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THERMODYNAMICS

The 4 Laws

There are 4 laws to thermodynamics, and they are some of

the most important laws in all of physics. The laws are as

follows

systems are each in thermal equilibrium with a third,

then they are in thermal equilibrium with each other.

First law of thermodynamics Energy can neither be

Contents

created nor destroyed. It can only change forms. In any

process, the total energy of the universe remains the 1 The 4 Laws

same. For a thermodynamic cycle the net heat supplied 2 Entropy and Phase Space

to the system equals the net work done by the system. 3 The Zeroth Law

Second law of thermodynamics The entropy of an 4 The First Law

isolated system not in equilibrium will tend to increase 4.1 Fundamental

over time, approaching a maximum value at equilibrium. thermodynamic relation

Third law of thermodynamics As temperature 5 The Second Law

approaches absolute zero, the entropy of a system 6 The Third Law

approaches a constant minimum. 7 The Basics

8 Different Measures of

Before I go over these laws in more detail, it will be easier if Energy

8.1 Maxwells Relations

I rst introduce Entropy.

Entropy is a very important thing in the realm of thermodynamics. Its the core idea behind the second

and third laws and shows up all over the place. Essentially entropy is the measure of disorder and

randomness in a system. Here are 2 examples

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Lets say you have a container of gas molecules. If all the molecules are in one corner then this would

be a low entropy state (highly organised). As the particle move out and ll up the rest of the container

then the entropy (disorder) increases.

If you have a ball ying through the air then it will start off with its energy organised i.e. the kinetic

energy of motion. As it moves through the air however, some of the kinetic energy is distributed to

the air particles so the total entropy of system has increased (the total energy is conserved however,

due to the rst law)

To get a more detailed picture of entropy we need to look at the concept of Phase Space. Some of the

concepts for this may be a bit confusing but bear with me, once youve got your head round it its not

that bad.

A phase space is just like a graph, but a point on this graph represents the whole state of a system. Lets

use an example. Imagine I have a box with 4 gas particles inside. Each point in the phase space for this

system tells you where all 4 balls are located in the box.

In our example we are only interested in the positions of the 4 particles, so each point in phase space

must contain an x, y, and z co-ordinate for each particle so our phase space is 3N dimensional, where N is

the number of particles in the system. So in our case, the phase space is 12 dimensional, in order that

each point can describe the location of 4 bodies.

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In all the diagrams I will depict the phase space as 2D to make it easier to convey what it actually

represents. For our purposes we will not need to consider the dimensions.

If we imagine that each of the particles is a different colour so we can keep track of their positions

easier. If we imagine the case where all of the particles are located in one corner of the container then

we have the situation

In terms of the system, there are multiple other combinations of the 4 particles that will be as organised

as the above state

and so on. Each of these set-ups will correspond to a different position in phase space as they are all

different layouts of the system of the 4 particles. If we add these to the phase space along with the

original we get something like

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These 5 layouts of the 4 particles, along with the 11 other combinations, make up a set of states that are

(apart from the colours) indistinguishable. So in the phase space we could put a box around the 16 states

that de nes all the states inside it as being macroscopically indistinguishable.

The total phase space of a system will have many regions all of different shapes and sizes and could look

like the following

But how is all this abstract representation linked to entropy. Entropy, given in equations as the symbol

, is de ned then as

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Where is Boltzmann constant ( ) and is the volume of the box in phase space. All

the points in a region of phase space have the same entropy, and the value of the entropy is related to

the logarithm of the volume (originally Boltzmann never put the constant in the formula as he wasnt

concerned with the units. The insertion of the k seemed to have come rst from Planck).

Entropy can also be de ned as the change when energy is transfered at a constant temperature

Where is the change in entropy, is the energy or heat, and T is the constant temperature.

The Zeroth law is so named as it came after the other 3. Laws 1, 2, and 3 had been around for a while

before the importance of this law had been fully understood. It turned out that this law was so

important and fundamental that it had to go before the other 3, and instead of renaming the already

well known 3 laws they called the new one the Zeroth law and stuck it at the front of the list.

