Why is Qir < than Qr? Carnot cycle and change in G

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The discussion centers on the differences between reversible and irreversible gas expansions, particularly regarding the heat and work involved in each process. It clarifies that the Khan Academy video incorrectly equates Gibbs Free Energy (ΔG) for chemical reactions instead of focusing on gas expansions, leading to misunderstandings about heat transfer and work done. The key point is that irreversible expansions require less work due to viscous stresses, resulting in less heat absorbed from the reservoir. The conversation emphasizes that while both processes have the same change in entropy (ΔS), the total entropy change for the irreversible process is greater than zero due to energy dissipation. Understanding these concepts is crucial for grasping the foundational principles of thermodynamics.
  • #31
Chestermiller said:
Excellent!

Now, before we continue, I'm going to give you a little more information about reversible and irreversible processes, so that you can better understand what is happening to the gas in each case.

REVERSIBLE PROCESSES
As we said earlier, in a reversible process, the system experiences a deformational and thermal path that is only slightly removed from a continuous sequence of thermodynamic equilibrium states. For a thermodynamic equilibrium state of a gas within a cylinder, the temperature, pressure, and specific volume (reciprocal of density) of the gas are uniform throughout the cylinder, and the compressive stresses (forces per unit area) within gas are the same in all directions; for an ideal gas:
$$\sigma_x=P=\frac{RT}{V}$$
$$\sigma_y=P=\frac{RT}{V}$$
$$\sigma_z=P=\frac{RT}{V}$$where the ##\sigma##'s are the compressive stresses in the coordinate directions, T is the uniform temperature of the gas within the cylinder, p is the uniform pressure, and V is the total volume of the gas in the cylinder divided by the number of moles (i.e., the uniform specific volume)

IRREVERSIBLE PROCESSES
The mechanical behavior of a gas, in general, is more complicated than the (equilibrium) equation of state of the gas; it depends not only on the P-V-T behavior of the gas, but also on the rate at which the gas is being deformed. The latter is described by the spatial derivatives of the velocity of the gas. The more general equations for the compressive stresses in a gas that is not in thermodynamic equilibrium (derived in 3D from Newton's Law of viscosity) are given by:
$$\sigma_x=P-2\mu\frac{\partial u_x}{\partial x}=\frac{RT}{V}-2\mu\frac{\partial u_x}{\partial x}$$
$$\sigma_y=P-2\mu\frac{\partial u_y}{\partial y}=\frac{RT}{V}-2\mu\frac{\partial u_y}{\partial y}$$
$$\sigma_z=P-2\mu\frac{\partial u_x}{\partial x}=\frac{RT}{V}-2\mu\frac{\partial u_z}{\partial z}$$where the u's are the velocity components in the coordinate directions and ##\mu## is the viscosity of the gas. In these equations, we still call P the pressure of the gas, although this "thermodynamic pressure" is no longer the total force per unit area acting on every surface; the local pressure P just contributes to the force per unit area. Note also that, in an irreversible process, the temperature, pressure, and specific volume of the gas in these equations are no longer uniform spatially within the cylinder (e.g., the specific volume is no longer the total volume of the cylinder divided by the total number of moles); all three are functions of the spatial coordinates x, y, and z. Thus, T = T(x,y,z), P = P(x,y,z), and V = V(x,y,z). Note also that, when the velocity components of a gas become very small, as in a reversible deformation, the equations for the stresses reduce to those for a reversible process.

There are several reasons why the temperature, pressure, and specific volume are not uniform in an irreversible process. First of all, the gas has mass, so it has to be accelerated just like the piston is accelerated. But it is not solid like the piston. So, in a rapid deformation, it experiences a kind of "sloshing" effect, where different parts of the gas experience different velocities and accelerations. Secondly, heat transfer is occurring at a finite rate from the reservoir to the gas, so portions of the gas near the wall experience temperature changes at a different rate than portions of the gas closer to the axis. This also causes the viscosity of the gas (which is temperature dependent) to affect the compressive stresses in the gas non-uniformly. Finally, there can be small scale turbulence in the gas as it deforms, and this influences the effective value of the viscosity (which feeds back into the compressive stresses).

The bottom line is that, in an irreversible process, many complicated phenomena are occurring within the gas that affects its behavior in a difficult-to-quantify manner, and we can't simply say that the compressive stress acting on the piston face can be determined by merely using the ideal gas equation under the assumption that the pressure, temperature, and specific volume are uniform throughout.

Now, back to our problem. The equation you wrote for the force exerted by the gas on the piston face was as follows:
$$F(t) = m(g + a(t))$$where we now know that ##F(t)=\sigma_zA=(\frac{RT}{V}-2\mu\frac{\partial u_z}{\partial z})A##, with the spatial derivative of vertical gas velocity evaluated at the piston face. Another way of writing your equation is:
$$F(t)=m(g+\frac{du}{dt})$$where u is the piston velocity. If we multiply this equation on both sides by u=dz/dt, we obtain:
$$F(t)\frac{dz}{dt}=m(g\frac{dz}{dt}+u\frac{du}{dt})$$
If I integrate the left hand side of this equation with respect to t, from time zero to time t, I get:
$$W(t)=\int_0^t{F(t')\frac{dz'}{dt'}dt'}=\int_{z_0}^{z(t)}{F(z')dz'}$$where W(t) is the work done by the gas on the piston from time zero (at which the pile of rocks was suddenly removed) to time t, z' and t' are dummy variables of integration, and ##z_0## is the elevation of the piston at time zero. What do you get when you integrate the right hand side of the equation with respect to t, and then combine the results?
I am trying my best to understand the information that you have given about reversible and irreversible processes.
I hope I got the difference between compressive stress and pressure right. Compressive stress is the force exerted by the gas on an area within the gas whereas pressure is the force exerted by the gas on an external object?
Forgive me for this- I am yet to learn spatial derivatives, differentials or integration in my college. I just know the basics of differentiation (and a little integration).
 
