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Chapter 17
Temperature, Thermal
Expansion, and the Ideal Gas
Law

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Topics

Topics in next four chapters 17 -20:


Temperature
Heat
Thermodynamics
Kinetic theory of gases

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Definitions

• System: object or set of objects with a defined


boundary (that may or may not be closed)
• Environment: Everything outside the system
• State: The condition of a system defined by a set of
variables associated with the system
• Microscopic Variables: Variables describing a
system at the level of atoms and molecules.
• Macroscopic Variables: Variables that describe a
system in terms that can be detected by our senses.
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Definitions

• Thermodynamics: The field that deals with the


description of systems in terms of macroscopic
quantities, for example pressure, temperature,
volume,…
• The number of variables depends on the type of
system.
• State Variables: Quantities that can be used to
describe the state of a system.

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17-1 Atomic Theory of Matter

• Idea of atoms can be traced to Greek philosopher


Democritus (c. 460 – 370 B.C.).
• Others include:
 Rene Descartes (1596 – 1650)
 James Dalton (1766 – 1814)
 Robert Brown (1773 – 1858)
 Albert Einstein (1879 – 1955)

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Unified Mass Unit (u)

• Based on assigning the carbon atom 12 C, the value of


exactly 12.000… unified mass units.
• 1 u = 1.66 x 10-27 kg.
• The atomic mass of hydrogen is then = 1.0078 u.
• See Appendix D in text for complete list.

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Carbon
A
Z X
Where A = total number of nucleons (protons +
neutrons); Z is the atomic number = number of
protons (and electrons in a neutral atom); N = A – Z is
the number of neutrons.
12
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C
For carbon 12, 1 u = 12.000 exactly, by definition.
The weighted average for all carbon isotopes is u =
12.0107.
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Carbon
mp = 1.6726 x 10-27 kg
mn = 1.6749 x 10-27 kg
me = 9.1094 x 10-30 kg
6 x mp = 1.6726 x 10-27 kg = 1.00356 x 10-26 kg
6 x mn = 1.6749 x 10-27 kg = 1.00494 x 10-26 kg
6 x me = 9.1094 x 10-30 kg = 5.46564 x 10-30 kg
2.00855 x 10-26 kg
12 x 1 u = 12 x 1.6605 x 10-27 kg
= 1.9926 x 10-26 kg; ∆ = .01595 x 10-26 kg which is the
binding energy (B) of the nucleus.
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Binding Energy

Binding energy mass = .01595 x 10-26 kg


E = mc2
E = (.01595 x 10-26 kg)(3.0 x 108 m/s)2
= 4.785 x 10-20 kg.m2/s2 (J)
The nucleus has a lower energy than the energy of the
sum of its parts. That is why it “sticks” together. If it
is split, (nuclear fission), some of this energy is
released. This is what powers nuclear power plants
and the original “atom” bombs.
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Brownian Movement

• Named after biologist Robert Brown.


• Discovered in 1827.
• Looking through his microscope, he noticed that tiny
pollen grains, suspended in water, seemed to bounce
around in a zigzag path even in still water.
• Early evidence for the existence of atoms.

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Albert Einstein
• His 1905 paper put Brownian motion on sound
theoretical grounds based on the assumption that
atoms really exist.
• Until that time many considered atoms merely a
convenient model for calculation with no basis in
reality.
• Einstein calculated the approximate size and mass of
atoms and molecules based on experimental data.
o
• Size 10 m. (1 Angstrom (A) = 10-10 m)
-10

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Three Phases of Matter

• Solid
• Liquid
• Gas

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Molecular Bonding
• Molecular bonding causes molecules and solids to
bond together.
• Bonding forces are electrical (governed by the
electrons surrounding the nucleus of each atom.
• When atoms get too close to each other, the repulsive
electrical forces take over.
• Principal types of bonds:
Ionic
Covalent
Metallic

