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Zeroth law of
thermodynamics

i  
 


 


   


 


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ï |hermometers can be calibrated by
placing them in thermal contact with
an environment that remains at
constant temperature
‡ Environment could be mixture of ice and
water in thermal equilibrium
‡ Also commonly used is water and steam
in thermal equilibrium
 

ï |emperature of an ice-
ice-water mixture
is defined as 0º C
‡ |his is the @  of water
ï |emperature of a water-
water-steam
mixture is defined as 100º C
‡ |his is the —
 of water
ï Œistance between these points is
divided into 100 segments
£ 

ï ºhen the pressure of a gas goes to
zero, its temperature is ±273.15º C
ï |his temperature is called ÷— 

 
ï |his is the zero point of the Kelvin
scale
‡ ±273.15º C = 0 K
ï |o convert: |C = |K ± 273.15
£ 
|  
ï =ome
representative
Kelvin
temperatures
ï Note, this scale is
logarithmic
ï Absolute zero has
never been
reached
6   

ï Most common scale used in the U=
ï |emperature of the freezing point is
32º
ï |emperature of the boiling point is
212º
ï 180 divisions between the points
  |  


TC Ô TK è 

TF Ô TC  è


TF Ô TC

|   
ï |he thermal expansion of an object is a
consequence of the change in the average
separation between its constituent atoms
or molecules
ï At ordinary temperatures, molecules
vibrate with a small amplitude
ï As temperature increases, the amplitude
increases
‡ |his causes the overall object as a whole to
expand
  
  
ï 6or small changes in temperature

°   °u
ï |he coefficient of linear expansion,  , depends
on the material
ï =imilar in two dimensions (area expansion)

   u  è
ï « and in three dimensions (volume expansion)

Ô  u   Ô Ô
 

 
 
 
 


 
 
 
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 | 
  

1. |hermostats
‡ Use a —  ÷

  
‡ |wo metals expand differently
2. Pyrex Glass
‡ |hermal stresses are smaller than for ordinary glass
3. =ea levels
‡ ºarming the oceans will increase the volume of the oceans
ë     

ï At the temperature of water increases from 0ºC


to 4 ºC, it contracts and its density increases
ï Above 4 ºC, water exhibits the expected
expansion with increasing temperature
ï Maximum density of water is 1000 kg/m3 at 4 ºC
i
ï Properties of gases
‡ A gas does not have a fixed volume or pressure
‡ In a container, the gas expands to fill the container
ï Ideal gas:
gas:
‡ Collection of atoms or molecules that move randomly
‡ Molecules exert no long-
long-range force on one another
‡ Molecules occupy a negligible fraction of the volume of their
container
ï Most gases at room temperature and pressure
behave approximately as an ideal gas
M
ï It¶s convenient to express the amount of
gas in a given volume in terms of the
number of moles, n
V 

V  V 

ï One mole is the amount of the substance


that contains as many particles as there
are atoms in 12 g of carbon-
carbon-12
!   
ï Equal volumes of gas at the same
temperature and pressure contain
the same numbers of molecules

‡ Corollary: At standard temperature


and pressure, one mole quantities of
all gases contain the same number of
molecules
‡ |his number is called NA
‡ Can also look at the total number of
particles: N = n NA
!  
ï |he number of particles in a mole is
called ! ÷   —
‡ NA=6.02 x 1023 particles / mole
ï |he mass of an individual atom can
be calculated:
   
  Ô
!
!    
i
ï Ooyle¶s Law
‡ At a constant temperature,
temperature,
pressure is inversely proportional to
the volume

ï Charles¶ Law
‡ At a constant pressure,
pressure, the
temperature is directly proportional
to the volume

ï Gay--Lussac¶s Law
Gay
‡ At a constant volume,
volume, the pressure
is directly proportional to the
temperature
i"

ï =ummarizes Ooyle¶s Law, Charles¶ Law,


and Guy-
Guy-Lussac¶s Law
ï PV = n R |
‡ R is the ë  ÷
÷  ÷
‡ R = 8.31 J / mole K
‡ R = 0.0821 L atm / mole K
ï P V = N kO |
‡ kO is O
 ÷  ÷
‡ kO = R / NA = 1.38 x 10-23 J/ K
£ 
|  ##
!  
ï |he number of molecules in the gas is large and the
average separation between them is large compared to
their dimensions
ï |he molecules obey Newton¶s laws of motion, but as a
whole they move randomly
ï |he molecules interact only by short-
short-range forces during
elastic collisions
ï |he molecules make elastic collisions with the walls
ï |he gas under consideration is a pure substance, all the
molecules are identical
* i
ï |he pressure is
proportional to the
number of molecules
per unit volume and
to the average
translational kinetic
energy of a molecule
     è
Ô  â  â
è è
M
i    
|  
ï |emperature is proportional to the
average kinetic energy of the molecules
 è
 Ô  |
è è
ï |he total kinetic energy is proportional to
the absolute temperature

