Chapter 3

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QUIZ #3 email your answers
John BROWN, st. #391245  to: athul066@uottawa.ca
 cc: stadnik@uottawa.ca
1. D
2. C
3. E
4. A

Temperature Thermal Contact

 We associate the concept of temperature  Two objects are in thermal contact with
with how hot or cold an objects feels each other if energy can be exchanged
 Our senses provide us with a qualitative between them
indication of temperature  The exchanges we will focus on will be in the
 Our senses are unreliable for this purpose form of heat or electromagnetic radiation
 We need a reliable and reproducible  The energy is exchanged due to a temperature
method for measuring the relative hotness difference
or coldness of objects

3 4
Zeroth Law of Thermodynamics
Thermal Equilibrium

 Thermal equilibrium is a situation in


which two objects would not exchange
energy by heat or electromagnetic
radiation if they were placed in thermal
contact  Object C (thermometer) is placed in contact with A until they
achieve thermal equilibrium
 The thermal contact does not have to be  The reading on C is recorded
physical contact  Object C is then placed in contact with object B until they
achieve thermal equilibrium
 The reading on C is recorded again
 If the two readings are the same, we can conclude that A
5 and B are in thermal equilibrium with each other 6

Zeroth Law of Thermodynamics Temperature − Definition

 If objects A and B are separately in  Temperature can be thought of as the


thermal equilibrium with a third object C, property that determines whether an object
then A and B are in thermal equilibrium is in thermal equilibrium with other objects
with each other  Two objects in thermal equilibrium with
 Let object C be the thermometer
each other are at the same temperature
 If two objects have different temperatures, they
 Since they are in thermal equilibrium with are not in thermal equilibrium with each other
each other, there is no energy exchanged
among them

7 8
Thermometers
 A thermometer is a device that is used  These properties include:
to measure the temperature of a system  The volume of a liquid
The dimensions of a solid
Thermometers are based on the principle


 The pressure of a gas at a constant volume
that some physical property of a system  The volume of a gas at a constant pressure
changes as the system’s temperature  The electric resistance of a conductor
changes  The color of an object
 A temperature scale can be established on
the basis of any of these physical properties
9 10

Thermometer, Liquid in Glass


Calibrating a Thermometer
 A common type of  A thermometer can be calibrated by placing it
thermometer is a liquid- in contact with some natural systems that
in-glass remain at constant temperature
 The material in the  Common systems involve water
capillary tube expands as  A mixture of ice and water at atmospheric pressure
it is heated  Called the ice point of water

 The liquid is usually  A mixture of water and steam in equilibrium


mercury or alcohol  Called the steam point of water

 Once these points are established, the length


between them can be divided into a number
11 of segments 12
Problems with Liquid-in-Glass Thermometers
Celsius Scale
 An alcohol thermometer and a mercury
 The ice point of water is defined to be 0oC thermometer may agree only at the calibration
 The steam point of water is defined to be points
100oC  The discrepancies between thermometers are
 The length of the column between these especially large when the temperatures being
two points is divided into 100 increments, measured are far from the calibration points
called degrees  The thermometers also have a limited range of
values that can be measured
 Mercury cannot be used under –30oC
 Alcohol cannot be used above 85oC
13 14

Constant-Volume Gas Thermometer Using a constant-volume gas thermometer to measure temperature

 The physical change exploited


is the variation of pressure of a
fixed volume gas as its
temperature changes
 The volume of the gas is kept
constant by raising or lowering
the reservoir B to keep the
mercury level at A constant
 The pressure is indicated by
the height difference between
reservoir B and column A
15 16
Constant-Volume Gas Thermometer Absolute Zero

 The thermometer is calibrated by using


 The thermometer readings are
a ice water bath and a steam water
bath virtually independent of the gas
used
 The pressures of the mercury under
each situation are recorded  If the lines for various gases
 The volume is kept constant by adjusting A are extended, the pressure is
 The information is plotted always zero when the
 To find the temperature of a substance, temperature is
the gas flask is placed in thermal –273.15oC
contact with the substance  This temperature is called
 The pressure is found on the graph absolute zero
 The temperature is read from the graph
17 18

Absolute Temperature Scale


 Absolute zero is used as the basis of the  The absolute temperature scale is now
absolute temperature scale based on two new fixed points
Adopted by in 1954 by the International
The size of the degree on the absolute


Committee on Weights and Measures
scale is the same as the size of the  One point is absolute zero
degree on the Celsius scale  The other point is the triple point of water
 To convert:  This is the combination of temperature and
pressure where ice, water, and steam can all
TC = T – 273.15, T = TC + 273.15 coexist

