Thermodynamics
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Thermodynamics (part 1)
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Thermodynamics (part 2)
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Thermodynamics (part 3)
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Thermodynamics (part 4)
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Thermodynamics (part 5)
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Macrostates and Microstates
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Quasistatic and Reversible Processes
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First Law of Thermodynamics/ Internal Energy
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More on Internal Energy
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Work from Expansion
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PV-diagrams and Expansion Work
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Proof: U=(3/2)PV or U=(3/2)nRT
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Work Done by Isothermic Process
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Carnot Cycle and Carnot Engine
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Proof: Volume Ratios in a Carnot Cycle
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Proof: S (or Entropy) is a valid state variable
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Thermodynamic Entropy Definition Clarification
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Reconciling Thermodynamic and State Definitions of Entropy
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Entropy Intuition
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Maxwell's Demon
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More on Entropy
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Efficiency of a Carnot Engine
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Carnot Efficiency 2: Reversing the Cycle
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Carnot Efficiency 3: Proving that it is the most efficient
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Enthalpy
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Heat of Formation
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Hess's Law and Reaction Enthalpy Change
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Gibbs Free Energy and Spontaneity
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Gibbs Free Energy Example
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More rigorous Gibbs Free Energy/ Spontaneity Relationship
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A look at a seductive but wrong Gibbs/Spontaneity Proof
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Stoichiometry Example Problem 1
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Stoichiometry Example Problem 2
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Limiting Reactant Example Problem 1
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Empirical and Molecular Formulas from Stoichiometry
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Example of Finding Reactant Empirical Formula
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Stoichiometry of a Reaction in Solution
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Another Stoichiometry Example in a Solution
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Molecular and Empirical Forumlas from Percent Composition
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Hess's Law Example
Carnot Cycle and Carnot Engine Introduction to the Carnot Cycle and Carnot Heat Engine
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- Let's start with this classic system that I keep referring
- to in our thermodynamics videos.
- I have a cylinder.
- It's got a little piston on the top of it, or it's got a
- ceiling that's movable.
- The gas, and we're thinking of monoatomic ideal gases in
- here, they're exerting pressure onto this ceiling.
- And the reason why the ceiling isn't moving all the way up,
- is because I've placed a bunch of rocks on the top to offset
- the force per area of the actual gas.
- And I start this gas when it's in equilibrium.
- I can define its macrostates.
- It has some volume.
- It has some pressure that's being offset by these rocks.
- And it has some well-defined temperature.
- Now, what I'm going to do is, I'm going to place this system
- here-- I'm going to place it on top of a reservoir.
- And I talked about what a reservoir was either in the
- last video or a couple of videos ago.
- You can view it as an infinitely large object, if
- you will, of a certain temperature.
- So if I put it next to-- if I put our system next to this
- reservoir-- and let's say I start removing pebbles from
- our system.
- We learned a couple of videos ago that if we did it
- adiabatically-- what does adiabatically mean?
- If we removed these pebbles in isolation, without any
- reservoir around, the volume would increase, the pressure
- would go down, and actually the temperature would
- decrease, as well.
- We showed that a couple of videos ago.
- So by putting this big reservoir there that's a lot
- larger than our actual canister, this will keep the
- temperature in our canister at T1.
- You can kind of view a reservoir as-- say I had a cup
- of water in a stadium.
- And the air conditioner in the stadium is at 60 degrees.
- Well, no matter what I do to that water, I could put it in
- the microwave and warm it up, but if I put it back in that
- stadium, that stadium is going to keep
- that water at 60 degrees.
- And you might say, oh, won't the reservoir's temperature
- decrease if it's throwing off heat?
- Well, it would, but it's so much larger that its impact
- isn't noticeable.
- For example, if I put a cup of boiling water into a super
- large covered-dome stadium, the water will get colder to
- the ambient temperature of the stadium.
- The stadium will get warmer, but it will be so marginally
- warmer than you won't even notice it.
- So you can kind of view that as a reservoir.
- And theoretically, this is infinitely large.
- So the effect of this is, as we remove these little rocks,
- we're going to keep the temperature constant.
- And remember, if we're keeping the temperature constant,
- we're also keeping the internal energy constant,
- because we're not changing the kinetic
- energy of the particles.
- So let me see what happens.
- So I keep doing that.
- And so I get to a point-- let me see-- where my volume has
- increased-- so let me delete some of my rocks here.
- Delete some of the rocks.
- So some of the rocks are gone.
- And now my overall volume is going to be larger.
- Let me move this up a little bit.
- And then let me color this in black.
- Oh, whoops.
- Let me color this in, just to give an idea.
- So our volume has gotten a bit larger.
