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Carnot Theorem

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The Carnot cycle, traditionally defined by a sequence of reversible isothermal and adiabatic steps involving an ideal gas, serves as a foundational model for understanding heat engines. However, the principles derived from this specific cycle extend far beyond it to encompass a wide variety of other engine types, such as the Rankine cycle used in steam engines and the Otto cycle found in combustion engines. While engineers often focus on the specific mechanical details of these distinct cycles, thermodynamics allows us to generalize the efficiency limits regardless of the working substance or the exact path taken, provided the processes remain reversible. This universality means that the fundamental relationship between heat input, work output, and temperature reservoirs applies to any cyclic process, not just those strictly adhering to the Carnot sequence. At the heart of this generalization lies the First Law of Thermodynamics and the concept of entropy as a state function. For any complete cycle, whether it is a standard Carnot loop or a more complex engine design, the net change in internal energy is zero because the system returns to its initial state. Consequently, the net work produced by the engine must equal the difference between the heat absorbed from the hot reservoir and the heat rejected to the cold reservoir. By defining efficiency as the ratio of useful work output to the total heat input, we can express this efficiency in terms of heat quantities. When combined with the Clausius theorem, which relates heat transfer to temperature changes for reversible processes, it becomes evident that the ratio of these heats is directly proportional to the ratio of the absolute temperatures of the reservoirs. This synthesis leads to the Carnot Theorem, a pivotal result stating that the efficiency of any reversible heat engine operating between two specific temperatures depends solely on those temperatures and not on the nature of the working fluid or the specific cycle design. Mathematically, this efficiency is expressed as one minus the ratio of the cold reservoir's temperature to the hot reservoir's temperature. This formula holds true for all reversible engines, proving that no matter whether the engine uses an ideal gas, a real gas, or any other material, the maximum theoretical efficiency is capped by this temperature ratio. The derivation relies fundamentally on the reversibility of the steps and the Second Law of Thermodynamics, establishing a universal limit for energy conversion in heat engines that transcends the specific mechanics of individual designs like the Rankine or Otto cycles.
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okay so what we've seen so far about the carnot cycle is that if we run a carnot cycle for an ideal gas we get a heat engine with an efficiency that's one minus this ratio of the cold temperature the cold reservoir to the hot temperature the temperature of the hot reservoir that's not just specific to the carnot cycle for ideal gases as it turns out but for lots of other types of heat engines as well so first let me explain what i mean by other types of heat engines the carnot cycle is a sequence of adiabatic and isothermal expansions so we do an isothermal reversible and isothermal expansion adiabatic expansion isothermal compression adiabatic compression each one of those steps is reversible and either isothermal or adiabatic the net work we get out of that process we can calculate numerically we don't have to do just isothermal and adiabatic steps though we can imagine just for the sake of argument let's say we did an isothermal expansion from here to here and then somehow we need to get from our hot temperature to some colder temperature but we don't have to do an adiabatic expansion to get to the colder temperature maybe we just drop straight down to the cold temperature so on this pv diagram that would correspond to our second step being not an adiabatic expansion it's not an expansion at all our volume's not changing it's just a pressure drop in order to reduce the temperature so that's an we could call that an isochoric constant volume decrease in temperature and then we could reversibly and isothermally compress to here and then do another isochoric heating to get back up to the initial conditions so that's another heat engine we would end up using heat to do work in that process so that's not the carnot cycle it's it's a different cycle so there's a number of these different types of cycles there's a few that we won't dwell on the details of the rankine cycle is a sequence of adiabatic followed by isobaric expansions and compressions that corresponds to what happens in a steam engine the auto cycle is corresponds more to what happens in a combustion engine those are different steps it's in fact more than just four steps involved in an auto cycle but engineers chemical engineers care a great deal about the details of specific flavors of heat engines chemists are less interested in the details of specific types of heat engines and more interested in the thermodynamics of the process so we're going to not delve into the details of these different heat engines too much but the question is how general is this statement what can we say about heat engines in general even if we're doing something that's not a carnot cycle so let's go back to again thinking about the carnot cycle but in a more general way so again we had four different steps for the carnot cycle and if i just remind you without as much of the math we had at the hot temperature and cold temperature