:

!
."
:"
."

%
)

."

PV = mRT
PV = n.MR T

R = R/M

PV = nRT

nRT
V=
P

* )
%1 2 3

& '
!+ , -./ ! 2 .
24 56
: 7

T = 273 K

R = 8.314 J / mole.K

n =1

V = 0.0226 [m ] 0 < '= > <

:
.
6.02 1023

molecules
mole

m3
0.0226
mole

: 7

P = 110 Pa [N / m ]

8*

6.02 1023

! -./
$ !

* 6 :;

= 0.266 1026 = 2.66 1025

A B ?%@
3 1025
19

3 10

3 1016

molecules
m3
molecules
cm3
molecules

mm3

& K (rigid sphere ";

. $EG (Random) B N
."

1 m3

H I$ ) G 0 , 2 %<) E ) 9
N$ ) G E
", / /

9A SB

2E R
9
6 PQ 5 2, "EA O 5 > $ SB
: < O 5 3 10-10 m 9

3 1025
: < - ER G

1 m3
3 10

25

30 10

."

! L:M 2, ." 0 <

30 10

SB
1
27 3

27

0 L

3 10

/W
9

! )
G

--./

Q -./
> I 8*

VQ4 U 0

A T

310-10

310-9

:9

3 10

3 10
2
."

"

>I

W :A
." 2$
."E A 2$

10

2 3 10

10

6 PQ

5 6 :;

(10 1) 3 10

10

SB

]^ L

6 2Q

5T

:
Continuum $ ' )
:9
* Mean free path (MFP)
: "E %_
.
` 0 =2
,
", / 0 = ! 2, ) 2Q 5 > $
`
=2 W ,
", / 0 = ! 2, ) G 2Q 5 a :.
)
.(
" W
2Q 5 > $ W < - ER G
*
> I W < Mean free path
$ + ' 9
6 PQ 5
> I W < Mean free path
$ b
9
6 PQ 5

Mean free path

1
4 r .N

: NE: !

= 8 10
8 10

m
9

6 2Q

$ + ' 9

8 10
3 10

6 2Q
8

10

K5

$A

2D

c E, )

= 26

3 10
9

a *< = r
* =N

*) " 9
."5
gA

6 2Q
2$

ef L / MFP T
> I (" MFP

= 266
." 9

ef^ L

/ MFP 6 + -G

. ,
`
2
`
, :A
A D i _ O 5 2 2D
)
A
. :A
"' / >; - R$E

`
-G
G
G E j S

KG ' h G * ." (elastic) U $ l Lk , G 0

9
"9D u >R5 `
) < G ;A . G
.

9
,

K% D )t A

H S

u 3
3$9D
9D W"_
.A

--M B PN
E

AhG 9

W( `

6 i
-!
K% D t A
.( G
PS
2 KG , h G `
%_ 2
. < G ;A
>R5 W0
U

* &%B WxS
w : "_

+ ,- $ ( ()

8 9

75

/ 0 :;

#C

$C B

% &'$

8 91
( :; ;
8 9

$4

dN = .d
D .

# $ ")
.(Homogeneity)

8 9 75
d => ? :;

324 5

,2 % 1 / 0 .

75)

24 / A @ (d ) => ? :;

+ ,- $

75 <( 8 1
. 1

. <
O 5 E yQ$;
9D
9
", / "_
D :$/ -"
All directions of molecular velocity are assumed to be equally probable
WG
: "_
G
< 2$5
gA
4 5 b, !
6
W :A VSB b' 2SRA / 0 ' W"_
G
6
W
R$A 2SRA 2
." 0 < V
"
0 ' xS
V@ R j RA

V1

V2

V3
V'1

V'3

Common origin

V'2

:
2 (r a *<

o b,

2 0 ,

"_

./ % + ,- &
)G

)*

& '( # $%

"9D V@ R ) j RA 6 > $
*
:xS / z

4 r2
:

N
4 r

%_ Wj RA

* 6 W 4 50 '

dA xS

.dA
2
:) ,

d N

N
4 r

dA
r 2 .sin d d

$;

9D 0

9A "_

"9D 2, ( 9
)
= *
: "E %_ W <

;$A Notation
"_

+d
+d
2

d N

N
=
sin d d
4
:A

d2 N
yQ$;

G "_

+d
+d

= d2
0

=
:

- ER (-./)

2 * { @

sin d d
(G
:0 I

2$ EA ) -./ /
"_
9D

*
G

(Collisions with a stotionary wall) 3 6 45

* 2+ - A 2' "
G
6
0
0

D
WdA xS

(
~

A WG

G "_
Wdt

v collisions)
I
gA

+d
+d
v + dv

3 & 123

U$
|
K5 2% I
y *
A -$ : R$A
'
2IN
."
K5 :G W
/
xS /
:
9D
:
2, " xS
: dA
.(dA
%: ) '
= W"_
W 5 } "9D
Wv "_
* 2+
. ,