19 20
 The triple point of water occurs at
0.01°C and 4.58 mm of mercury (610 Pa, 0.006 atm)
 This temperature was set to be 273.16 on the
 The absolute scale is also called the Kelvin scale
absolute temperature scale: Ttriple = 273.16 K
 Named for William Thomson, Lord Kelvin
 This made the old absolute scale (based on the ice
and steam points) agree closely with the new one  The triple point temperature is 273.16 K
 The units of the absolute scale are kelvins  No degree symbol is used with kelvins
 The kelvin is defined as 1/273.16 of the difference
between absolute zero and the temperature of the
triple point of water
21 22

Fahrenheit Scale
 The figure at right gives some
absolute temperatures at  A common scale in everyday use in the US
which various physical  Named for Daniel Fahrenheit
processes occur
 The scale is logarithmic  Temperature of the ice point is 32oF
 The temperature of absolute  Temperature of the steam point is 212oF
zero cannot be achieved  There are 180 divisions (degrees)
Experiments have come close
between the two reference points

23 24
Comparison of Scales

 Celsius and Kelvin have the same size  To compare changes in temperature
degrees, but different starting points
TC = T – 273.15
 Celsius and Fahrenheit have different  Ice point temperatures
sized degrees and different starting points  0oC = 273.15 K = 32oF

 Steam point temperatures


 100oC = 373.15 K = 212oF

25 26

Thermal Expansion

Thermal Expansion
 Demo: the metal ring and metal sphere

27 28
Thermal Expansion

 Thermal expansion is the increase in the size of  As the washer shown at right is
an object with an increase in its temperature heated, all the dimensions will
 Thermal expansion is a consequence of the increase
change in the average separation between the  A cavity in a piece of material
atoms in an object
expands in the same way as if the
 If the expansion is small relative to the original cavity were filled with the material
dimensions of the object, the change in any
dimension is, to a good approximation,  The expansion is exaggerated in
proportional to the first power of the change in this figure
temperature
29 30

Linear Expansion ∆L = αLi ∆T

 Assume an object has an initial length L  This equation can also be written in
 That length increases by ∆L as the terms of the initial and final conditions
temperature changes by ∆T of the object:
 We define the coefficient of linear  Lf – Li = α Li (Tf – Ti)
expansion as  The coefficient of linear expansion, α,
∆L / Li has units of (oC)-1
α=
∆T
 A convenient form is ∆L = αLi ∆T
31 32
 Some materials expand along one
dimension, but contract along another as the
temperature increases
 Since the linear dimensions change, it
follows that the surface area and volume
also change with a change in temperature
 A hole in a piece of material expands in the
same way as if the cavity were filled with
33
the material 34

Films Volume Expansion


 14-07 Thermal Expansion of Wire  The change in volume is proportional to
 14-10 Pin Breaker the original volume and to the change
in temperature
 ∆V = βVi ∆T
 β is the coefficient of volume expansion
 For a solid, β = 3α
 This assumes the material is isotropic, the
same in all directions
 For a liquid or gas, β is given in the table

35 36
Area Expansion
 The change in area is proportional to the
original area and to the change in
temperature:
 ∆A = 2αAi ∆T

37 38

Opening a Tight Jar Lid Bimetallic Strip

 Each substance has its own


characteristic average
coefficient of expansion
 This can be made use of in
the device shown, called a
bimetallic strip: as the
 The lid will heat before the glass, and temperature of the strip
expand sooner. Also, metals generally increases, the two metals
expand more than glass for the same expand by different amounts
→ the strip bends
temperature difference.
 It can be used in a thermostat
39 40
Why a pond begins freezing at the surface rather than at the bottom?
Water’s Unusual Behavior

 As the temperature increases


from 0°C to 4°C, water
contracts
 Its density increases

 Above 4°C, water expands  When the atmospheric temperature drops from, e.g., 7°C to 6°C, the surface
water also cools and consequently decreases in volume → the surface water is
with increasing temperature denser than the water below it, which has not cooled and decreased in volume →
 Its density decreases the surface water sinks, and warmer water from below is forced to the surface to
be cooled.
 The maximum density of water
When the atmospheric temperature is between 4°C to 0°C, however, the surface
(1.000 g/cm3) occurs at 4°C 
water expands as it cools, becoming less dense than the water below it → the
mixing process stops, and eventually the surface water freezes.
 As the water freezes, the ice remains on the surface because ice is less dense
than water → the ice continues to build up at the surface, while water near the
bottom remains at 4°C. If this were not the case, then fish and other forms of
41 42
marine life would not survive.