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Solid

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Characteristics of Solids
• Any Solid
Maintains a fixed shape and fixed size even if a
large force is applied
Attractive forces so strong that atoms stay in more
or less fixed positions—they vibrate about these
fixed positions. As heat is added, they vibrate
more.
• Crystal
Regular periodic array of atoms (crystal lattice)
Long-range order
• Amorphous
No regular periodic array of atoms
No long-range order
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Basic Crystal Lattice Structures

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Liquid

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Characteristics of Liquids

• Short-range order
• No long-range order
• Well defined boundary
• Incompressible
• Atoms in solid have begun to vibrate so much that
long-range order is lost. This happens when heat
causes the atoms in a solid to vibrate about their fixed
positions so much that the long-range order is lost.

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Gas

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Characteristics of Gases

• No short or long range order


• Transparent
• Little resistance to flow
• Diffuse rapidly in space and through porous barriers
• Expand greatly on heating or reduction of applied
pressure

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Vapors

• Molecules of a liquid exhibit an energy distribution.


• Molecules that are most energetic, close to the surface
have the best chance to escape (vaporization).
• The escaped molecules may be recaptured if they
reach and are held by the attractive forces of the
liquid (condensation)
• Any condensable gas is called a VAPOR.
• The fundamental properties of a vapor are the
same as those of a gas.
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Vaporization
A high rate of vaporization (evaporation) is favored by:
2. High temperature of the liquid
3. Small attractive forces in the liquid
4. A large surface area
5. Low atmospheric pressure above the liquid—to
decrease the number of collisions with other
molecules and thereby minimize return of the
molecules to the liquid
6. A mass motion of the atmosphere above the liquid
to carry away vaporized molecules and thereby
minimize reentry.
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Example 17-1

Distance between atoms.


The density of copper is 8.9 x 103 kg/m3 and each
copper atom has a mass of 63 u, where u = 1.66x10-27
kg. Estimate the average distance between
neighboring atoms.

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17-2 Temperature

• Temperature is one of the usual state variables in


thermodynamics.
• Many properties of materials change with
temperature.
• For example, most materials expand when heated.
• Water is the odd ball. It expands when cooled
between 0o and 4o Celsius. That’s why water pipes
can break in a winter freeze, and why ice floats.
• Temperature is a measure of energy.

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Temperature Scales

• Celsius (C)
• Fahrenheit (F)
• Kelvin (absolute)
• Science uses either Celsius or Kelvin.

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Example 17-2

Taking your temperature.


Normal body temperature is 98.6o F. What is this on
the Celsius scale?

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17-3 Thermal Equilibrium and the Zeroth
Law of Thermodynamics
• If two objects at different temperatures are placed in
thermal contact with each other (thermal contact
means thermal energy can pass from one object to the
other), the two objects will eventually reach the same
temperature.
• They are then said to be in thermal equilibrium.
• The zeroth law of thermodynamics:
If two objects are in thermal equilibrium with a
third object, then they are in thermal equilibrium
with each other.

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17-4 Thermal Expansion

Linear Expansion

∆L = αLo∆T
where α is the coefficient of linear expansion.
Its units are (Co)-1.
This equation is empirical.
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Example 17-3
Bridge expansion.
The steel bed of an expansion bridge is 200 m
long at 20o C. If the extremes of temperature to
which it might be exposed are – 30o to + 40o C,
how much will it contract and expand?

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Conceptual Example 17-4

Do holes expand or contract?


A circular hole is cut from a sheet of metal. When
the metal is heated in an oven, does the hole get
larger or smaller?

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Example 17-5

Ring on a rod.
An iron ring is fit snugly on a cylindrical iron rod. At
20o C, the diameter of the rod is 6.445 cm and the
inside diameter of the ring is 6.420 cm. To slip over
the rod, the ring must be slightly larger than the rod
diameter by about 0.008 cm. To what temperature
must the ring be brought if its hole is to be large
enough so it will slip over the rod?

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Thermal Expansion

Volume Expansion

∆V = βVo∆T
where β is the coefficient of volume expansion.
Note: β  3α.
The units of β are (Co)-1.