Q 2$ EA ) -./ /
G
* 2' - $< W"_ 0 I
:
: "E %_ 575+d5 676+d6
"9D 0 I
W( G

d2

676+d6
:

sin d d
9D 0 I
%_ W( G

v7 v+ dv "_
Q 2$ EA ) -./ /

d v
=
sin d d
4

0
G

2 K
S
* W575+d5

d = dA(v.dt.cos )
d v
v = (dA.v.dt.cos ) (
sin .d d )
4

d d

"_

"9D

d N

v7 v+dv ~

d N

9A "_
R 2'
= G
:" 575+d5 676+d6 ~

*
9A

d v
= dA.v.dt.
sin .cos .d d
4

b A dA xS
3

, 5
;K
: "E %_

9
xS

i
/

d v
=
.v.sin cos .d d
dA.dt
4
v

*
i

5
* 6

R
"EA

:-

dN v
1
=
.v.d
dA.dt 4
v7 v+dv "_

2 sin
v 0

dN v 1
= .vd
dA.dt 4
"_

"9D

cos d
1
2

>

6 :

G5 6
2
0

`$A

d
2

xS

/ 2
/
G
: "E
" %_ : 9

* T
9D i :

R )G 0

dN v 1
N
=
=
vd
dA.dt
dA.dt 4

:
v

xS 2
= )G
: "E %_ xS /

* L$ 9A
/

N1v1 + N 2 v 2 + ...
v=
=
N1 + N 2 + ...

N i vi

:B

Ni
: &?

I5

$K

GH 8 F E

i vi

v=

v=
: $4 ;

vd

@PQ

M$ K

v.d
;

N
1
=
v
dA.dt 4

v.d

I$ @

.L 1 @8 9 B

$K

= v

@UV H 8 T

S $R

PQ

8 9 N O5

75

c E' G
{ G0

0
xS

9
/

> $ "_
G

i
/

*
G

: 7
W T = 0C
K5 NE: U > <
W < ^ m/sec L% R e K
.
G
* 2+
xS /

1
1
=
v = (3 1025 ) 450 = 3.3 1027
4
4
"

Q%B

G 3;

Pressure of a Gas:
+

:dA PQ

KT

4 Z[ &W

4 . Y &W

1
(2mv cos )( .v.d
4
dt $4

1
=
m.v
m
v 2 .d
d
2
@K

( L- $) 9 U N &W 8 '5

( mv cos ) = 2mv cos

mv cos

I$

@PQ

575+d5
R

v .sin

dA PQ

.cos .d .d .dA.dt)

:; ; X 4 9:v-collisions

75

= d3 N

2
.sin
sin
.cos
cos
.d
d .d
d .dA.dt
dA dt
v

676+d6 \ KT
K

1
=
m.v 2 .d v dA.dt.
2

5 68T
2 sin
0

.cos
1
3

S
$R

d .

K
PQ

2
0

,- $ N &W 8 '5
v7 v+dv ] S K
8 9 N &W 8 '5
v7 v+dv ] S

1
d .d = m.v 2 .d
3
2

v .dA.dt

1
= m.
3

v 2 .d

:"_

v2 =

v 2 .d
G "9D

G "9D

Ni Vi2
Ni
v

.dA.dt

v2 =

: )
i

xS

Ni
:

xS

`$A & < 2 6

: i $:

1
d(mv) = m. v 2 .dA.dt
3

F dt = d(mv)
A> $

1
F.dt = m v 2 .dA.dt
3

2
v
i i

= v2
:

i $:

F 1
= m v2
dA 3

u 6
:"_

1
2
P = mv
3

."

R 6 :; * 2Q/

Absolute Temperature:

1
1N
2
P = mv =
.m.v 2
3
3
1
P = .N.m.v
N m v2
3
N
R
P = nRT =
.R.T =
NT
No
No
k = Boltzmanns constant

k=

8.3144 j/ mole.K
6.02 10

23

molecules / mole

= 1.3803 10

23

j/ molecules.K

1
P = .N.m.v 2
3
P = N.k.T

1
NkT = .N.m.v 2
3

1
T=
.m.v 2
3K

Average or mean translational

kinetic energy of a gas molecule

:2

1
3
2
.m.v = .kT
2
2
At a given temperature all gas molecules-no mater what their mass,
have the same average translational kinetic energy, namely, 3/2 kT.
Where we measure the temperature of a gas, we are measuring the
average translational kinetic energy of its molecules.

: 7
.
"
T = 300K )
! > $ K% D )t A -a
.
"
"_ root-mean-square R < c E,
-b
a- Mean kinetic energy of a molecule

1
3
3
2
.m.v = .kT = 1.38 10
2
2
2
= 6.2110

21

23

) j/ molecule.K 300 K

j/ molecule

t A > $

b-

m=

0.032 kg / kmole
6.02 10

26

molecules / kmole

= 5.3110

26

kg / molecules

3kT l

V = 2
2 m
2

V 2 = 23.4 104 (m / s) 2

V = 482 m / s = Vrms
: <

2% I

"_

W 2E R

m2
1000 2
s
C = kRT = (1.4) (0.289 kJ / kg.K) (300 K)
1 kJ / kg
!
3

kJ 10 (N.m)
=
=
kg
kg

347 m / s
"

m
).m
2
2
m
s
= 103 2
kg
s

103 (kg.

