Thermodynamics

I.  Internal Energy

- energy of atoms and molecules
- thermal equilibrium
- ideal gas law
- temperature & kinetic theory
II. Heat
- thermal conductivity
- 1st law of thermodynamics
- heat engines & cycles
- 2nd law of thermodynamics
© Matthew W. Milligan
 The student will be able to: HW:
Define and apply concepts of internal energy, thermal
1 equilibrium, zeroth law of thermodynamics, and 1–3
temperature.
State and apply the ideal gas law in terms of Boltzmann’s
2 constant and solve related problems with variables 4–7
pressure, volume, and temperature.
State and apply the stipulations of the kinetic theory of
gases and solve related problems involving pressure, force,
3 8 – 13
kinetic energy, Boltzmann’s constant, temperature, and
speed distributions of particles
Define and apply the concept of thermal conductivity and
4 14 – 19
solve related problems involving heat flow.
State and apply the first law of thermodynamics and solve
5 related problems including work, heat, heat engines & 20 – 26
cycles, P-V diagrams.
Define and describe entropy; state and apply qualitatively
6 27 – 30
the second law of thermodynamics.
© Matthew W. Milligan
 Internal Energy
•  All material is thought to consist of atoms and
molecules. These particles can have various
types of potential and kinetic energy.
•  The total energy of the atoms and molecules
within a particular object or other defined
quantity of matter is the internal energy (or
thermal energy) of the system.
•  Conservation of energy dictates that the
internal energy of a system remain constant
unless there is a transfer of energy or
interaction with surroundings.
© Matthew W. Milligan
 Internal Energy
•  The amount of internal energy in a system or
object depends on factors such as:
- motion of atoms (translation, rotation, vibration)
- phase (solid, liquid, gas, plasma)
- chemical energy related to bonds
•  The state of a system at a particular point in time
may be specified by measures such as:
- temperature
- pressure
- volume
•  Changes in internal energy can be correlated with
changes in state. © Matthew W. Milligan
 100 ºC
0 ºC
ice steam
1 atm
water (isobar)
611.7 Pa

273.16 K

diagram credit: Matthieumarechal, Wikipedia

 (isotherm)

water

vapor

20 ºC
diagram credit: Matthieumarechal, Wikipedia
water vapor

diagram credit: FL X, YouTube https://

www.youtube.com/watch?v=oFKk25fX28o
diagram credit: Donald L. Smith, H Padleckas, Kyu Ho Lee, Wikipedia
 Temperature
•  The temperature of a substance is a measure of
“how hot” or “how cold”, but also it relates to
internal energy and state of matter.
•  Common scales (related to water at 1 atm):
freezing boiling
Celsius (centigrade) 0.0 ºC 100.0 ºC
Fahrenheit 32.0 ºF 212 ºF
Kelvin 273 K 373 K
•  Zero kelvin is the lowest possible temperature.
Kelvin is an “absolute temperature” scale.
On this scale temperature is a measure of…
© Matthew W. Milligan
 Temperature
•  Absolute temperature is directly proportional
to the average translational kinetic energy of
the molecules in a substance.
•  When two substances or objects with different
temperatures are put into contact, energy
transfers from the hotter to the colder until
thermal equilibrium is reached with both
substances at the same temperature.

© Matthew W. Milligan
Object or materials at different temperatures brought
into contact…

TA = 20 ºC TB = 15 ºC

© Matthew W. Milligan
 …reach a state of Thermal Equilibrium when
temperatures are equal.

TA = 17 ºC TB = 17 ºC

© Matthew W. Milligan
TA = 18 ºC

© Matthew W. Milligan
If two substances are measured
to be the same temperature will
TB = 18 ºC
there be thermal equilibrium if
put into contact with one
another?

TA = 18 ºC

© Matthew W. Milligan
 Zeroth Law of Thermodynamics
•  If two systems are each in thermal equilibrium
with a third system, then the two systems are in
thermal equilibrium with one another.
•  The zeroth law is a necessary postulate to
establish the concept temperature and its
measurement.
•  The “third system” can be thought of as a
thermometer itself – like the previous few slides.
•  While this seems obvious, it is not possible to
prove and so its validity relies on repeated
experimental observations.
© Matthew W. Milligan
 The student will be able to: HW:
Define and apply concepts of internal energy, thermal
1 equilibrium, zeroth law of thermodynamics, and 1–3
temperature.
State and apply the ideal gas law in terms of Boltzmann’s
2 constant and solve related problems with variables 4–7
pressure, volume, and temperature.
State and apply the stipulations of the kinetic theory of
gases and solve related problems involving pressure, force,
3 8 – 13
kinetic energy, Boltzmann’s constant, temperature, and
speed distributions of particles
Define and apply the concept of thermal conductivity and
4 14 – 19
solve related problems involving heat flow.
State and apply the first law of thermodynamics and solve
5 related problems including work, heat, heat engines & 20 – 26
cycles, P-V diagrams.
Define and describe entropy; state and apply qualitatively
6 27 – 30
the second law of thermodynamics.
© Matthew W. Milligan
 Ideal Gas Law
An “ideal gas” is a useful model so long as pressure
is not too great (well beyond an atm) and the
temperature is not too low (near boiling point).

