, water (in liquid and vapour forms) is the working substance that expands when it absorbs heat and thereby does work by pushing a piston or turning a turbine blade. 10
35 The Atmospheric Heat Engines Why do we study heat engines and Carnot Cycles? 11
36 The Atmospheric Heat Engines Why do we study heat engines and Carnot Cycles? The atmosphere itself can be regarded as the working substance of an enormous heat engine. 11
37 The Atmospheric Heat Engines Why do we study heat engines and Carnot Cycles? The atmosphere itself can be regarded as the working substance of an enormous heat engine. Heat is added in the tropics, where the temperature is high. 11
38 The Atmospheric Heat Engines Why do we study heat engines and Carnot Cycles? The atmosphere itself can be regarded as the working substance of an enormous heat engine. Heat is added in the tropics, where the temperature is high. Heat is transported by atmospheric motions from the tropics to the temperate latudes 11
39 The Atmospheric Heat Engines Why do we study heat engines and Carnot Cycles? The atmosphere itself can be regarded as the working substance of an enormous heat engine. Heat is added in the tropics, where the temperature is high. Heat is transported by atmospheric motions from the tropics to the temperate latudes Heat is emitted in temperate latitudes, where the temperature is relatively low. 11
40 The Atmospheric Heat Engines Why do we study heat engines and Carnot Cycles? The atmosphere itself can be regarded as the working substance of an enormous heat engine. Heat is added in the tropics, where the temperature is high. Heat is transported by atmospheric motions from the tropics to the temperate latudes Heat is emitted in temperate latitudes, where the temperature is relatively low. We can apply the principles of thermodynamic engines to the atmosphere and discuss concepts such as its efficiency. 11
41 Alternative Statements of 2nd Law One way of stating the Second Law of Thermodynamics is as follows: Heat can be converted into work in a cyclic process only by transferring heat from a warmer to a colder body. 12
42 Alternative Statements of 2nd Law One way of stating the Second Law of Thermodynamics is as follows: Heat can be converted into work in a cyclic process only by transferring heat from a warmer to a colder body. Another statement of the Second Law is: Heat cannot of itself pass from a colder to a warmer body in a cyclic process. That is, the uphill heat-flow cannot happen without the performance of work by some external agency. 12
43 Entropy 13
44 Entropy We define the increase ds in the entropy of a system as ds = dq T where dq is the quantity of heat that is added reversibly to the system at temperature T. 13
45 Entropy We define the increase ds in the entropy of a system as ds = dq T where dq is the quantity of heat that is added reversibly to the system at temperature T. For a unit mass of the substance, ds = dq T (s is the specific entropy). 13
46 Entropy We define the increase ds in the entropy of a system as ds = dq T where dq is the quantity of heat that is added reversibly to the system at temperature T. For a unit mass of the substance, ds = dq T (s is the specific entropy). Entropy is a function of the state of a system and not the path by which the system is brought to that state. 13
47 Entropy We define the increase ds in the entropy of a system as ds = dq T where dq is the quantity of heat that is added reversibly to the system at temperature T. For a unit mass of the substance, ds = dq T (s is the specific entropy). Entropy is a function of the state of a system and not the path by which the system is brought to that state. The First Law of Thermodynamics for a reversible transformation may be written as dq = c p dt α dp, 13
48 Therefore, ds = dq T = c p dt T α T dp = ( ) dt c p T Rdp p In this form the First Law contains functions of state only. 14
49 Therefore, ds = dq T = c p dt T α T dp = ( ) dt c p T Rdp p In this form the First Law contains functions of state only. From the definition of potential temperature θ (Poisson s equation) we get ( ) dθ c p θ = dt c p T Rdp p 14
50 Therefore, ds = dq T = c p dt T α T dp = ( ) dt c p T Rdp p In this form the First Law contains functions of state only. From the definition of potential temperature θ (Poisson s equation) we get ( ) dθ c p θ = dt c p T Rdp p Since the right hand sides of the above two equations are equal, their left hand sides are too: ds = c p dθ θ. 14
51 Therefore, ds = dq T = c p dt T α T dp = ( ) dt c p T Rdp p In this form the First Law contains functions of state only. From the definition of potential temperature θ (Poisson s equation) we get ( ) dθ c p θ = dt c p T Rdp p Since the right hand sides of the above two equations are equal, their left hand sides are too: ds = c p dθ θ. Integrating, we have s = c p log θ + s 0 where s 0 is a reference value for the entropy. 14
