Thermodynamics Carnot cycle

Rankine Cycle Thermodynamics. Carnot cycles provide the highest theoretical efficiency possible, but these are entirely gas phase. A drawback to a Carnot cycle is the need for gas compression. Producing efficient, large-volume compressors has been such a problem that combustion turbines and jet engines were not practical until the late 1940s. 

Thus, Sadi Carnot s analysis of Carnot cycle provided the theory for the formulation of the first and the second law of thermodynamics. His concept is that for a system undergoing a cycle, the net heat transfer is equal to the net work done, which led to the first law of thermodynamics. Similarly, the concept that a heat engine cannot convert all the heat absorbed from a heat source at a single temperature into work even under ideal condition led to the second law of thermodynamics. Carnot cycle efficiency gives the idea about the maximmn theoretical efficiency of an engine. Sadi Carnot was rightly honored with the title Father of Thermodynamics for his invaluable contribution to thermodynamics. 

French physicist, who first worked as a miiitary engineer. He then turned to scientific research and in 1824 published his analysis of the efficiency of heat engines. The key to this analysis is the thermodynamic Carnot cycle. He died at an early age of cholera. 

Carnot Sadi Nicolas Leonard (1796-1832) Fr. phys., founder of thermodynamics (Carnot cycle)... 

Carnot, Nicolas Leonard Sadi (1796-1832)AFrenchphysicistwhobeganhlscareer as a military engineer before turning to scientific research. In 1824 he published a book Reflections on the Motive Power of Fire, which provided for the first lime a general theoretical approach to understanding the conditions under which the efficiency of heat engines could be maximized. The thermodynamic Carnot cycle eventoally led to the concept of entropy. He died aged 36 from cholera. 

The Carnot cycle is formulated directly from the second law of thermodynamics. It is a perfectly reversible, adiabatic cycle consisting of two constant entropy processes and two constant temperature processes. It defines the ultimate efficiency for any process operating between two temperatures. The coefficient of performance (COP) of the reverse Carnot cycle (refrigerator) is expressed as... 

The thermal efficiency of the process (QE) should be compared with a thermodynamically ideal Carnot cycle, which can be done by comparing the respective indicator diagrams. These show the variation of temperamre, volume and pressure in the combustion chamber during the operating cycle. In the Carnot cycle one mole of gas is subjected to alternate isothermal and adiabatic compression or expansion at two temperatures. By die first law of thermodynamics the isothermal work done on (compression) or by the gas (expansion) is accompanied by the absorption or evolution of heat (Figure 2.2). 

The second law of thermodynamics may be used to show that a cyclic heat power plant (or cyclic heat engine) achieves maximum efficiency by operating on a reversible cycle called the Carnot cycle for a given (maximum) temperature of supply (T ax) and given (minimum) temperature of heat rejection (T jn). Such a Carnot power plant receives all its heat (Qq) at the maximum temperature (i.e. Tq = and rejects all its heat (Q ) at the minimum temperature (i.e. 7 = 7, in) the other processes are reversible and adiabatic and therefore isentropic (see the temperature-entropy diagram of Fig. 1.8). Its thermal efficiency is... 

It was pointed out in Chapter I that the desire for higher maximum temperature (T nx) in thermodynamic cycles, coupled with low heat rejection temperature (Tmin), is essentially based on attempting to emulate the Carnot cycle, in which the efficiency increases with... 

Applying the first law of thermodynamics to the Carnot cycle gives... 

A concept of the cycle of thermodynamic processes, introduced later than the Carnot cycle. Modifications of the Rankine cycle are of practical importance in boiler design, in relating the successive thermodynamic changes as water is converted to steam, expands and converted to mechanical energy in a turbine, then condenses and returns to the boiler. 

In the next chapter, we will return to the Carnot cycle, describe it quantitatively for an ideal gas with constant heat capacity as the working fluid in the engine, and show that the thermodynamic temperature defined through equation (2.34) or (2.35) is proportional to the absolute temperature, defined through the ideal gas equation pVm = RT. The proportionality constant between the two scales can be set equal to one, so that temperatures on the two scales are the same. That is, 7 °Absolute) = T(Kelvin).r... 

To summarize, the Carnot cycle or the Caratheodory principle leads to an integrating denominator that converts the inexact differential 8qrev into an exact differential. This integrating denominator can assume an infinite number of forms, one of which is the thermodynamic (Kelvin) temperature T that is equal to the ideal gas (absolute) temperature. The result is... 

In summary, the Carnot cycle can be used to define the thermodynamic temperature (see Section 2.2b), show that this thermodynamic temperature is an integrating denominator that converts the inexact differential bq into an exact differential of the entropy dS, and show that this thermodynamic temperature is the same as the absolute temperature obtained from the ideal gas. This hypothetical engine is indeed a useful one to consider. 