Collisions with a moving wall:

quasi-) K _ 75 K- ; 1? &? $ K? ; N C
.

. '

u "_

-M B 2N

K => ? @u 1? K C
.(equilibrium
" k_ 9 W 6'
$E
: < y * %EA "_

V1n = 15 cm/s

V1n = 20 cm/s
+

V1t
V1

{
V1

V2n = 15 cm/s

zwv z{{
V2n = -15 cm/s

V2

V2

5 m/s

" 1

%EA "_
4 .Y b K

4 Z[ b K
(-15)

* W I$ 0

b K
Vin = (20)-(5) = 15 m/s
=

4 Z[ `VQ$ K
KT

( 10) ##

= `VQ$ K

( K
(5)

" /
.A
(u) 2 K

vcos}
vcos}-u
- (vcos}-u)
b K

PQ 1

( $)

4 Z[

- ( vcos}-u) =

vcos + 2 u

LV$ `VQ$ K
4 Z[

KT

4 .Y
PQ
PQ

2 K

LV$ `VQ$ K

c(u)

vv'cos}'=
cos} = (vcos}-2u)
(vcos} 2u)
:1hiF

L- $

Ke 1 Kd ;

[ PQ
4 .Y
4 7

`VQ$ K
L- $ b K
L- $ b K

4 Z[

L- $ `VQ$ K

4 Z[

j h $ 1hiF

1
1
2 1
2
(E k = m(v cos )
m(v' cos ') = m(v cos ) 2
2
2
2
1
1
2
2
= mv cos
m v 2 cos 2 + 4u 2 4uv cos
0
2
2
U

K% D )t A 3G ,

= 2mvu cos

L- $ ``VQ$ K
L- $ g &

I$

f 8 '5

1
m [ v cos
2

2u ]

I$

&&? $
2 1 vK
$4 ; PQ ;
1? 2 + ,- $ 75
M$ @ 575+d5 676+d6 #C K KT
S v7 v+dv #C K

1
vd
4
1 vK

v sin

cos d d

676+d6 (lF 5 k)

NR

$4 PQ

1? 2 + ,- $
: &&? $

75
2

1
vd v sin cos d d
2
v v + dv ,
+d
.< G

`$A 6 8E/

W-$ :

5 2S

:4 K 5
2

muv d

v 0

/2

1
2
mu v d
3

+ ,- $ .? f o ?

sin cos
1
3

v2 .

1
muv 2
3

1
P = mv 2
3
(E k = P.u
L- $ Mg & \f o d
PQ ;
$4 ;

m n (E
k

N O5

75 E

; X 4 1 + ,- $ g & f o ?
6 NR
) $4 ;
PQ
( v7 v+dv

$4 ;

PQ ; X 4 1 + ,- $ g & f o ?
( v7 v+dv
S 8 9K
)

$4 ;

PQQ

; X 4 1 + ,- $ g & f o ?
( v $R
6@ 5 $R )
: g 1Q 4

:xS &'

A.P.u

F.u

()t A 3G , A)

." ?%S ! k, !
* ( t A 3G ' A)
A) "
$E
0<
.(
"' / 2
j E%A >
0 "
6

8 S
/
G
:_
u "_
B
$E

9A U $
t A W A "5
.(" 0 < 0 G K Lk%B Q U

)t A 3G , (J/S)

!$

/ z
(W)

) |
0 " -GN T
K% D t A 3G ' 6
/
$E
0 < i .A '
$E W
8D 2' $E
0 < i .A ' A F.u 6
.G
KA
t A
` V%
G
j E%A
2')
3G '

The Distribution of molecular velocities:

G 2N

V1
"_

2N

2,

gA

* 2IN

G
." dNvx

& < (Velocity coordinates) $_

. $EG V1z V1y W V1x W

* W dvx O _ 2
vx
* <

: "E %_

$;
$;

: U ;$A
v x + dv x * Wx "9D

vx

&' 2 W

* 6 "%EA

dNv x
N
. '

dNv x
N

dNvx

* W vx "9D

A ;$A

vz

v1z
v1
v1x

vx

v1y

vy

vz

vx

vy

dvx

vz

vx

vx
dvx
vx

vy

vy
dvy

dNv x
= f (v x ).dv x
N
0

:T W '

dNv x
N

R W vx

2' .A

I
2' G
. $EG vx 7 vx + dvx "_
.

dNv x = N.f (v x ).dv x

N=N

"_

V W f(vx)

f(vx)

dNv x = f (v x ).dv x .N

i A Wvx

f(vx)

)
f (v x ).dv x
0
=1

%]^^

dvx

."

vx

6 :; & B b A dNvz dNvy

R 5

dNv y = N.f (v y ).dv y

dNv z = N.f (v z ).dv z
."