we had we absorbed heat from the surroundings during the first expansion step and we gave some heat back to the colder surroundings in the third step the isothermal compression step so we had in step number one reversible isothermal expansion absorbed some heat adiabatic expansion there was no heat isothermal compression we gave some heat back to the surroundings so these two terms have opposite signs from each other and then no heat in the final adiabatic expansion adding those up there was some net amount of heat from that process i'm going to skip all the rest of the details of this diagram and just remind you that for a cyclic process any cyclic process whether it's a rankine cycle or an otto cycle any cyclic process is going to have zero net change in the internal energy because it's a state function and the work done by this process again even if it's not a carnot cycle even if it's some other type of cycle the work is the area enclosed by this diagram so there's some total amount of work so what this tells us what the first law tells us is these two amounts of heat plus that amount of work must add up to the net change in energy zero so q cold plus q hot plus work is zero or if i move the work to the opposite side of the equal sign negative w is q hot plus q cold that's enough information i don't really have to delve into the details of this diagram and what they are for an ideal gas or van der waals gas or some other type of gas if i'm interested in the efficiency of this process remember that's the amount of work i get out compared to the amount of heat i had to put in just the first law is enough to tell me that the amount of work i get out is equal to negative w is equal to qh plus qc the net heat for the process divided by qh that ratio is the efficiency qh over qh is one qc over qh is qc over qh so written in terms of heat the efficiency of the process is 1 plus this ratio of the heats and remember qc is a negative number qh is a positive number so that ratio that's going to end up decreasing the efficiency below one we had seen previously that those this expression involves temperatures not heats so let's remind ourselves the clausius theorem which says remember a change in entropy an infinitesimally small change in entropy is is dq for the reversible uh process divided by t each one of these steps as we've described them was reversible reversible isothermal reversible adiabatic reversible isothermal reversible adiabatic so all our steps are reversible so we can use the clausius theorem and relate the heats for our steps to entropies so i can say for this total process for my four-step process going around this full cycle the net change in entropy is going to be heat divided by temperature so qh divided by temperature and that happens at the hot temperature this step had no heat this step the heat was q cold and that happened at the colder temperature tc and then the fourth step had no heat so total change in entropy is the sum of these terms of which only two of them contribute anything but entropy is a state function so when i start here i go all the way around the cycle when i get back to where i started the net change in the entropy has to be 0 for that state function so this term plus this term have to add up to 0 qh over th must be the negative of qc over tc or since what i'm interested in is ratios of q's or ratios of ts let's rearrange this a little bit and write q c over qh so i'm going to take this qh and bring it down underneath the qc and then i have to take that tc and put it above the th so qc over qh and there's a negative sign involved is negative of tc over th that's what i get by rearranging this equation so i can use that the clausius theorem applied to this cyclic process tells me that this ratio of heats is negative the ratio of the temperatures so if i plug that in here i find that the efficiency is one instead of plus qc over qh i've got minus tc over th so that's not surprising because we've seen it before we saw it for the case of an ideal gas for the carnot cycle what we've just done here notice i haven't said anything about ideal gases there were no nrt one over v's or log v's or anything like that that came from the ideal gas law only the first law is essentially the only fact we had to use here so at least for the carnot cycle where i have some adiabatic steps we've seen that the efficiency is always going to be one minus this ratio of temperatures whether it's an ideal gas a real gas any type of material the efficiency can be given by this form this is in fact called the carnotherum and it's even more general than just the carnot cycle all types of heat engines all cyclic processes on this pva diagram will have an efficiency given by this result even regardless of what kind of heat engine they are as long as the processes are reversible so that's the carnot theorem the carnot theorem says any reversible heat engine has this efficiency proving that for something other than carnot cycle uh is a little more involved in particular it requires us to make use of the second law of thermodynamics which we haven't covered just yet so i'll postpone that for a little bit but but it's useful to be able to use that result now and say regardless of what type of heat engine we have the efficiency is given by this result one minus the ratio of cold temperature over hot temperature for any reversible heat engine operating between two heat reservoirs at these two different temperatures so what we'll do next is now that we understand how heat engines are good at converting heat into work it's also sometimes useful to do the reverse process converts some work into heat so that's the next thing we'll talk about