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1.4 Review 2 Phys.131 Boltzmann Kinetics
1.4 Review 2 Phys.131 Boltzmann Kinetics
((Ludwig Boltzmann))
Ludwig Eduard Boltzmann (February 20, 1844 – September 5, 1906) was an Austrian
physicist famous for his founding contributions in the fields of statistical mechanics and
statistical thermodynamics. He was one of the most important advocates for atomic
theory when that scientific model was still highly controversial.
This equation was originally formulated by Ludwig Boltzmann between 1872 to 1875,
but later put into its current form by Max Planck in about 1900. To quote Planck, "the
logarithmic connection between entropy and probability was first stated by L. Boltzmann
in his kinetic theory of gases."
Reference
Carlo Cercignani, Ludwig Boltzmann The man who trusted atoms (Oxford University
Press, 1998)
E.A. Guggenheim, Boltzmann’s distribution law (North-Holland, 1955).
G. Gallavotti, W.L. Reiter, and J. Yngvason edited, Boltzmann’s Legacy (European
Mathematical Society, 2008).
We consider molecules that strike a unit area of the wall of a container. Let vx denote the
velocity component normal to the plane of the wall.
The particles are inside the cube with the volume V. There are N particles. We
consider the particle (mass m) with the velocity (vx , v y , vz ) . After the reflection at the wall,
the velocity of the particles is changed into (vx , v y , vz ) .The change of the linear
momentum gives a force on the plane normal to the x axis.
p x 2mv x F1x t
As a result of the Newton’s third law (the action-reaction), the force
2mvx
Fx F1x
t
is exerted on the wall (as an impulse), contributing to the pressure. Here we assume that
the number of molecules per unit volume (number density), which have velocity
componenets of vx – (vx+dvx), vy – (vy+dvy), and vz – (vz+dvz) is given by
1 1
N ( v ) d 3 v N ( v x , v y , v z ) dv x dv y dv z
V V
N N (v )d
3
v
The number of particles (velocity v) colliding with the plane is evaluated as follows.
Avx t
2mv x 1 A
( Av x t ) N ( v )d 3v 2mv x N (v )d 3v
2
t V V
total 2
F 1 2 Amv x
P x N ( v )d 3 v
A A V
1
2
2mv x N ( v )d 3 v
V vx 0
2 Thermal equilibrium
In thermal equilibrium, the gas is assumed to be homogeneous for each direction. So
it is natural to consider that N(v) is dependent only on the magnitude of v.
1 1
PV 2mv 2mvx N (v )d 3v mv 2 N (v )d 3v
2
N ( v ) d 3v
2
x
v x 0
2 3
1
E mv 2 N (v )d 3v
2
Then we have
2
PV E .
3
PV Nk BT ,
3
k BT
2
N (v ) G ( v 2 ) g ( v x ) g (v y ) g ( v z ) (1)
Then we have
1 2
g (v x ) G (v x )
2
Similarly,
1
g (v y )
2
G (v y )
2
1
g (v z )
2
G (v z )
2
G ( v 2 ) G (v x v y v z ) g ( v x ) g (v y ) g ( v z )
2 2 2
1
2 2 2
G (v x )G (v y )G (v z )
6
1
G ( ) G ( )G ( )G ( ) .
6
Taking a derivative of the above equation with respect to and putting = = 0,
1
G ' ( ) G ( )G ' (0)G (0) aG ( )
6
or
G ( ) Ae a
where
1
a G ' (0)G (0) .
6
N ( v ) G ( v x v y v z ) A exp[ a ( v x v y v z )] A exp( av 2 )
2 2 2 2 2 2
(Gaussian form)
(a) Determination of A
N N (v )d 3v
A[ exp(av x )dv x ]3
2
A( )3 / 2
a
or
A ( )3 / 2 N
a
where
exp(avx )dvx exp(avx )dvx
2 2
a
1
2A a 3 / 2
2
A( )3 / 2
a
((Mathematica))
J @n_D := ‡ x n ExpA− a x2 E x êê Simplify@ , a > 0D &
∞
−∞
(b) Determination of a
The total energy <E> is given by
1
E m(v x v y v z ) N ( v )dv x dv y dvz
2 2 2
2
1
m(v x v y v z ) A exp[ a (v x v y vz )]dv x dv y dv z
2 2 2 2 2 2
2
1 2
mv A exp( av 2 )4v 2 dv
2
1
mA4 v 4 exp(av 2 )dv
2 0
1 1
mA4 v 4 exp(av 2 )dv
2 2
1 13
mA4
2 2 4a 5 / 2
3 3 / 2
mA 5 / 2
4a
where v is the radius of the sphere in the (vx, vy, vz) and 4v 2 dv is the volume element
enclosed by the spherical shell of inner radius v and outer radius v +dv,
v 2 vx v y vz
2 2 2
d 3v dv x dv y dv z 4v 2 dv
Then we have
3 3 / 2 3
E mA m 5/ 2
4a 4a 3m 3 k T
5/ 2
N 1 4a 2
B
A( )3 / 2
a a3/ 2
m
a
2k BT
m 3/ 2 mv 2
N (v ) N ( ) exp( ).
