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
Work Done by Isothermic Process Isothermic and Adiabatic processes. Calculating the work done by an isothermic process. Seeing that it is the same as the heat added.
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- Let's start with our classic system that I keep using over
- and over again.
- And that's because it tends to be very useful for
- instruction.
- It also tends to be the system that is most covered in
- classrooms. So hopefully it'll be productive for you and your
- school work.
- So I have this container.
- It has a movable piston on top, or kind
- of a movable ceiling.
- Well, of course, inside of my system I have a bunch of
- molecules or atoms bouncing around, creating some type of
- pressure on the system.
- So let's say it has some pressure, P1.
- This volume right here, let's call that V1.
- And let's say it also has some temperature that
- it starts off with.
- Everything is in equilibrium.
- Remember these are macro states.
- The only way I can even tell you what the volume, or the
- pressure, or the temperature is, is if the system is in
- equilibrium, if everything in it is uniform.
- The temperature is consistent throughout.
- Fair enough.
- And in order to keep it placed down, I have to put
- some rocks on top.
- And I've done this in multiple processes so far.
- And, of course, I'm doing these little pebbles, because
- I'm going to remove them slowly.
- Because I want to approximate a quasi-static process.
- Or I want to approximate a system that's always close
- enough to equilibrium that I'm cool with defining our macro
- states, our pressure, our temperature, or our volume.
- Let me write V for volume.
- Now, in this video, I'm going to study what's called an
- isothermic process.
- And really what it just means is, I'm going to keep the
- temperature the same.
- Iso- just means the same.
- You probably remember when we studied the periodic table.
- Isotopes, those are the same element just with different
- mass numbers.
- So this is the same temperature we're going to run
- our process.
- So my question is, how can we do that?
- Because as I remove pebbles, what's going to happen?
- If I just did this, without any-- if it was completely
- isolated from the world.
- And actually I'll add in a word right here.
- If it was an adiabatic process-- If it was
- adiabatic-- fancy word.
- All that means is, completely isolated from the world.
- So no heat is going into or out of this system.
- If this was the case, what would happen as I released or
- I took away some of these little particles?
- Let me copy and paste it.
- Well, let me just redraw it actually.
- So I have my one wall.
- I have another wall.
- I have another wall.
- As I release a couple of pebbles, one at a time, my
- volume is going to increase.
- So I'm going to have a slightly higher volume.
- My volume's going to go up.
- I have fewer pebbles here now.
- And since I have the same number of molecules, they're
- going to bump into this less.
- So pressure is going to go down.
- Volume is going to go up.
- And if I was adiabatic, if I had no extra heat being added
- to the system, what do I know is going to happen to the
- temperature?
- Well, think about it this way.
- Some work was done, right?
- Our old ceiling was maybe some place around here.
- We pushed it up with some force for some distance.
- So we did work.
- And so we changed some kinetic energy, or we transferred some
- kinetic energy, out of the system.
- That's essentially what the work did.
- That kinetic energy was turned into work.
- And temperature is just a macro measure of average
- kinetic energy.
- In fact, we just-- well, I won't go into it.
- But in the last video, the kind of proof you want-- if
- you didn't watch it because you didn't want to go through
- the math, which is completely fair enough because it
- normally wouldn't be done in an intro chemistry class-- I
- showed that the internal energy is equal to the total
- kinetic energy, which was equal to 3/2 times the number
- of moles, times R, times temperature.
- So temperature is just, by some scaling factor, a measure
- of kinetic energy.
- Now, when I do some work, it's essentially a transfer of
- kinetic energy.
- And I can't replace that energy with some heat because
- it's adiabatic.
- There's no heat going into or out of the system.
- So in that situation, the kinetic energy of
- the system went down.
- The average kinetic energy of the system went down.
- So the temperature would've also gone down.
- And actually, just as a bonus point, what happened to the
- internal energy?
- Well, the internal energy is the total kinetic energy of
- the system.
- And I could even right down the original formula.
- Change in internal energy is equal to change-- let me not
- do that, because I said I shouldn't-- is equal to heat
- added to the system, minus work done by the system.
- This is work done by the system.
- That's why we're subtracting it.
- Now, it's adiabatic, so there's no heat
- added to the system.
- So the change in internal energy is equal to the minus
- the work done by the system.
- Well, in this situation, the system did do work.
- It pushed this piston up by some distance with some force.
- So, your delta U is negative.
- It's less than 0.
- So U went down, and that makes sense.
- If temperature changed, then the internal
- energy is going to change.
- And for our simple system, where internal energy is
- represented by the kinetic energy of these molecules,
- that's always going to be the case.
- If temperature doesn't change, internal energy won't change.
- If temperature goes up, internal energy goes up.
- If temperature goes down, internal energy goes down.
- And, of course, they're not the same thing, though.
- The difference between internal energy and
- temperature is the scaling factor, 3/2 times the number
- of molecules, times our ideal gas constant.
- So fair enough.
- I went through this whole exercise just to show you that
- if I was completely isolated, and if I removed a couple of
- these pebbles, that my temperature
- is going to go down.
