Web-Notes 4

The Second Law Formulations for Cyclical Processes

Objective

Author: Dr. Sushil Chaturvedi Old Dominion University

The primary objective of this module is to introduce students to the Kelvin-Plank and Clausius statements of the second law, the Carnot theorem and the Clausius inequality for cyclical processes. Concepts such as reversible and irreversible processes, perpetual machines and theoretical performance limit of refrigerators and heat engines are discussed.

Motivation and Relevance

The basic concepts as well as the second law formulations discussed in this module lay foundation for introduction of a thermodynamic property entropy, discussed in a subsequent module. The second law allows one to calculate the performance of a perfect (reversible) cyclical machine. The revelation that real-life heat engines and refrigerators have a upper (theoretical) limit on their performance, imposed by the second law, is particularly relevant to the present

day global problem of limited supply of good quality fossil fuels for power generation. This calls for more efficient utilization of existing energy resources through energy conservation and enhancement of power plant energy conversion efficiency. In this context the knowledge of theoretical limit not only serves as a limitation which cannot be overcome in real life, it also serves as an ultimate goal for those who seek to design power plants with higher efficiency. Aside from providing the theoretical limit on performance, the second law also provides a framework for improving efficiency of energy conversion cycles.

Concepts, Definition and Analysis

The Second Law of Thermodynamics Some introductory remarks are in order. The first and the foremost, it is important to understand that the second law of thermodynamics like the first law is an empirical law, based only on experimental observations. In other words, the second law, unlike some other laws, cannot be derived from other laws or principles but must be inferred from experiments. The second law can also be thought of as a law governing the directionality of a process. For instance, it may allow a process or a cycle to proceed in a given direction but may prohibit the process from being executed in the opposite direction. This directionality feature of the law allows one to determine

Author: Dr. Sushil Chaturvedi Old Dominion University

if a process in a given direction is possible or impossible. Finally it should be noted that there are multiple formulations of the second law and several of them are discussed in this module.

The Kelvin-Plank Statement The Kelvin-Plank statement is one of the original formulation of the second law of thermodynamics and it deals with cyclical heat engines. It states that it is impossible to construct a cyclical heat engine whose thermal efficiency (th) is 100%. In other words, as shown in Fig. 4.1, the condition QL = 0 is not possible. All cyclical engines must reject heat.

TH

QH
Wnet = QH Impossible Heat engine TL
Figure 4.1 The Kelvin-Plank statement

QL = 0

The Clausius Statement This statement of the second law governs cooling and heating devices such as refrigerators and heat pumps. According to this formulation, shown in Fig. 4.2, it is impossible to construct and operate a cyclical heat pump or a refrigerator whose sole effect is to pump heat from a low temperature source (TL) to a higher temperature sink (TH) without consuming work (Wnet = 0). In other words in a refrigerator or a heat pump QH cannot be equal to QL. It should be noted that the reverse is true and happens all the time in real life. Heat flows spontaneously from a higher temperature body to a lower temperature body without intervention in form of work. The Clausius statement is based on observations that heat cannot flow spontaneously from a low temperature body to a higher temperature body unless work is done to achieve this outcome.

Author: Dr. Sushil Chaturvedi Old Dominion University

TH

QH = QL

Impossible Refrigerator TL

Wnet = 0

Figure 4.2 The Clausius statement

It should be noted that both statements are equivalent, and the violation of the Kelvin-Plank statement will result in the violation of the Clausius statement and vice-versa. A proof of the equivalence is provided in the Exploration section of this module.

Perpetual Machines of the First and Second Kind If a cyclical device, heat engine or refrigerator, violates the first law of thermodynamics ( Q = W), it is termed as the perpetual machine of the first kind. Such a machine would not conserve energy and would create or destroy energy. Such a device cannot be realized (constructed and operated) in real life. A cyclic machine that violates the second law of thermodynamics is known as the perpetual machine of the second kind. Once again such a machine belongs to the domain of the impossible. These terms are not only of academic interest but are also used by the U.S. Patent Office which by many accounts receives several schemes , pertaining to conversion of energy from one form to another, that are in violation of either the first law or the second law or both. The U.S. Patent Office, guided by the laws of thermodynamics, routinely rejects claims for patents involving perpetual machines of the first and second kind.