2k BT 2k BT
We define n(v) as
N (v ) m 3/ 2 mv 2
n (v ) ( ) exp( )
N 2k BT 2 k BT
with
1 n(v )d 3v n(v)4v 2 dv
(1) n(v)dv is the probability of finding particles whose velocities are vx – (vx+dvx), vy
– (vy+dvy), and vz – (vz+dvz.).
(2) Note that n(v)4v2dv is the probability of finding particles whose magnitude of
velocities are between v and (v + dv).
3/ 2
M Mv 2
n (v ) exp( )
2RT 2 RT
The function n(v) has a Gaussian type with a peak at v = 0. Here we introduce the
probability f (v) dv of finding the particle having the velocity between v and v + dv, as
where
f (v)dv 1
0
3/ 2
M Mv 2
f (v ) 4v 2 exp( )
2RT 2 RT
((Note))
1
N (v )dv n(v )dv 4v 2 n(v)dv f (v)dv
N
2 k BT 2 RT RT
vmp 1.41421 (most probable speed)
m M M
((Note))
3/ 2
df (v) M Mv 2 Mv 2 Mv
4 {2v exp( ) v 2 exp( )( )
dv 2RT 2 RT 2 RT RT
3/ 2
M Mv 2 Mv 2
4 ( )v ( 2) 0
2RT 2 RT RT
2 2M
f max
e RT
f (v ) v v
( ) 2 exp[1 ( ) 2 ]
f max vmp vmp
f
fmax
1.0
0.8
0.6
0.4
0.2
v
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 vmp
vavg vrms 6
1 ( 1.128) ( 1.225)
vmp vmp 2
v v
n n
f (v )d v
2 RT RT
vavg v 2 1.59577
M M
2 3RT
vrms v 2
M
or
3RT RT
vrms v 2 1.73205
M M
2
vrms (v v ) (v v ) v v v 2
where v 0 .
We note that
1 2 3k T
mvrms B .
2 2
(c)
2 RT 3 / 2 RT 3 / 2
v3 8 ( ) 6.38308( )
M M
(d)
RT 2
v 4 15( )
M
In summary,
or
vavg vrms 6
1 ( 1.128) ( 1.225)
vmp vmp 2
((Molecular velocities))
As is shown above, the most probable speed is given by
RT
vmp 1.41421
M
M vmp 2 RT
where
R = 8.314472 J/mol K
Then we have
10 3 M 0 10 2 vmp 2 RT
0
0 2 1
M 0 vmp RT RT
10 2 10 3 5
0 6 0
Since vrms vmp , we have
2
0 6
M 0 vrms RT
2 5
________________________________________________________________________
Table
The root-mean square speed for various gases (experimental values at T = 273 K)
________________________________________________________________________
0
vmp0 (0.1 km/s) vavg0 (0.1 km/s) M0 (g/mol) vrms M0
________________________________________________________________________
H2 :
M = 2.0 g/mol = 2.0 x 10-3 kg/mol
T = 300 K
1 eV = 1.602176487 x 10-19 J
mn = 1.674927211 x 10-27 kg (mass of neutron)
NA = 6.02214179 x 1023
kB = 1.380650410 x 10-23 J/mol K (Boltzmann constant)
R = 8.314472 J/K (gas constant)
Mn=mnNA = 1.00728 x 10-3 kg (molar mass of neutrons)
The neutron temperature, also called the neutron energy, indicates a free neutron's
kinetic energy, usually given in eV. The term temperature is used, since hot, thermal and
cold neutrons are moderated in a medium with a certain temperature. The neutron energy
distribution is then adopted to the Maxwell-Boltzmann distribution known for thermal
motion. Qualitatively, the higher the temperature, the higher the kinetic energy is of the
free neutron. Kinetic energy, speed and wavelength of the neutron are related through the
De Broglie relation.
Fast neutrons have an energy greater than 1 eV, 0.1 MeV or approximately 1 MeV,
depending on the definition.
Slow neutrons have an energy less than or equal 0.4 eV.
Epithermal neutrons have an energy from 0.025 to 1 eV.
Hot neutrons have an energy of about .2 eV.
Thermal neutrons have an energy of about 0.025 eV.
Cold neutrons have an energy from 5x10-5 eV to 0.025 eV.
Very cold neutrons have an energy from 3x10-7 eV to 5x10-5 eV.