- Now, I told you already that I want to do
- an isothermic process.
- So I want to do this process while keeping the
- temperature the same.
- So how can I do that?
- Well, what I'm going to do is I'm going to place my system
- on top of what we'll call, a reservoir.
- So a reservoir, you can kind of view as an infinitely large
- amount of something that is the temperature that we
- started off with.
- So this reservoir is T1.
- So even though if, I took two relative things
- of comparable size.
- That says, temperature A.
- This is temperature B.
- And I've put them next to each other.
- They're going to average out to A plus B over 2, whatever
- their temperatures are.
- But if B is massive-- if A is just a speck of particle--
- let's say it's iron dust-- while B is the Eiffel Tower,
- then essentially B's temperature will
- not change a lot.
- A will just become B's temperature.
- Now, a reservoir is
- theoretically infinitely large.
- It's an infinitely large object.
- So if something is next to a reservoir and is given enough
- time, it'll always assume the heat of the reservoir, or the
- temperature of the reservoir.
- So what's going to happen?
- So this is adiabatic, but now I'm actually putting it next
- to a reservoir.
- So this isn't going to happen.
- The adiabatic situation isn't going to happen.
- Now, I'm going to have a situation where I'm going to
- stay the same temperature.
- So what's that going to look like on the PV diagram?
- So let me draw the PV diagram.
- This is my pressure.
- This is my volume.
- So this is my starting point right here.
- And what I'm saying is, if I'm doing an isothermic process,
- so I just keep removing these pebbles.
- So I start at this state right here.
- Let me copy and paste it since I've done so
- much art already here.
- So I'm going from there to here where I'm removing a
- couple of the particles.
- So let's say I've removed a couple of them over here.
- And because of that, I've increased the volume.
- So let's say the volume, it's not there anymore.
- Let's say it's a little bit higher.
- Let's say the volume is-- just for the sake of our
- discussion-- let's say the volume has expanded a little
- bit, because I've remove some particles, the little pebbles
- on the top keeping it down.
- So it's like the adiabatic process, but instead of the
- temperature going down, my temperature stays at T1.
- My temperature's at T1 the entire time, because I'm next
- to this theoretical thing called a reservoir.
- So because of that, I will travel along what we'll call
- an isotherm.
- So this is my first state.
- When I'm done, I might end up some place over here.
- And so this is state 2.
- So this is state 2, this is state 1.
- What I'm claiming is that my path along this is going to be
- on some type of a rectangular hyperbola, or at
- least part of it.
- If I were to add rocks to it and compress it, I claim that
- my PV diagram would go like this.
- If I were to keep removing rocks from this diagram, I
- claim that my PV diagram would keep going like that.
- And so what's the intuition?
- That if I keep the temperature constant, that I'm essentially
- moving along this hyperbola.
- Well, let's just take out the ideal gas formula.
- Let me box off all this stuff over here.
- If I just take the ideal gas formula, PV is equal to nRT.
- If T is constant-- we know that R is a constant, it's the
- ideal gas constant.
- We know that we're not changing the number of moles
- of particles.
- Then that means that PV is equal to some constant.
- This whole thing is equal to some constant.
- And then, if we wanted to write P as a function of V, we
- would just write P is equal to K over V.
- Now, this might not look 100% familiar to you, but if I
- wrote it in algebraic terms, if I told you to graph y is
- equal to 1 over x, what does that look like?
- That's a rectangular hyperbola.
- That looks like this.
- And this is the y-axis, that's the x-axis, at least in this
- quadrant it looks like this.
- It also looks like that in the third quadrant, but we won't
- worry about that too much.
- So whenever you hold temperature constant, you're
- on some rectangular hyperbola like this, like an isotherm.
- Now, if the temperature was a different temperature, if it
- was a lower temperature, you'd be on a different isotherm.
- So you would be on an isotherm that looked like
- this, maybe over here.
- It would also be a rectangular hyperbola
- but at a lower state.
- Why is that?
- Because, if you're at a lower temperature, for any volume,
- you should have a lower pressure and that works out.
- That's why this is some temperature T2, that
- is lower than T1.
- So I want to do a couple of things in this video.
- I inadvertently explained to you what an adiabatic process
- is, and why the temperature would naturally go down on its
- own if you didn't have this reservoir here.
- But the whole reason why I even thought about doing this
- video is because I wanted you get comfortable with this idea
- of, one, that a reservoir will keep you in kind of an
- isothermic state.
- It will keep the temperature the same.
- And that if you keep the temperature the same, that you
- will travel along this isotherm, these rectangular
- hyperbolas.
- And that each temperature has
- associated with it an isotherm.
- So if you take that, let's just do one more step.
- And let's think about the actual work we did by
- traveling from this state to this state.
- Or if you just want to think of it in visual terms, from
- removing our pebbles slowly and slowly with this reservoir
- down here the whole time, from this state to this state.
- Where our volume has increased, our pressure has--
- So our volume has increased.
- Our pressure has gone down. but our temperature has stayed
- the same the entire time.
- So, several videos ago, we learned that the work done is
- the area under this graph.