52 Transformations in which entropy (and therefore potential temperature) are constant are called isentropic. 15
53 Transformations in which entropy (and therefore potential temperature) are constant are called isentropic. Therefore, adiabats are generally referred to as isentropes. 15
54 Transformations in which entropy (and therefore potential temperature) are constant are called isentropic. Therefore, adiabats are generally referred to as isentropes. The potential temperature can be used as a surrogate for entropy, and this is generally done in atmospheric science. 15
55 Miscellaneous Remarks Equation for adiabats (p V γ ) 16
56 Miscellaneous Remarks Equation for adiabats (p V γ ) Available and unavailable energy 16
57 Miscellaneous Remarks Equation for adiabats (p V γ ) Available and unavailable energy Entropy: the link between: Second Law of Thermodynamics Order versus disorder Unavailable energy 16
58 Miscellaneous Remarks Equation for adiabats (p V γ ) Available and unavailable energy Entropy: the link between: Second Law of Thermodynamics Order versus disorder Unavailable energy Entropy change when a mass of gas is heated/cooled 16
59 Miscellaneous Remarks Equation for adiabats (p V γ ) Available and unavailable energy Entropy: the link between: Second Law of Thermodynamics Order versus disorder Unavailable energy Entropy change when a mass of gas is heated/cooled Entropy change when heat flows from one mass of gas to another 16
60 The Clausius-Clapeyron Equation [The subject matter of this section (CC Equation) will not form part of the examinations.] 17
61 The Clausius-Clapeyron Equation [The subject matter of this section (CC Equation) will not form part of the examinations.] We can use the Carnot cycle to derive an important relationship, known as the Clausius-Clapeyron Equation. 17
62 The Clausius-Clapeyron Equation [The subject matter of this section (CC Equation) will not form part of the examinations.] We can use the Carnot cycle to derive an important relationship, known as the Clausius-Clapeyron Equation. The Clausius-Clapeyron equation describes how the saturated vapour pressure above a liquid changes with temperature. [Details will not be given here. See Wallace & Hobbs.] 17
63 The Clausius-Clapeyron Equation [The subject matter of this section (CC Equation) will not form part of the examinations.] We can use the Carnot cycle to derive an important relationship, known as the Clausius-Clapeyron Equation. The Clausius-Clapeyron equation describes how the saturated vapour pressure above a liquid changes with temperature. [Details will not be given here. See Wallace & Hobbs.] In approximate form, the Clausius-Clapeyron Equation may be written de s dt L v T α where α is the specific volume of water vapour that is in equilibrium with liquid water at temperature T. 17
64 The vapour exerts a pressure e s given by the ideal gas equation: e s α = R v T 18
65 The vapour exerts a pressure e s given by the ideal gas equation: e s α = R v T Eliminating α, we get 1 e s de s dt L v R v T 2 18
66 The vapour exerts a pressure e s given by the ideal gas equation: e s α = R v T Eliminating α, we get 1 e s de s dt L v R v T 2 If we write this as de s = L v dt e s R v T 2 we can immediately integrate it to obtain log e s = L ( v 1 ) + const R v T 18
67 The vapour exerts a pressure e s given by the ideal gas equation: e s α = R v T Eliminating α, we get 1 e s de s dt L v R v T 2 If we write this as de s = L v dt e s R v T 2 we can immediately integrate it to obtain log e s = L ( v 1 ) + const R v T Taking the exponential of both sides, e s = e s (T 0 ) exp [ Lv R v ( 1 T 0 1 T )] 18
68 Since e s = 6.11 hpa at 273 K R v = 461 J K 1 kg 1 and L v = J kg 1, the saturated vapour pressure e s (in hpa) of water at temperature T (Kelvins) is given by [ ( e s = 6.11 exp )] T 19
69 Since e s = 6.11 hpa at 273 K R v = 461 J K 1 kg 1 and L v = J kg 1, the saturated vapour pressure e s (in hpa) of water at temperature T (Kelvins) is given by [ ( e s = 6.11 exp )] T Exercise: Using matlab, draw a graph of e s as a function of T for the range 20 C < T < +40 C. 19
70 Generalized Statement of 2nd Law The Second Law of Thermodynamics states that for a reversible transformation there is no change in the entropy of the universe. In other words, if a system receives heat reversibly, the increase in its entropy is exactly equal in magnitude to the decrease in the entropy of its surroundings. 20
71 Generalized Statement of 2nd Law The Second Law of Thermodynamics states that for a reversible transformation there is no change in the entropy of the universe. In other words, if a system receives heat reversibly, the increase in its entropy is exactly equal in magnitude to the decrease in the entropy of its surroundings. the entropy of the universe increases as a result of irreversible transformations. 20
