Chapter 20

The First Law of Thermodynamics

Thermodynamics – Chapter Overview
Will discuss internal energy, the first law of thermodynamics, and
applications of the first law
The first law of thermodynamics describes systems in which the only
energy change is that of internal energy.
The transfers of energy are by heat and work.
Will consider work done on deformable systems
Internal Energy

Internal energy is all the energy of a system that is associated with its
microscopic components.
 These components are its atoms and molecules.
 The system is viewed from a reference frame at rest with respect to the
center of mass of the system.
Internal Energy and Other Energies
The kinetic energy due to its motion through space is not included.
Internal energy does include kinetic energies due to:
 Random translational motion
 Rotational motion
 Vibrational motion
Internal energy also includes potential energy between molecules.
Heat

Heat is defined as the transfer of energy across the boundary of a system

due to a temperature difference between the system and its surroundings.
The term heat will also be used to represent the amount of energy
transferred by this method.
There are many common phrases that use the word “heat” incorrectly.
Heat, internal energy, and temperature are all different quantities.
 Be sure to use the correct definition of heat.
 You cannot talk about the “heat of a system,” you can refer to heat
only when energy has been transferred as a result of a temperature
difference.
Units of Heat

Historically, the calorie was the unit used for heat.

 One calorie is the amount of energy transfer necessary to raise the
temperature of 1 g of water from 14.5oC to 15.5oC.
 The “Calorie” used for food is actually 1 kilocalorie.
In the US Customary system, the unit is a BTU (British Thermal Unit).
 One BTU is the amount of energy transfer necessary to raise the
temperature of 1 lb of water from 63oF to 64oF.
The standard in the text is to use Joules.
Heat Capacity

The heat capacity, C, of a particular sample is defined as the amount of

energy needed to raise the temperature of that sample by 1oC.
If energy Q produces a change of temperature of T, then Q = C T.
Specific Heat

Specific heat, c, is the heat capacity per unit mass.

If energy Q transfers to a sample of a substance of mass m and the
temperature changes by T, then the specific heat is
Q
c
m T

The specific heat is essentially a measure of how thermally insensitive a

substance is to the addition of energy.
 The greater the substance’s specific heat, the more energy that must
be added to a given mass to cause a particular temperature change.
The equation is often written in terms of Q : Q = m c T
Some Specific Heat Values
Internal Energy Revisited

The change in internal energy of a system can be identified with m c Δ T.

 If we ignore any thermal expansion or contraction of the system.
Then ΔEint = Q
The internal energy of a system can be changed by transferring energy into
the system by any mechanism.
 This also indicates temperature is related to the energy of the
molecules of a system.
Specific Heat of Water

Water has the highest specific heat of common materials.

This is in part responsible for many weather phenomena:
 Moderate climates near large bodies of water
 Global wind systems
 Land and sea breezes
Calorimetry

One technique for measuring specific heat involves heating a material,

adding it to a sample of water, and recording the final temperature.
This technique is known as calorimetry.
 A calorimeter is a device in which this energy transfer takes place.
The system of the sample and the water is isolated.
Conservation of energy requires that the amount of energy that leaves the
sample equals the amount of energy that enters the water.
 Conservation of Energy gives a mathematical expression of this:
Qcold= -Qhot
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
The negative sign in the calorimetry equation is critical for consistency
with the sign convention.
Calorimetry, final
Tf is the final temperature after the
system comes to equilibrium.
The subscript w represent values for
water and x represents the values for
the sample whose spcific heat is to
be determined.
Since each Q = mcT, the
calorimetry equation can be
m c T as
expressed
w w f T   m c T  T
w x x f x 

 This can be solved for the

unknown specific heat.
 Technically, the mass of the
container should be included,
but if mw >>mcontainer it can be
neglected.
Phase Changes

A phase change is when a substance changes from one form to another.

 Two common phase changes are
 Solid to liquid (melting)
 Liquid to gas (boiling)

During a phase change, there is no change in temperature of the

substance.
 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.
Latent Heat
Different substances react differently to the energy added or removed
during a phase change.
 Due to their different internal molecular arrangements
The amount of energy also depends on the mass of the sample.
 The higher-phase material is the material existing at the higher
temperature.
 Example, water is the higher-phase material in an ice-water mixture
 The initial amount of the higher-phase material in a system is mi .
If an amount of energy Q is required to change the phase of a sample is
L ≡ Q /Δm
 Δm = mf – mi is the change in mass of the higher-phase material
Latent Heat, cont.

The quantity L is called the latent heat of the material.

 Latent means “hidden”.
 The value of L depends on the substance as well as the actual phase
change.
The energy required to change the phase is Q = L Δm.
 Δ m refers to the higher-phase material.
 If the entire amount of the lower-phase material undergoes a phase
change, the change in mass of the higher-phase material is equal to
initial mass of the lower-phase material
Latent Heat, final
The latent heat of fusion is used when the phase change is from solid to
liquid.
The latent heat of vaporization is used when the phase change is from
liquid to gas.
If energy is enters the system:
 This will result in melting or vaporization
 The amount of the higher-phase material will increase
 Δ m and Q are positive
If energy is extracted from the system:
 This will result in freezing or condensation
 The amount of the higher-phase material will decrease
 Δ m and Q are negative
Sample Latent Heat Values
State Variables
State variables describe the state of a system.
Variables may include:
 Pressure, temperature, volume, internal energy
The state of an isolated system can be specified only if the system is in
thermal equilibrium internally.
 For a gas in a container, this means every part of the gas must be at
the same pressure and temperature.
Transfer Variables

Transfer variables are zero unless a process occurs in which energy is

transferred across the boundary of a system.
Transfer variables are not associated with any given state of the system,
only with changes in the state.
 Heat and work are transfer variables.
Transfer variable can be positive or negative, depending on whether energy
is entering or leaving the system.
Isobaric Processes
An isobaric process is one that occurs at a constant pressure.
 May be accomplished by allowing the piston to move freely so that it is
always in equilibrium between the net force from the gas pushing
upward and the weight of the piston plus the force due to atmospheric
pressure pushing downward
The values of the heat and the work are generally both nonzero.
The work done is W = -P (Vf – Vi) where P is the constant pressure.
Conduction
The transfer can be viewed on an atomic scale.
 It is an exchange of kinetic energy between microscopic particles by
collisions.
 The microscopic particles can be atoms, molecules or free electrons.
 Less energetic particles gain energy during collisions with more
energetic particles.
Rate of conduction depends upon the characteristics of the substance.
Conduction, cont.

In general, metals are good thermal conductors.

 They contain large numbers of electrons that are relatively free to move
through the metal.
 They can transport energy from one region to another.
Poor conductors include asbestos, paper, and gases.
Conduction can occur only if there is a difference in temperature between
two parts of the conducting medium.
Convection

Energy transferred by the movement of a substance.

It is a form of matter transfer:
 When the movement results from differences in density, it is called
natural convection.
 When the movement is forced by a fan or a pump, it is called forced
convection.
Convection example
Air directly above the radiator is
warmed and expands.
The density of the air decreases, and
it rises.
A continuous air current is
established.
Radiation
Radiation does not require physical contact.
All objects radiate energy continuously in the form of electromagnetic
waves due to thermal vibrations of their molecules.
Rate of radiation is given by Stefan’s law.
Stefan’s Law

P= σAeT4
 P is the rate of energy transfer, in Watts.
 σ = 5.6696 x 10-8 W/m2 . K4
 A is the surface area of the object.
 e is a constant called the emissivity.
 e varies from 0 to 1
 The emissivity is also equal to the absorptivity.

 T is the temperature in Kelvins.