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Example 17-6

Gas tank in the sun.


The 70-L steel gas tank of a car is filled to the top
with gasoline at 20o. The car is then left to sit in the
sun, and the tank reaches a temperature of 40o C,.
How much gasoline do you expect to overflow from
the tank?

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17-5 Anomalous Behavior of Water
Below 4oC
• Most substances expand more or less uniformly with
an increase in temperature (as long as no phase
change occurs).
• Water, however, does not follow the usual pattern.
• If water at 0o C is heated, it actually decreases in
volume until it reaches 4o C.
• Above 4o C water behaves normally.

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17-6 The Gas Laws and Absolute
Temperature
• Equation of state of a gas is the relationship between
pressure, volume, and temperature.
• Will consider only equilibrium states of a system.
That is, the state variables are constant in time
throughout the system.
• Why?
• The field is called non-equilibrium
thermodynamics. It was developed in the mid-20th
century by Ilya Prigogene.

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Boyle’s Law

• It has been found our experimentally that, to a good


approximation, the volume of a gas is inversely
proportional to the pressure applied to it when the
temperature is held constant.
• After Robert Boyle (1627 – 1691)

V  1
P

or PV = constant
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Charles’s Law

• The volume of a given amount of gas is directly


proportional to the absolute temperature when the
pressure is kept constant.

VT

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Gay-Lussac’s Law

• At a constant volume, the pressure of a gas is


directly proportional to the absolute temperature.

P T

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The Three Laws
• The laws due to Boyle, Charles, and Gay-Lussac are
not really laws in the sense that we use this term
today.
• That is, precise, deep, and of wide-ranging validity.
• They are really only approximations that are accurate
for real gases only as long as the pressure and density
of the gas are not too high, and the gas is not too
close to condensation.
• The term law applied to these three relationships has
become traditional however.

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17-3 The Ideal Gas Law

• The three laws of Boyle, Charles, and Gay-Lussac


were obtained by holding one variable constant and
varying the other two.
• They can be combined into a more general
relationship between the pressure, volume, and
temperature for a fixed quantity of gas:

PV  T.

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The Ideal Gas Law

• Experiments show that at a constant temperature and


pressure, the volume of an enclosed gas increases in
direct proportion to the mass m of the gas present.
PV  mT

• This proportion can be made into an equation by


inserting a constant of proportionality.
• Experiment shows this constant is the same for all
gases if instead of mass m we use the number of
moles.
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The Ideal Gas Law

PV = nRT

Where n represents the number of moles and R is the


Universal gas constant.
R = 8.315 J/(mol.K) and is determined
experimentally.

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The Ideal Gas Law

• The term “ideal” is used because real gases do not


follow the law precisely.
• The law is not accurate at
 high pressure and density
 when the gas is near the liquefaction (boiling)
point
• However, at pressures less than an atmosphere or so,
and temperatures not close to the liquefaction point, it
is quite accurate for real gases.
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Absolute Temperature
• Known as the Kelvin scale.
• Degrees are same size as Celsius scale.
• Absolute zero = 0 K (read zero Kelvins—not degrees
Kelvin).
• At standard atmospheric pressure:
 “Room Temperature” is about 293 K (20oC).
 “Standard Temperature” is 273 K
 Liquid nitrogen temperature is 77 K.
 Liquid helium temperature is 4 K.
 T (K) = T (oC) + 273.15
 Water freezes at 273.15 K and boils at 373.15 K.
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If any gas could be cooled to
-273oC, the volume would be
zero.

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Since zero volume is
impossible, one can
never reach absolute
zero.

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Mole

• 1 mole (mol) of a substance is defined as the amount


of a substance that contains as many atoms or
molecules as there are in 12.00 grams of Carbon 12.
• Mass (12C) = 12 u.
• 1 mol is the number of grams of a substance
numerically equal to the molecular mass of a
substance.