72 Generalized Statement of 2nd Law The Second Law of Thermodynamics states that for a reversible transformation there is no change in the entropy of the universe. In other words, if a system receives heat reversibly, the increase in its entropy is exactly equal in magnitude to the decrease in the entropy of its surroundings. the entropy of the universe increases as a result of irreversible transformations. The Second Law of Thermodynamics cannot be proved. It is believed to be valid because it leads to deductions that are in accord with observations and experience. 20
73 Generalized Statement of 2nd Law The Second Law of Thermodynamics states that for a reversible transformation there is no change in the entropy of the universe. In other words, if a system receives heat reversibly, the increase in its entropy is exactly equal in magnitude to the decrease in the entropy of its surroundings. the entropy of the universe increases as a result of irreversible transformations. The Second Law of Thermodynamics cannot be proved. It is believed to be valid because it leads to deductions that are in accord with observations and experience. Evidence is overwhelming that the Second Law is true. Deny it at your peril! 20
74 Quotes Concerning the 2nd Law Sir Arthur Eddington, one of the most prominent and important astrophysicists of the last century. 21
75 Quotes Concerning the 2nd Law Sir Arthur Eddington, one of the most prominent and important astrophysicists of the last century. If someone points out to you that your pet theory of the universe is in disagreement with Maxwell s equations, then so much the worse for Maxwell s equations. And if your theory contradicts the facts, well, sometimes these experimentalists make mistakes. But if your theory is found to be against the Second Law of Thermodynamics, I can give you no hope; there is nothing for it but to collapse in deepest humiliation. 21
76 Charles Percy Snow ( ) a scientist and novelist, most noted for his lectures and books regarding his concept of The Two Cultures. 22
77 Charles Percy Snow ( ) a scientist and novelist, most noted for his lectures and books regarding his concept of The Two Cultures. A good many times I have been present at gatherings of people who, by the standards of the traditional culture, are thought highly educated and who have with considerable gusto been expressing their incredulity at the illiteracy of scientists. Once or twice I have been provoked and have asked the company how many of them could describe the Second Law of Thermodynamics. The response was cold: it was also negative. 22
78 Nothing in life is certain except death, taxes and the second law of thermodynamics. All three are processes in which useful or accessible forms of some quantity, such as energy or money, are transformed into useless, inaccessible forms of the same quantity. That is not to say that these three processes don t have fringe benefits: taxes pay for roads and schools; the second law of thermodynamics drives cars, computers and metabolism; and death, at the very least, opens up tenured faculty positions. 23
79 Nothing in life is certain except death, taxes and the second law of thermodynamics. All three are processes in which useful or accessible forms of some quantity, such as energy or money, are transformed into useless, inaccessible forms of the same quantity. That is not to say that these three processes don t have fringe benefits: taxes pay for roads and schools; the second law of thermodynamics drives cars, computers and metabolism; and death, at the very least, opens up tenured faculty positions. Professor Seth Lloyd, Dept. of Mech. Eng., MIT. Nature 430, 971 (26 August 2004) 23
80 Entropy is a measure of the disorder (or randomness) of a system. The Second Law implies that the disorder of the universe is inexorably increasing. 24
81 Entropy is a measure of the disorder (or randomness) of a system. The Second Law implies that the disorder of the universe is inexorably increasing. The two laws of thermodynamics may be summarised as follows: (1) The energy of the universe is constant (2) The entropy of the universe tends to a maximum. 24
82 Entropy is a measure of the disorder (or randomness) of a system. The Second Law implies that the disorder of the universe is inexorably increasing. The two laws of thermodynamics may be summarised as follows: (1) The energy of the universe is constant (2) The entropy of the universe tends to a maximum. They are sometimes parodied as follows: (1) You can t win (2) You can t break even (3) You can t get out of the game. 24
83 End of
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