0<O 5

"9D 2

"_

V & <

& B d2Nvxvy Wdvy

9A y "9D

"_

dNv x

A ;$A
." y *
9A x "9D
"_ 2,
= * 6
: "E %_ W" vy7vy+dvy ~ I

W dvy O _ 2
I

Wvy "9D

: ' O 5 (Maxwell)

dNv y

E'

N
100
1000

10
100

* &' 2 vy 7 vy+ dvy 0 I

vy7 vy + dvy vx 7 vx + dvx
vx 7 vx + dvx "_ 0 I

d 2 Nv x v y

V@ R

vx7vx+dvx ~

d 2 Nv x v y
d 2 Nv x v y

dvx

dNv x
d 2 Nv x v y =

dNv y

y "9D 2N
G
"_ 0 I
G
G
Q &' 2 (dvy

N.f (v y )dv y

N
N
dNv x f (v y ) dv y
N.f (v x )dv x

Q
Q
dvx

* "%EA 2' "

* 6 2
* "%EA = {
G
Q
A G : V@ R & ) W
(dvx
A : & )

= f (v y ) dv y

d 2 Nv x v y = N.f (v x ) f (v y ) dv x dv y
: < 2$5

gA

b A vz "9D

l/

d Nv x v y v z = N.f (v x ) f (v y )f (v z ) dv x dv y dv z
W vx7vx+dvx ~ I
W 9A z "9D
"_

9A x "9D "_ 2, "

= * Wd3Nvxvyvz
W vy7vy+dvy ~ I
9A y "9D
"_
. $EG vz7vz+dvz ~ I
(velocity space -./ /
G
*) 9
2$ EA 6
: <
y *
3

d Nv x v y v z
dv x dv y dv z

velocity space

WI = I (vx,vy,vz) -

= N.f (v x ) f (v y ) f (v z )
-./

"

vz

vy Wvx V W G
:"
& B

*
*
*
d =
dv x +
dv y +
dv z
*v x
*v y
*v z

2$ EA 2' <
2S
2$ EA

(A)

0
u

* (Nf (v x ) f (v y ) f (v z ))
*
=
= N.f '(v x )f (v y ) f (v z )
*v x
*v x

*
= N.f (v x )f '(v y ) f (v z )
*v y
*
= N.f
N f ((v x )f ((v y ) f '((v z )
*v z
N.f (v x )f (v y ) f (v z )

I5 (A) qQ

p<2

f '(v y )
f '(v x )
f '(v z )
d
dv x +
dv y +
dv z
=
N.f (v x )f (v y ) f (v z ) f (v x )
f (v y )
f (v z )

W;K "_

W( A : " 1 V = Vx + Vy + Vz * ) A : " 1
A u "_
:T W"
g5
& B
u
" 1 W dvx, dvy, dvz 5 2$ EA

G 2N
=

v 2 = v 2x + v 2y + v 2z = cte
= cte

f '(v y )
f '(v x )
f '(v z )
dv x +
dv y +
dv z
d =0 =
f (v x )
f (v y )
f (v z )
:

& EAA N 2 * 2'

'x K 8

2Q|
2Q|E

f '(v y )
f '(v x )
f '(v z )
0=
dv x +
dv y +
dv z
f (v x )
f (v y )
f (v z )
:

&/

(Constraint or condition equation) j <

v 2 = v 2x + v 2y + v 2z = cte
W"

0 < 9 K (Lagrange) cA

l>

2' Method of undetermined multipliers

."

&/
0 < 0 N$

Lagranges Method of Undetermined Multipliers:

:<
xn x1

u$ n

?$K

W2$

PO 52

P = P (x1, x 2 ,...., x n )
": B W

W" ;4 W"/ E WO _ W @

gA -$E

2Q

G 2 ;K x1, x2, , xn Q' " /

. '
;K
0
:- $E,
" )

*P
*P
*P
dP = 0 =
dx i =
dx1 +
dx 2 + ...
*x1
*x 2
i =1 *x i
n

:A <" _
l *

* m
@ <
(Constraints)

2' $EG

B 2'

D 2Q|E

bA @ < l *

+1 (x1 , x 2 ,...x n ) = 0
+ 2 (x1 , x 2 ,...x n ) = 0
+ m (x1, x 2 ,...x n ) = 0
G u$

* n

(2)

(1)
G

Ll :*

."

(xi) &R$E
. <

"

5 @ <

l *

PD
*

D G xi 6 *

l * 0 `$
&B /
)

*+ j

i =1

*x i

W Oi

dx i

+i

* m

Lm=n

2 G xi L m > n
PD

( j = 1,..., m )

+j = 0
d+ j = 0 =

&/ )

(Least square)
.

* n (+ ) @ < l *

G u$

n-m L m < n
:" / 6
@ <2 * m

( j = 1,..., m )
W $EG G xi V

2' WOm ...

O2

O1

y *
:-

*+1
,1d +1 = ,1
dx i = 0
i =1 * x i
n

...................

$EG i Q* A G O
.A <
0 A

(2)

...................

, m d+ m

Lagrange multipliers

*+ m
dx i = 0
= ,m
i =1 * x i
n

:- $< (]) 2S

0 k_ 2

*P
dP =
dx i = 0
i =1 *x i
n

: (e) (]) >

*+1
*+ m
*P
+ ,1
+ ... + , m
dx i = 0
*x i
*x i "
i =1 ! *x i
n

(3)

' V:D

(dxi) i

() 2S

2' A < ;$A

S
:

Om ... O2 O1 W() 2S
< N )
& /
& <2 2 * n6
.

