1)

) (

( ). ) = ->

F
i r j

F
( . . r U(r) .

dU F ! dr
:
2.5

F "0 |

dU dr

0|

dU "0 dr

U(r) :
2r0
0 0.5 1 1.5 2 2.5

; , U(r)=0 nm:
(London 1930)

U (r )

1.5 1 0.5 0 -0.5

:
3

-1

-1.5

1 ~ 1kJ / mol

! 1010 m ! 0.1nm

London : (

aa : U ij r w  i 6 j r .

( :

) .

ai : !
(r0 2r0 van der Waals ) .

Lennard-Jones :
2.5

U (r )

1.5 1 0.5 0 0 -0.5 0.5 1 1.5 2 2.5

W 12 W 6 U (r ) ! 4I  r r
2r0 r
3

-1

-1.5

! 1010 m ! 0.1nm

(r0 van der Waals ) dU ! 0 p 2r0 ! 21/ 6 W , U (21/ 6 W ) ! I dr

~ 1kJ / mol

2) :

, .

r1  1=-q q

r2  q2=+q
+ -

! qi r i , : i 

! ql

1 D = 1 debye = 10-18 (erg cm3) =1/3 x 1029 Cb m

 N
H H H
1.47 debye

H Br
0.80 debye

 O H H
1.84 debye

+ +

:
j U ij r w  , i (Kessom) r 6 kbT

kb !

R NA

3)

+ +

U ij r w  : ,

ai r6

:
j

(Debye) . . . ,
U ( rij ) ! . 1 qi q j 4TI 0 rij

4) :

: , . . ~ 8-40 KJ/mol ,

(Coulomb)

~ 200-400 KJ/mol )

: Maxwell, Boltzmann, Claussius,

: ) ) ) ) . ) ( . ) m , ), : (
2.5 2 1.5 1 0.5

19
(

.
)

: )

( )

2r0
0 0.5 1 1.5 2 2.5 3

) 1) 2) 3)
3

0 -0.5 -1

<< V,

-1.5

<< . ) , .

. : = ( ) ,
uz
u 

uy

ux

m : x x : ; t . m ux . m u
x

x. u x .

2m u x ux t
( N ux

ux
x x :

ux

A ux 1 N ux V 2

: 2m u x

ux A ux t 1 mA 2 * 2m u x ! N ux N ux ux t 2 V V mA ux t N  u x ux V ux
:

ux t
2

ux

N ux ux N ux

!
ux

N  u x u x 2 ! N

ux 2 N

ux

: mA N u 2 x

= ( : ,

mA N ux 2 ) V

P!

mN u x 2 PV ! Nm u x 2 V

u 2 ! ux2  u y 2  uz 2 u 2 ! ux2  u y 2  uz 2 p ux 2 ! 1 2 u 3

1 PV ! N m u 2 3

1 PV ! N m u 2 3
( , ) PV ! nRT N n! NA

1 N 1 R 2 2 PV ! N m u ! RT m u ! T ! kbT NA NA 3 3
:k ! R ! b N A 6.023 v1023
8.314 J mol K mol ! 1.3805 v1023 J K

1 1 3 m u 2 ! kbT p Etransl ! m u 2 ! kbT 3 2 2

1 kbT 2
):

( A x2 , A px2 , x : 1 px

kbT

E!
i !1

2 2 mux ,i  mu y ,i  muz2,i

!
i !1

2 2 px ,i  p y ,i  pz2,i

2m

3 E ! NkbT 2
), . .

kT RT u2 ! 3 b ! 3 m M
CO2 25 C : M=44 g/mol=44 10-3 Kg/mol

u2

J 8.314 v 298 K mol K RT ! 411 m ! 1480 km ! 3 ! 3 s h 3 g M 44 v10 mol

Maxwell-Boltzmann

f ( x) dx
0 . 1 0 2

f ( x)

0 . 1 0

0 . 0 8 0

0 . 0 6 0

f ( x) dx

0 . 0 4 0

0 . 0 2 0

-10

-5

x x  dx 0

10

x ! x ! xf ( x) dx

1 f ( x) dx ! 1 , f ( x) w x

x  x

! x  x
2

g x ! g x f ( x) dx

f ( x, y )dxdy

f ( x, y )dxdy ! 1
:

f ( x, y)dy f ( x) ! f ( x, y)dxdy
1

f ( x, y ) ! f1 ( x) * f1 ( x)
: Maxwell-Boltzmann

f (u x , u y , u z ) ! f1 (u x ) v f1 (u y ) v f1 (u z )
:
2 2 f (u x , u y , u z ) ! F u x  u 2  u z y

f1 (u x ) ! Ae

u x 2

f (u x , u y , u z ) ! A e
g

3  u2

 x2

dx !