Concepts of Reversibility and Irreversibility The second law of thermodynamics is intimately related to the concepts of reversibility and irreversibility. When we drive an automobile forward a few hundred meters and then drive it

Author: Dr. Sushil Chaturvedi Old Dominion University

back in reverse gear by the same distance, one gets the appearance of the restoration of the automobile to its original location or state. But have things really been returned to their original states? What about the gasoline consumed in the forward as well as in the backward movements? What about tire wearing out a bit due to road friction? What about the atmosphere which has received combustion gases from the tail pipe? The most reasonable answer is that although the automobile may appear to be back to its original position many other effects cause both the automobile and its surroundings to be not in the same state as before, when the automobile ride was initiated. This discussion leads us to define a reversible or an irreversible process, strictly in the thermodynamic sense.

Reversible and Irreversible Processes A thermodynamic process, involving a system, is said to be reversible if after having taken place, it is possible to bring the system as well as surrounding back to their original states, thus leaving no trace if the process ever occurred. If it is not possible to accomplish the restoration of both, system and surrounding, then we designate the process as being an irreversible process.

It should be noted that all real life processes are irreversible while all reversible processes are conceptual or ideal and cannot be realized in real life.

Factors that Cause Irreversibility As noted earlier all real life processes, including human life, are irreversible. This irreversible behavior or irreversibility is caused by many factors that are present in real-life processes. They are: 1. Friction between solid and solid surfaces or fluid and solid surfaces. 2. Heat transfer through finite temperature difference. 3. Mixing of dissimilar fluids. 4. Combustion through rapid chemical reactions 5. Quick compression or expansion 6. Resistance heating (I2R losses) 7. Turbulent mixing.

Author: Dr. Sushil Chaturvedi Old Dominion University

When above factors are absent in a process, it is termed as a reversible process. It should be noted that heat transfer through small temperature difference is a reversible process eventhough heat transfer through finite temperature difference is an irreversible process.

The Connection Between Quasi-equilibrium and Reversible Processes This point needs clarification. As we noted earlier, quasi-equilibrium processes are slow processes in which the system does not significantly depart from intermediate equilibrium states. A reversible process is also very slow and it also maintains quasi-equilibrium condition in all its intermediate states. In fact one can state that a quasi-equilibrium process is essentially an internally reversible (internal to the system) process. In an internally reversible process, a system is in quasi-equilibrium even though there may be non-equilibrium effects outside the system boundary.

The Carnot Cycle The Carnot cycle holds a special place in thermodynamics because it has also been used for bench marking thermal performance of real cycles. Figure 4.3 shows the schematics of a Carnot cycle that operates much like a steam power plant. The four processes along with energy exchanges are as follows: 12 23 34 41 Reversible adiabatic compression process in the pump. It pressurizes liquid water to a high pressure P2 (Wpump). Reversible isothermal heat addition process in the boiler to generate steam (QH). Reversible adiabatic expansion process in the turbine. In this process, pressure falls and work is produced (Wturb). Reversible isothermal heat rejection in the condenser (QL).

Note that even in an ideal cycle such as Carnot cycle, heat must be rejected in accordance with the Kelvin-Plank statement. Adiabatic condition (no heat transfer) is much easier to achieve than the reversible condition. For instance one can achieve adiabatic condition in real life by employing a lot of insulation to reduce heat loses to negligible values (or zero value in the ideal case). However, the reversible condition is almost impossible to achieve. For instance, if factors such as friction are present the process will degenerate into an irreversible process. Reducing

Author: Dr. Sushil Chaturvedi Old Dominion University

friction between moving parts is a laudable goal, but its complete elimination is not possible in real life processes. So how do we propose to make processes reversible? We do it by conceptualizing or idealizing that liquid water and steam have zero viscosities and experience no frictional effects as they flow through the cycle. We term this steam as the conceptual steam. It has all the properties of real steam as listed in steam tables except that unlike real steam, the conceptual steam has zero viscosity or no friction.

TH QH Boiler at TH

2
Wpump

3 Pump Turbine

Wturb

1
Condenser at TL

QL
TL
Figure 4.3 Schematics of a Carnot cycle

One can also construct a Carnot cycle using a piston-cylinder configuration that uses air as the working fluid. These two configurations are shown in the sub-module Thermodynamic Cycles.

Because the Carnot cycle is a reversible cycle, the flow direction as well as direction of energy interactions can be reversed to make it operate as a Carnot refrigerator. In the reversible or conceptual world, a Carnot heat engine can be made to work as a Carnot refrigerator by a mere

Author: Dr. Sushil Chaturvedi Old Dominion University

flick of a switch! In real life such a reversal is not possible and consequently the automobile engine cannot be turned into a refrigerator. Following relationship holds for a Carnot cycle,

4.1

Using this result, one can write following expressions for Carnot heat engines and refrigerators.