*+1
*+ m
*P
+ ,1
+ ... + , m
= 0 i = 1, 2,..., n
*x i
*x i
*x i
+j = 0
.

j = 1,..., m
& % W 9. (n+m)

:- $< b A @ < l *

(2 * m)

* W(O)m
( ) 0 :G 2 W(x
( i)n
) 2 * (n+m) 0 `$

+1 (x, y, z) = x 2 + y 2 + z 2 1 = 0
.

(2 * n)

(Maximize) 7' / WP 2,

@ <P *
"

) @

*P
*P
*P
dP =
dx + dy + dz (1)
*x
*y
*z
dP = 8yzdx + 8xzdy + 8xydz = 0

U &/ 2 2Q|E T

P (x,y,z) = 8xyz V : 7
(x,y,z) "%7

R .

gA

*+1
*+1
*+1
d+1 =
dx +
dy +
dz = 0
*x
*y
*z

(2)

,1d+1 = ,1 (2x)dx + ,1 (2y)dy + ,1 (2z)dz = 0

: (e) (]) l * V:D

(8yz + 2,1x) dx + (8xz + 2,1y) dy + (8xy + 2,1z) dz = 0

(3)

8yz + 2,1x = 0 (4 1) 8xz + 2,1y = 0 (4 2) .

8xy + 2,1z = 0 (4 3) /
2

x + y + z = 1 (4 4)
4 yz (4 1) ,1 =
x
4xz .
(4 2) ,1 =
y /

(4)

2 * n=3

2 * m=1
:A

y x
=
x y

x 2 = y2

6 *

O1 z W y W x

x=y

9.

4xz (4 2) ,1 =
y
.
4xy
(4 3) ,1 =
z /

z=y

4xy (4 3) ,1 =
z
.
4yz
(4 1) ,1 =
x /

x=z

x + y + z =1
Pmax = 8xyz =

3x = 1
8

3 3

1
x=y=z=
3

:- <

dI = ^

W dP = ^

. WIV

WPV

D 2 2' -

f '(v y )
f '(v x )
f '(v z )
d =0=
dv x +
d1 y +
dv z
f (v x )
f (v y )
f (v z )
: "E %_ 2Q|E

@ <2 * G

E' 2Q|E 2

(1)
2$ EA 2Q|E

+ = v 2x + v 2y + v z2 = cte
:T

*+
*+
*+
0 = d+ =
dv x +
dv y +
dv z
*v x
*v y
*v z
2v x

2v y

2v z

d+ = 0 = v x dv x + v y dv y + v z dv z

, d+ = 0 = , v x dv x + , v y dv y + , v z dv z

(2)
:(l) (s) 1- 7$

(1) + (2)

d 3r

f '(v y )
f '(v x )
f '(v z )
+ , v x dv x +
+ , v y dv y +
+ , v z dv z = 0
! f (v x )
"
! f (v z )
"
! f (v y )
"

.K 1- 7$$ n = u t 1Q

n=3
1- 7$

f '(v x )
+ ,v x = 0
f (v x )
f '(v y )
+ ,v y = 0
f (v y )
.
f '(v z )
+ ,v z = 0
f (v z )

Tw v 1- 7$ v

1- 7$ m = 1 2
v x + v 2y + v 2z = v 2
M%
/

f '(v x )
+ ,v x = 0
f (v x )
df (v x )
d(v x )
+ ,v x = 0
f (v x )

df (v x )
= , v x dv x
f (v x )

ln f (v x ) = ,

v 2x
2

+ C
ln 3

f (v x )
v 2x
ln
= ,
2
3

f (v x ) = 3 e
f (v x ) = 3 exp (

v 2x
,
2

4 2 v 2x )

f (v y ) = 3 exp ( 4 2 v 2y )
f (v z ) = 3 exp ( 4 2 v 2z )

,
4 =
2"
!
2

<

:2S

d 3 Nv x v y v z = N.f (v x )f (v y )f (v z ) dv x dv y dv z
:-

= N 3 exp

2
vx

2
vy

2
vz

dv x dv y dv z

v2
3

d Nv x v y v z = N.3 exp

d 3 Nv x v y v z
dv x dv y dv z

2 2

4 v

= N.3 exp

dv x dv y dv z
2 2

4 v

:# 0 " 9:
."
& <2

4
3

:./

$/ v7 v + dv 0

4
3

( v + dv )

(v)

v + dv + 3v dv + 3vdv

-./

velocity space
:"

dN v = d

v + dv ~

: ;$A >

: :

G
I
."

