Chapter 18

Temperature, Heat and the

First Law of
Thermodynamics
Temperature

Thermodynamics is the branch of physics that is built

upon the fundamental laws that heat and work obey.

The collection of objects on which attention is being

focused is called the system, while everything else
in the environment is called the surroundings.

Walls that permit heat flow are called diathermal walls,

while walls that do not permit heat flow are called
adiabatic walls.

To understand thermodynamics, it is necessary to

describe the state of a system.
Thermal Contact

• Two objects are in thermal contact with each other if energy can be exchanged between them
• The exchanges we will focus on will not involve mechanical work (forced movement); we
will call the energy exchanged – HEAT; this is energy exchanged due to a temperature
difference
• The thermal contact does not have to also be physical contact.

• Thermal equilibrium is a situation in which two objects would not exchange energy (HEAT) if
they were placed in thermal contact
• Two objects are in thermal equilibrium if they have the same temperature
Zeroth Law of Thermodynamics

• A & B are in thermal equilibrium

with C,
• A & B are in thermal equilibrium
with each other,
• A& B are at the same temperature.
Thermometers

• Thermometers are devices used to

measure the temperature of a system.
• All thermometers make use of some
physical property ( volume of a liquid,
Electrical resistance…) that changes with
temperature and can be calibrated to make the
temperature measurable.
Thermometers

• Thermometers are devices used to

measure the temperature of a system.
• All thermometers make use of some
physical property ( volume of a liquid,
Electrical resistance…) that changes with
temperature and can be calibrated to make the
temperature measurable.
Thermometers

Schematic
diagram of a
mercury
thermometer
Thermometers
A constant-volume gas thermometer.

• It consists of a gas-filled bulb connected by a tube to a mercury

manometer. By raising and lowering reservoir R, the mercury level
in the left arm of the U-tube can always be brought to the zero of
the scale to keep the gas volume constant.

• The pressure is indicated by the height difference between reservoir B and

column A
• The thermometer is calibrated by using an ice water bath and a steam
water bath
• The pressure (ρgh) at each temperature is recorded
• The volume is kept constant by adjusting A
Thermometers

Absolute zero is used as the basis of the absolute temperature scale

Celsius Scale

Kelvin temperature

T  Tc  273.15
Fahrenheit Scale

Temperatures are reported in degrees

Celsius or degrees Fahrenheit.

Temperatures changed, on the other hand, are

reported in Celsius degrees or Fahrenheit
degrees:
9 
1C  F


Change in temperature

9
TFahrenheit ( F )  TC  32
5
Thermal Expansion

LINEAR THERMAL EXPANSION OF A SOLID (1D)

The length of an object changes when its temperature changes:

1D

L  L0 T
1
α  average coefficien t of linear expansion ( C ) 

L 0  initial lenght at T0
T  (T - T0 )
Some Coefficients
Thermal Expansion

2D
A0  L at T0
2
0

A  L at T with L  L0  αL0 T
2

 A  ( L0  αL0 T )  A0  2αA0 T   T A0
2 2 2

 A  A0  A0 T
with   2  coefficien t of area expansion
Volume Expansion

3D
V  V0 T
with   coefficien t of volume expansion
Volume Expansion
Expansion of liquids
liquids expand 10 times more than solids except for
water:
Volume Expansion

• As the temperature increases from 0oC to 4oC, water

contracts
• Its density increases
• Above 4oC, water expands with increasing temperature
• Its density decreases
• The maximum density of water (1.000 g/cm3) occurs at 4oC
Volume Expansion

How can marine life survive very cold winters?

Temperature from 20 oC to 4 oC:

Deep water gets colder ( mixing due to buoyancy).
Volume Expansion

Temperature from 4oC to 0 oC :

r decreases thus the water expands at the surface of the
lake.
• Cold water (then ice) remains at the surface and blocks
colder air from reaching deep water ( no more mixing)
Absorption of Heat

• Heat Q is energy that is transferred between a system and its

environment because of a temperature difference between
them. Heat flows from a higher-temperature object to a lower-
temperature object because of a difference in temperatures.

• Two objects are in thermal contact if they can exchange heat

between them.

• Two objects are in thermal equilibrium when the two

objects in thermal contact cease to exchange heat.

• It can be measured in joules (J), calories (cal), kilocalories

(Cal or kcal), or British thermal units (Btu), with
Heat and Temperature Change: Heat Capacity
Absorption of Heat by Solids and Liquids
• The heat capacity C of an object is the proportionality constant between the heat Q that the object
absorbs or loses and the resulting temperature change ΔT of the object; that is,

in which Ti and Tf are the initial and final temperatures of the object.