g

 f1 (u x ) ! e

u x 2

2 x

1 2 1 3kbT kbT ! u ! ! 3 3 m m
g

2 x

2  ! u f (u x ) du x ! u x e g g
g 2 x 1

u x 2

du x

1 m ! 2 kbT m f1 (u x ) ! e 2 k bT
 m u x 2 2 k bT

y 3 y 5 y n  1 1/ 2 1 nu2 2 y (2 )n / 2 g 2 x n e  x dx ! n  1 0 ! 2 n u1 n 1 / 2 2

m f (u x , u y , u z ) ! e 2 kbT

3 2

m 2 u 2 k bT

:
:

Maxwell-Boltzmann
Maxwell-Boltzmann

f (u x , u y , u z ) ! f1 (u x ) v f1 (u y ) v f1 (u z )
:

f1 (u x ) ! Ae

u x 2

f (u x , u y , u z ) ! A e

3  u2

:
g

f1 (u x )du x ! 1 xu x  y2 1 dy ! Ae dy ! 1 p xy g
g

g

Ae  du x ! 1 p
2 ux

g g

y!

u x g

Ae  y

 y2

dy ! 1 p

!1p A !

g

:
.:

Maxwell-Boltzmann  u f1 (u x ) ! e  1 2 1 3kbT kbT 2 ux ! u ! ! m 3 3 m

ux 2
1
1

g k BT 2  ux2 2 ! u x f1 (u x )du x ! p u x e du x ! m g g
g

u
y

2 x

e
e

2 ux

du x p
y! ux

1
1
g

g
g

 y2

g

xu x dy ! xy

y

dy !

ye

2  y2

g

g

k BT dy ! m

p
g

1
2

ye

2 2 y

dy !

k BT ! p 2 m

m ! 2 k BT

g

x 2e  x dx

g

de x  x2 ! e dx 2 g

 x2

x de  2 dx dx ! g

 x2

1  x2 g 1  x2  xe  1e dx ! g 2 2 2 g !  fg d p !  g f d  fg d fg d  fg d f d p g dx  fg d  fd p gdx

fg d ! dx

fg d ! ? fg A  f ddx g dx
y 3 y 5 y n  1 1/ 2 1 nu2 n/2 2 y (2 ) g 2 x n e  x dx ! n  1 0 ! 2 n u1 n 1 / 2 2

Maxwell-Boltzmann


f1 (u x ) ! Ae

u x 2

A!
m f1 u x ! e 2 kbT
u2

m ux 2 2 kbT

m ! 2 k BT

Maxwell-Boltzmann

f (u x , u y , u z ) ! f1 (u x ) v f1 (u y ) v f1 (u z )

m f (u x , u y , u z ) ! e 2 k bT

3 2

1 mu 2  2 kbT

Maxwell-Boltzmann

0 . 1 0

f1 (u x )
0 . 1 0 0 . 0 8 0 0 . 0 6 0

k BT 1/ 2 m

0 . 0 4 0

0 . 0 2 0

-10

-5

0 0

ux
2

10

m  2 kbT ux f1 u x ! e 2 k bT

:(

Maxwell)
)

m f (u x , u y , u z ) ! e 2 k BT uz

3 2

1 mu 2  2 kbT

& 2 2 u ! u x  u y  u z2

& fu ( u )

& & fu ( u )d u
u u+du

uy f u du ! ux

. .

f (u x , u y , u z )du x du y du z ! 4 u 2 f (u )du p
3 2 1 mu 2  2 k bT 2

m f u du ! 4 ue 2 k BT
K Maxwell :

du

:( CO2 25o C (M=44x 10-3 Kg/mol)

Maxwell)

3kbT 3RT ! ! !0 C m M CO2 25

:

J 3 v 8.314 v 298 K mol K ! 411 m s 3 kg 44 v10 mol

1 mu 2  2 kbT

df u ! 0 2ue du  2 RT u ! M
1/ 2

1 mu 2  2 kbT

2 mu u e 2 k bT
2

 2 k BT !0pu ! m

1/ 2

CO2 250 C

J v 298 K 2 v 8.314 mol K ! 335.58 m s kg 44 v103 mol

1/ 2

 8m f u u ! 2 e k BT

m u ! u f u du ! 4 ue 2 k BT

3 2

1 mu 2  2 k bT 3

m du ! 4 2 k BT

3 2

1! m 2 2 k BT
2

8 k BT u ! m

1/ 2

CO2 250 C

J 8 v 8.314 v 298 K mol K ! 378.66 m s kg v 44 v 103 mol

 u

y 3 y 5 y n  1 1/ 2 1 nu2 n/2 2 y (2 ) g 2 x n e  x dx ! n  1 0 ! 2 n u1 n 1 / 2 2

:( CO2 (M=44x 10-3 Kg/mol)

0.003 0.0025 f u(u) (s/m) 0.002 0.0015 0.001 0.0005 0 0 umax <u> <u > 200 400
2 0.5