PV = nRT

where: P = pressure
V = volume R = 0.0821 mol⋅K
L⋅atm

n = number of moles
T = temperature R = 8.315 J
mol⋅K

R = universal gas constant

© Matthew W. Milligan
 Ideal Gas Law
An “ideal gas” is a useful model so long as pressure
is not too great (well beyond an atm) and the
temperature is not too low (near boiling point).

PV = NkT

where: P = pressure −23 J

V = volume
k = 1.38 ×10 K

N = number of molecules
T = temperature
k = Boltzmann’s constant
© Matthew W. Milligan
 The student will be able to: HW:
Define and apply concepts of internal energy, thermal
1 equilibrium, zeroth law of thermodynamics, and 1–3
temperature.
State and apply the ideal gas law in terms of Boltzmann’s
2 constant and solve related problems with variables 4–7
pressure, volume, and temperature.
State and apply the stipulations of the kinetic theory of
gases and solve related problems involving pressure, force,
3 8 – 13
kinetic energy, Boltzmann’s constant, temperature, and
speed distributions of particles
Define and apply the concept of thermal conductivity and
4 14 – 19
solve related problems involving heat flow.
State and apply the first law of thermodynamics and solve
5 related problems including work, heat, heat engines & 20 – 26
cycles, P-V diagrams.
Define and describe entropy; state and apply qualitatively
6 27 – 30
the second law of thermodynamics.
 Kinetic Theory of Gases
•  An ideal gas contains particles moving with
random velocities.
•  The average distance between particles is
much greater than the size of the particles.
•  The only significant interactions between
particles are collisions, which are assumed to
be perfectly elastic.
•  Interactions with the walls of a container are
also assumed to be perfectly elastic collisions.
•  Using these assumptions the ideal gas laws can
be derived using classical mechanics!
 (T = 298 K)
relative number of molecules

K = 23 kT

K = m (v 1
2
2
) avg

diagram credit: Pdbailey, Wikipedia

Argon-40 at 200 K, 300 K, 600 K, 900 K

K = 23 kT

K = m (v
1
2
2
) avg

© Matthew W. Milligan
 The student will be able to: HW:
Define and apply concepts of internal energy, thermal
1 equilibrium, zeroth law of thermodynamics, and 1–3
temperature.
State and apply the ideal gas law in terms of Boltzmann’s
2 constant and solve related problems with variables 4–7
pressure, volume, and temperature.
State and apply the stipulations of the kinetic theory of
gases and solve related problems involving pressure, force,
3 8 – 13
kinetic energy, Boltzmann’s constant, temperature, and
speed distributions of particles
Define and apply the concept of thermal conductivity and
4 14 – 19
solve related problems involving heat flow.
State and apply the first law of thermodynamics and solve
5 related problems including work, heat, heat engines & 20 – 26
cycles, P-V diagrams.
Define and describe entropy; state and apply qualitatively
6 27 – 30
the second law of thermodynamics.
© Matthew W. Milligan
What governs the rate at which energy flows?

TA = 17 ºC TB = 15
17 ºC

© Matthew W. Milligan
What governs the rate at which energy flows?
Greater temperature difference,…
TA = 20
17 ºC TB = 15
17 ºC

© Matthew W. Milligan
What governs the rate at which energy flows?
…, better heat conducting material,…
TA = 20
17 ºC TB = 15
17 ºC

© Matthew W. Milligan
What governs the rate at which energy flows?
…, greater cross-sectional area,…
TA = 20
17 ºC TB = 15
17 ºC

© Matthew W. Milligan
 What governs the rate at which energy flows?
…, or shorter length, all lead to greater heat flow!
TA = 20
17 ºC TB = 15
17 ºC

© Matthew W. Milligan
 Thermal Conductivity
•  Heat is the transfer of thermal energy by
convection, radiation, or conduction.
•  Conduction when thermal energy is “transmitted”
through a material from a higher temperature
“source” to a lower temperature “sink”.
•  The rate at which energy is transferred is a function
of the type of material and its dimensions. Greater
flow rate will occur with greater cross sectional
area and/or less length.
•  Metals are generally good thermal conductors.
Poor thermal conductors are called insulators –
materials such as plastics, air, Styrofoam, etc.
© Matthew W. Milligan
 Thermal Conductivity
The rate of heat flow by means of conduction can
be modeled as a function of temperature difference
and characteristics of the material:

Q kAΔT
=
Δt L
where: Q = heat
k = thermal conductivity
A = cross-sectional area
T = temperature
L = length
© Matthew W. Milligan
 k Q A
T1
L T2

Q kAΔT
=
Δt L
© Matthew W. Milligan
Material Thermal conductivity, k (J/s·m·K)
Silver 420
Copper 380
Aluminum 230
Steel 40
Ice 2
Glass 0.84
Water 0.56
Wool 0.042
Air 0.023
© Matthew W. Milligan