Common Unit for Specific Heat Capacity: J/(Co)

T  0 (energy tr ansfered to a substance)  Q  0

T  0 (energy removed from a substance)  Q  0
Heat and Temperature Change: specific heat capacity
Absorption of Heat by Solids and Liquids
• If the object has mass m, then,

where c is the specific heat of the material making up the object.

• The specific heat is essentially a measure of how thermally sensitive a substance is to the addition
of energy. The greater the substance’s specific heat, the more energy that must be added to cause
a particular temperature change
• Technically, the specific heat varies with temperature
Tf
• The correct equation is

Q  m c dT
Ti
• However, if the temperature intervals are not too large, the variation can be ignored and c can be
treated as a constant
• For example, for water there is only about a 1% variation between 0o and 100oC
Heat and Temperature Change: specific heat capacity

Q
Specific heat  c  in J 
m.T Kg. C

Water has the highest c for commonly encountered

substances. For the same amount of energy, DT of
water is smaller than for other substances.
Heat and Temperature Change: specific heat capacity
• On a hot day the
air above the
sand warms
faster than the
air above the
cooler water.
• The cooler air
over the water
moves towards
the beach,
displacing the
rising warmer
air.
Heat and Temperature Change: specific heat capacity

• At night the
sand cools
more rapidly
than the
water
• The air
current
reverses
direction
Calorimetry

The two substances

exchange Heat until
Thermal equilibrium is
reached :
Final temperature T is
reached for the whole
system.
Calorimetry
Conservation of energy with:

QTOT  O
 Q x  Qw  0

m x c x (T  Tx )  m w c w (T  Tw )  0

Thus cx can be determined. The principle of conservation of

energy allows you to solve all Calorimetry problems.
Calorimetry
Case of three objects
0.4 kg water initially at 40°C is poured into 0.3 kg glass beaker
having a temperature of 25°C. A 0.5 kg block of aluminum at
37°C is placed in the water and the system insulated. Calculate
the final equilibrium temperature of the system.

The system is insulated

Qw  QAl  Qbea ker  0
mwcw T  Tw   m Al c Al T  TAl   mbea ker cbea ker T  Tbea ker   0
T  37.9C
Phase Changes

The flow of Heat to a substance usually results in:

• Temperature change
• Phase Change ( from solid to liquid , from liquid to gas…)
Phase Changes

Energy required for Phase Change,

Q:
Q   mL
Q  Energy required for phase change
m  Mass of the substance
L  Latent Heat in J
Kg
Phase Changes
Equilibrium between phases of matter

Only when the temperature and vapor

pressure correspond to a point on the curved
line do the liquid and vapor phases coexist in
equilibrium.

The pressure of vapor that coexists in equilibrium with the liquid is

called the equilibrium vapor pressure of the liquid.
Latent Heat

• The latent heat, L, is the energy per kilogram that must be

added to or removed from a substance to change its phase
at a constant temperature.
Phase change:
• From solid to liquid: Lf = Latent heat of fusion
• From liquid to gas: Lv = Latent heat of vaporization

Lv  L f
Example: Ice to Steam
Energy required to convert 1g of ice at -30oC to steam at
120oC
Example: Ice to Steam
A- Ice from –30oC to 0oC:
Q A  mi ci T  (1  10 3 Kg ).( 2090 J ).(30  C )  62.7 J
Kg. C

B- T=0oC Ice to water

QB  mL f  (1  10 3 Kg ).(3.33  10 5 J )  333 J
Kg
Example: Ice to Steam
C- Water from 0oC to 100oC:
QC  m w c w T  (1  10 3 Kg ).( 4.19  10 3 J ).(100  C )  419 J
Kg. C
Example: Ice to Steam

D- T=100oC water to vapor:

QD  mLv  (1  10 3 Kg ).( 2.26  10 6 J )  2260 J
Kg
Example: Ice to Steam
o o
E- Vapor from 100 C to 120 C
QE  mv cv T  (1 10 3 Kg ).( 2.01 103 J ).( 20C )  40.2 J
Kg. C

Total Energy needed   Qi  3.11 103 J

i
Example: Partial Melting
A 5.00 kg block of ice at 0 ̊ C is added to an insulated container partially filled with 10.0 kg of
water at 15.0 ̊ C.
a) Find the final temperature, neglecting the heat capacity of the container.

 T f  0 C
Example: Partial Melting

b) Find the mass of the ice that was melted.

Thermodynamics
The collection of objects on which attention is being focused is called the system,
while everything else in the environment is called the surroundings.

To understand thermodynamics, it is necessary to describe the state of a system.