* 6$5 2 W Q P 8 4 2% I
"_
$_

9
$;

* 6$5 : 2Q/
v+dv v G a *< 0 '
vz

dv

v7 v + dv ~

(v

(v

v + dv)

9A "_

4
=
3

vx

(3v dv ) = 4
2

v dv

2, Wvelocity space -./ /

v + dv)
2 2

dN v = N 3 3 exp( 4 v ) (4 v 2 dv)
d

vy

velocity space

-./

dN v
= 4 N 3 3 v 2 exp( 4 2 v 2 )
dv
Maxwell velocity distributions

dN v
dv

?$K

35

)
dN
v
0

=4

3 ) 2
N3 0 v

exp( 4 2 v 2 ) dv

:6 *

) n ax 2
x e
dx
0

5 (n) =

`$A

5 ( (n + 1) / 2 )

) n 1 t
t e dt
0

5 (n + 1) =

2a (n +1) / 2
(n > 0)

n 5 (n)

= n!

n (n 1) 5 (n 1)

1
5
=
!2"
1
(2m 1)
5 (m + ) =
2
2m

m = 1, 2, 3,...

V 0c

:-

v,

) 2
v
0

2,

42

exp( 4 2 v) dv =

2 +1
(
)
2
2
4
( n +1)
2a 2

3
1
2(1) 1
5
= 5 1+
=
2"
2 (1)
!2"
!
) 2
v
0

2 2

exp( 4 v ) dv =

/2
24

"_

V 2E R

1
(2m 1)
5= m+
=
2"
2m
!

2 +1
5
! 2 "
2

y *

443

3
5
2"
!
=
243

m =1

N = 4 N3
:K

dN v =

4N

! 44 "
Qx ;

3 2

3 =
5 M$ @P /p;

3
2 43

3=

Speed distribution function 6

2 2

4 v exp ( 4 v ) dv
: CK

1
1 4N 43
V=
v.dN v =
N
N

vdN v
V=
@ 5 M$ 1Q y2 4
N

) 3
v exp(
0

4 2 v 2 ) dv

v,

) 3
v exp(
0

3,
2 2

4 v )=

3 +1
5
! 2 "
2

5 ( n + 1) = n !
) 3
v exp(
0

2 2

4=

1
.
V

3+1
42 2

" /6

5 (2)
24 4

5 (2) = 1! = 1

4 v )=

1 4N 43
V=
N

:-

1
24 4

) 3
v exp(
0

:> $ "_

2 2

4 v )=

443

1
24

2
4

v rms =

v dN v
N

v =

1/2

1/2

v rms =

3
4
N
4
v2 =
N

) 4
v
0

exp( 4 2 v 2 ) dv
3
8 45
: "E %_ 0 < '=

v,

v rms =

n
3 1
24

4,

4=

42
3 1
.
2 v rms

2 2. $A

:- $< 0 = U U $

t A

1
3
2
mv = kT
2
2

3kT
v =
m
2

4=

v rms =

3 1
=
.
2 v rms

v =

3kT
m

1
=
3kT
m

m
2kT

1
43
T

Most probable velocity:

dN v 6 $ b 2' "
dv

:<

dN v
d(
)
dv = 0
dv

$_

Wvmp a B

:2. $A

d dN v
d 4N 3 2
.4 .v .exp
=
dv ! dv " dv
=
+

4N

.43 .(2v).exp

4N

.43 .v 2 .

42 v 2

) (

24 2 v exp

:$/ 6 $K

B N

42 v 2

)
)

42 v 2 = 0

dv 8E/

=0

"_

2% I

?$K

v.exp

) ( ) (
) exp ( 4 v ) = 0

42 v 2
2 2

v 1 4 v

4 2 v 3 exp

42 v2 = 0

2 2

:"

1) v = 0
2) v

)
2 2

3) (1 4 v ) = 0

dN v
dv

1
v=
4

"_

N
I

* " /2
7' /

$' /

5 2S
/

Q)

( %A " 9

v mp

1
=
4
."

"%7

4=

m
2kT

v mp
v=

1
= =
4
2
4

v rms =

v rms
=
v mp
v
v mp

2kT
m

2kT 1
=2
=
m
3 1
=
24

8 kT
kT
= 2.55
! m "
! m "

3kT
m

3
= 1.224
2
2.55
= 1.128
2

v rms 8 v 8 v mp

:
:K

N (0

vx )

vx
0

? MO{g$

I$ 4 @x KT

"# $ # %

1i- $

I$ 1? z 9

dNv x

dNv x = N.f (v x ).dv x = N.3.exp (

dNv x = N .3. exp
4

vx
x=
= v x .4
v mp

dx = 4 dv x

#C K

2 2
4 vx

x
vx =
4
dx
dv x =
4

) dv

2 2
4 v x ) dv x

' $ '5

dNv x = N.

erf (x) =
erf () ) =
Nv x =
v x (0

2
x
dx
2
4 . 2
4
4

exp

dNv x =

x2

dx

:& < 2 error function y *

x
x2
e
0

)
x2
e
0

x
x2
e
0

dx
dx = 1

dx =

N
!

N
erf (x) = .erf (x)
2
" 2

x)
.

Werf(x) =--/^ 2 We

$ b

`$A

: dNvx dW3 Nv

:v

dNv =

4N

m
2kT

W dNv 4 =
x , v y , vz

v + dv

b` D

3
2

2
m
mv
v 2 exp
dv
! 2kT "
! 2kT "

d 3 Nv x , v y , v z =

v x + dv x -

vy

v y + dv y .

vz

v z + dv z /
3
2

( )

vx

3
2

m
mv 2
exp
dv x dv y dv z
! 2kT "
! 2kT "

v x + dv x

: vx

dNv x =

1
2

2
mv x

m
exp
dv x
! 2kT "
! 2kT "
."< A b A E 8E/

>

1
E = mv 2
2

W"

v mp 3 T 9 v mp =
."