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Mole

• 1 mol of CO2 has a mass of [12 + (2x16)] = 44


grams/mol.
mass (grams)
• n (mol) =
molecular mass (g/mol)

• The number of mols in 132 grams of CO2 is:


132g
• n=
44g/mol = 3.0 mol
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17-8 Problem Solving with the Ideal Gas
Law
• Standard Temperature and Pressure (STP)
• T = 273 K (0oC)
• PA = 1.00 atm = *1.013 x 105 N/m2 = 101.3 kPa (k
= 103)
• Gauge pressure: Pabs = PA + PG. Gauge pressure is
the pressure measured by a gauge (e.g. tire pressure
gauge) above atmospheric pressure.
* This is the atmospheric pressure at sea level.

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Example 17-8
Volume of one mol at STP.
Determine the volume of 1.00 mol of any gas,
assuming it behaves like an ideal gas, (a) at STP, (b)
20oC.

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Example 17-9

Mass of air in a room.


Estimate the mass of air in a room whose dimensions
at 5 m x 3 m x 2.5 m high, at 20oC.

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Example 17-10

Check cold tires.


An automobile tire is filled to a gauge pressure of 200
kPa at 10oC. After driving 100 km, the temperature
within the tire rises to 40oC. What is the pressure
within the tire now?

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17-9 Ideal gas Law in Terms of
Molecules: Avogadro’s Number
• Amedeo Avogadro (1776 – 1856)
• Avogadro’s hypothesis states: equal volumes of gas
at the same pressure and temperature contain equal
numbers of molecules.
• Avogadro’s number:
NA = 6.02 x 1023 molecules/mole.
• That is, Avogadro was the first to clearly realize that
the volume of a gas depends on the number of
molecules it contains.
• Or, 1 mole of any substance contains NA numbers of
molecules (or atoms as the case may be). 59
In Other Words

A mole of oxygen (32 g) is 16 times as massive as a


mole of hydrogen gas (2 g), but is made of
molecules that are 16 times as massive as
hydrogen. Therefore, one mole of oxygen contains
the same number of molecules as one mole of
hydrogen.

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Calculation of Avogadro’s Number

1 atom of mass m of 12C = 1.9926 x 10-26 kg/molecule


The atomic mass of 12C = 12 g/mol (12 x 10-3 kg/mol)

Therefore Avogadro’s Number NA =

12 x 10-3 kg/mol
= 6.0214 x 1023
molecules/mol
1.9926 x 10 kg/molecule
-26

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Boltzmann’s Constant
The total number of molecules, N, in a gas is equal to
the number of mols times the number of
molecules/mole:
N = nNA

N NA
PV = nRT = RT

PV = NkT

where: k = R/NA
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Example 17-11

Hydrogen atom mass.


Use Avogadro’s number to determine the mass of a
hydrogen atom.

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Homework Problem 1

How does the number of atoms in a 26.5-g gold ring


compare to the number in a silver ring of the same
mass?

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Homework Problem 2

How many atoms are there in a 3.4-g copper penny?

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Homework Problem 13

An ordinary glass is filed to the brim with 350.0 mL


of water at 100o C. If the temperature is decreased to
20o C, how much water could be added to the glass?

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Homework Problem 15

A quartz sphere is 8.50 cm in diameter. What will be


its change in volume if it is heated from 30o C to 200o
C?

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Homework Problem 32

A storage tank contains 21.6 kg of nitrogen (N2) at an


absolute pressure of 3.65 atm. What will be the
pressure if the nitrogen is replaced by an equal mass
of CO2?

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Homework Problem 36

A tank contains 30.0 kg of O2 gas at a gauge pressure


of 8.70 atm. If the oxygen is replaced by helium,
how many kilograms of the latter will be needed to
produce a gauge pressure of 7.00 atm?

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Homework Problem 46

Estimate the number of (a) moles, and (b) molecules


of water in all the Earth’s oceans. Assume water
covers 75 percent of the Earth to an average depth of
3 km.

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