- And let me get my pen correctly.
- So our volume has gotten larger by roughly this amount.
- We have the same number of particles.
- They're going to bump into the ceiling a little less
- frequently, so my pressure would have gone down.
- But because I kept this reservoir here, because this
- reservoir was here the whole time during this process, the
- temperature stayed at T1.
- And that was only because of this reservoir.
- And I want to make that clear.
- And also, just as review, this is a quasi-static process,
- because I'm doing it very slowly.
- The system is in equilibrium the whole time.
- So let's draw what we have so far on our famous PV diagram.
- So this is the P-axis.
- That's the V-axis.
- You label them.
- This is P.
- This is V.
- Let me call this-- I'm going to do it in a good color.
- This is state A of the system.
- This is state B of the system.
- So state A starts at some pressure and volume-- I'll do
- it like that.
- That's state A.
- And it moves to state B.
- And notice, I kept the temperature constant.
- And what did we learn in, I think it was one
- or two videos ago?
- Well, we're at a constant temperature, so we're going to
- move along an isotherm, which is just
- a rectangular hyperbola.
- Because when your temperature is constant, your pressure
- times your volume is going to equal a constant number.
- And I went over that before.
- So we're going to move over-- our path is going to look
- something like this, and I'll move here, to state B.
- I'll move over here to state B.
- And the whole time, this was at a constant temperature T1.
- Now, we've done a bunch of videos now.
- We said, OK, how much work was done on this system?
- Well, the work done on the system is the
- area under this curve.
- So some positive work was-- not done on the system, sorry.
- How much work was done by the system?
- We're moving in this direction.
- I should put the direction there.
- We're moving from left to right.
- The amount of work done by the system is
- pressure times volume.
- We've seen that multiple times.
- So you take this area of the curve, and you have the work
- done by the system from A to B.
- Right?
- So let's call that work from A to B.
- Now, that's fair and everything, but what I want to
- think more about, is how much heat was
- transferred by my reservoir?
- Remember, we said, if this reservoir wasn't there, the
- temperature of my canister would have gone down as I
- expanded its volume, and as the pressure went down.
- So how much heat came into it?
- Well, let's go back to our basic internal energy formula.
- Change in internal energy is equal to heat applied to the
- system minus the work done by the system
- Now, what is the change in internal
- energy in this scenario?
- Well, it was at a constant temperature
- the whole time, right?
- And since we're dealing with a very simple ideal gas, all of
- our internal energy is due to kinetic energy, which
- temperature is a measure of.
- So, temperature didn't change.
- Our average kinetic energy didn't change, which means our
- kinetic energy didn't change.
- So our internal energy did not change while we moved from
- left to right along this isotherm.
- So we could say our internal energy is zero.
- And that is equal to the heat added to the system minus the
- work done by the system.
- Right?
- So if you just-- we put the work done by the system on the
- other side, and then switch the sides, you get heat added
- to the system is equal to the work done by the system.
- And that makes sense.
- The system was doing some work this entire time, so it was
- giving energy to-- well, you know, it was giving
- essentially maybe some potential
- energy to these rocks.
- So it was giving energy away.
- It was giving energy outside of the system.
- So how did it maintain its internal energy?
- Well, someone had to give it some energy.
- And it was given that energy by this reservoir.
- So let's say, and the convention for doing this is
- to say, that it was given-- let me write this down.
- It was given some energy Q1.
- We just say, we just put this downward arrow to say that
- some energy went into the system here.
- Fair enough.
- Now let's take this state B and remove the reservoir, and
- completely isolate ourselves.
- So there's no way that heat can be transferred to and from
- our system.
- And let's keep removing some rocks.
- So if we keep removing some rocks, where do we get to?
- Let me go down here.
- So let's say we remove a bunch of more rocks.
- So let me erase even more rocks than we had in B.
- Maybe I only have one rock left.
- And obviously, the overall volume would have increased.
- So let me make our piston go up like that, and I can make
- our piston is maybe a lot higher now.
- And let me just fill in the rest of our, just so that we
- don't have some empty space there.
- So if I fill that in right there-- OK Let
- me fill that in.
- And then I just use the blue-- I should be talking about
- thermodynamics, not drawing.
- But you get the idea.
- And then I have some more-- you know, I
- shouldn't add particles.
- But my volume has increased a good bit.
- My pressure will have gone down, they're going to bump
- into the walls less.
- And because I removed the reservoir, what's going to
- happen to the temperature?
- My temperature is going to go down.
- This was an adiabatic process.
- So an adiabatic just means we did it in isolation.
- There was no exchange of heat from one system to another.
- So let me just-- this arrow continues down here.
- I'll say adiabatic.