Maxwell)

T= 600 C T=25 C

600

800 u (m/s)

1000

1200

1400

1600

1800

 u

u2

Maxwell

s
Maxwell Doppler

P.W. Atkins, Physical Chemistry

Z1
;

Z11
, , ;

2.5 2 1.5 1 0.5 0 0 -0.5 -1 -1.5 0.5 1

2r0
1.5 2 2.5 3

u
2

collision cross section ~ 0.1-1 nm2 :

N V

)
u u

2 u 0 u u u u u 2 u u

) )

N 2 V

N 2 V
N 2 V Z1 !

u
u t

;
2

Z1 ! 4

t P 2 mkBT
;

N ! 2 V

P u ! 2 k BT

8 k BT m

1/ 2

1 1 1 N Z11 ! Z1 v N v v ! 2 V 2V
P n P N ! ! RT V k BT V

2 2

?AA!

Z11 !

n N ! V VN A

4 k BT m
1/ 2

1/ 2

8 k BT u ! m

N Z1 ! 2 V

u !4

P 2 mkBT

Z11 !

4 k BT m

1/ 2

2 A

?AA

: :

1 1 ! N Z1 2 V
:

1 ! u ! Z1 2 1 2 ~T P
1 2

u
2

u N V ! 2 ,

! k BT 1 ! 2 N A ?A A 2 2P ~ ?A A
1 2

N V
2

1

( P T

(gaseus effusion)

<< )

PAo dN !  Z Ao !  1/ 2 dt 2 mk BT
P, w m-1/2

( 1 ,

Graham)

Po.

PAo PAo dN !  Z Ao !  ! ! 1/ 2 1/ 2 dt 2 mkBT 2 1 2 mN A 2 k BT NA PAo N A PAo N A dN ! ! 1/ 2 1/ 2 dt 2 MRT 2 mN N k T

A B

N A kb ! R, M ! N A m

PAo N A dN ! 1/ 2 dt 2 MRT

N PV !n! | NA RT

N!

PV PV ! NA k BT RT P

PAo N A Ao V dP dP ! p ! NA 1/ 2 RT dt V dt 2 MRT 1 dP ! P dt V 2 M , ! Ao RT
1/ 2

RT 2 M

1/ 2

dP 1 dP dt 1 1 ! P !  d ln P !  dt p d ln P !  dt p dt P ln P0 0
t  P t ln P  ln P0 !  ln !  P ! P0 e P0

ln P

1.2 1

Po
0.8 0.6 0.4
P

w V Ao-1 M1/2 T-1/2

0.2 0 0 2 4
t

(
Po

.(

Knudsen)

T Cs
, Torr. 0,5 mm. 385 mg.

500 C (Cs). 100 s 500 C ?

= 500 C=773.2 K d=0.5 mm=5x10-4m m=-385x10-6 Kgr t= 100 s-> m/ m=-3.86x10-6Kgr/s Po=81 Torr=81/760x1.013x105 Pa=10796 Pa -> P= Po

81

Cs

d2 dN Po N A !  Z Ao !  1/ 2 dt 4 2 MRT
1/ 2

d2 M Po N A Po dm dN M ! ! ! 1/ 2 1/ 2 dt dt N A 2 MRT 4 N A 2 RT

d 2 1/ 2 M p 4

J 32 x8.314 x783.2 K 2 dm 2 32 RT 385 x106 Kg mol K ! ! M !  Kg 2 2 4 4 s 10796 2 Pa 2 5 x104 m 4 dt Po d 100 S.I. 1 atm ! 760 Torr ! 1.01325 bar =1.01325 x 10 Pa Kg g Kg Kgm p M ! 0.133 ! 133 1Pa ! 1N / m ! 1 , 1J ! 1Nm ! 1 mol mol ms s

ci !

Ni N AV

): . .

J i,z
Az

xci mol , 4 xz m xvx 1 , xz s

(shear rate)

mol Ji,z 2 m s

m2 D s

 Fx

Jz ! 

Fx Az

?Pa A | ms 2
Kg
x z

z x
Jz

?Pa s A

T z z
, Jz( )=(

xT K , xz m

W Jz 2 m

W mK

z)/ [(

z)(

)]

:
J i,z xc ! D i xz
Fick

Jz 

 x ! 

xvx ! xz

zx

Jz  

! 
Fourier

Newton
x.

x xz

ai

.
z J i,z
0.4 0.35 0.3 0.25 c 0.2 0.15 0.1 0.05 0 1 2

z
xc xz 0
0

c 

~ c 0 

~ c 0 

xc xz 0

Z A t
Z !

!
NA c  4

NA c  4

J ap !

A t J
pa

1 c  4 1 c 4

k BT 2 2P
1/ 2

u
k BT , P

8 k BT u ! m
:

J z ! J ap  J Jz  

pa

c 

u
4

u
4

!