The second law of thermodynamics says that in a Carnot cycle Q/T = constant. This law allows for the definition of a temperature scale if we arbitrarily assign the value of a reference temperature. If we give the value T3 = 273.16K to the triple point (see Gibbs law, Section 8.2) of water, the temperature in kelvin units [K] can be expressed as ... 

The experimental realization of a Carnot cycle to measure the temperature T is unusual. The coincidence of the thermodynamic temperature T with the temperature read by a gas thermometer, for example, allows the use of such thermometer to know T. As we shall see, also other laws of physics relating T with physical parameters other than heat can be used to get an absolute measure of T. 

It follows that the efficiency of the Carnot engine is entirely determined by the temperatures of the two isothermal processes. The Otto cycle, being a real process, does not have ideal isothermal or adiabatic expansion and contraction of the gas phase due to the finite thermal losses of the combustion chamber and resistance to the movement of the piston, and because the product gases are not at thermodynamic equilibrium. Furthermore the heat of combustion is mainly evolved during a short time, after the gas has been compressed by the piston. This gives rise to an additional increase in temperature which is not accompanied by a large change in volume due to the constraint applied by the piston. The efficiency, QE, expressed as a function of the compression ratio (r) can only be assumed therefore to be an approximation to the ideal gas Carnot cycle. 

A fascinating point, especially to physical chemists, is the potential theoretical efficiency of fuel cells. Conventional combustion machines principally transfer energy from hot parts to cold parts of the machine and, thus, convert some of the energy to mechanical work. The theoretical efficiency is given by the so-called Carnot cycle and depends strongly on the temperature difference, see Fig. 13.3. In fuel cells, the maximum efficiency is given by the relation of the useable free reaction enthalpy G to the enthalpy H (AG = AH - T AS). For hydrogen-fuelled cells the reaction takes place as shown in Eq. (13.1a). With A//R = 241.8 kJ/mol and AGr = 228.5 under standard conditions (0 °C andp = 100 kPa) there is a theoretical efficiency of 95%. If the reaction results in condensed H20, the thermodynamic values are A//R = 285.8 kJ/ mol and AGR = 237.1 and the efficiency can then be calculated as 83%. 

In the conversion of fossil and nuclear energy to electricity, the value of high temperature solution phase thermodynamics in improving plant reliability has been far less obvious than that of classical thermodynamics in predicting Carnot cycle efficiency. Experimental studies under conditions appropriate to modern boiler plant are difficult and with little pressure from designers for such studies this area of thermodynamic study has been seriously neglected until the last decade or two. 

It is commonly expressed that a fuel cell is more efficient than a heat engine because it is not subject to Carnot Cycle limitations, or a fuel cell is more efficient because it is not subject to the second law of thermodynamics. These statements are misleading. A more suitable statement for... 

As the magnirnde of the heat exchanged in an isothermal step of a Carnot cycle is proportional to a function of an empirical temperature scale, the magnitude of the heat exchanged can be used as a thermometric property. An important advantage of this approach is that the measurement is independent of the properties of any particular material, because the efficiency of a Carnot cycle is independent of the working substance in the engine. Thus we define a thermodynamic temperature scale (symbol T) such that... 

THE PROOF THAT S IS A THERMODYNAMIC PROPERTY Any Substance in a Carnot Cycle... 

Carnot efficiency is one of the cornerstones of thermodynamics. This concept was derived by Carnot from the impossibility of a perpetuum mobile of the second kind [ 1]. It was used by Clausius to define the most basic state function of thermodynamics, namely the entropy [2]. The Carnot cycle deals with the extraction, during one full cycle, of an amount of work W from an amount of heat Q, flowing from a hot reservoir (temperature Ti) into a cold reservoir (temperature T2 < T ). The efficiency r] for doing so obeys the following inequality ... 

The Carnot cycle is of historical importance. The reversible cycle was introduced by a French engineer N.S. Carnot in 1824 and led to the development of the second law of thermodynamics. The importance of the Carnot cycle is that it sets up a standard thermal cycle performance for the actual cycles to compare with. 

A hypothetical cycle for achieving reversible work, typically consisting of a sequence of operations (1) isothermal expansion of an ideal gas at a temperature T2 (2) adiabatic expansion from T2 to Ti (3) isothermal compression at temperature Ti and (4) adiabatic compression from Ti to T2. This cycle represents the action of an ideal heat engine, one exhibiting maximum thermal efficiency. Inferences drawn from thermodynamic consideration of Carnot cycles have advanced our understanding about the thermodynamics of chemical systems. See Carnot s Theorem Efficiency Thermodynamics... 

A principle stating that for any engine working between the same two temperatures, maximum efficiency will occur by a engine working reversibly between those same two temperatures. Thus, all reversible engines have the same efficiency between the same temperatures and that efficiency is dependent only on those temperatures and not on the nature of the substance being acted upon. See Efficiency Thermodynamics, Laws of Carnot Cycle... 

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