- Now, since I'm moving from one temperature to
- another, this is at T2.
- So I will have moved to another isotherm.
- This is the isotherm for T1.
- If I keep my temperature constant, I
- move along this hyperbola.
- And I would have kept moving along this hyperbola.
- But now that we didn't keep our temperature constant, we
- now move like this.
- We move to another isotherm.
- So let's say I have another isotherm at T2.
- It looks something like this.
- So let me draw like that.
- So let's say I have another-- it should actually curve up a
- little bit.
- So let's say, everything at temperature T2, depending on
- its pressure and volume, is someplace along this curve
- that asymptotes up like that, and then goes to
- the right like that.
- Now, I would have moved down to this isotherm, and my
- pressure would have kept going down, and my volume would have
- kept going down.
- So this move, from B to state C, will look like this.
- Let me do to it in another color.
- Let me do it in the orange color of this arrow.
- So it will look like this.
- And now we're at state C.
- Now, this was adiabatic.
- Which means, there is no exchange of heat.
- So I don't have to figure out how much heat got transferred
- into the system.
- Now, there's something interesting here.
- We still did do some work.
- We can take the area under this curve.
- And we're going to leave it to a future video to think about
- where that work energy-- well, the main thing is, is what was
- reduced by that work energy.
- And, well, if you think [UNINTELLIGIBLE]
- to leave it to future video.
- Our internal energy was reduced, right?
- Because our temperature went down.
- So our internal energy went down.
- We'll talk more about that in the future video.
- So now that we're at state C, and we're at temperature T2.
- Let's put back another sink here.
- But this sink, what it's going to have is a reservoir.
- So let me put two things right here.
- So I'm going to add-- let me erase some of
- these blocks in black.
- So now I'm going to add blocks back.
- I'm going to add little pebbles back into it.
- But I'm going to do it as an isothermic process.
- I'm going to do it with a reservoir here.
- But this reservoir here, it's not going to be the same
- reservoir that I put up there.
- I swapped that one out.
- I got rid of any reservoir when I went from B to C.
- And now I'm going to swap in a new reservoir.
- Actually, let me make it blue.
- Because it's going to be--
- Because here's what's happening.
- I'm now adding pebbles in.
- I'm compressing the gas.
- If this was an adiabatic process, the gas would
- want to heat up.
- So what I'm doing is, I need to put a reservoir to keep it
- at T2, to keep it along this isotherm.
- So this is T2.
- Remember, this reservoir is kind of a cold reservoir.
- It keeps the temperature down.
- As opposed to here.
- This was a hot reservoir.
- It kept the temperature up.
- So you can imagine.
- The heat generated in the system, or internal energy
- being generated in the system-- well, no, I
- shouldn't say that.
- The temperature of the system will want to go up, but it's
- being released, because it's able to transfer that heat
- into our new reservoir.
- And that amount of heat is Q2.
- So I move along this.
- This is right here.
- I'm moving along another isotherm, I'm moving along
- this isotherm.
- Until I get to state D.
- We're almost there.
- This is state D.
- So state D will be someplace here, along this isotherm
- right here.
- Maybe this is state D.
- And once again, you can make the argument that we moved
- along an isotherm Our temperature did not change
- from C to D.
- We know that our internal energy went down from B to C,
- because we did some work.
- But from C to D, our temperature stayed the same.
- It was at temperature-- let me write it down-- T2, right?
- Because we had this reservoir here.
- It stayed the same.
- If your temperature stays the same, then your internal
- energy stays the same.
- At least for the system we're dealing with, because it's a
- very simple gas.
- It's actually the system you'll deal with most of the
- time, in an intro thermodynamics course.
- So.
- Given our internal energy didn't change, we can apply
- the same argument that the heat added to the system is
- equal to the work done by the system.
- Right?
- Same math as we did up here.
- Now, in this case, the work wasn't done by the system.
- The work was done to the system.
- We compressed this piston.
- The force times distance went the other way.
- So given that work was done to the system, the heat added to
- the system was negative, right?
- We're just applying the same thing.
- If our internal energy is 0, the heat added to the system
- is equal to the work done by the system.
- The work done by the system is negative.
- Work was done to it.
- So the heat added to the system would be negative.
- Or another way to think about it is that the
- system gave away heat.
- We put that with Q2.
- And where did it give that heat?
- It gave it to this reservoir that we put here, this kind of
- cold reservoir.
- You could almost view it as a-- well, it's
- accepting the heat.
- OK.
- We're almost there.
- Now, let's say we remove this reservoir from under our
- system again, so it's completely isolated from
- everything else, at least in terms of heat.
- And what we do is, we start adding-- so state D, we still
- had a few less pebbles.
