Chapter 15

Physics 1214
Chapter 15
Thermal Properties of Matter
Equations of State
The conditions in which a particular gaseous material exists are described by physical
quantities such as pressure, volume, and temperature.
The primary variables, state variables or state coordinates, used in describing the
particular state of the gas are pressure, volume, temperature, and quantity.
The quantity of gas atoms can be specified by the total mass of the gas or, alternatively,
by the number of moles of gas atoms (or molecules) contained in the volume.
The molar mass of a substance is the mass of 1 mole: 𝑀𝑀 = 𝑁𝑁𝐴𝐴 𝑚𝑚
The total mass: 𝑚𝑚𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = 𝑛𝑛𝑛𝑛 where, 𝑛𝑛, is the number of moles of the substance.
For most nonideal gases, the relationship among 𝑝𝑝, 𝑉𝑉, 𝑇𝑇, and 𝑚𝑚 (or 𝑛𝑛) can be
expressed as an equation called the equation of state.
We’ll consider only equilibrium states, states in which the temperature and pressure
are uniform throughout the system.
The Ideal-Gas Equation
Most gases at low pressures have particularly simple equations of state.
The volume, 𝑉𝑉, is proportional to the number of moles, 𝑛𝑛,
and thus to the number of molecules: 𝑉𝑉/𝑛𝑛 = constant
Boyle’s law: The volume, 𝑉𝑉, varies inversely with the
pressure, 𝑝𝑝: 𝑝𝑝𝑝𝑝 = constant
Gay-Lussac’s law: The pressure is directly proportional to the
absolute (Kelvin) temperature. 𝑝𝑝/𝑇𝑇 = constant
These three relationships can be combined neatly into a

single equation, Ideal-gas equation:
𝑝𝑝𝑝𝑝 = 𝑛𝑛𝑛𝑛𝑛𝑛
Where 𝑅𝑅 = 8.3145 𝐽𝐽⁄ 𝑚𝑚𝑚𝑚𝑚𝑚 ⋅ 𝐾𝐾 is the ideal-gas constant.
Units: 𝑝𝑝 is in Pa, 𝑉𝑉 is in 𝑚𝑚3 , 𝑛𝑛 is in mol, and 𝑇𝑇 is in Kelvins.
PV Diagrams
For a given quantity of a material, the equation of state is a
relationship among the three state coordinates: pressure,
volume, and temperature.
PV diagrams are useful graphical representation of this
relationship. It is a set of graphs of pressure as a function of
volume, each for a particular constant temperature.
Isotherm: Curve representing behavior at a specific
temperature
For a material that does not obey the ideal-gas equation, at

