Chapter 19 Physics 340, Winter 2020

Thermodynamic system:
A collection of objects that are considered as a unit that may exchange heat with
surroundings or other systems.
Thermodynamic process:
Any process that may result changes in
the state of a thermodynamic system.
Sign conventions:

Q : quantity of heat added to the system

Q > 0 when it flows into the system
Q < 0 when it flows out of the system

W : work done by the system to the surrounding

W > 0 : the system does work to the surrounding
W < 0 : surrounding does work to the system

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 Chapter 19 Physics 340, Winter 2020

Work done by the gas during the expansion:

dW =F ⋅ dx =pA ⋅ dx =p ⋅ dV ⇒ W =∫ p dV

Work done is directly related to the volume

change. It is the area under the pV-diagram
between the initial and final states. Therefore
it depends on not only the initial and final states,
but also how to get from the initial to the
final state.
Expansion: W >0
Compression: W < 0
Constant volume: W = 0

Recall the work done by a mechanical system?

W = ∫ F dx
Generally, the work is also path dependent, unless
the force is conservative.

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 Chapter 19 Physics 340, Winter 2020

Work done during a constant-pressure (isobaric)

process:
W
= ∫ pdV dV p (V
= p ∫= 2 − V1 )

(No ideal-gas law assumption is made)

Work done by an ideal gas during a constant-temperature

(isothermal) process:
V  p 
= W nRT= ln  2  nRT ln  1 
 V1   p2 
(with the ideal gas law assumption)

Proof:
nRT dV  V2 
W
= ∫=
pdV ∫ V = dV nRT ∫V
= nRT ln  
 V1 
V  p 
Since p1V1 = p2V2 ⇒ W = nRT ln  2  = nRT ln  1 
 V1   p2 

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 Chapter 19 Physics 340, Winter 2020

Thermodynamic path
When a thermodynamic system changes from one state
to another, it passes a series of intermediate states which
trace out a path.

The work done by a thermodynamic system depends not

only on the initial and final states, but also on the path it
takes.

The work done by the three different paths from ( p1 ,V1 )

to ( p2 ,V2 ) are alll different with
W(b) > W(d ) > W(c )

Recall the similar situation in mechanics?

the work done by a non-conservative force in mechanics!

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 Chapter 19 Physics 340, Winter 2020

Internal Energy U:
The sum of kinetic and potential energies of all of its constituent particles.
For an ideal gas, it depends only on its temperature and the amount of gas,
not on its pressure or volume!
As the gas expands in volume as shown in (a)
on the right, the molecules bounce back with
smaller speed, thus the gas loses internal energy,
i.e., cools down. The energy in this case is turned
into the work done by the gas. If no heat exchange
with the surrounding: the temperature will
decrease T
Conversely, as the gas is compressed in volume
as shown in (b), the molecules bounce back with
higher speed, thus the gas gains internal energy,
i.e., heats up. The energy gained is supplied by
the work done to the gas by an external force. If
no heat exchange with surroundings:
T
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 Chapter 19 Physics 340, Winter 2020

First law of thermodynamics:

Q =∆U + W
Q : heat added to the system
W : work done by the system
∆U : change in internal energy, ∆U = U2 − U1
The first law of thermodynamics is a statement of energy conservation.

The work W is path-dependently. For ideal gases, ∆U depends on its temperature

only, not the path. Thus the heat Q added to the system must be path-dependent
as well!

For infinitesimal changes of state, the first law has the differential form:
dQ =dU + dW =dU + pdV

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 Chapter 19 Physics 340, Winter 2020

Consider the expansion at a constant temperature

as illustrated in Fig. (a) on the right. As it expands,
the piston moves as the gas pressure overcomes
the atmospheric pressure outside. So the gas does
work. To maintain the temperature, heat will need ∆U =0
to be added during the expansion. W >0
Q>0

Free expansion
Now examine the case shown in Fig. (b) where
the expansion is into the vacuum. When the
partition breaks, the gas quickly fill up the large
volume. Since there is no pressure to overcome,
there is no work done by the gas in the process.
The container is insulated, thus there is no heat
exchange. Even though the volume is increased, ∆U =0
the temperature remains the same. This is an W =0
example of an isolated system. Q=0

The two processes have the same initial and final states,
but the work and heat involved are different.

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 Chapter 19 Physics 340, Winter 2020

Isolated system:
A system has no heat exchange with and does no work to the surroundings:
Q= 0, W = 0 ⇒ ∆U= 0
The internal energy of an isolated system does not change.

Cyclic processes:
A process represented by a closed path, i.e., with identical initial and
final states. In this process, there will be no change in the internal energy.
∆U= 0 ⇒ Q= W
All the heat added to the system is converted
into the work done by the system.
Conversely, all the work done to the system
is converted into the heat flowing out of the
system (right).
The total work done by the system is positive
for a clock-wise path and negative for
a count-clock-wise path. The magnitude of
the work is the area enclosed by the path.

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 Chapter 19 Physics 340, Winter 2020

Special thermodynamic processes

Isothermal process (path: isotherm, a→4)
process at a constant temperature,
T = constant ⇒ ∆U = 0
 Vf 
Q
= W= nRT ln 
 Vi 

Isochoric process (path: isochor, a→2)

process at a constant volume,
V = constant ⇒ W = 0
Q =∆U =nCV (Tf − Ti )

Isobaric process (path: isobar, a→3)

process at a constant pressure,
p = constant ⇒ W = p(Vf –Vi )
Q =∆U + p (Vf − Vi ) =nC p (Tf − Ti )

Adiabatic process (path: adiabat, a→1)

process with no heat exchange with the surroundings,
Q=0
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 Chapter 19 Physics 340, Winter 2020

Example: Liquid vaporization

When liquid vaporizes, its internal energy is significantly increased as it absorbs
heat during the vaporization. For a substance with mass m, the increase can be
calculated from the 1st law of thermodynamics:
Q =∆U + W ⇒ ∆U =Q − W =mLv − p (Vf − Vi )
Here Vf is the volume of the vapor and Vi is the volume of the liquid.