State Variables
• In the macroscopic approach to thermodynamics, state variables are used to
describe the state of the system
• Examples of state variables are: Pressure, temperature, volume, internal
energy,…..
• The macroscopic state of an isolated system can be specified only if the system is in
internal equilibrium
• For a gas in a container, this means every part of the gas must be at the same
pressure and temperature
Work in Thermodynamics

• Work can be done on a deformable system, such as a

gas
• Consider a cylinder with a moveable piston
• A force is applied to compress the gas:

 
Won   F .dr    Fdy    PAdy    PdV

Therefore, the work done on the gas is:

dW = -P dV
N.B. dy<0, we get
dV  0  Won  0
Work in Thermodynamics

Won    PdV
The work done BY THE GAS:

Wby  Won   PdV

• If the gas is compressed, dV < 0 and work done BY the gas is negative
• If the gas expands, dV > 0 and the work done by the gas is positive
• If the volume remains constant, the work is zero

The total work done BY the gas is:

Vf
W    P dV
V i
PV Diagrams
• Used when the pressure and volume are known at each step of the
process – True for quasi-static process
• The state of the gas at each step can be plotted on a PV-diagram, in
this case
• The curve is called the path
• The diagram is time independent and therefore must indicate
equilibrium

• The work done by a gas in a quasi-static process that takes the gas
from an initial state to a final state is the area under the curve on the
PV diagram, evaluated between the initial and final states
• This is true whether or not the pressure stays constant
• The work done does depend on the path taken
Work in Thermodynamics

Work and the area under pressure-volume

graph

Vf
W   P.dV  Area under the curve of a PV diagram
Vi

• The shape of the curve, i.e. the way with which the final point is reached from
the initial point, determines the value of the work done on the gas.
Heat Transfer

HEAT IS PATH DEPENDENT: Qa  Qb  Qc

• Energy transfers by heat, like the work done, depend on the initial, final, and intermediate states of
the system
• Both work and heat depend on the path taken
• Neither can be determined solely by the end points of a thermodynamic process
Internal Energy

• Internal energy is the kinetic and potential

energy associated with the translational,
rotational, and vibrational motion of the system
The First Law of Thermodynamics
• The First Law of Thermodynamics is a special case of the Law of Conservation of Energy
• It takes into account changes in internal energy and energy transfers by heat and work
• The First Law of Thermodynamics states that

DEint = Q - W
• The minus sign is added to make W work done BY the system (W transfer is out of the system)
Isolated Systems
• An isolated system is one that does not interact with its surroundings
• No energy transfer by heat takes place
• The work done on the system is zero
• DEint = Q - W
• Q = W = 0, so DEint = 0
• The internal energy of an isolated system remains constant
THERMAL PROCESSES:

1- Isobaric process (constant pressure)

2- Isothermal process (constant temperature, ΔU = 0)

3- Isovolumetric process (constant volume, W = 0)

4- Adiabatic process (no thermal energy transfer, Q = 0)

5- Generic process (don’t fall into one of the above processes

Isobaric Processes
• An isobaric process is one that occurs at a constant
pressure
• The values of the heat and the work are generally both
nonzero
• The work done by the gas is W = P (Vf – Vi) where P is the
constant pressure
Adiabatic Process
• An adiabatic process is one during which no energy enters or leaves the system by
heat
• Q=0
• This is achieved by:
• Thermally insulating the walls of the system
• Having the process proceed so quickly that no heat can be exchanged

• Since Q = 0, DEint = -W
• If the gas is compressed adiabatically, W is negative so DEint is positive and the
temperature of the gas increases
• If the gas expands adiabatically, the temperature of the gas decreases
Isovolumetric Processes
• An isovolumetric process is one in which there is no change in the
volume
• Since the volume does not change, W = 0
• From the first law, DEint = Q
• If energy is added by heat to a system kept at constant volume, all of the
transferred energy remains in the system as an increase in its internal
energy
Isothermal Process
• An isothermal process is one that occurs at a constant temperature
• Since there is no change in temperature, DEint = 0
• Therefore, Q = W
• Any energy that enters the system by heat must leave the system by work

• The PV diagram of an isothermal expansion

• The curve is a hyperbola
• The curve is called an isotherm
Isothermal Process
T  0  U  0
PV  nRT

PV nRT

dV dV
Vf 
dV W  nRT ln  
PdV  nRT
V  Vi 
Vf Vf
dV
V PdV  nRT V V
i i
Cyclic Processes

• A cyclic process is one that starts and ends in the same state
• The change in internal energy must be zero since Eint is a state variable
• On a PV-diagram, a cyclic process appears as a closed curve
• If DEint = 0, Q = W
• In a cyclic process, the net work done by the system per cycle equals the
area enclosed by the path representing the process on a PV diagram
Figure 18-1 shows a p-V diagram, that is, a plot of the pressure of a gas versus the volume of the gas. A
complete cycle of abcda is indicated; that is, the gas is taken through various changes in pressure and
volume but is returned to its initial state at the upper left corner. Here are energy transfers as heat, to
or from the gas.

