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PHY1039

Properties of Matter
Heat Capacity of Ideal Gases (CP and
CV) and
Adiabatic Expansion of Ideal Gas
(See Finns Thermal Physics, Ch. 4)

March 12 and 15, 2012

Lectures 11 and 12
From next week:

Lectures on Monday at 3 pm will meet in


Lecture Theatre E.

Week 7 (next week) only:

Lecture on Monday, March 19 at 4 pm in


35AC04 (instead of tutorial)

Tutorial will be held on Thursday, March 22


at 9 am in the Austin Pearce Building, Lab2
Two Types of Heat
Capacity
Isochoric Isobaric
P Process: CV
P
Process, CP
P2 T2 (V1, P2)
T1 T2
P1
(V1, P1) (V2, P1)

P1 T1 (V1, P1)

V1
V V1 V2 V
T2 > T1 T2 > T1
Internal Energy, U, of
Monoatomic Monoatomic
gases have one atomGas
per molecule:
e.g. He, Ne, Xe, and Kr.

All of the kinetic


z
energy of a
monoatomic gas is
contained in
translational motion
There
with are three
a velocity
degrees of
. y
freedom.
x Translational energy
Each d.o.f. has kT in
thermal energy.
KE = =
k = 1.38 x 10-23 J/K
The total energy of each
molecule (ignoring
Ideal Gas
potential energy) is .
Internal Energy, U, of
Diatomic
Diatomic gases have Gas
two atoms per molecule: e.g. H , 2
O2, N2, CO, Cl2.
Diatomic molecules have translational, rotational
and vibrational energy:
Three translational degrees of freedom: x, y, z

Three rotational degrees of freedom: about x, y and z axes.

Figure from Understanding Properties of Matter by M. de


Podesta
But the energy of rotation about the molecules axis is not accessible
at lower temperatures.
Internal Energy, U, of
Diatomic
Diatomic molecules can also have
Gas r
vibrational energy, but it is not N N
accessible at lower T.
(Kinetic energy and potential energy PE = K (r
of vibration each contribute one
d.o.f.) ro)2
Inaccessible Accessible state
states

There are five degrees of freedom accessible at lower


temperatures.
The total energy of each molecule (ignoring
potential energy) is 5(1/2)kT = (5/2)kT at lower T,
Internal Energy, U, of
Triatomic
Linear triatomic gases have threeGas
atoms per
molecule that all lie along the same axis: e.g. CO2.
O=C
=O
Like a diatomic molecule, a linear triatomic molecule has
three translational and only two accessible rotational
degrees of freedom.
A linear molecule with N
atoms has 3N-5 modes
of vibration.
There are two degrees
of freedom for
vibrational energy
accessible at lower
temperatures.
At lower temperatures, in total
Symmetric & anti-
there are seven accessible
degrees of freedom. symmetric stretching
vibration
The total energy of each molecule is 7(1/2)kT = Bending
Internal Energy, U, of
Triatomic
Non-linear triatomic Gasatoms per
gases have three
molecule that do not lie along the same axis: e.g.
N2O; SO2; H2O
For a non-linear triatomic
molecule, there are rotations
about three axes at lower T:
three rotational degrees of
freedom.
A non-linear molecule with N
atoms has 3N-6 modes of
vibration. A non-linear Figure from P. Atkins The
triatomic molecule has three Elements of Physical Chemistry
degrees of freedom.
In total, there are 9 possible degrees of freedom (3
translational, 3 rotational, and three vibrational), but only 7 are
accessible at lower temperatures.
The total energy of each molecule is 7(1/2)kT =
Greenhouse Effect: A Problem of
Thermodynamics

http://jcwinnie.biz/wordpress/?p=2235
http://www.dailymail.co.uk/sciencetech/article-483191/Arctic-ice-cap-melts-smallest-size.html

Earth can be treated as a thermodynamic


system.
Why Do Water and Carbon Dioxide
Block Thermal Radiation from Earth?
Most Intense Thermal Radiation
from Earth
The resonant
frequency of
molecular
vibrations is in
the same
frequency as
infrared http://en.wikipedia.org/wiki/File:Atmosfaerisk_spredning.gif
radiation.
Thermal Wavelength (m)
radiation
transmitted Thermal
through radiation from
atmosphere to colder Earth
Earth from Sun transmitted
through
atmosphere
en.wikipedia.org/wiki/User:Dragons_flight/Images
Heat Capacity of Ideal
Gases
Type of
Accessible Internal
d.o.f. at Cv
Gas Energy,
lower T
Monoatomic 3 3/2 nRT U 3/2 nR

Diatomic 5 5/2 nRT 5/2 nR

Triatomic 7 7/2 nRT 7/2 nR

U for ideal gases (ignoring potential energy) depends


only on T.

Cv depends only on the amount of gas (through n).


Important Conclusions
Isothermal processes:
U of an ideal gas is a function of T only. If the
temperature is constant (T = 0), then internal energy is
constant: U = 0. Changes in P and V will not affect U.

First Law tells us: U = 0 = Q + W

So, W = - Q. If there is isothermal work on an ideal gas


(W is positive), then heat must go out of the gas.
Adiabatic processes:
In an adiabatic process, Q = 0.

First Law tells us: U = 0 + W.

If work is done on an ideal gas, such as by compression, W is


positive, and hence U is positive.

As U is proportional to nRT, the temperature of the gas will


Molar Heat Capacity, CP, of
Monoatomic Gas
CP = 3/2 nR + nR =
5/2 nR

Figure from Understanding Properties of Matter by M. de


Podesta
At higher temperatures, more degrees of freedom are not excited.
There is no T dependence of CV or CP.
Molar Heat Capacity, CP, of Diatomic
Gas
CP = 5/2 nR + nR =
7/2 nR

Figure from Understanding Properties of Matter by M. de


Podesta
As temperature is increased from room temperature,
more degrees of freedom are accessible (rotational
Molar Heat Capacities of Various
Gases at 25 C

From Tiplers Physics


Adiabatic versus Isothermal
Expansions (or
Compressions) of an Ideal Gas
P
P2 Adiabatic
compression:

Isothermal
compression:
P1

V2 V1 V