temperatures below a critical temperature the isotherms
develop flat parts—regions where the material can be
compressed without an increase in pressure.
Phase Diagrams
A phase diagram shows what phase occurs for each
possible combination of temperature and pressure.
Ordinarily, a transition from one phase to another
takes place under conditions of phase equilibrium
between the two phases.
The intersection point of the three equilibrium
curves in is called the triple point, all three phases
can coexist.
A gas at a temperature above the critical temperature
doesn’t separate into two phases when it is
compressed.
Its properties change gradually and continuously from those we ordinarily associate
with a gas (low density and high compressibility) to those of a liquid (high density and
low compressibility) without a phase transition.
Triple Point and Critical Point
Kinetic Theory of an Ideal Gas
The goal of the kinetic theory of matter is to understand the macroscopic properties of
matter in terms of its atomic or molecular structure and behavior.
The assumptions of the simplest kinetic model:
• A container with volume 𝑉𝑉 contains a very large number 𝑁𝑁 of identical molecules,
each with mass 𝑚𝑚.
• The container has perfectly rigid walls that do not move.
• The molecules behave as point particles; their size is small in comparison to the
average distance between particles and to the dimensions of the container.
• The molecules are in constant random motion; they obey Newton’s laws. Each
molecule occasionally makes a perfectly elastic collision with a wall of the
container.
• During collisions, the molecules exert forces on the walls of the container; these
forces create the pressure that the gas exerts. In a typical collision, the velocity
component parallel to the wall is unchanged, and the component perpendicular to
the wall changes direction, but not magnitude.
Step 1: Find the total change in momentum associated with each collision.
Step 2: Find the number of collisions per unit time for a certain wall area.
Step 3: Find the total change in momentum per unit time due to these collisions and,
from that, the force on area needed to cause that change in momentum.
Step 4: Obtain an expression for the pressure, which is force per unit area, and
compare it with the ideal-gas equation.
Δ𝑃𝑃𝑥𝑥 𝑁𝑁𝑁𝑁𝑁𝑁𝑣𝑣𝑥𝑥2 𝐹𝐹 𝑁𝑁𝑁𝑁𝑣𝑣𝑥𝑥2
= = 𝐹𝐹 ⇒ 𝑝𝑝 = =
Δ𝑡𝑡 𝑉𝑉 𝐴𝐴 𝑉𝑉
⇒ 𝑝𝑝𝑝𝑝 = 𝑁𝑁𝑁𝑁𝑣𝑣𝑥𝑥2
𝑣𝑣 2 = 𝑣𝑣𝑥𝑥2 + 𝑣𝑣𝑦𝑦2 + 𝑣𝑣𝑧𝑧2 ⇒ 𝑣𝑣 2 𝑎𝑎𝑎𝑎 = 𝑣𝑣𝑥𝑥2 𝑎𝑎𝑎𝑎 + 𝑣𝑣𝑦𝑦2 + 𝑣𝑣𝑧𝑧2 𝑎𝑎𝑎𝑎 = 3 𝑣𝑣𝑥𝑥2 𝑎𝑎𝑎𝑎
𝑎𝑎𝑎𝑎
1 2 1 2
⇒ 𝑣𝑣𝑥𝑥2 𝑎𝑎𝑎𝑎 = 𝑣𝑣 𝑎𝑎𝑎𝑎 𝑝𝑝𝑝𝑝 = 𝑁𝑁𝑁𝑁 𝑣𝑣𝑥𝑥2 𝑎𝑎𝑎𝑎
= 𝑁𝑁𝑁𝑁 𝑣𝑣 𝑎𝑎𝑎𝑎
3 3
2 1 2 3
𝑝𝑝𝑝𝑝 = 𝑁𝑁 𝑚𝑚 𝑣𝑣 2 𝑎𝑎𝑎𝑎 = 𝐾𝐾𝑡𝑡𝑡𝑡 = 𝑛𝑛𝑛𝑛𝑛𝑛 ⇒ 𝐾𝐾𝑡𝑡𝑡𝑡 = 𝑛𝑛𝑛𝑛𝑛𝑛
3 2 3 2
𝐾𝐾𝑡𝑡𝑡𝑡 3 𝑛𝑛𝑛𝑛𝑛𝑛 3 𝑛𝑛𝑛𝑛𝑛𝑛 3 𝑅𝑅 3
⇒ 𝐾𝐾𝑎𝑎𝑎𝑎 = = = = 𝑇𝑇 = 𝑘𝑘𝑘𝑘
𝑁𝑁 2 𝑁𝑁 2 𝑛𝑛𝑁𝑁𝐴𝐴 2 𝑁𝑁𝐴𝐴 2 Maxwell-Boltzmann
Distribution
𝑅𝑅
Boltzmann Constant: 𝑘𝑘 = = 1.381 × 10−23 𝐽𝐽/𝐾𝐾
𝑁𝑁𝐴𝐴
𝑛𝑛𝑛𝑛 = 𝑁𝑁𝑁𝑁
3𝑘𝑘𝑘𝑘 3𝑅𝑅𝑅𝑅
𝑝𝑝𝑝𝑝 = 𝑁𝑁𝑁𝑁𝑁𝑁 𝑣𝑣𝑟𝑟𝑟𝑟𝑟𝑟 = 𝑣𝑣 2 𝑎𝑎𝑎𝑎 = 𝑚𝑚 = 𝑀𝑀
Molar Heat Capacity
The amount of heat needed for a certain temperature change is
proportional to the temperature change and to the number of
moles of substance: 𝑄𝑄 = 𝑛𝑛𝑛𝑛Δ𝑇𝑇 Units: 𝐽𝐽/(𝑚𝑚𝑚𝑚𝑚𝑚 ⋅ 𝐾𝐾)
3
Δ𝐾𝐾𝑡𝑡𝑡𝑡 = 𝑛𝑛𝑛𝑛Δ𝑇𝑇
2 3 3
⇒ 𝑛𝑛𝐶𝐶𝑉𝑉 Δ𝑇𝑇 = 𝑛𝑛𝑛𝑛Δ𝑇𝑇 ⇒ 𝐶𝐶𝑉𝑉 = 𝑅𝑅
𝑄𝑄 = 𝑛𝑛𝐶𝐶𝑉𝑉 Δ𝑇𝑇 2 2
For Diatomic Ideal Gases:

5
𝐶𝐶𝑉𝑉 = 𝑅𝑅
2
The First Law of Thermodynamics
If an amount of heat is added to a system (such
as an ideal gas) and that system does an
amount of work, then the internal energy of
the system will change according to the
equation:
Δ𝑈𝑈 = 𝑄𝑄 − 𝑊𝑊
Work done during volume changes
𝑊𝑊 = 𝐹𝐹Δ𝑥𝑥 = 𝑝𝑝𝑝𝑝Δ𝑥𝑥 = 𝑝𝑝Δ𝑉𝑉

Work done during volume changes
Isothermal Process:
𝑉𝑉2
𝑊𝑊 = 𝑛𝑛𝑛𝑛𝑛𝑛 ln
𝑉𝑉1
𝑊𝑊 = 𝑝𝑝1 𝑉𝑉2 − 𝑉𝑉1