1
,
4

$K "_

43
<

2 2D

1 : 2 2D
T
$K

2+ G W6

bA

:;
E' V

V & <

%1

The molecules stick to the glass plate,

and the number arriving at any portion
can be determined by removing the plate
and measuring with a recording
microphotometer the darkening that has
resulted.

IN
"' / G '
=
'
0

0 RA ;
:E

The Principle of Equipartition of Energy:

: "E %_ x "9D

1
E x = mv 2x
2
1
E x = mv 2x
2

R$A "' / 2 j

: E' "_

v 2x = v 2x .dN vx =

m
! 2kT "

1
2

4 4

dNv x =

2
mv x

t A

D O 5

2
mv
kT
2
x
v x .exp
dv x =
m
! 2kT "
.

1
2

U$

m
exp
dv x
! 2kT "
! 2kT "

=
3

1
3

m 2
(
)
2kT
: "E %_ dNvx 2'

2
vx

Ex

kT
=
m

1
1
kT
1
2
= m vx = m
= kT
2
2 ! m " 2

The mean kinetic energy of a molecule associated with the x-component of the
molecules velocity.

: 2'

Ey

1
1
2
= m v y = kT
2
2

1
1
2
E z = m v z = kT
2
2

<

52 K

<0

6 :; &' U $

t A W&%B

1
3
2
E = m v = kT
2
2
."
2 6

t A T W"

"9D 2

0 < - ER ) E

S WyQ$;

R$A ", / ) )
PD
." 0 < - ER
E 2 W

2
U

9D 6 )t A 6
W
D

2' .A
2D

We have equipartition of energy among the three translational degrees of freedom.

G

<*

)t A
:"N

W K

+ )t A &7 W) ` ) 9 t A W < %A
W <0
'2
:_ S 5 &

: !
6

W"<

W '

;K

"

2D

vx 8E/
.

."

1
kT
2

2' <
.<

2D

> $

1
kT
2

2D

V
*

"_

1
1
m v 2x = kT
2
2

+ t A W<

W
u$

2D
2 j

a A G
t A
t A > $

R
: 7

V U (vx) x "9D

Ex =

u$ i

1 2
II:
:x
2

2N

2 j

t A > $

W K

K% D t A
R 2' (

+ "' / 2 j

1
m v zx )
2
t A

1
2
kx
x "
A
5 " 1 8 4 k) "
& EA $ t A 2' Harmonic oscillator U
2
1
kT & EA $ t A > $ W( <
2 W z y x "9D 2
u ) ."
5 @
2
.( G

2
."

t A &' R W <
D 6 t A

i 2D V U
E
- ER &

t A W 9A
2'
6 . <
- ER

& K

G 2D

i:
6
G 2D 6

u
2D
E

Classical Theory of Specific Heat:

4C 1

f
E = kT
2

9 =2 B

$ f

f
f N
f
U = N.E = N. . k T =
.R .T = . n.R .T
2 R
2 No
2
No

LV$

75 : N

75 : n

4E

8.31

Joules
= 4E}T K |: R
m ole.K

4C 8

75 : f

"

t A zR 2 *

W2$E -$E

U (U) Q

t A

u U k' U
.

U2

U1 = Q

W
:-

f
f
U = .N.kT = .n.R .T
2
2
U
f
u=
= .R .T
n
2

"

2'

Specific heat:

*u
f
= .R
cv =
! * T " v = cons tan t 2
:& '

h = u + pv

d h = d u + RdT

RT

cp

cv = R

fR
f +2
cp =
R
+R =
2
2

U k' U

*h
*u
=
+R
*T *T
cp

cv

;=
"
i:

."
X

cp
cv

f +2
R
f +2
2
2
=
=
= 1+ > 1
f
f
f
R
2

9 Q
2D
-$E 2'
"
. :A :A u -$E

f =3
R 6

8E/ ; , c p , c v Wl
| 2$5
'2
O 56
$A 6 2$% . <
$ 1 _
$E A
V
G 2D
'
" *% Equipartition of energy &

R$A ", / 2 W f
b "

R 6 $:, b A ."

R &B / 2' f = 3

2
; = 1 + = 1.67
3

<

"%7 f

+ W"

$ + 'XW<

"%7

:Ll
W
G

X > 1 :L A 1

$ b f 2+ G :L7 1
: "

: (Monoatomic gas) : !
Three translational degrees of freedom

f =3
5
f +2
cp =
R = R
2
2

f
3
cv = R = R
2
2
cp
cv

cp

5
=
2
R

cv
3
=
2
R

f + 2 3+ 2 5
=;=
=
=
f
3
3

: : U

$A

U$

| $A 2E R

cp / R

Gas

c v j / m ol.k

c p j / m ol.k

cv / R

He

12.63 j/mol.k

20.95 j/mol.k 12.63 = 1.519 20.95 = 2.52

Ar

12.55

20.95

4E= &

~5

"

1.509

2.52

3/2=1.5

5/2=2.5

."
.A 0<
."
."