2 xc u p 4 xz 0

D w T 3/ 2 , P 1 ,

-1

! 

1 2

xc xz 0 1 D! 2

1 k T u ! 2 B m

1/ 2

k BT P

3 1 k BT D! 8 2 m

1/ 2

k BT ! 2.628 v 103 P

T3 2 M cm P 2 s

P ~ 1atm, T~300 K D ~ 0.1 cm2/s : (binary diffusion coefficient)

D!

3 1 k BT 8 2 m

1/ 2

k BT ! 2.628 v 103 P

M1  M 2 2 M 1M 2 cm2 2 s 1 2 P 2 T3
2

& l

D!
& l !

u !
! u

rn

rn

!n & rn ! li
i !1

n & n & li li ! i !1 i !1
2

&& n n && lili  2 j j lil j i !1 i !1 !1{

n

n i !1

p && li l j
n j !1{ j

!0

rn r

&& ! li li &&! 2 n
n i !1 ll !

n~t/
2

p r

t w Dt
Dw
2

r 2 ! 6 Dt
rn 2 w t

Einstein

rn 2 w t 2

! k BT : ! 3/ 2
0.4 0.35 0.3 0.25 0.2 0.15 0.1

0.05 0

! kBT 
J ap ! 1N 4V 1N ! 4V

 u  u

k BT 

pa

J z ! J ap  J Jz  

N V

 u

pa

! 

1N 2V

N 2 x u ! V 4 xz 4 4 xT xT 1N ! u kB u kB xz xz 2V 

! k BT

dN dU ! p kB N ! dT dT

Fourier

Jz  

! 

x 1 n p ! Cv xz 2 V

dU dU n kB N An ! kB N A ! ! Cv dT dT

.
1 n ! Cv 2 V u !
n P k BT ! , ! V RT 2 2P 1/ 2

1 P Cv 2 RT

kB T 1 1 u ! 2 NA 2 2P

1 2

Cv u !

1 C k T ! 2 v B NA m

25 1 kBT ! 32 2 m

1/ 2

Cv NA

D, . Knudsen ( w .

P. ! , ), ~
Jz  Jz     x !   x !
zx

.
Az

xvx ! zx xz xv 1N u m x p ! xz 2V

 Fx
z

x vx 
z

!

1N m u 2V
:

v x z ! u x

ux

z!

vx 

ux

5 1 k BT ! m 16 2 m

1/ 2

z !

: 2x 10-5 kg/(ms)= 2x 10-4 g/(cms) [P] 1 cP =10-2P

3 1 k BT D! 8 2 m

1/ 2

k BT P

25 1 kBT ! 32 2 m

1/ 2

Cv NA

5 1 k BT ! m 2 16 m

1/ 2

5 P ! m D 6 k BT

P kg ! 3 k BT m

5 ! ~ 0.83 D 6

e Ar N2 CH4 O2

0.73 0.75 0.74 0.70 0.74

schmidt

Cv 2 2 mN A ! p ! p 5 Cv 5 C p ! 3 Cv M
5M

 Cp

2 ! ~ 0.67 5
: e Ar N2 CH4 O2 0.66 0.67 0.71 0.74 0.72

Prandtl

 J Cp Kg K

Eucken:

15 R 4 Cv 3 15 R  5 4 M

-(
:

van der Waals.)

f ( P , v, T ) ! 0
( , ) P, v, T. (Gibbs phase rule): C (C-1) x P 2 (C -1) x P + 2 [(C -1) [ (xi) P , P P ] ] .: ( (U,H, S) ( ) ) . ->

P C x (P-1) C : F=(C -1) x P + 2 - C x (P-1) = C -P +2 : C=1 -> F= 3-P P=1 F=2 P=2 F=1 P=3 F=0 (

] P .)

f ( P , v, T ) ! 0

gb1
P=1 F=2 (T,P) P=2 F=1 Ts(P) Ps(T) P=3 F=0

gb2

(
( . .
20, 2S)

) M L M M G

n ! nL  nG nv ! nL vL  nG vG

vL

vG

nL v  nG v ! nL vL  nG vG
. 20 .,
http://www.eng.usf.edu/~campbell/ThermoI/Proptut/tut1.html

m3/mol

L -------- M -------- G

nL v  vL ! nG vG  v nL MG ! nG LM

Slide 38 gb1 gb2 Click 3D graph to open the htm file with the projection of the phase diagrams to Pv, Tv, PT.
Acer, 11/14/2006

The read boxes have not been presented. And the projections have been presented but not descased in detail.
Acer, 11/14/2006

P Pc

T> c:

vc

. .

20,

2S)

xP x2P f ( Pc , vc , Tc ) ! 0 , !0 !0 , 2 xv T !Tc xv T !T
c