Lecture 2

Thermodynamic Laws
 Thermodynamic System
 A thermodynamic system is any collection of objects that may exchange energy
with its surroundings.
 In a thermodynamic process, changes occur in the state of the system.
 First Law of Thermodynamics
 First law of thermodynamics: The change in the internal energy U of a system is equal to the
heat added minus the work done by the system: U = Q – W.

 The first law of thermodynamics is just a generalization of the conservation of energy.

 Both Q and W depend on the path chosen between states, but U is independent of the path.

 If the changes are infinitesimal, we write the first law as dU = dQ – dW.
 Four kinds of Thermodynamic Processes

 Adiabatic: No heat is transferred into or out of the system, so Q = 0.

 Isochoric: The volume remains constant, so W = 0.

 Isobaric: The pressure remains constant, so W = p(V2 – V1).

 Isothermal: The temperature remains constant.

 The Four Processes on a pV-diagram
 Figure 19.16 shows a pV-diagram of the four different processes.
 Isothermal Process
 An isothermal process is one in which the temperature does not change.
 Adiabatic Processes for an Ideal Gas
 In an adiabatic process, no heat is transferred in or out of the gas, so Q = 0.

 Figure 19.20 at the right shows a pV-diagram for an adiabatic expansion. Note that an
adiabatic curve at any point is always steeper than an isotherm at that point.

 Follow the derivations showing how to calculate the work done during an adiabatic
process.
 Isobaric and Isochoric Processes
 An isobaric process (a) occurs at constant pressure; an isovolumetric or isochoric
one (b) occurs at constant volume.

(a) (b)
 Heat Capacities of Gases
 The degrees of freedom are the number of velocity components needed to describe a
molecule completely. A monatomic gas has three degrees of freedom and a diatomic gas
has five. Figure illustrates the motions of a diatomic molecule.

 Follow the derivation of the molar heat capacity (molar specific heat) at constant volume,
CV, for monatomic and diatomic gases and for solids. The results are:
CV = 3/2 R for an ideal monatomic gas
CV = 5/2 R for a diatomic gas
CV = 3R for an ideal monatomic solid.
 Molar Heat Capacities
 Table shows that the calculated values for CV for monatomic gases and diatomic gases
agree quite well with the measured values.
 The Ratio of Heat Capacities
 The ratio of heat capacities is  = Cp/CV. For ideal gases,  = 1.67 (monatomic) and  =
1.40 (diatomic).
 Table 19.1 shows that theory and experiment are in good agreement for monatomic and
diatomic gases.
 Heat Capacities of an Ideal Gas
 CV is the molar heat capacity at constant volume.

 Cp is the molar heat capacity at constant pressure.

 Figure shows how we could measure the two molar heat capacities.
 Relating Cp an CV for an Ideal Gas
 Figure shows that to produce the same temperature change, more heat is required at
constant pressure than at constant volume since
U is the same in both cases.

 This means that Cp > CV.

 Cp = CV + R.
 Heat and Thermodynamic Processes
 For gases, the specific heat depends on the process

 Isochoric Process:

 Isobaric Process:

 Adiabatic Process:

 Isothermal Process:
 Work Done During Volume Changes
 Figures below show how gas molecules do work when the gas volume changes.
 Work on a pV-diagram
 The work done equals the area under the curve on a pV-diagram.

 Work is positive for expansion and negative for compression.

 Work in a Isothermal Process for Ideal Gas
 For an isothermal process, . Integrating to find the work done in taking the gas
from point A to point B gives:
 Work in a Isobaric and Isochoric Processes
 A different path takes the gas first from A to B in an isochoric process; because the
volume does not change, no work is done.

 Then the gas goes from A to B at constant pressure; with constant pressure no
integration is needed, and .
 Work and Thermodynamic Processes
 For gases, the specific heat depends on the process

 Isochoric Process:

 Isobaric Process:

 Adiabatic Process:

 Isothermal Process:
 Internal Energy
 The sum total of all the energy of all the molecules in a substance is its internal (or
thermal) energy.

 The internal energy of an ideal gas depends only on its temperature, not on its
pressure or volume.

 The temperature of an ideal gas does not change during a free expansion.
Internal Energy and Thermodynamic Processes
 For gases, the specific heat depends on the process

 Isochoric Process:

 Isobaric Process:

 Adiabatic Process:

 Isothermal Process:
 The Second Law of Thermodynamics
 The first law of thermodynamics tells us that energy is conserved.
 The second law of thermodynamics is a statement about which processes
occur and which do not. There are many ways to state the second law; here is
one:
Heat can flow spontaneously from a hot object to a cold object; it will not flow
spontaneously from a cold object to a hot object.
 It is easy to produce thermal energy using work, but how does one produce
work using thermal energy?

This is a heat engine; mechanical energy

can be obtained from thermal energy
only when heat can flow from a higher
temperature to a lower temperature.
 Heat Engines
A steam engine is one type of heat engine.
 Heat Engines
The internal combustion engine is a type of heat engine as well.
 Heat Engines
 A heat engine need a temperature difference. Otherwise the work done on the
system in one part of the cycle would be equal to the work done by the system
in another part, and the net work would be zero.

 The efficiency of the heat engine is the ratio of the work done to the heat
input:

 Using conservation of energy to eliminate W, we find:

 No heat engine can have an efficiency of 100%. This is another way of writing
the second law of thermodynamics: No device is possible whose sole effect is
to transform a given amount of heat completely into work.
 Entropy and Disorder

 Entropy provides a quantitative measure of disorder.

 The total entropy always increases when heat flows from a warmer object to a
colder one in an isolated two-body system. The heat transferred is the same, and
the cooler object is at a lower average temperature than the warmer one, so the
entropy gained by the cooler one is always more than the entropy lost by the
warmer one.

 The fact that after every interaction the entropy of the system plus the
environment increases is another way of putting the second law of
thermodynamics: The entropy of an isolated system never decreases. It either
stays constant (reversible processes) or increases (irreversible processes).
 Entropy and The Second Law
 Entropy is a measure of the disorder of a system. This gives us yet another
statement of the second law: Natural processes tend to move toward a state
of greater disorder.
 In Figure below, the entropy (disorder) of the ink-water system increases as
the ink mixes with the water. Spontaneous unmixing of the ink and water is
never observed.