Chapter 3: Gas Processes

• In this chapter we want to continue to discuss gases.

We developed the ideal gas law in chapter 2 PV = Nk BT

Now we want to understand some of the processes that
occur as we change the P, V or T of a gas

We will also be interested in what happens as we add or
subtract thermal (internal) energy from the system.
• Once again it is important to establish rigorous
definitions before we start to consider the physical
phenomena.

In this case we need to make sure we have strict
definitions of work and heat.
• Heat: “This is the flow of energy across a boundary
between to systems (objects) that are in thermal
contact and a temperature difference exists between
them”

KEY POINT:

KEY POINT:

• Work: “Any other flow of energy across a boundary that

is not considered heat”

Example:

Important:

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 Q (heat) or W (work) or k-W??
• This is exercise T3X.1 and T3X.2 in Moore:

• Using a Q to label heat and W to label W, classify each

of the case below:

Soup (B) in a pan on an electric stove (A) gets hot

You (A) compress air (B) in a bike pump, making it warm.

Your hands (A) are warmed when they face a fire (B).

The atmosphere (A) warms a reentering spacecraft (B).

A hot pie (A) becomes cooler while sitting in the kitchen
(B).

Your chair (B) becomes warmer after you (A) sit in it for a
while.

A drill bit (B) becomes hot after being spun by a drill (A)
• Using a W for thermal work and a K for “k-work”,
classify each case below:

The total Kinetic Energy of the molecules in a gas bottle
increase as the bottle falls in a gravitational field.

The total Kinetic Energy of the molecules in a gas bottle
increase as the gas is stirred with a fan in the bottle.

Air drag on a falling meteorite causes the meteorite’s
temperature to increase.

Air drag on a falling meteorite causes it to slow down (lose
kinetic energy)

Gas in a bottle gains energy from a spark.

A small pellet is vaporized by a laser beam.

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 Q vs W
• We must be a little bit careful when classifying Q and
W.

The distinction between the two is a little bit artificial and
depends on how we are defining the boundary of our
system.
• Moore has a good example with an electrical circuit
through water as shown below.

Boundary A

Boundary B

Case A: We define the water, the container, and the

resistor as the system.


Case B: We define the water alone to be the system.



• Be careful how you label an energy transfer across a

boundary…it may depend critically on where you define
that boundary.

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 Q, W and U
• Both heat and work represent ways of transferring energy into
a system.

U, represents the total internal energy of a system.

Q, W represent an amount of energy that is being added (or taken
away) from the system across its boundary.

By conservation of energy we get:
First Law of Thermodynamics

Important feature:
 Q > 0 if energy is flowing into the system Sign definition is
 W > 0 if energy is flowing into the system not universal.

• Let’s consider a way that we might perform work on a gas.

One way that is of interest is to compress the gas.

Here is our model: dr
Fext

We want to think about performing this compression in a very

specific way:
 We move the piston a small distance dr by pushing on the
piston with an external force Fex.
 We move it slowly enough that the piston does not gain
significant kinetic energy.

These two points imply something very important.
 The gas must be extracting energy from the piston at the very
See Page 44 same rate that we are performing work on the piston.
 
[dK ]piston
for a
= Fext ⋅ dr = Fext dr
dK is the work done on the
explanation piston by the external force.
of how piston dW is the work done by the
adds energy
to molecules
dW = Fext dr piston on the gas…the total
work done on the piston is
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 Compression, W
• Now since the piston is not gaining any kinetic energy,
the total force on it must be zero. Therefore the force
exerted by the gas must be equal to the force exerted
by the external force.
Fext = Fgas (but pointed in opp. dir.)
• Now if we substitute this back into our earlier equation
we find.

• Where we have noted that the force of the gas is just

the pressure times the area and that Adr equals a
small (negative) change in the volume – dV.
• This gives us and important relationship for how work
can be performed on a gas by compressing it.
dW = − PdV
• Notes:

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 Macrostate of a Gas
• Let’s make a connection back to some ideas of
quantum mechanics. In QM we talked about “state
vectors” which contained information regarding the
particle.

In the case of hydrogen we defined the state in terms of a
small number of variables n, l, m, ms
• Can we define the “state of a gas”?

The answer is yes, but we must be careful to distinguish
between “macrostate” and “microstate”.

The macrostate is described in terms of the macroscopic
variables (in addition you need to know chemical comp.)
 Pressure (P)
 Temperature (T) Properties of the
 Volume (V) whole object versus
individual pieces.
 Total Internal Energy (U)
 Number of Molecules (N)
 Total Mass (M)
• But we have discovered that many of these quantities
are related M f
N= NA PV = Nk BT U= Nk BT
MA 2
• It turns out that if you know a triplet of these (almost
any triplet, see T3X.4), the other variables can be
calculated. For example, if you know P, V and T:

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 P-V Diagrams
• In many cases, the amount of gas (N) is not changing
and known. Therefore, we can pick two of the other
macroscopic quantities to define the macroscopic state
of the gas. It is very common to pick Pressure (P) and
Volume (V).
• P and V are independent in the sense that for any
volume all values of pressure are allowed.
• We can make a plot of P versus V and every point on
the graph represents a specific macroscopic state of
the gas (for known N).

