Please send (in seven minutes)

QUIZ #6 your answers as an email text

John BROWN, st. #391245  to: [email protected]
 cc: [email protected]
1. D
2. C
3. E
4. A

Molar Specific Heat

Molar Specific Heat
Several processes can change the
We define specific heats for two

temperature of an ideal gas 
 The temperature change can be processes that frequently occur:
achieved by taking a variety of
paths from one isotherm to another  Changes with constant pressure, isobaric
Since ∆T is the same for each

process, ∆U is also the same
 Changes with constant volume,
 The work done by the gas (the area isovolumetric
under the curves) is different for
each path  Using the number of moles, n, we can
 Therefore, the heat (Q = ∆U + W ) define molar specific heats for these
associated with a particular change
in temperature is not unique: the processes
heat Q for a process depends on
the process 3 4
 Molar Specific Heat
Ideal Monatomic Gas

 A monatomic gas contains one atom per

molecule
 When energy is added to a monatomic
Molar specific heats:
gas in a container with a fixed volume, all


 Q = nCV ∆T for constant-volume processes

 Q = nCP ∆T for constant-pressure processes of the energy goes into increasing the
 CV - molar specific heat at constant volume
translational kinetic energy of the gas
 CP - molar specific heat at constant pressure

 Q (constant pressure) must account for both the increase in internal  There is no other way to store energy in such
energy and the transfer of energy into the system by work a gas
 Qconstant P > Qconstant V for given values of n and ∆T
 Therefore, CP > CV 5 6

Ideal Monatomic Gas

∆U = nCV ∆T

This equation applies to all processes taking

 Therefore, 
place between the same temperatures
 U is a function of T only  All five processes (right) have the same
 In general, the internal energy of an ideal gas change in U because they all take place
is a function of T only through the same temperature difference ∆T
 The exact relationship depends on the type of gas  Surprise: because above equation contains
CV ; explanation: U is a state variable (its
 At constant volume (W = 0), Q = ∆U = nCV ∆T change depends only on the temperature
 Q = nCV ∆T → ∆U = nCV ∆T change, so it is independent of the particular
process)
 This applies to all ideal gases (those gases having
more than one atom per molecule), not just  Equation ∆U = nCV ∆Τ gives us the change in
U for all processes using the constant volume
monatomic ones 7
specific data 8
 Ideal Monatomic Gas

 In the limit of infinitesimal changes,

 Using , one gets

 For all monatomic gases

 This is in good agreement with experimental results
for monatomic gases

9 10

Monatomic Gases

 In a constant-pressure process (i → f ‘ ),

 This also applies to any ideal gas

 CP = 5/2 R = 20.8 J/mol.K 11 12
 Molar Specific Heats of Other Materials
Ratio of Molar Specific Heats
 We can also define  The internal energy of more complex
C P 5R / 2 gases must include contributions from the
γ
= = = 1.67
CV 3R / 2 rotational and vibrational motions of the
 Theoretical values of CV , CP , and γ are in molecules
excellent agreement for monatomic gases  In the cases of solids and liquids heated
 But they are in serious disagreement with the at constant pressure, very little work is
values for more complex molecules done since the thermal expansion is small
Not surprising since the analysis was for

monatomic gases
and CP and CV are approximately equal

13 14

Equipartition of Energy Equipartition of Energy

 With complex molecules, other  Rotational motion about the

contributions to internal energy
various axes also contributes
must be taken into account
 We can neglect the rotation
 One possible energy is the
around the y axis since it is
translational motion of the
negligible compared to the x
center of mass
and z axes (ideally, if the
 The center of mass can two atoms can be modeled
translate in the x, y, and z as particles, Iy is zero)
directions  Rotational motion
 This gives three degrees of contributes two degrees of
freedom for translational freedom
motion
15 16
 Equipartition of Energy Equipartition of Energy

Taking into account the degrees of freedom from just the

 The molecule can also 
translation and rotation contributions
vibrate
 There is kinetic energy and
potential energy associated
with the vibrations
 The vibrational mode adds
two more degrees of
freedom
 This is in good agreement with most of the data for diatomic
molecules (it is rather surprising as we have not yet accounted
17
for the possible vibrations of the molecule) 18

Equipartition of Energy

 Taking into account the degrees of freedom from the

translation, rotation, and vibration contributions

 This value is inconsistent with experimental data for

molecules such as H2 and N2 and suggests a breakdown of
the model based on classical physics

19 20
 Molar specific heat of hydrogen as
a function of temperature

 Molar specific heat is a function of temperature; three

plateaus at 12.5, 20.8, and 29.1 J/(mol⋅K)
 At low temperature, a diatomic gas acts like a monatomic gas
(CV = 3/2 R )
 At about room temperature, the value increases to CV = 5/2 R
 This is consistent with adding rotational energy but not vibrational
energy
 At high temperatures, the value increases to CV = 7/2 R
21  This includes vibrational energy as well as rotational and translational
22

Complex Molecules

 For molecules with more than two atoms,

three axes of rotation are available and the
vibrations are more complex than for
diatomic molecules
 The number of degrees of freedom is larger
 The more degrees of freedom available to a
molecule, the more “ways” there are to
store energy
 This results in a higher molar specific heat
23 24
 Quantization of Energy