Ultra cold neutrons have an energy less than 3x10-7 eV.
h 30.7895
n Å
mn vmp T (K )
4 Equipartition of energy
3 1
The energy k BT is ascribed to a contribution k BT from each “degree of
2 2
freedom” of each particle, where the number of degrees of freedom is the number of
dimensions of the space in which the atoms move: 3 in this example.
1 1 2 1 3k T 3
mvrms mv m B k BT
2
2 2 2 m 2
v 2 vx v y vz 3 v x
2 2 2 2
or
1 2 1
mvx k BT
2 2
1 2 1
mv y k BT
2 2
1 2 1
mvz k BT
2 2
1 2 2 2 3
m(vx v y vz k BT
2 2
Let us now modify one of the basic assumption in the model of the ideal gas. Instead
of considering a molecule to be presented as a point particle, let it be considered as two
point particles separated by a given distance. This model gives a better description of
diatomic gases. Such molecules can acquire kinetic energy by rotating about its center of
mass, and it is therefore necessary to consider in the internal energy the contribution of
rotational kinetic energy as well as the translational kinetic energy. The rotational kinetic
energy of a diatomic molecules can be written as
1 1
I x ' x ' I y ' y '
2 2
K rot
2 2
where I is the rotational inertia of the molecule for rotations about a particular axis. The
x’y’z’ coordinate system is fixed to the center of mass of the molecule. There is no kinetic
energy associated with rotation about the z’ axis, because Iz’ = 0.
1 1
I x ' x ' k BT
2
2 2
1 1
I y ' y ' k BT
2
2 2
1
E K U 2 K 2 U ℏ k B T 2 ( k B T )
2
7 Agreement with Experiment
At low temperatures, 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. This includes vibrational energy as well as rotational and translational
The mean free path (the mean distance per collision) could then be taken as the length of
the path divided by the number of collisions.
vt 1
l 2
(d vt )nV d nV
2
Where d 2 vt is the volume of interaction, nV is the number of molecules per unit volume.
The problem with this expression is that the average molecular velocity is used, but the
target molecules are also moving. The frequency of collisions depends upon the average
relative velocity of the randomly moving molecules.
since v1 = v2 = v and
v1 v 2 v1v2 cos 0
2
v rel v1 v 2 2v
which revises the expression for the effective volume swept out in time t. The resulting
mean free path is
1
l
2d 2 nV
The number of molecules per unit volume can be determined from Avogadro's number
and the ideal gas law, leading to
N P N P
nV A ,
V k BT RT
where
PV = NkBT
1 RT
l
2d nv
2
2d 2 N A P
The mean free path depends on T, P, and the diameter of gas atoms.
1
l = 2.44 x 10-7 m = 2440 Å
d 2 nv
vrms 1310
7
5.37 109 / s
l 2.44 10
((Note))
Being a measure of number density, the Loschmidt constant is used to define the
amagat, a practical unit of number density for gases and other substances:
Estimate the mean free path of an air molecule at 273 K and 1 atm, assuming it to be
a sphere of diameter 4.0 x 10-10 m (4Å). Estimate the mean time between collisions for an
oxygen molecule under these conditions, using v = vrms = 517 m/s
RT (8.31J / K )(273 K )
l 10 2
5.2342 10 8 m
2d 2 N A P 2 (4 10 ) (6.02 10 )(1.01 10 Pa )
23 5
5.2342 10 8 m
t 1.0 10 10 s
517 m / s
RT (8.31J / K )(273 K )
l
2d 2 N A P 10 n
2 (4 10 10)(6.02 10 )(1.01 10 Pa )
23 5
760
8 n 5
760 10 5.2342 10 m 3.978 10 m
n
l = 3978 m.
((Link))
9.1
Container A in Fig. holds an ideal gas at a pressure of 5.0 x 105 Pa and a temperature
of 300 K. It is connected by a thin tube (and a closed valve) to container B, with four
times the volume of A. Container B holds the same ideal gas at a pressure of 1.0 x 105 Pa
and a temperature of 400 K. The valve is opened to allow the pressures to equalize, but
the temperature of each container is maintained. What then is the pressure in the two
containers?
((Solution))
Before opening valve
PA = 5.0 x 105 Pa, TA = 300 K
PB = 1.0 x 105 Pa, TB = 400 K, VB = 4 VA
PB→P, TB = 400 K.
PVA
n1
PVA n1RTA RTa
PVB n2 RTB PVB
n2
RTB
PAV A PBV B 1 PV PV
n A nB ( A A B B)
RT A RT B R Ta TB
PV A PV B P V V
n1 n 2 ( A B)
RT a RT B R Ta T B
Since n A nB n1 n2 , we have
PAVATB PBVBTA
P 2.0 105 Pa
VATB VBTA
________________________________________________________________________
9.2
((Solution))
CP = 7R/2
CV = 5R/2
CP / CV 7 / 5 1.40
Pf = 2.40 atm.