4.2

= =

4.3

4.4

Note that all temperature values are in absolute unit ( degree Kelvin). The Carnot Theorem This theorem deals with the performance comparison of a Carnot cycle with a real-life heat engine or refrigerator cycle. The theorem states that a real-life heat engine operating between two thermal reservoirs (TH and TL) has a thermal efficiency (th) which cannot exceed thermal efficiency of a Carnot heat engine (Carnot) operating between the same temperature difference.

4.5

For refrigerators the following relationship holds.

Author: Dr. Sushil Chaturvedi Old Dominion University

4.6

The Clausius Inequality For a cyclical process, following results hold

<0 = >0

Of the three results, the Clausius equality can be proved rather easily if one uses a Carnot cycle (Fig. 4.3). Since process 23 and 41 are reversible heat transfer processes, the temperature difference between reservoirs TH and TL and the working fluid are infinitesimally small. The fluid temperature is essentially the same as TH or TL. Expressing experienced by the working fluid in the Carnot cycle one gets, = =
2 1

into four processes

3 2

4 3

1 4

23 41 + =

Thus from Eq. (4.1) for a Carnot cycle we have, =0 Although this result is proved for the Carnot cycle, a reversible cycle in a universe of infinite number of reversible cycles, one can generalize this result for all reversible cycles.

To prove the result

> 0 for impossible process, let us use the Fig. 4.3 again but construct a

violation of the Kelvin-Plank statement by postulating that QL = 0. The other processes remain the same as in the Carnot cycle.

Author: Dr. Sushil Chaturvedi Old Dominion University

 = + 1 Adiabatic

3 2

+ + 3 4 Adiabatic QL=0

23 = = >0

Since QH >0 and TH is always positive (absolute temperature), it leads to the following result

To construct a proof for real cycles (

< 0) we start with a Carnot cycle in Fig. 4.3, and

convert it into a real cycle by introducing fluid friction or irreversibility in processes 12 and 34, while maintaining the adiabatic condition in those processes. As a result, processes 12 and 34, become irreversible adiabatic processes. The other two processes 23 and 41 remain the same.

Note that the heat rejected (QL)irrev is greater than QL, heat rejected in the Carnot cycle. This follows from the Carnot theorem, which states that between two given thermal reservoirs, TH and TL, the irreversible cycle (with frictional effects) is less efficient than the Carnot cycle. This would also mean that the Carnot cycle will reject less heat compared to the irreversible cycle.
2

= + 1 Adiabatic

0
3 2

+ + 3 Adiabatic

1 4

23 41 1 = + = = = = for a Carnot cycle

Since

Since QL< (QL)irrev and TL > 0, it follows that

< 0 for the irreversible cycle chosen here.

This result can be generalized to all irreversible cycles.

10

Author: Dr. Sushil Chaturvedi Old Dominion University

Exploration
Relating Reversibility to the Second Law of Thermodynamics In order to explore the connection between reversibility and the second law let us revisit the definition of reversible and irreversible processes. A process is said to be reversible if after it has taken place, it is possible to restore the system as well as the surrounding to their original state, without leaving a trace or even a hint that the process ever took place. Since interactions between a system and surrounding are generally in form of heat and work exchanges, we have constructed one example, involving only heat interactions. The other examples involving only work interactions or simultaneous exchange of heat and work between system and its surroundings can also be constructed. Readers are encouraged to pursue those options.

Heat Exchange Between Two Bodies In Fig. 4.4, two copper blocks A and B of equal mass m and different temperatures, T A and TB (TA > TB), are brought into thermal contact. Heat flows from A to B and eventually a final thermal equilibrium state in which both A and B have the same temperature Tf is reached. One can show through application of first law that = + 2

The quantity Q is the amount of heat transferred in this process.