Quantization of Energy
 To explain the results of the various  This energy level diagram shows the
rotational and vibrational states of a
molar specific heats, we must use some diatomic molecule
quantum mechanics  The lowest allowed state is the ground
 Classical mechanics is not sufficient state; the black lines show the energies
allowed for the molecule
 In quantum mechanics, the energy is
The vibrational states are separated by
proportional to the frequency of the wave


larger energy gaps than are rotational

representing the system states
 The energies of atoms and molecules  At low temperatures, the energy gained
during collisions is generally not enough
are quantized: only certain energies are to raise it to the first excited state of
allowed 25
either rotation or vibration 26

Quantization of Energy Quantization of Energy

 Even though rotation and vibration are

classically allowed, they do not occur at
low temperatures
 As the temperature increases, the energy
of the molecules increases
 In some collisions, the molecules have
enough energy to excite to the first  At about 1000 K, vibrational energy levels
rotational excited state are reached
 As the temperature continues to  At 10000 K, vibration is contributing fully
increase, more molecules are in excited to the internal energy and CV = 7/2 R
to this state
 At about room temperature, the second
plateau has been reached and rotation
contributes fully to the molar specific
heat 27 28
 Molar Specific Heat of Solids
Molar Specific Heat of Solids

 Molar specific heats in solids  At high temperatures, the molar

specific heats approach the value of
also demonstrate a marked 3R = 24.9 J/mol⋅K (the DuLong -
temperature dependence Petit law )
 Solids have molar specific  This occurs above 300 K
heats that generally  The molar specific heat of a solid at
decrease in a nonlinear high temperature can be explained
manner with decreasing by the equipartition theorem: SHM
temperature
Each atom of the solid has six
 It approaches zero as the 

degrees of freedom
temperature approaches
absolute zero
29 30

Adiabatic Processes for an Ideal Gas

 An adiabatic process is one in which no energy is

transferred by heat between a system and its
surroundings: Q = 0  Integrating this expression
gives

 Because γ > 1, the PV curve is

 Substituting R = CP − CV and dividing by PV gives steeper than it would be for an
isothermal expansion (PV =
31 constant) 32
 Adiabatic Processes for an Ideal Gas
Adiabatic Processes for an Ideal Gas
 Adiabatic expansion

 The temperature of the gas decreases

 Adiabatic compression: the temperature
increases

33 34

Adiabatic Processes: Work

 Demo: Adiabatic Expansion

 Films: 15-03 (CO2 Expansion Cooling),
15-04 (Adiabatic Expansion)

35 36
 The First Law of Thermodynamics – Review
The Second Law of Thermodynamics

 The first law is a statement of Conservation of Energy  Establishes which processes do and which do not occur
 The first law states that a change in internal energy in a  Some processes can occur in either direction according to
system can occur as a result of energy transfer by heat, by the first law
work, or by both  They are observed to occur only in one direction
 The law makes no distinction between processes that occur  This directionality is governed by the second law
spontaneously and those that do not  These types of processes are irreversible
 Only certain types of energy-conversion and energy-transfer  An irreversible process is one that occurs naturally in one
processes actually take place in nature direction only
 No irreversible process has been observed to run backwards
 An important engineering implication is the limited efficiency
of heat engines
37 38

Operation of a Heat Engine

Heat Engine
(1) The working substance absorbs energy by heat from a
A heat engine is a device that takes in


high-temperature energy reservoir
energy by heat and, operating in a  (2) Work is done by the engine
cyclic process, expels a fraction of that  (3) Energy is expelled by heat to a lower-temperature
energy by means of work reservoir
 Example: operation of a steam engine
 A heat engine carries some working
substance through a cyclical process

39 40
 Heat Engine Heat Engine

 The working substance absorbs  Since it is a cyclical process,

energy by heat from a high ΔU = Uf − Ui = 0
temperature energy reservoir (Qh)  Its initial and final internal
energies are the same
 Work is done by the engine (Weng)
 Energy is expelled as heat to a
lower temperature reservoir (Qc)
 The work done by the engine
equals the net energy
transferred to it
 The work is equal to the area
enclosed by the curve of the
41
PV diagram 42

Thermal Efficiency of a Heat Engine

 Thermal efficiency is defined as the ratio  In practice, all heat engines expel only
of the net work done by the engine a fraction of the input energy by
during one cycle to the energy input at mechanical work
the higher temperature
 Therefore, their efficiency is always less
than 100%
 To have e = 100%, Qc must be 0

 We can think of the efficiency as the

ratio of what you gain to what you give
43 44
 Second Law: Kelvin-Planck Form
Perpetual Motion Machines: *.flv

 It is impossible to construct a  A perpetual motion machine of the first kind

heat engine that, operating in a produces work without the input of energy. It thus
cycle, produces no other effect violates the first law of thermodynamics: the law of
than the absorption of energy conservation of energy
from a reservoir and the  A perpetual motion machine of the second kind is a
performance of an equal amount machine which spontaneously converts thermal energy
of work into mechanical work. When the thermal energy is
equivalent to the work done, this does not violate the law
of conservation of energy. However, it does violate the
 Means that Qc cannot equal 0
second law of thermodynamics
 Some Qc must be expelled to the

environment
 Means that e cannot equal 100% 45 46

 M1-8

47