During stage ab, how much energy is transferred as heat and what is the change ΔEab in the internal
energy?
Mechanisms of Energy Transfer by Heat
• We want to know the rate at which energy is transferred
• There are various mechanisms responsible for the transfer:
• Conduction
• Convection
• Radiation
Conduction

• Conduction is the process whereby thermal energy is transferred directly

through a material, any bulk motion of the material playing no role in the
transfer.
• Metals are good thermal conductors ( free electrons + atomic vibrations)
• Plastics are thermal insulators ( poor thermal conductivity)
Conduction
• The slab at right allows energy to move from the region of higher temperature to the
region of lower temperature
• The rate of transfer is given by:

Q dT k  thermal conductivi ty ( J )
  kA 
s.m. C
t dx
• A is the cross-sectional area
• Δx is the thickness of the slab
• Or the length of a rod
Conduction
Temperature Gradient

• The quantity |dT / dx| is called the temperature gradient of the

material
• It measures the rate at which temperature varies with
position
• For a uniform long rod, the temperature gradient can be
expressed as:
dT Th  Tc

dx L
 Th  Tc 
• Using the temperature gradient for the slab, the rate of energy transfer becomes:   kA  L 
 
P= (k/L)A ∆T
P/(A∆T) =G= k/L (W/K/m2)
G is the thermal conductance of the material
Conduction
COMPOUND SLAB
Case of a slab where each portion of the slap has a certain thickness Li and thermal conductivity ki

ATH  TC 
H
Li
i ki

In order to decrease the heat flow, materials with low thermal conductivity should be added to the slab
(Home Insulation)
Conduction
Cross sectional view of a wall containing (a)
air space (b) an insulator.
Conduction

To find the temperature at the junction between two different materials:

H1  H 2
k2 ATH  TX  k1 ATX  TC 
 Solve for Tx.
L2 L1
Conduction
Example 4 Layered insulation

One wall of a house consists of plywood backed

by insulation. The thermal conductivities of
the insulation and plywood are, respectively,
0.030 and 0.080 J/(s·m·Co), and the
area of the wall is 35m2.

Find the amount of heat conducted

through the wall in one hour.
Conduction
Q  Qinsulation  Qplywood

But first we must solve for the

interface temperature.

 kAT t   kAT t 
   
 L  insulation  L  plywood

0.030 J s  m  C A25.0 C  T t  0.080 J s  m  C AT  4.0 Ct

   

0.076 m 0.019 m

T  5.8 C
Conduction

Qinsulation 
0.030 J s  m  C 35 m 25.0 C  5.8 C3600 s 
 2  

0.076 m

 9.5 105 J
Convection

• Warmer water rises

( lower density)
• Cooler water sinks,
gets warmer and
moves up
• Continuous convective
heat flow
Convection
• Convection is the process in which the thermal
energy is carried from place to place by the bulk
movement of a fluid.
• Natural convection: difference in density (a pan of
water)
• Forced convection: Substance is forced to move by
a fan or a pump.
• It is difficult to quantify.
Radiation

• Radiation is the
process in which
energy is
transferred by
means of
electromagnetic
waves.
Radiation

Stefan’s law
Energy
P
Unit time
 Power Radiated P  AeT 4

  Cst  5.67  10 W 8
m2 K 4
A  Surface area of the body
e  Emissivity  0  e 1
T  Temperatur e of the body
• If the body keeps radiating energy it would loose all its energy and its temperature will go to 0 K.
Radiation
• For a body at T, surroundings at T0 we define Pnet as:

net energy lost or gained

Pnet 
Unit time
Pnet  Ae(T  T ) 4
0
4

The object can absorb energy from its surroundings .

At equilibriu m Pnet  0 since T  T0
T T0  Pnet  0  Object wil l cool down
Radiation
• An ideal absorber is when e=1, a black body (also called an ideal radiator).
• A perfect reflector is when e=0.
Radiation
The Dewar Flask
A thermos bottle minimizes heat transfer via conduction, convection, and radiation.

• The space between the walls is a vacuum to minimize

energy transfer by conduction and convection
• The silvered surface minimizes energy transfers by
radiation
• Silver is a good reflector
• The size of the neck is reduced to further minimize energy
losses