- It's the area under that graph.
- Or, if we want to do in calculus terms-- and I'm about
- to break into calculus, so if you don't want to see calculus
- cover your eyes or ears.
- It would be the integral.
- And the rest of this video will be a little bit mathy,
- and I guess I should make that statement on the
- title of the video.
- But if I want to calculate what this area is,
- I can now do this.
- The isotherm assumption makes our math a little bit easier.
- Because we know that PV is equal to nRT, ideal gas law.
- Or we could say P, if we divide both sides by V, is
- equal to nRT, divided by V.
- So there we have it.
- We have P as a function of V.
- This function right here, this graph right here, is this.
- We could write P as a function of v is equal to nRT over V.
- So if we want to figure out the area under the curve, we
- just integrate this function from our starting, our V1 to
- our ending point, to our V2.
- So what is that going to be?
- Well, we're going to integrate from V1 to V2.
- Actually, that shouldn't be an equal.
- The work is going to be the integral from V1 to V2, times
- our function, P as a function of V, times dV.
- We're summing up all of the little rectangles here.
- We did that a couple of videos ago.
- So what's P as a function of V?
- So work done is equal to, from V1 to V2, nRT
- over V, times dV.
- Now, this is our simplifying assumption.
- We said we're sitting on top of a reservoir.
- That this reservoir keeps our temperature the
- same the whole time.
- And we're going to learn in a second, it's doing that by
- transferring heat into the system.
- And we're going to calculate how much heat is transferred
- into the system.
- So, if we look at this right here, temperature-- since
- we're assuming we're on an isotherm, is a constant. n and
- R are definitely constants.
- So we can rewrite this integral as the integral from
- V1 to V2 of 1 over V, dV.
- And then we could put the nRT out here.
- I should have done that first. nRT, it's
- just a constant term.
- Now, what's the antiderivative of 1 over V?
- It's the natural log of V.
- So our work is equal to nRT times the natural log-- this
- is the antiderivative-- of V, evaluated at V2 minus it
- evaluated at V1.
- So that is equal to nRT times, evaluated at V2, so the
- natural log of V2.
- Minus the natural log of V1.
- Now we know from logarithm properties is the same thing
- as nRT times the natural log of V2 over V1.
- So there you have it, we actually
- calculated the real value.
- If we know our starting volume and our finishing volume, we
- can actually figure out the work done in
- this isothermic process.
- The work done in this isothermic process is the area
- under this.
- And we figured out what it was.
- By pushing up that piston, it was nRT.
- These are the number of moles we have, ideal gas constant.
- Our temperature that we're sitting on.
- It would be T1 in this case.
- And the natural log of our finishing volume divided by
- our starting volume.
- Now, let me ask a follow-up question.
- How much heat was put into the system by this isotherm here?
- It put in heat to keep the temperature up, otherwise the
- temperature would have gone down, right?
- Heat was going into the system the entire time.
- How much was it?
- Well, since it's an isotherm, since the temperature did not
- change, what do we know about the internal energy?
- Did the internal energy change?
- The temperature not changing told us that the kinetic
- energy didn't change.
- If the kinetic energy didn't change, then the internal
- energy did not change.
- And we know that the change in internal energy is equal to
- the heat put into the system minus the
- work done by the system.
- Now, if this is 0-- so we know that this didn't change,
- because the temperature didn't change.
- So that means 0 is equal to Q minus W, or that
- Q is equal to W.
- So this is the work done by the system.
- You'll end up getting something in joules.
- And this is also equal to the heat put into the system.
- It's also equal to Q.
- So when you look at this, if we were to just draw this part
- of the curve-- let me redraw it just to make things neat.
- I want to give you a little bit of the convention of what
- people in the thermodynamics world tend to do.
- I'll make a neat drawing here.
- We started here, at state 1.
- And we moved along this rectangular hyperbola, which
- is an isotherm, to state 2.
- And now we calculated the area under this, which is the work
- done, which was this value right here.
- Let me write it there.
- It's nRT natural log of V2 over V1.
- This is V2.
- This is V1.
- This whole axis, remember, was the V-axis, volume axis.
- This axis here was the pressure axis.
- And the convention is that because we did work, but we
- were constant temperature, so our internal energy didn't
- change, we had to add energy to the system to make up for
- the work we did.
- So some heat must have been added to the system.
- And then what they do is they just put this little downward
- arrow and they write a Q right there.
- So some heat was put into the system during this isothermic
- process right there.
- And the value of that Q is equivalent to the work we did.
- We put the exact amount of heat into the system as the
- work that was performed.
- And because of that, our internal energy didn't change.
- Or you could say our temperature didn't change.
- Or you could go the other way.
- Because our temperature didn't change, these two things have
- to be equal.
- Anyway, I want to leave you there.
- Hopefully I gave you a little bit more of an intuition of
- how PV diagrams work, a little bit more intuition behind what
- isotherms and adiabatic mean.
- And the most important thing is, once we get a little bit
- mathy, this result can be useful for coming up with
- other interesting things about a lot of these thermal systems
- that we're dealing with.
- See you in the next video.
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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