  Ô à 
è
i 
ï In a monatomic gas, the KE is the only
type of energy the molecules can have
Ô à 
è
ï U is the   ÷
  of the gas
ï In a polyatomic gas, additional
possibilities for contributions to the
internal energy are rotational and
vibrational energy in the molecules
  M

ï Expressed as the 
  ÷
÷  ÷  (rms)
speed
 | |
 Ô Ô
 M

ï At a given temperature, lighter molecules


move faster, on average, than heavier
ones
‡ Lighter molecules can more easily reach
escape speed from the earth
Energy in |hermal Processes
i $
ï i  ÷
 ,
, U, is the energy associated with
the microscopic components of the system
‡ Includes kinetic and potential energy associated with the
random translational, rotational and vibrational motion
of the atoms or molecules
‡ Also includes the intermolecular potential energy

ï å÷ is energy transferred between a system


and its environment because of a temperature
difference between them
‡ |he system Q is used to represent the amount of energy
transferred by heat between a system and its
environment
ë  Units
=I Joule (J)
CG= Calorie (cal)
U= Customary O|U (btu)
ï Calorie
‡ An historical unit, before the connection between
thermodynamics and mechanics was recognized
‡ A ÷
  is the amount of energy necessary to raise
the temperature of 1 g of water from 14.5°
14.5° C to
15.5°
15.5 °C.
ï A Calorie (food calorie) is 1000 cal
ï Joule 1 cal = 4.186 J
‡ |his is called the M ÷ ÷
  ÷
 @å÷
ï O|U (U= Customary Unit)
‡ O|U stands for Oritish |hermal Unit
‡ A O ë is the amount of energy necessary to raise the
temperature of 1 lb of water from 63°
63° 6 to 64°
64° 6
 


ï Every substance requires a unique amount
of energy per unit mass to change the
temperature of that substance by 1°
1° C
‡ directly proportional to mass (thus, per unit
mass)
ï |he  @ ÷   of a substance is a
measure of this amount

 Units
 =I Joule/kg °C (J/kg °C)
°| CG= Calorie/g °C (cal/g °C )
 %  



ï Q = m c Ʃ|
‡ Ʃ| is always the final temperature
minus the initial temperature
‡ ºhen the temperature increases,
increases, Ʃ|
and ƩQ are considered to be positive
and energy flows into the system
‡ ºhen the temperature decreases,
decreases, Ʃ|
and ƩQ are considered to be negative
and energy flows out of the system
 &%"
        
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A  å   



 
  °
 Î mc l T
=    ± kg ± J ±
kg l R l 
Rèè Joules
Al =900 J/kg°C

    ö


6 

Q=?
! 
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ï ºater has a high
specific heat
compared to land
ï On a hot day, the
air above the land
warms faster
ï |he warmer air
flows upward and
cooler air moves
toward the beach
cSi Ô  J kg lC
 ! cH èO Ô X  J kg lC
l  
ºhat happens at night?

1. same
2. opposite
3. nothing
4. none of the above

"   


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ï A technique for determining the
specific heat of a substance is called
calorimetry
ï A ÷
    is a vessel that is a
good insulator that allows a thermal
equilibrium to be achieved between
substances without any energy loss
to the environment
  
ï Analysis performed using a calorimeter
ï Conservation of energy applies to the isolated
system
ï |he energy that leaves the warmer substance
equals the energy that enters the water
‡ Qcold = -Qhot
‡ Negative sign keeps consistency in the sign
convention of Ʃ|
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è
 water R metal Ô
=  "#
º =4186 J/kg°C = $ 
 
  

°C water R metal  mmetal cmetal Tmetal R m è c è T è

è °C ± kg cmetal ± l l

± ±
R ± kg X  J kg l l è l

°C 
± cmetal R è J 

6  cmetal Ô è ¦ J kg l ö
=   =?