11

Author: Dr. Sushil Chaturvedi Old Dominion University

A TA Q

B TB

Initial State

A Tf Q Thermal Reservoir D W (heat) (Q+W) Q (heat)

B Tf

Final State

W (work) Work C Reservoir F Cyclical Refrigerator

W (heat)
E

W (work)
Cyclical Heat Engine

Figure 4.4 Heat transfer process and the restoration process Figure 4.4 shows both the heat transfer and the restoration process. One may consider A to be the system and B to be its surrounding. Since heat Q flowed from A to B, the main task in the restoration process should be to remove exactly the same amount of heat Q from the block B and put it back into the block A. The heat removal is done by employing a cyclical refrigerator C that, let us say, in one cycle removes heat Q from B. However, in accordance with the Clausius statement of the second law it must do so by using non-zero value of work (W). The output of the refrigerator, in accordance with the first law is Q + W, all in form of heat. Of this total heat, the amount Q is directed to A, thus restoring both A and B to their original state. However, as the energy flow diagram indicates the remaining amount of heat, W, must be deposited in a thermal reservoir D, which is a part of surrounding. This restoration process has disturbed the thermal reservoir D and hence D must be restored back to its original state employing a cyclical heat engine E. This heat engine would draw W amount of heat from the thermal reservoir D and convert all of it into work W. If engine E can accomplish this, the closed loop will be completed since work output W of the heat engine E can be used to replenish work W that was originally drawn by the refrigerator from the work reservoir. However, there is one problem with the last

12

Author: Dr. Sushil Chaturvedi Old Dominion University

link of this restoration loop involving the conversion of heat of amount W, all into work W by the heat engine E since it translates into 100% thermal efficiency for the heat engine E, a scenario prohibited by the Kelvin Plank statement of the second law. In other words this cyclical heat engine is a perpetual machine of the second kind. As a result, one concludes that the full restoration of the system A and its surrounding is not possible. Consequently this process of transfer of heat through a finite temperature difference is an irreversible process.

13

Author: Dr. Sushil Chaturvedi Old Dominion University

Practice Problem Set

The Second Law Formulations for Cyclical Processes
1. A Carnot cycle refrigerator extracts 2 kW of heat from a refrigerated space maintained at 5 C. The heat from the refrigerator is transferred to the atmosphere at 30 C. Determine the power required and heat transferred to the atmosphere. 2. An inventor claims of developing a cyclical engine that operates between two thermal reservoirs at 1000C and 25C respectively. One test performed on the engine yielded following results concerning heat supplied to and rejected from the engine during one cycle. = 2 Evaluate the performance and determine if the inventors claim is valid or not. 3. During the month of January in a location, the average outdoor air temperature is 10C while a house located in that location is maintained at 25C. For every 1C temperature difference, the house loses 1000 MJ of heat through the house shell during the month. A heat pump is used to supply heat to the house to maintain it at 25C. According to the electrical utility the energy required to power the heat pump is 2000 kWhr for the entire month. Determine the coefficient of performance in the heating mode. 4. For the problem 3, what is the minimum possible electrical energy required to supply heat to the house during the month of January? 5. Two cyclic devices operate between 300 K and 250 K reservoirs. For given data determine if these devices are feasible, Carnot or impossible.

14

Author: Dr. Sushil Chaturvedi Old Dominion University

6. Three cyclical heat engines A, B and C operate between two thermal reservoirs at 1000 K and 300 K. a. Mark the following statements as true (T) or false (F). i. ii. iii. The device B is a Carnot heat engine. The device A is impossible in view of the second law of thermodynamics. The device C is a Carnot heat engine.

b. What is the combined thermal efficiency of all three heat engines, operating as a single cyclic device?

7. A two-stage heat pump transfers heat from a 250 K heat source to an intermediate sink at 300 K, using its first stage. The second stage pumps heat from the intermediate temperature level to the 350 K temperature level sink. The heat deposited to the 300 K thermal reservoir is exactly the

15

Author: Dr. Sushil Chaturvedi Old Dominion University

same as the heat drawn from that reservoir by the second stage of the heat pump. Determine the overall coefficient of performance for the heating mode, assuming that both stages operate as Carnot cycles.

8. A dual power cycle employs a Brayton gas power cycle as the topping cycle, and a steam power Rankine cycle as the bottoming cycle. The thermal efficiency of the Brayton and the Rankine cycles are given as 42% and 25% respectively. Determine the overall thermal efficiency of the dual cycle. What is the overall efficiency of the dual cycle if both cycles are replaced by Carnot cycles?

16

Author: Dr. Sushil Chaturvedi Old Dominion University

9. A Carnot heat engine delivers all the power required to drive a Carnot heat pump used for heating a house. During the winter season, the house requires 5000 MJ of heat to maintain it at 300 K. a. How much heat must be supplied to the heat engine during the winter season to achieve the desired result? b. What is the overall efficiency of the heat engine/ heat pump combination?

10. A steam power plant has following interactions with its surroundings. Determine the thermal efficiency of the cycle.

17

Author: Dr. Sushil Chaturvedi Old Dominion University