0
0
0

8.31

8.31

A e C @

U bA

%B & B $A 2' G
G

"

(Continuous calorimeter) 2$

"

(C =

;R T )

"_

KA 2E R

0c

$: ' >
0

A >

cp
;

: (Diatomic gas) R

f =

\ 4C 1 )
2 ( g > Kd ;

f =2

\ 4C 1 )
Kd ; f
(M 75

\ 4C 1 )
3 Kd ;
(M- I

9
c p = R = 4.5R
2

cp

7
c v = R = 3.5R
2

cv
= 3.5
R

f =7

4E\
4C 1

= 4.5

9
; = = 1.286
7

Gas

c v j / m ol.k

c p j / m ol.k

cv / R

cp / R

H2

20.27 j/mol.k

28.44 j/mol.k

2.438

3.42

O2

20.82

29.27

2.504

3.52

N2

20.35
4E= &

29.10

2.448

3.50

7/2=3.5

9/2=4.5

~5

"

.A
2A

W K

+ "' /

cv
= 2.5
R

cp
R

<*

", /

= 3.5

W> I ) G

A "R S
2' 2 D 6

gA

) < f=5
:(-G
G

7
; = = 1.40
5
.G

KA

"R S 2'

:(Transport properties) > ? + < =1

1- Mean free path
. :

WG

U 2' "

S $ 2Q

* W Mean free path

. < r a *< U $ l
2R
$B 9 0
L:$/ W

G 0 ' WG
. '

.< er
B er a *< 2

Wv W0
D
Q U -./
$:' 9A b'
b' 2Q
2A $

&

> $ "_
"' / @
5 2'

W `

2 A O 52
0
G

b'

T
I$

. '
" 1

I$

W < er a *< 2

2A $

b'
.

2A ) a *< 2

VB

6,

0 '

)9

-./ 6'

I$

* W "

)9

P$ EA

G 2SRA

6'

w : >R5

`
%_ 2
:- ' O 5 er ( SB

W" 1 ) 9
I$
i
* 6
: "
* 2, W(Collision cylinder) er a *< 2
Q

r
2r
2r
2r

r
r

= 2$ EA

(2 r ) 2

.t

vi N i
Ni

6'

)9

Z = 4 r 2 v.

:(Collision frequency)
:

v.t
4 r 2 .v.t.
=

P$ EA

2% I

& < 2 Mean free path 6

The total distance covered in time t

T he num ber of collisions in tim e t

1
4 r2.

Mean free path of a molecule is defined as the average distance a molecule travels
between two successive collisions.

W2D

NE: U

4 r2

= 8 10
8

8 10
3 10
8 10
3 10
.

m
9

K5) S I > <

(r = 1.610-10) c E,

: 7
:(I = 31025

1
4(3.1415) (1.6 10
8

10 2

) (3 10 25 )

m
."

310-10 m c E'

SB

260

10

."

310-9 m c E'

6 2Q

26

RA W> I

`$

j < W < Mean Free Path 2 ! bA 9

6 PQ

32 kg / km ole
m =
= 5.31 10
26 m olecule
6.02 10
km ole
V =

kT
(2.55)
=
m

(2.55)

Collision frequency = Z = 4

(1.38 10

23

5.31 10

26

kg

) (273)
26

= 426 m / sec

r2 v

= 4 (3.1415) (1.6 10

10 2

) (426) (3 10 25 )

= 5.1 10 9 collisioin / sec

2- The distribution of free paths

free path V

6 :; ":EB 6
2Q 5 6

No
x

dx

* 2+) "
<

x+dx

x PQ

$K 9

dN =

QD

dN

* 2+ free path 2'

.( '
R+ G G

Q W

<
`

gA "' / %
. <
-, G 0

Ai

Q No
*

Pc .N.dx
@

dx
.

3G ' W0
.dx

b5> <V

A{

A{
%

"E A dx N V 2'

x 2Q

G
5

* dx
0

A{

u : dN

: (-) " k_
* :N

:$/ 8 4) Collision probability : Pc

.("

dN = Pc .N.dx

:dx
"' / %

x 2Q

dx 2Q

dN
=
N

0 '{

A{

G
G

*
* =N

* = dN

* 6

Pc .dx

ln N =

Pc x + const

x=0
N = No

ln N o = const

N
=
ln
No
.

Pc . x

x=

2
0

N = N o exp( Pc .x )

3G ' W x 3 b5

:A

S W 5

: Pc

"

dN = Pc . N.dx
dN =

Pc . N o exp( Pc .x ) dx
N

%_ 2

A 0 '{
W x+dx x 2Q 5
.<
x7x+dx 2Q 5

Mean free path

)
0

i
1
2' "
9A free path 2' "

x dN

xi Ni
No

dN: Number of molecules having x as the free path

x: free path

G
G

* : dN
* W `

)
P N .x.exp(
0 c o

Pc .x) dx

No

Pc .N o
=
No

)
x.exp(
0

1
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