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ï A ÷  ÷ occurs when the


physical characteristics of the
substance change from one form
to another
ï Common phases changes are
‡ =olid to liquid ± melting
‡ Liquid to gas ± boiling
ï Phases changes involve a change
energy, but 
in the internal energy,
÷   ÷ 
  

ï Œuring a phase change, the amount of heat is


given as
‡Q=mL
ï L is the
÷  ÷ of the substance
‡ Latent means hidden or concealed
ï Choose a positive sign if you are adding
energy to the system and a negative sign if
energy is being removed from the system
ï ÷  ÷ @@  is used for melting or
freezing
ï ÷  ÷ @ ÷ ÷  is used for boiling
or condensing
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* #
#   %
ï Use consistent units
ï |ransfers in energy are given as Q=mcƩ| for
processes with no phase changes
ï Use Q = m Lf or Q = m Lv if there is a phase
change
ï In Qcold = - Qhot be careful of sign, Ʃ| = |f -
|i
M  |
ï Need to know the rate at which
energy is transferred
ï Need to know the mechanisms
responsible for the transfer
ï Methods include
‡ Conduction
‡ Convection
‡ Radiation
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ï |he transfer can be viewed on an
atomic scale
‡ It is an exchange of energy between
microscopic particles by collisions
‡ Less energetic particles gain energy
during collisions with more energetic
particles
ï Rate of conduction depends upon the
characteristics of the substance

 
ï |he molecules vibrate
about their equilibrium
positions
ï Particles near the flame
vibrate with larger
amplitudes
ï |hese collide with adjacent
molecules and transfer
some energy
ï Eventually, the energy
travels entirely through the
rod

  
  
   
 
 
 
   


ï |he slab allows
energy to transfer
from the region of
higher temperature
to the region of
lower temperature

 ï
 Ô Ô   

 

å    





ï A is the cross-
cross-sectional area
ï L = Ʃx is the thickness of the slab or
the length of a rod
ï P is in ºatts when Q is in Joules and t
is in seconds
ï k is the  ÷
     of the
material
‡ Good conductors have high k values and
good insulators have low k values
i  
ï =ubstances are rated by their ´ ÷

‡R=L/k
ï More multiple layers, the total R value is
the sum of the R values of each layer
ï ºind increases the energy loss by
conduction in a home
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ï Energy transferred by the movement of a
substance
‡ ºhen the movement results from differences
in density, it is called ÷ ÷
  
‡ ºhen the movement is forced by a fan or a
pump, it is called @    

 
ï Air directly above the
flame is warmed and
expands
ï |he density of the air
decreases, and it rises
ï |he mass of air warms
the hand as it moves
by
ï Applications:
‡ Radiators
‡ Cooling automobile
engines
$-  
ï Radiation does not require physical
contact
ï All objects radiate energy continuously in
the form of electromagnetic waves due to
thermal vibrations of the molecules
ï Rate of radiation is given by = @÷ ÷
-   

ï |he electromagnetic waves carry the


energy from the fire to the hands
ï No physical contact is necessary
-  !  
ï P = ıAe|4
‡ P is the rate of energy transfer, in ºatts
‡ ı = 5.6696 x 10-8 º/m2 K4
‡ A is the surface area of the object
‡ e is a constant called the     
ï e varies from 0 to 1
‡ | is the temperature in Kelvins
!  
   -  
ï ºith its surroundings, the rate at
which the object at temperature |
with surroundings at |o radiates is
‡ Pnet = ıAe(|4 ± |4o)
‡ ºhen an object is in equilibrium with its
surroundings, it radiates and absorbs at
the same rate
ï Its temperature will not change
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Po er Ô A | X ï | X

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Po er Ô A  K X ï ' K X
( =? ±
Ô  ¦ ï ± ± ± ' ¦
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KX
Ô  ' ¦  J s ö
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ï An ÷
÷—  — is defined as an object
that absorbs all of the energy incident on
it
‡e = 1
ï |his type of object is called a —
÷ —
‡ An ideal absorber is also an ideal radiator of
energy
ï An ÷
 @
  absorbs none of the
energy incident on it
‡e = 0
! 
 -  
ï Clothing
‡ Olack fabric acts as a good absorber
‡ ºhite fabric is a better reflector
ï |hermography
‡ |he amount of energy radiated by an object
can be measured with a thermograph
ï Oody temperature
‡ Radiation thermometer measures the intensity
of the infrared radiation from the eardrum
-  |
ï Œewar flask/thermos bottle
ï Œesigned to minimize
energy transfer to
surroundings
ï =pace between walls is
evacuated to minimize
conduction and convection
ï =ilvered surface minimizes
radiation
ï Neck size is reduced
  
ï Greenhouse example
‡ Visible light is absorbed and re
re--emitted
as infrared radiation
‡ Convection currents are inhibited by the
glass
ï Earth¶s atmosphere is also a good
transmitter of visible light and a
good absorber of infrared radiation