CHAPTER 20

THE FIRST LAW OF

THERMODYNAMICS
 1. 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.
 2. 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.
• 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.
 3. HEAT CAPACITY AND SPECCIFIC HEAT
• The heat capacity, C, of • Specific heat, c, is the heat capacity per
a particular sample is unit mass.
defined as the amount of • If energy Q transfers to a sample of a
energy needed to raise substance of mass m and the
the temperature of that temperature changes by DT, then the
sample by 1oC. specific heat is:
• If energy Q produces a Q
T f

change of temperature of c  Q  m  cdT

DT, then: m DT Ti

Q • The specific heat is essentially a

Q  C DT  C  measure of how thermally insensitive a
DT substance is to the addition of energy.
Some Specific Heat Values
 Example

A 50 g sample of copper is at 25oC. If 1200 J of energy is added to it by

heat, what is the final temperature of the copper?

From: Q
Q  mc DT  DT 
mc
But, DT  Tf  Ti  Tf  Ti  DT
 4. 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.
• 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
 4. CALORIMETRY
• 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 = mcDT, the calorimetry equation
can be expressed as
mw cw Tf  Tw   mx c x Tf  Tx 
mw cw Tf  Tw 
 cx 
mx Tx  Tf 
 5. 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.
• If an amount of energy Q is required to change the
phase of a sample is
Q Q
L 
Dm mf  mi
Δm = mf – mi is the change in mass of the higher-phase material
Sample Latent Heat Values
Example
 6. STATE AND TRANSFER VARIABLES
State Variables Transfer Variables
• State variables describe the state of a • Transfer variables are zero unless a
system. process occurs in which energy is
• Variables may include: transferred across the boundary of a
system.
• Pressure, temperature, volume,
internal energy • Transfer variables are not associated
with any given state of the system, only
• The state of an isolated system can be
with changes in the state.
specified only if the system is in
thermal equilibrium internally. • Heat and work are transfer variables.
• For a gas in a container, this • Transfer variable can be positive or
means every part of the gas must negative, depending on whether energy is
be at the same pressure and entering or leaving the system.
temperature.
 7. WORK IN THERMODYNAMICS
• Work can be done on a deformable system,
such as a gas.
• Consider a cylinder with a moveable piston,
The piston is pushed downward by a force
through a displacement of:
 
dW  F  d r  Fˆj  dyˆj  Fdy  PA dy
A.dy is the change in volume of the gas, dV.
•Therefore, the work done on the gas is:
Vf

dW  PdV  W    PdV
Vi
 7. WORK IN THERMODYNAMICS
PV Diagrams
• Used when the pressure and volume are known at
each step of the process.
• The state of the gas at each step can be plotted
on a graph called a PV diagram, allowing us to
visualize the process through which the gas is
progressing.
• The curve is called the path.
• The work done on a gas in a quasi-static process
that takes the gas from an initial state to a final
state is the negative of the area under the curve on
the PV diagram, evaluated between the initial and
final states.
EXAMPLE
 8. ENERGY TRANSFER
• The energy transfer, Q, into or out of a
system also depends on the process.
• The energy reservoir is a source of
energy that is considered to be so great
that a finite transfer of energy does not
change its temperature.
• The piston is held at its internal position
by an external agent.
• The gas does no work because it does
not apply a force.
• Energy transfers by heat, like the work
done, depend on the initial, final, and
intermediate states of the system.
 9. THE FIRST LAW OF THERMODYNAMICS
• The First Law of Thermodynamics is a special case of the Law of
Conservation of Energy.
• The First Law of Thermodynamics states that:
DEint  W  Q

• One consequence of the first law is that there must exist some quantity
known as internal energy which is determined by the state of the system.
• The internal energy is therefore a state variable.
• In isolated systems, it does not interact with its surroundings. Thus, no
energy transfer by heat and work done on the system is zero. The internal
energy remains constant.
 10. SPECIAL PROCESSES
10.1. Cyclic Processes
• A cyclic process is one that starts and ends in the same
state.
• This process would not be isolated.
• On a PV diagram, a cyclic process appears as a closed
curve.
• The internal energy must be zero since it is a state variable.
• If DEint  0  W=-Q
•In a cyclic process, the net work done on the system per
cycle equals the area enclosed by the path representing the
process on a PV diagram.
 10. SPECIAL PROCESSES
10.2. Adiabatic Process
• An adiabatic process is one during which no
energy enters or leaves the system by heat.
Vf

Q  0  DEint  W=-  PdV

Vi

• This is achieved by:

• Thermally insulating the walls of the
system
• Having the process proceed so quickly that
no heat can be exchanged
 10. SPECIAL PROCESSES
10.3. 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.
• Where P is the constant pressure, the
work done is:
W  P Vf  Vi 
Q  mc DT
DEint  W  Q
 10. SPECIAL PROCESSES
10.4. Isovolumetric Processes
• An isovolumetric process is one in which there is no
change in the volume.
• This may be accomplished by clamping the piston
at a fixed position.
• Since the volume does not change, W = 0.
• From the first law, DEint  Q  mc DT
• 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.
 10. SPECIAL PROCESSES
10.5. Isothermal Process
• An isothermal process is one that occurs at a
constant temperature.
• This can be accomplished by putting the
cylinder in contact with some constant-
temperature reservoir.
• Since there is no change in temperature:
 Vi 
DEint  0  W  Q  nRT ln  
 Vf 
• Any energy that enters the system by heat must
leave the system by work.
 11. CONDUCTION
• The transfer can be viewed on an atomic scale.
• It is an exchange of kinetic energy between microscopic particles by
collisions.
• Less energetic particles gain energy during collisions with more energetic
particles.
• Rate of conduction depends upon the characteristics of the substance.
• 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.
 11. CONDUCTION
• The slab at right allows energy to transfer
from the region of higher temperature to the
region of lower temperature.
• The rate of transfer is given by:
Q dT
P  kA
Dt dx
A is the cross-sectional area.
dT is the temperature difference.
dx is the thickness of the slab.
P is in Watts when Q is in Joules and t is in seconds.
k is the thermal conductivity of the material.
 EXAMPLE

DEint  DEint AB  DEint BC  DEint CD  DEint DA  0

 DEint AB   WBC  QBC   0  WDA  QDA    WBC  QBC  WDA  QDA
 PB (VC  VB )  QBC  PA (VA  VD )  QAD
 PB (VC  VB )  PA (VA  VD )  QBC  QAD
 EXAMPLE

PV1 1  nRT1  PV
1 1 nRT1
  PV
1 1  P2V2  V2  
P2V2  nRT2  P2 P2
Vf
V2
W    PdV  nRT ln
Vi
V1
DEint  0  Q  W
EXAMPLE

W  WAB  WBC  WCD  WDA

 WBC  WDA
 3Pi (3Vi  Vi )  Pi (Vi  3Vi )
 4PV
i i

DEint  W  Q  0
 Q  W  4PV
i i