Thermodynamics – Historical Background


T14 film 15-15
 Film 14-14 (Negative Expansion  Thermodynamics and mechanics were considered to be
separate branches
Coefficient of Water)  Until about 1850
Experiments by James Joule and others showed a connection
 Film 15-15 (Ice Bomb) 
between them
 A connection was found between the transfer of energy
by heat in thermal processes and the transfer of
energy by work in mechanical processes
 The concept of energy was generalized to include
internal energy
 The Law of Conservation of Energy emerged as a
universal law of nature
43 44
Internal Energy and Other Energies
Internal Energy
 Internal energy is all the energy of a  The kinetic energy due to its motion
system that is associated with its through space is not included
microscopic components  Internal energy does include kinetic
 These components are its atoms and molecules energies due to:
 The system is viewed from a reference frame  Random translational motion
at rest with respect to the center of mass of  Rotational motion
the system  Vibrational motion
 Internal energy also includes potential
energy between molecules
45 46

Heat Changing Internal Energy


 Heat is defined as the transfer of energy  Both heat and work can change the
across the boundary of a system due to a internal energy of a system
temperature difference between the  The internal energy can be changed
system and its surroundings even when no energy is transferred by
 The term heat will also be used to heat, but just by work
represent the amount of energy  Example, compressing gas with a piston
transferred by this method  Energy is transferred by work

47 48
Mechanical Equivalent of Heat
Units of Heat
 Historically, the calorie was the unit used for heat  Joule established the equivalence
between mechanical energy and
One calorie is the amount of energy transfer necessary to
internal energy

raise the temperature of 1 g of water from 14.5°C to 15.5°C


 His experimental setup is shown at right
 The “Calorie” used for food is actually 1 kilocalorie
 The loss in potential energy associated
 In the US Customary system, the unit is a BTU with the blocks (2mgh) equals the work
(British Thermal Unit) done by the paddle wheel on the water
 One BTU is the amount of energy transfer necessary to raise  Joule found that it took approximately
the temperature of 1 lb of water from 63°F to 64°F 4.18 J of mechanical energy to raise the
temperature of 1 g of water by 1°C
 The standard in the text is to use Joules

49 50

Mechanical Equivalent of Heat


Heat Capacity
 Later, more precise, measurements determined  The heat capacity, C, of a particular
the amount of mechanical energy needed to raise sample is defined as the amount of
the temperature of water from 14.5°C to 15.5°C energy needed to raise the temperature
 1 cal = 4.186 J of that sample by 1°C
This is known as the mechanical equivalent of heat
If energy Q produces a change ∆T in


 A more proper name would be the equivalence between
mechanical energy and internal energy, but the the temperature of a sample, then
historical name is well entrenched in our language,
despite the incorrect use of the word heat
Q = C ∆T

51 52
Q
c≡
m ∆T
Specific Heat
 Specific heat, c, is the heat capacity  The specific heat is essentially a measure of
how insensitive a substance is to the addition of
per unit mass energy
 If energy Q transfers to a sample of a  The greater the substance’s specific heat, the more
substance of mass m and the energy that must be added to cause a particular
temperature change
temperature changes by ∆T, then the
 From the definition of c, one can relate the
specific heat is energy Q transferred between a sample of
Q mass m of a material and its surroundings to a
c≡ temperature change ∆T as
m ∆T
53
Q = m c ∆T 54

Some Specific Heat Values


More Specific Heat Values

55 56
Film: 14-17 (Specific Heat) Sign Conventions
 If the temperature increases:
 Q and ∆T are positive
 Energy transfers into the system
 If the temperature decreases:
 Q and ∆T are negative
 Energy transfers out of the system

57 58

Specific Heat Varies With Temperature


Specific Heat of Water
 Technically, the specific heat varies with  Water has the highest specific heat of
temperature T common materials
The corrected equation is = ∫T c dT
f
Q m

i  This is responsible for many weather
 However, if the temperature intervals are phenomena
not too large, the variation can be ignored Moderate temperatures near large bodies of
and c can be treated as a constant

water
 There is only about a 1% variation between
Global wind systems
0° and 100°C

 Land and sea breezes


59 60
Calorimetry
Calorimetry
The system of the sample and the water
One technique for measuring specific heat

 is isolated
involves heating a material, adding it to a  Conservation of energy requires that the
amount of energy that leaves the
sample of water, and recording the final sample equals the amount of energy
temperature that enters the water
Conservation of energy allows one to
 This technique is known as calorimetry 
write the mathematical representation of
 A calorimeter is a device in which this energy this energy statement: Qcold = −Qhot
transfer takes place
 Technically, the mass of the container
should be included, but if mw >>mcontainer
61 it can be neglected 62