Pi = 1.20 atm
Vi = 0.2 m3
Adiabatic process
PV PiVi Pf V f
1/
Vf P
i 2 1 /
Vi Pf
V f 2 1 / 1.40Vi 0.122m3
Vf Vf
W PdV PiVi V dV
Vi Vi
PiVi 1 1
[V f Vi ]
1
Pf V f 1 PiVi 1
Vf Vi
1 1
Pf V f PiVi
1 1
1
( P V PiVi )
1 f f
1.3312 10 4 J
Figure shows a cycle undergone by 1.00 mol of an ideal monatomic gas. The
temperatures are T1 = 300 K, T2 = 600 K, and T3 = 455 K. For 1 → 2, what are (a) heat Q,
(b) the change in internal energy Eint, and (c) the work done W? For 2 → 3, what are (j)
Q, (e) Eint, and (f) W? For 3 → 1, what are (g) Q, (h) Eint,, and (i) W? For full cycle,
what are (j) Q, (k) Eint, and (j) W? The initial pressure at point 1 is 1.00 atm (= 1.013 x
105 Pa). What are the (m) volume and (n) pressure at point 2 and the (o) volume and (p)
pressure at point 3?
((Solution))
n = 1 mol (monatomic gas)
State-1: T1 = 300 K
State-2 T2 = 600 K
State-3 T3 = 455 K
CV = 3R/2 = 12.47 J, CP = CV + R = 20.78 J.
Path 1-2
(a), (b), and (c)
Path 3-1
(g), (h), and (i)
Q CP T 20.78 (300 455) 3220.9 J
E CV T 12.47 (300 455) 1932.9 J
W E Q 1288 J
(j)
Qtotal 3742 0 3220 520 J
(k)
Etotal 3742 1808 1933 0
(l)
(m)
(n)
9.4
Air that initially occupies 0.140 m3 at a gauge pressure of 103.0 kPa is expanded
isothermally to a pressure of 101.3 kPa and then cooled at constant pressure until it
reaches its initial volume. Compute the work done by the air. (Gauge pressure is the
difference between the actual pressure and atmospheric pressure.)
((My solution))
1 atm = 1.01325 x 105 Pa
Vi = 0.140 m3, Pi = 103.0+101.325 = 204.325 kPa
Pf = 101.3 kPa
PiVi Pf V f
Vf
W1 2 PdV
Vi
________________________________________________________________________
9.5
N 0 t is the number of particles striking the wall over an area during the time t
________________________________________________________________________
9.6
Figure shows a hypothetical speed distribution for a sample of N gas particles (note
that
P (v ) 0
for v>2v0. What are the values of (a) av0, (b) vavg/v0, and (c) vrms/v0? (d) What fraction of
the particles has a speed between 1.5 v0 and 2.0 v0?
1 P (v)dv
vavg v vP(v)dv
vrms v 2
3
v 2 v 2 P (v)dv
vrms v2
v0 v0
vf
Pr obability P(v)dv
vi
________________________________________________________________________
9.7
The volume of an ideal gas is adiabatically reduced from 200 L to 74.3 L. The initial
pressure and temperature are 1.00 atm and 300 K. The final pressure is 4.00 atm. (a) Is
the gas monatomic, diatomic, or polyatomic? (b) What is the final temperature? (c) How
many moles are in the gas?
((Solution))
________________________________________________________________________
10.5
An ideal gas, at initial pressure T1 and initial volume 2.0 m3, is expanded
adiabatically to a volume of 4.0 m3, then expanded isothermally to a volume of 10 m3,
and then compressed adiabatically back to T1. What is its final volume?
V1 = 2.0 m3, V2 = 4.0 m3, V3 = 10.0 m3
T2 T3
P2V2 P3V3
P3V3 P4V4
P3V3 P3V3
T3 T4
T4 T1
P4V4 P1V1
________________________________________________________________________
10.6
An ideal gas is taken through a complete cycle in three steps; adiabatic expansion
with work equal to 125 J, isothermal contraction at 325 K, and increases in pressure at
constant volume. (a) Draw a P-V diagram for the three steps. (b) How much energy is
transferred as heat in step 3, and (c) is it transferred to or from the gas?
11. Link
Kinetic theory
http://en.wikipedia.org/wiki/Kinetic_theory
Maxwell-Boltzmann distribution
http://en.wikipedia.org/wiki/Maxwell-Boltzmann_distribution
Molecular speed
http://hyperphysics.phy-astr.gsu.edu/Hbase/kinetic/kintem.html