If two thermodynamic systems are each in thermal equilibrium with a third, then they are in

thermal equilibrium with each other.

Basically, if A=B and C=B then A=C. This may seem so obvious that is doesnt need stating but without

this law we couldnt de ne temperature and we couldnt build thermometers.

The rst law of thermodynamics basically states that energy is conserved; it can neither be created nor

destroyed, just changed from one for to another,

The energy in a system can be converted to heat or work or other things, but you always have the same

total that you started with.

As an analogy, think of energy as indestructible blocks. If you have 30 blocks, then whatever you do to or

with the blocks you will always have 30 of them at the end. You cant destroy them, only move them

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around or divide them up, but there will always be 30. Sometimes you may loose one or more, but they

still have to be taken account of because Energy is Conserved.

From the second law we can write that the change in the internal energy, , or a system is equal to heat

supplied to the system, , minus any work done by the system, ,

(1)

From the de nition of entropy above we can replace , and we can also make the replacement

giving us

(2)

Now if we have a system of particles that are different then we may get chemical reactions occuring, so

we need to add one more term to take this into account

(3)

This is possibly the most famous (among scientists at least) and important laws of all science. It states;

In other words Entropy either stays the same or gets bigger, the entropy of theuniversecan never go

down.

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The problem is, this sint always true. If you take our example of 4 atoms in a box then all of them being

in one corner is a highly ordered system and so will have a low entropy, and then over time theyll move

around become more disordered and increasing the entropy. But there is nothing stopping them all

randomly moving back to the corner. Its incredible unlikely, but not actuallyimpossible.

If you look at the problem in terms of phase spaceyou can see that over time its more likely youll move

into a bigger box, which means higher entropy, but theres no actual barrier stopping you moving back

into a smaller box.

The third law provides an absolute reference point for measuring entropy, saying that

As the temperature of a system approaches absolute zero (273.15C, 0 K), then the value of

the entropy approaches a minimum.

The value of the entropy is usually 0 at 0K, however there are some cases where there is still a small

amount of residual entropy in the system.

The Basics

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When you heat something, depending on what its made of, it takes a different about of time to heat up.

Assuming that power remains constant, this must mean that some materials require more energy to

raise their temperature by 1K (1K is actually the same as 1C, they just start at a different place. For

more information click here) than others. If you think about it, this makes sense. A wooden spoon takes

a lot longer to heat up than a metal one. We say that metal is a good thermal conductor and wood a poor

thermal conductor. The energy required to raise 1kg of a substance by 1K is called its speci c heat

capacity. The formula we use to nd how much energy is required to raise 1 kg of a substance by 1K is:

1a. Laura is cooking her breakfast before work on a Sunday morning (please send your sympathy

messages that I had to work on a Sunday here). She doesnt want to have to do any more washing up that

is absolutely necessary, so decides to stir the spaghetti she is cooking with her fork, rather than have to

wash a wooden spoon. She leaves the fork in the pan whilst she spreads her toast with margarine and

grates some cheese. The stove provides 1000J of energy to the fork in the time she leaves it unattented.

What would be the temperature increase in the fork, assuming half the energy provided will be lost to

the surroundings and the initial temperature of the fork was 20C, and the mass of the fork is 50g and is

made of a material with a speci c heat capacity of 460 Jkg-1K-1

Although Im fairly sure I read somewhere that trying to work out energy changes in forks rst thing in

the morning was a symptom of insanity, its something I nd myself doing from time to time. For this

question, were going to need the equation Q=mcT this is an equation youll probably need a lot, so its

worth trying to memorize it. It also springs up in chemistry too. First things rst, we need to rearrange

the equation to make T the subject. Once youve rearranged this question you should get T=Q/(mc).

Substituting the values given to us in the question you get:

T= 43K

So since the initial temperature of the fork was 20C, the nal temperature of the fork would be 63C.

Internal Energy:

Helmholtz free energy:

Enthalpy:

Gibbs Free Energy:

Maxwells Relations

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Maxwells Relations

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(4)

(5)

(6)

(7)

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