Example:
work done by one mole of van der Waals gas through isothermal expansion

From the equation of state

 a  RT a
 p +  ( V − b=) RT ⇒ p
= −
 V2  V − b V2
The work done through the isothermal expansion:
 RT a   Vf − b   1 1 
W = ∫ pdV = ∫  − 2  dV = RT ln   + a  − 
 V − b V  V
 i − b   Vf Vi 

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 Chapter 19 Physics 340, Winter 2020

Heat capacities of an ideal gas

1  dQ 
CV   : molar
= heat capacity at a constant volume ⇒ dQ nCV dT
n  dT V
1  dQ 
Cp   : molar
= heat capacity at a constant pressure ⇒ dQ nC pdT
n  dT  p

By definition, for a constant-volume (isochoric) process:

dW =pdV =0 ⇒ dQ =dU =nCV dT ⇒ dU =nCV dT
Thus for ideal gases, ∆U= nCV ∆T , regardless the process.
The internal energy of an ideal gas depends only on the
temperature, not the volume nor the pressure !

For a constant-pressure (isobaric) process:

dQ =dU + dW ⇒ nC pdT = nCV dT + pdV

For an ideal gas: pV = nRT ⇒ pdV = nRdT ,

thus the relationship:
C=
p CV + R

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 Chapter 19 Physics 340, Winter 2020

Ratio of heat capacities Ideal gas:

1 γ
Cp = CV = R, Cp R
γ≡ , note γ > 1 always γ −1 γ −1
CV
3 5 5R 2 5
For ideal monatomic gas: CV = R ⇒ C p = R and γ= = = 1.67
2 2 3R 2 3
For ideal diatomic gas with rotational, but not vibrational excitation:
5 7 7R 2 7 Speed of sound
CV = R ⇒ C p = R and γ= = = 1.40 in ideal gases:
2 2 5R 2 5
γp
υ=
ρ

These predictions agree remarkably well with the measurements.

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 Chapter 19 Physics 340, Winter 2020

Molar heat capacity

The concept of heat capacity can be extended to other thermodynamic
1 dQ
processes C≡
n dT
From the first law of the thermodynamics:
dQ =dU + dW =nCV dT + pdV
Thus molar heat capacitities of a given process ( C ) and constant-volume ( C V )
have the following relationship:
1 dQ p dV
C= = CV +
n dT n dT

The heat capacity C is process-dependent as dV dT depends on the process.

It is easy to show that
C = CV for a constant-volume (isochoric) process
C= CV + R for a constant-pressure (isobaric) process
C = 0 for abiabatic process
and C is undefined for the isothermal process.
Note: If a thermodynamic process is given by functions of (p, V) or (p, T), one will need
to find the corresponding relation between V and T in order to evaluate dV/dT.
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 Chapter 19 Physics 340, Winter 2020

Adiabatic process for an ideal gas

dQ =dU + dW =0 ⇒ nCV dT + pdV =0
nRT dT R dV
For an ideal gas, p = ⇒ + = 0
V T CV V

R C p − CV
Note that = = γ − 1, which leads to
CV CV
dT dV
+ ( γ − 1) =0
T V
Since γ > 1, dT and dV always have opposite signs for an adiabatic process.
Integrating the above equation,
lnT + ( =
γ − 1) lnV constant ⇒= TV γ−1 constant

Replacing T with V using the ideal gas law leads to

pV γ = constant
Insert V = nRT p leads to
p1−γ T γ = constant

Note: the constants here in different equations are different.

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 Chapter 19 Physics 340, Winter 2020

Work done by an ideal gas in an adiabatic process

dQ =
dU + dW =
0 ⇒ dW =
−dU =
−nCV dT ⇒ W = nCV (Ti − Tf )
− ∫ nCV dT =

Expressed in terms of pressure and volume using the ideal gas law

W = −∆U = nCV (Ti − Tf )

 pV p V 
= nCV  i i − f f 
 nR nR 
C
= V ( pV i i − p f Vf )
R
pV − p f Vf
= i i
γ −1

Question: if a gas is a mixture of two different molecules, what are the impact to
the above derivations?
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 Chapter 19 Physics 340, Winter 2020

Example:
An ideal gas in a cylindrical canister of cross section A is in equilibrium
with the surrounding. The piston at the top is free to move. The gas m
initially occupies a length L0 . A block of mass m is then put on top of
the cylinder and consequently the piston slowly moves down. Find the
final length L and the heat exchanged with the surrounding assuming
the piston is massless and the temperature is constant during the L
compression. The atompspheric pressure is p0 .

Solution:
A
Initial state: p0 ( AL0 ) = nRT
 mg 
 mg  ⇒ p0 ( AL0 ) = p
 0 +  ( AL )
Final state:  p0 +  ( AL ) =nRT  A 
 A 
Thus the final length
p0 L0
= L = L0
p0 + mg A 1 + mg Ap0
For isothermal expansion ( ∆U = 0)
 Vf  L  mg 
Q =∆U + W =nRT ln  =nRT ln  = − p0 AL0 ln 1 + 
V
 i  L
 0  Ap 0 

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