- But we start adding more pebbles again.
- We start adding more pebbles to get it to state A.
- So let me change my pebble color.
- So we start adding more pebbles again to
- get it to state A.
- So that's this process right here.
- Let me do a different color.
- Let's say this is green.
- So as we add pebbles, that's this movement right here.
- We're moving from one isotherm up to another isotherm at a
- higher temperature.
- And remember, this whole time we went
- this clockwise direction.
- So a couple of interesting things are going on here.
- Because we're assuming an ideal scenario, nothing was
- lost of friction.
- This piston just moves up and down.
- No heat loss due to that.
- What we can say is that we've achieved-- we are back at our
- original internal energy.
- In fact, this is one of the properties of a state
- variable, is that if we're at the same point on the PV
- diagram, the same exact point, we have
- the same state variable.
- So now we have the same pressure, volume, temperature,
- and internal energy as what we started with.
- So we've done here is completed a cycle.
- And this particular cycle, it's an important one, it's
- called the Carnot cycle.
- It's named after a French engineer who was trying to
- just optimize engines in the early 1800s.
- So Carnot cycle.
- And we're going to study this a lot in the next few videos
- to really make sure we understand entropy correctly.
- Because in a lot of chemistry classes, they'll
- throw entropy at you.
- Oh, it's measure of disorder.
- But you really don't know what they're talking about, or how
- can you quantify it, or measure it anyway.
- And we really need to deal with the Carnot cycle in order
- to understand where the first concepts of entropy really
- came from, and then relate it to kind of more
- modern notions of it.
- Now, a system that completes a Carnot cycle is called a
- Carnot engine.
- So our little piston here that's moving up and down, we
- can consider this a Carnot engine.
- You might say, oh, Sal, this doesn't seem
- like a great engine.
- I have to move pebbles and all of that.
- And you're right.
- You wouldn't actually implement an engine this way.
- But it's a useful engine, or it's a useful theoretical
- construct, in order for understanding how heat is
- transferred in an engine.
- I mean, if you think about what's happening here, is this
- first heat sink transferred some heat to the system, and
- then the system transferred a smaller amount of heat back to
- the other reservoir.
- Right?
- So this system was transferring heat from one
- reservoir to another reservoir.
- From a hotter reservoir to a colder reservoir.
- And in the process, it was also doing some work.
- And what was the work that it did?
- Well, it's the area under this curve, or the area inside of
- this cycle.
- So this is the work done by our Carnot engine.
- And the way you think about it is, when you're going in the
- rightward direction with increasing volume, it's the
- area under the curve is the work done by the system.
- And then when you move in the leftward direction with
- decreasing volume, you subtract out the work done to
- the system, and then you're left with just
- the area in the curve.
- So we can write this Carnot engine like this.
- It's taking, it's starting-- so you have a reservoir at T1.
- And then you have your engine, right here.
- And then it's connected-- so this takes Q1
- in from this reservoir.
- It does some work, all right?
- The work is represented by the amount of-- the work right
- here is the area inside of our cycle.
- And then it transfers Q2, or essentially the remainder from
- Q1, into our cold reservoir.
- So T2.
- So it transfers Q2 there.
- So the work we did is really the difference
- between Q1 and Q2, right?
- You say, hey.
- If I have more heat coming in than I'm letting out, where
- did the rest of that heat go?
- It went to work.
- Literally.
- So Q1 minus Q2 is equal to the amount of work we did.
- And actually, this is a good time to emphasize again that
- heat and work are not a state variable.
- A state variable has to be the exact same value when we
- complete a cycle.
- Now, we see here that we completed a cycle, and we had
- a net amount of work done, or a net amount of heat added to
- the system.
- So we could just keep going around the cycle, and keep
- having heat added to the system.
- So there is no inherent heat state variable right here.
- You can't say what the value of heat is at
- this point in time.
- All you could say is what amount of heat was added or
- taken away from the system, or you can only say the amount of
- work that was done to, or done by, the system.
- Anyway, I want to leave you there right now.
- We're going to study this a lot more.
- But the real important thing is, and if you never want to
- get confused in a thermodynamics class, I
- encourage you to even go off on your
- own, and do this yourself.
- Kind of-- you can almost take a pencil and paper, and redo
- this video that I just did.
- Because it's essential that you understand the Carnot
- engine, understand this adiabatic process, understand
- what isotherms are.
- Because if you understand that, then a lot of what we're
- about to do in the next few videos with regard to entropy
- will be a little bit more
- intuitive, and not too confusing.
Be specific, and indicate a time in the video:
At 5:31, how is the moon large enough to block the sun? Isn't the sun way larger?
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