1

:
The Gas Liquid & Liquid Liquid Interfaces

1-1


: Surface
..
: Interface

Surface and Interface

Gas Liquid

Gas Liquid

Liquid

Solid

emulsions

-Liquid

Liquid

suspensions

S/G
L/L
L/S

Solid -
Solid

- )
...(G/G
:
Free Energy
..
S/S

2




) Interface
(Interphase Region

10 100( ) A

.
Interface Region

Surface Tension

..






.

3
) ( :

) (.

) (
.. ) (F

F = 2 L
F
2L

dx
F

).. (F
) ( W
dW = F . dx = 2L dx
W = dA

= dA
dA = 2L dx

:
)
(
mJ
mN
= 1
m
m2

=1

ergs
J
dynes
N
= 10-3 2 = 10-3
= 2
cm
m
cm
m

Interfacial Tension

4

-
:

.
LL

SL

LL

o
C 20

) ( dyne/cm

) ( dyne/cm

28.9

26.8

27.1

35.8

18.4

21.8

485

24.6

27.33

17.0


72.8

35.0
45.0
32.8
22.9
51.1
50.8
375
1.6
8.5
10.7
Surface Free Energy

:
dG
dA

5
:
)
(:
= Gs

Gs
Ss

Gs = = Hs T Ss

Hs

Ss Hs

= Hs + T

20oC

20oC
) ( erg / cm2

d / dT = - Ss
))ergs/cm2 .
deg

) Hs = - T ( d/dT
))ergs / cm2

18.4

- 0.105

49.2

17.0

- 0.116

51.0

26.9

- 0.092

53.9

29.0

- 0.099

58.0

28.5

- 0.135

68.3

32.2

- 0.139

72.9

72.8

- 0.152

117.3

484

- 0.220

548

12

Intermolecular Forces

at Interface

) (w
wd
:wh
w = wd + wh

: Hg
Hg

d
Hg

6
Hg = Hgd + Hgm

.
- ) ( T > 2000 C
) ( > 1000 m J m
.
o

-2

C 20

)
) mJm
) C
-2

2.3

- 253

13.2

- 186

72.8

100

C1000

88

1390

98

1413

970

( (C

485

357

800

2180

Pressure Differences across Curved Interfaces

) ( :

.
Laplace Equation

) P = ( R + R
1
2

7
-1 ) = R = R
(
2

-2
-3

P = 0

R1

R2

R1 = R2 = r
2
r

dx
+
x
y

dz

= P

:
= P

R1

R2

y+dy

dz

r
.
) ( P
) ( P
: G
The Kelvin Equation

8
2M
2 VL
P
=
= o
P
r
r

):

VL

G = RT ln

) ( (

M
C 20
o

P
Po

erg

cm 72.8
2

)(2) (18.0) (72.8

(0.998) (8.31 107 )( 293) r

P
= exp
Po

P
1.08 10 7
=
exp
Po
r
M 18.0 g.mol -1 , R = 8.314 x 107 erg.mol-1.K-1 , 0.998 g.cm -3

1.011 & 2.9404

cm 10 4-10 .
-7

Spreading

) Adhesion ( Wa
B D

) (A
Dupre :
Wa = BA + DA - DB

) Cohesion ( Wc ) ( B


Wc = 2 BA
:

D
B

A ABAA

BB

B
B

9
)(

)) (B-B(
) ( O )

)adhesion (D-B

) (

)(
cohesion

Wa = WOW = OA + WA - OW
Wc = WOO = 2 OA

Wc
.

) ( O W ) )...
.
) (
.
.

Spreading of One Liquid on Another
OA

OW

WA

WA = OA cos 1 + OW cos 2

) (
2

WA - ( OA + OW ) > 0
) S = WA - ( OA + OW

Harkins ) (S
S
OA
O

WA

OW

10

OA

WA

OW

)(A
)(O
(( w
) (
)( )( +

CS


CH I

) S ( dynes cm-1

+ 50.4
+ 50.1
+ 49.1
+ 45.5
+ 36.8
+ 13.0
+ 8.9
+ 6.8
+ 3.4
+ 1.1
+ 0.22
- 7.6

- 9.3
- 9.6
- 26.5

o
C 20

11

mutual

saturation

: `S
) S` = `WA - ( `OA + OW

) ` (
) ( S = + 8.9
) ( S` = - 1.6
+
.


S =W
-W

S = W
- 2
OA

OW

OW

OO

C 20

) S = WA - ( OA + OW

72.8 ( 30.0 + 52.1 ) = - 9.3

72.8 ( 21.8 + 50.8 ) = + 0.2

72.8 ( 27.5 + 8.5 ) = + 36.8

`WA
62.2

`L A
28.8

WL
8.8+ 36.00
SWL

S`WL

1.6-

28.5

26.5

8.00

37.8 +

5.9-

CS2
CH2I2

70.5
72.2

31.8
50.5

48.6
45.8

8.223.8-

9.924.2-

- -

12
)
20

mNm-1

) ( A

SA/B
)(B
99
108
135
79
60
37.2

(A
)(B

) (positive adsorption


negative adsorption
.
Adsorption at Interfaces

:
Gibbs Adsorption Equation

13
c d
RT d c

= -

: excess concentration

.
d
: d c
.
: T R
C
.

-
.
2

1
3
C