Phase Changes
Latent Heat
 A phase change is when a substance changes  Different substances react differently to the
from one form to another energy added or removed during a phase
 Two common phase changes are change
 Solid to liquid (melting)  Due to their different molecular arrangements
 Liquid to gas (boiling)  The amount of energy also depends on the
 Solid to gas (sublimation) mass of the sample
 During a phase change, there is no change in  If an amount of energy Q is required to change
temperature of the substance the phase of a sample of mass m, L ≡ Q /m
 For example, in boiling the increase in internal energy is
represented by the breaking of the bonds between
molecules, giving the molecules of the gas a higher
intermolecular potential energy 63 64
Latent Heat Latent Heat
 The latent heat of fusion (Lf ) is used when the
 The quantity L is called the latent heat phase change is from solid to liquid
of the material  The latent heat of vaporization (Lv ) is used when
 Latent means “hidden” the phase change is from liquid to gas
 The value of L depends on the substance  The latent heat of sublimation (Ls ) is used when
as well as the actual phase change the phase change is from solid to gas
 The positive sign of Q is used when the energy is
 The energy required to change the transferred into the system
phase is Q = ± mL  This will result in melting or boiling
 The negative sign of Q is used when energy is
transferred out of the system
65
 This will result in freezing or condensation 66

Sample Latent Heat Values


For a given substance, Lv > Lf ; why?

67 68
A plot of temperature versus energy added when a
system initially consisting of 1.00 g of ice at Warming Ice, Graph Part A
−30.0°C is converted to steam at 120.0°C

 Start with one gram of ice


at –30.0ºC
 During phase A, the
temperature of the ice
changes from –30.0ºC to
0ºC
 Use Q = mici ΔT
 In this case, 62.7 J of energy
are added

69 70

Melting Ice, Graph Part B Warming Water, Graph Part C

 Once at 0ºC, the phase  Between 0ºC and 100ºC, the


change (melting) starts material is liquid and no phase
 The temperature stays the changes take place
same although energy is still  Energy added increases the
being added temperature
 Use Q = mi Lf  Use Q = mwcw ΔT
The energy required is 333 J
419 J are added


 On the graph, the values move from
62.7 J to 396 J  The total is now 815 J

71 72
Boiling Water, Graph Part D Heating Steam

 At 100ºC, a phase  After all the water is


change occurs converted to steam, the
(boiling) steam will heat up
 Temperature does not  No phase change occurs
change  The added energy goes to
 Use Q = mwLv increasing the temperature
 This requires 2260 J  Use Q = mscs ΔT
 The total is now 3070 J  In this case, 40.2 J are needed
 The temperature is increasing
from 100oC to 120oC
 The total is now 3110 J
73 74

Supercooling Superheating
 If liquid water is held perfectly still in a very clean  Water can rise to a temperature greater than 100oC without
container, it is possible for the temperature to drop below boiling
0oC without freezing  This phenomena is called superheating
 This phenomenon is called supercooling  The formation of a bubble of steam in the water requires
 It arises because the water requires a disturbance of some nucleation site (this could be a scratch in the container or an
sort for the molecules to move apart and start forming the impurity in the water)
open ice crystal structures (this structure makes the density  When disturbed, the superheated water can become
of ice less than that of water) explosive (the bubbles will immediately form and hot water
 If the supercooled water is disturbed, it immediately freezes is forced upward and out of the container)
and the energy released returns the temperature to 0oC

75 76
Molar Specific Heat
 Molar specific heats:
 Q = nCV ∆T for constant-volume processes
 n – number of moles in mass m  Q = nCP ∆T for constant-pressure processes
 M – molecular weight  Q (constant pressure) must account for
both the increase in internal energy and
 C – molar specific heat
the transfer of energy out of the system
 c – specific heat by work
 Qconstant P > Qconstant V for given values of n
and ∆T
77 78

Molar Specific Heat of Solids,


Molar Specific Heat of Solids Graph
 Molar specific heats in solids also  As T approaches 0, the
demonstrate a marked temperature molar specific heat
dependence approaches 0
 Solids have molar specific heats that  At high temperatures, CV
generally decrease in a nonlinear manner becomes a constant at
with decreasing temperature ~3R (R = 8.314 J/mol⋅K)
 It approaches zero as the temperature
approaches absolute zero

79 80
DuLong-Petit Law
 At high temperatures, the molar specific  M1-6, 7, 14
heats approach the value of 3R
 This occurs above 300 K
 The molar specific heat of a solid at high
temperature can be explained by the
equipartition theorem

81 82

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