P A

V
• As the gas undergoes changes it will map out a curve
or path in the P-V space. Above is an example of a
general process.

The gas started at macrostate A and moved through
some process to macrostate B.

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 Processes
• Although in general the path from A to B can be quite
general, there are some special processes or paths that
of interest for our study of thermal dynamics.
• Definition: Quasistatic: This means that the change
the state of the gas occurs slow enough that all parts of
the gas remain in equilibrium.
• Four Special Processes:
• (1) Isochoric: The gas is changed in such a way that
the volume of the gas remains fixed.

• (2) Isobaric: The gas is changed in such a way that the

pressure of the gas remains fixed

• (3) Isothermal: The gas is changed in such a way that

the temperature of the gas remains fixed.

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 Gas Processes
• (4) Adiabatic: In this process the gas changes state
but no heat is allowed to flow into or out of the gas.

1
Constant T P∝
V
P

_________

_______

800 K

450 K
200 K
V
__________ _________

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 Calculating Work
• One of the advantages of a P-V diagram is that it is
easy to calculate the amount of work done on (or by)
the gas.
• Recall the expression that we derive earlier
dW = − PdV
• This was for a infinitesimal amount of work. To
determine the work done when moving between two
separate states we must integrate the above equation.
V2

W = − ∫ P(V ) dV Work done on the gas.

V1
• Notice that P can be a function of volume. With our
four specific processes we can perform this integral.

Isochoric:

Isobaric:

Isothermal:

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 Work
• We will deal with the adiabatic process in a moment.
But first let’s make a general observation about the
value of the work.

The magnitude of the work is simply the area under the
curve on the P-V diagram

P
A

V
• One of the features that we need to pay attention to is
whether the work is positive of negative. This depends
on the “direction” of the process.

Going from A
B:

Going from B
A:

• When analyzing a change on the P-V diagram we can

make a useful table
Q W ∆U

A
B

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 Example
• Let’s consider analyzing the following example.
A
P Q W ∆U

A B

B C
B C A
C

V
• Going from A to B:

• Going from B to C:

• Going from C to A:

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 Example
• The three processes that took place in this last example
represent a cycle…the last state was the same as the
first state…it got back to the starting point.

However, the work done is NOT zero.

The net work is equal to the area enclosed by the cycle.
 Is it positive or negative?


In general if we go “clock-wise” around a cycle the
net work will be ___________
 If we go “counter-clockwise” around a cycle the net
work will be ___________

The internal energy must be back to it original value.
∆U TOT = 0

But since there is a net work, there must be a net amount
of heat (Q) which is opposite the net work.
• In this case we can actually calculate the amount of
work

− PB (VA − VB )
VB
WTOT = WA→ B + WB→C = − PAVA ln
VA

• It doesn’t seem to simplify any but we can certainly

calculate this with all the values.

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 Adiabatic Process
• Recall the definition of an adiabatic process: The
macrostate of the gas changes without the addition or
subtraction of heat from the gas. Q = 0.
• In this case we would like to know how P, V and T
change for an adiabatic process.
• Observations:

• Moore has a derivation of the condition on adiabatic

process. I do not find it very satisfying since it does a
number of things which are not obviously motivated and
it never clearly makes use of the condition above.
• Let’s start by stating what the condition is and then we
will show a derivation of it:
PV γ = constant ⇒ TV γ −1 = constant

Where γ is 5/3 for a monatomic gas, 7/5 for diatomic and
between 1 and 4/3 for a polyatomic gas.

This is only true for ideal gas.

This is a good approximation if the expansion or
compression occurs very rapidly so that the heat flow into
or out of the gas is negligible.

But the speed is still slower than thermal speed of
molecule.
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 Derivation of Adiabatic Process
• If we think about making a small adiabatic change we
should have
dU = dW = − PdV
f f
dU = Nk B dT ⇒ − PdV = Nk B dT
2 2
PV = Nk BT ⇒ PdV + VdP = Nk B dT
2
PdV + VdP = − PdV
f
2  2
P(1 + )dV + VdP = 0 define γ = 1 + 
f  f 
dV dP Divide by PV
γ + =0
V P
• Now integrating both side we find:
γ ln V + ln P = constant
( )
ln PV γ = constant ⇒ PV γ = constant
• Using the ideal gas law we can rewrite this relationship
as
Nk BT
PV = Nk BT ⇒ P=
V
 Nk BT  γ γ −1
 V = constant ⇒ TV = constant
 V 

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 Example
• T3R.1: Imagine the pressure at the top of a tall mountain
is about 0.65Pbottom. If a stiff breeze is flowing up the
mountain and it is 30 oC (86 oF) at the bottom. Assuming
the air travels up the mountain so rapidly that the air
expands adiabatically, what is the temperature at the
top?

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