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  • #32
DoubtExpert said:
I am trying my best to understand the information that you have given about reversible and irreversible processes.
I hope I got the difference between compressive stress and pressure right. Compressive stress is the force exerted by the gas on an area within the gas whereas pressure is the force exerted by the gas on an external object?
No. The term stress applies both to within the gas and on an external object. When you learned about pressure, it was called the force per unit area, but it was applied only to cases where the fluid was not deforming and, in these cases, it was the same in all directions. When a fluid is deforming, the mechanical behavior of the fluid is very different than when it is at equilibrium. The force per unit area is no longer the same on surfaces oriented in all directions, both internal and external. For a fluid that is deforming, we no longer call pressure the force per unit area; we now reserve the term "pressure" for the average force per unit area (averaged over all possible surface orientations). The remainder of the forces per unit area (which now depend on direction within the fluid) are "viscous stresses." These depend on the rate at which the fluid is deforming. In a deforming gas, the entity we now call the pressure is found to be very nearly equal to the 'thermodynamic pressure" calculated from the ideal gas law, but based on local values of the temperature and specific volume. The remaining contributions to the stress in different directions are related to the rate at which the gas is deforming.
 
  • #33
DoubtExpert said:
Forgive me for this- I am yet to learn spatial derivatives, differentials or integration in my college. I just know the basics of differentiation (and a little integration).
OK. Then I will provide the integration of the right hand side of the equation, and hope you are comfortable with it. So, the work done by the gas on the lower face of the piston (up to time t) is given by:
$$W(t)=mg[z(t)-z_0]+\frac{1}{2}mu^2(t)$$The first term on the right is the change in potential energy of the piston up to time t, and the second term is the change in its kinetic energy.

Now, my next question for you is "what do you think the frictionless piston motion will be like as time progresses?"
(a) It just keeps going higher and higher in elevation
(b) It overshoots the final equilibrium elevation, and then moves back downward again, oscillating back and forth about the equilibrium elevation forever (like as spring/mass system in simple harmonic motion)
(c) It begins oscillating as in (b), but the magnitude of the oscillation damps out, and vanishes when the piston finally settles at the equilibrium elevation (even though the piston is frictionless)
 
  • #34
Chestermiller said:
OK. Then I will provide the integration of the right hand side of the equation, and hope you are comfortable with it. So, the work done by the gas on the lower face of the piston (up to time t) is given by:
$$W(t)=mg[z(t)-z_0]+\frac{1}{2}mu^2(t)$$The first term on the right is the change in potential energy of the piston up to time t, and the second term is the change in its kinetic energy.

Now, my next question for you is "what do you think the frictionless piston motion will be like as time progresses?"
(a) It just keeps going higher and higher in elevation
(b) It overshoots the final equilibrium elevation, and then moves back downward again, oscillating back and forth about the equilibrium elevation forever (like as spring/mass system in simple harmonic motion)
(c) It begins oscillating as in (b), but the magnitude of the oscillation damps out, and vanishes when the piston finally settles at the equilibrium elevation (even though the piston is frictionless)
I think the right answer is Option (b). (Option (a) is not possible because of the pressure from the piston on the gas and Option (c) is not possible because there exist no agents that would assist in damping)
But I don't know why it undergoes a simple harmonic motion. Why do objects undergo a SHM? Why can't they settle in their new equilibrium position right away?
 
  • #35
DoubtExpert said:
I think the right answer is Option (b). (Option (a) is not possible because of the pressure from the piston on the gas and Option (c) is not possible because there exist no agents that would assist in damping)
But I don't know why it undergoes a simple harmonic motion. Why do objects undergo a SHM? Why can't they settle in their new equilibrium position right away?
Objects undergo SHM because there is nothing to drain the energy from the system. When the object passes through the equilibrium position, it has velocity so it overshoots. When it gets to an extreme position, its velocity is zero, but there is then a force acting on it from the spring. So, in the absence of an energy drain, the object keeps oscillating forever.

The actual correct answer to my question is Option (c), because there does exist an agent that would assist in damping. This is the viscous dissipation of mechanical energy to internal energy which occurs within the gas. The viscous forces within the gas act like a shock absorber in a a car, to dissipate mechanical energy. When you hit a bump, the car does not oscillate forever. The shock absorber causes the oscillation to damp out. In the case of a gas, both the springiness and the viscous dissipation are both present within the gas, rather than separately as in a car.

So, back to our problem. After an infinite amount of time, when our system achieves thermodynamic equilibrium and the piston has stabilized at its final equilibrium position, what is the equation for the amount of work that the gas has done on the piston?
 

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