09_Chaper 16C.2a_Solid-Vapor Interface.pdf

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http://bp.snu.ac.kr

Microscopic basis of surface tension.

force inwards tends to contract the surface, i.e. there is a surface tension

Force

relatively high potential energy (bulk) relatively low potential energy

Chap. 16C.2(a) Solid-Vapor Interface => Surface Tension (a – b Interface)

- A molecule in the bulk has a lower potential energy than one free in the gas (below the transition temperature).

- When a molecule is at the surface, its energy is intermediate between free molecule and the molecule in the bulk.

- Its potential energy would be lowered if it moved into the bulk, and so the molecules are under the influence of a force, which tends to draw them into the bulk.

- This force is attractive reducing total surface area, and we term it a tension, the surface tension.

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Solid-Vapor Interface Solid

Vapor

ppt 16-1 =

handwave argument

Dangling Bonds

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Interface Equilibrium – Si (001) Surface

2

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The work involved in forming a surface of area dArea is proportional to the area of the surface formed.

g

= surface tension

At constant pressure and temperature,

: which means that surfaces have a natural tendency to contract.

3

dArea Vdp

SdT

dG     g

dArea dG  g

0

0  

 d Area dG

Liquids (or solids) assume a shape that minimizes their surface area because it enables the maximum number of molecules to the bulk rather than surface.

Surface Tension = Interfacial Gibbs Free Energy

_______________

ppt 16-3 = exact

G ’ ≡ G ’ a + G ’ b + g A

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Figure 16C.6

The model used for calculating the work of forming a liquid film when a wire of length l is raised and pulls the surface with it through a height h.

Force 2gl

Total area 2hl

4

l h

hl h

w f

hl

g g

g

2 /

distance, the

times force

the is

work the

Since

2 Work



 ^(skip)

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P_in : the pressure inside the cavity P_out : the outside pressure

The internal pressure is due to the sum of the outside pressure P_out and the surface tension.

Consider a bubble (or cavity).

The change in surface area when the radius of a sphere changes from r and r +dr is

 As force  distance is work, the force opposing

stretching through the distance dr at this radius=8

prg.

2 2

4 ( ) 4 8

d





p

r dr 

p

r 

p

rdr 8

dw

g 

d

p g

r dr

  

dr ² is ignored

P_in

7

(skip - - -)

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2 2

4

p

r p_in 4

p

r p_out 8

p g

r

  

2

in out

p p

r

  g Laplace equation

Note: The Laplace equation shows that the pressure

inside a curved surface is always greater than the pressure outside, but the difference decreases to zero as the radius of curvature becomes infinite.

8

(skip - - -)

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Figure 4.22

The dependence of the pressure inside a curved surface on the radius of the surface, for two different values of the surface tension.

2

in out

p p

r

  g

r

Pressure inside, p in

Radius, r p_out

Increasing surface tension, g

9

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Assuming that the vapor is ideal,

Let the pressure on the system be increased. If the pressure on the liquid changes by dp(l), then the change in the

presence of its pressure, dp(g) will be such that ( ) ( ) ( ) ( )

m m

V g dp g V l dp l (at constant )T

m m m

d



V dp S dT  d



V dp at constant pressure

( ) .

m ( ) V g RT

 p g

( ) ( ) ( ) ( ) ( ) ( )

( ) ( )

m m

V l dp l

RT dp g

dp g V l dp l

p g   p g  RT

Consider droplets.

At equilibrium, the chemical potentials of a vapor and its liquid are equal.

( ) ( ) d



g  d



l

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One way of increasing the pressure on the liquid is to disperse it as droplets. The pressure differential across a curved surface is 2

g

/r.

On integration with boundary condition of p*(g)=p*(l), when the pressure exerted on the liquid is the normal pressure p*, i.e., p(g)=p* and p(l)=p*,

where p(mist) is the vapor pressure of a sample of mist with droplet radius r and p(bulk) is the pressure of a plane surface of the same material.

( ) ( ) exp _m( ) 2

p p V l

rRT

 g 

  

  Kelvin e

mist bulk quation

 

 

^*

ln * * exp

*

m m m

V V p V p

p p p p p p

p RT RT RT

 

   

         

*

* *

( ) 1

( ) ( ) ( )

p p p

m

p p

dp g V l dp l p g RT









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Figure 4.23

When a capillary tube is first stood in a liquid, the latter climbs up the walls, so curving the surface. The pressure just under the meniscus is less than that arising from the atmosphere by 2g/r. The pressure is equal at equal

heights throughout the liquid provided the hydrostatic pressure (which is

equal to rgh) cancles the pressure difference arising from the curvature.

The pressure exerted by a column

p 



gh



: liquid density

2 2

p p gh gh

r r

g   g

    

2 1

, 2

h ghr

gr

g g 







12

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Figure 4.24

The variation of the surface tension of water with

temperature. Temperature, q/C

Surface tension, g/(mN m-1 )

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Figure 4.25

The balance of forces that results in a contact angle, q_c.

cos cos

sg sl lg c

sg sl

c

lg

g g g q

g g

q g

 

0 

q

_c 90o

90o 

q

_c

g

_sg >

g

_sl

the liquid wets (spread over)

g

_sg <

g

_sl

g_lg

g_sl g_sg

q_c

14

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Thermodynamic work of adhesion

The thermodynamic work of adhesion, w_ad, required to

separate a unit area of a solid and a liquid phase forming an interface across which secondary forces are acting may be related to the surface and the interfacial free energies by the Dupre equation. The reversible work of adhesion, w_ad, in an inert medium may be expressed by:

w_ad= (sum of the surface free energies of the solid and liquid phase – the interfacial free energy)

ad sg lg sl

w 

g



g



g

sg sl lg cos c

g



g



g q

cos _c ^sg ^sl

lg

g g

q g

 

(2) (1)

(3) i.e.,

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Combining eq (1) and eq (3) gives

We now see that the liquid completely “wets” (spreads over) the surface fully, corresponding to

q

_c ^≈ 0, when w_ad ≥ 2

g

_lg. The liquid does not wet the surface

(corresponding to

q

_c > 90˚ when w_ad <

g

_lg ).

(4) cos _c ^ad 1

lg

q

w



g



16

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Figure 4.26

The variation of contact angle (shown by the semaphore-like object) as the ratio w_ad/g_lg changes.

w_ad/g_lg cosq c

1 0

1

-1

0 2

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