𝑊𝑊 = 𝑝𝑝2 𝑉𝑉2 − 𝑉𝑉1
Example 15.10
A series of thermodynamic processes is shown in the diagram. In process 𝑎𝑎𝑎𝑎, 150 𝐽𝐽 of
heat are added to the system, and in process 𝑏𝑏𝑏𝑏, 600 𝐽𝐽 of heat are added. Find:
A. The internal energy change in process 𝑎𝑎𝑎𝑎
B. The internal energy change in process 𝑎𝑎𝑎𝑎𝑎𝑎
C. The total heat added in process 𝑎𝑎𝑎𝑎𝑎𝑎
Thermodynamic Processes
𝑄𝑄 = 𝑊𝑊 + Δ𝑈𝑈
Adiabatic: 𝑄𝑄 = 0 Isochoric: Δ𝑉𝑉 = 0

Δ𝑈𝑈 = −𝑊𝑊 Δ𝑈𝑈 = 𝑄𝑄
Isothermal:
Isobaric: Δ𝑝𝑝 = 0
Δ𝑈𝑈 = 0
𝑊𝑊 = 𝑝𝑝Δ𝑉𝑉
𝑄𝑄 = 𝑊𝑊
Heat Capacity of an Ideal Gas
𝑄𝑄 = 𝑊𝑊 + Δ𝑈𝑈 𝑊𝑊 = 𝑝𝑝1 Δ𝑉𝑉 = 𝑛𝑛𝑛𝑛Δ𝑇𝑇
𝑄𝑄 = 𝑛𝑛𝐶𝐶𝑉𝑉 Δ𝑇𝑇 = Δ𝑈𝑈
𝑄𝑄 = 𝑛𝑛𝐶𝐶𝑃𝑃 Δ𝑇𝑇 = Δ𝑈𝑈 + 𝑊𝑊 = 𝑛𝑛𝐶𝐶𝑉𝑉 Δ𝑇𝑇 + 𝑛𝑛𝑛𝑛Δ𝑇𝑇 = 𝑛𝑛 𝐶𝐶𝑉𝑉 + 𝑅𝑅 Δ𝑇𝑇
𝐶𝐶𝑃𝑃 = 𝐶𝐶𝑉𝑉 + 𝑅𝑅
Adiabatic Process
𝑄𝑄 = 𝑊𝑊 + Δ𝑈𝑈 𝐶𝐶𝑃𝑃 Recall:
𝑝𝑝𝑝𝑝 = 𝑛𝑛𝑛𝑛𝑛𝑛 𝛾𝛾 =
𝐶𝐶𝑉𝑉
𝛾𝛾 𝛾𝛾
3
𝑝𝑝1 𝑉𝑉1 = 𝑝𝑝2 𝑉𝑉2 = const 𝑅𝑅 Monoatomic
2
𝛾𝛾−1 𝛾𝛾−1
𝐶𝐶𝑉𝑉 =
Δ𝑈𝑈 = 𝑛𝑛𝐶𝐶𝑉𝑉 Δ𝑇𝑇 𝑇𝑇1 𝑉𝑉1 = 𝑇𝑇2 𝑉𝑉2 = const 5
𝑅𝑅 Diatomic
2
𝐶𝐶𝑃𝑃 = 𝐶𝐶𝑉𝑉 + 𝑅𝑅
2
1 + ≈ 1.67 Monoatomic
𝐶𝐶𝑃𝑃 𝐶𝐶𝑉𝑉 + 𝑅𝑅 𝑅𝑅 3
𝛾𝛾 = = =1+ =
𝐶𝐶𝑉𝑉 𝐶𝐶𝑉𝑉 𝐶𝐶𝑉𝑉 2
1 + = 1.40 Diatomic
5
Example 15.11
Suppose a certain diesel engine compresses the air–fuel mixture by a factor of 15; this
means that the gas in its cylinders is compressed to one-fifteenth of its initial volume.
The initial pressure is 1.01 × 105 𝑃𝑃𝑃𝑃 and the initial temperature is 27°𝐶𝐶 300 𝐾𝐾 . Air is
mostly a mixture of diatomic oxygen and nitrogen.
Find the final pressure and temperature after compression.

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Physics 1214

The molar mass of a substance is the mass of 1 mole: 𝑀𝑀 = 𝑁𝑁𝐴𝐴 𝑚𝑚

These three relationships can be combined neatly into a

For a material that does not obey the ideal-gas equation, at

For Diatomic Ideal Gases:

𝑊𝑊 = 𝐹𝐹Δ𝑥𝑥 = 𝑝𝑝𝑝𝑝Δ𝑥𝑥 = 𝑝𝑝Δ𝑉𝑉

𝑊𝑊 = 𝑝𝑝1 𝑉𝑉2 − 𝑉𝑉1

Adiabatic: 𝑄𝑄 = 0 Isochoric: Δ𝑉𝑉 = 0

Find the final pressure and temperature after compression.

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