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Abhinandan Agrawal
1
June 29, 2005
Physical origin of surface tension/surface energy
www.fairfied.edu
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full dry hair vs. sticky wet hair spherical shape
June 29, 2005
Jose Bico, Nature, 2004 of bubbles
Mechanical definition: as a surface energy
Specific surface energy of a material is the excess energy per unit area due to the
existence of the free surface
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June 29, 2005
Estimation of surface tension based on intermolecular forces
U/2
U is the cohesion energy per molecule inside the liquid
U ≈ 1eV 4
June 29, 2005
hydrogen bonding strongly cohesive liquid
Mechanical definition: as a capillary force
Surface tension (γ) can also be viewed as a force per unit length (mN/m or N/m)
The term “surface tension” is tied to the concept that the surface stays under
a tension
Examples where surface tension manifests itself
as force
1) Slider 2) Capillary adhesion 3) Objects on water
(F1+F2) cosθ
θ F
F2 1
W
F dx = 2 γ l dx F end view of the leg
F1=F2=γl
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June 29, 2005
Contents
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June 29, 2005
1. Surface energy of liquids and melts
Ps is called parachor (from παρα = by the side of, and χορος = space to signify 9
comparative volumes)
June 29, 2005
Useful properties of parachor
Subtracting nCH2 from a series of values for the paraffins CnH2n+2, values for 2H can
be calculated
Unit Value Unit Value
CH2 40.0 Br 68.0
C 9.0 I 90.3
H 15.5 Double bond 16.3–19.1
O 19.8 Triple bond 40.6
O2 (in esters) 54.8 Three-membered ring 12.5
N 17.5 Four-membered ring 6.0
S 49.1 Five-membered ring 3.0
F 26.1 Six-membered ring 0.8
Cl 55.2 Seven-membered ring 4.0
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June 29, 2005
Quayle O.R. Chem. Revs. 53 (1953) 439
Example: ethanol
H H Unit Contribution to
parachor
O 19.8
H C C O H
C 9.0
H H H 15.5
⎝ ⎠ ⎝
V 58.3 ⎠
H H Unit Contribution to
parachor
O 19.8
C C O
C 9.0
H H H 15.5
⎝ ⎠ ⎝
V 39.28 ⎠
Solid/liquid
pair
air
Change in Gibbs free energy dG when the drop spreads
γl
liquid an infinitesimal amount
dA cos θ
θ' θ dG = γ sl dA − γ s dA + γ l dA cos θ
γs
dA γsl At equilibrium dG / dA = 0 → γ sl − γ s + γ l cos θ = 0
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June 29, 2005
2a. Estimation of solid surface energy from contact angle
1/ 3
γ sl = γ s + γ l − 2Φ(γ sγ l )
1/ 2 4(VV
s l)
Φ=
γ sl − γ s + γ l cosθ = 0 (V 1/ 3
+V )
1/ 3 2
s l
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June 29, 2005
2c. Estimation of γ from extrapolating data of polymer melt
1/ 2 1/ 3
⎛γ ⎞ 4(VV )
cosθ ≈ 2Φ ⎜ s ⎟ −1 Φ= s l
⎝ γl ⎠ (V
s
1/ 3
+V
l )
1/ 3 2
4(18 × 86.5)1/ 3
ρ H O = 1g/cm ; M H O = 18g/mol
3
Φ= = 0.93
2
M
2
(18 1/ 3
)
1/ 3 2
+ 86.5
VH 2O = = 18 cm /mol; γ H 2O = 72 mJ/m
3 2
ρ 1/ 2
⎛ 42.5 ⎞
cosθ ≈ 2 × 0.93⎜ ⎟ − 1 = 0.43
VPMMA = 86.5 cm3 /mol; γ PMMA = 42.5 mJ/m 2 ⎝ 72 ⎠
θ = 65o
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June 29, 2005
Temperature dependence of surface tension
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⎛ Ps ⎞
1) Since the parachor Ps is independent of the temperature γ =⎜ ⎟
⎝V ⎠
4
⎛ ρ (T ) ⎞
γ = γ (298) ⎜ ⎟
⎝ ρ (298) ⎠
The surface tension of homologous series tends to increase with increasing molecular
weight
The bulk properties (e.g. heat capacity, tensile strength, specific volume etc.) vary linearly
with the reciprocal of molecular weight
ke Polymer γ∞ ke
γ = γ ∞ − 2/ 3
Mn polyethylene 36 386
polystyrene 30 373
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June 29, 2005 “Polymer Interface and Adhesion” Wu S.
3. Estimation of interfacial surface energy
The additional free energy at the interface between two condensed phases is
known as interfacial energy
1/ 3
4(VV
s l)
Φ=
γ sl − γ s + γ l cosθ = 0 γ sl = γ s + γ l − 2Φ(γ sγ l )1/ 2
(V
s
1/ 3
+V
l )
1/ 3 2
eliminating γs
⎛ (1 + cosθ )2 ⎞
γ sl = γ l ⎜ − cosθ ⎟
⎜ 4Φ 2 ⎟
⎝ ⎠
γab adhesion
γb
∆Fab = γ ab − γ b − γ a
γa
γa cohesion
∆Faa = −2γ a
γa
1/ 3
4(VV
s l)
γ ab = γ a + γ b − 2Φ(γ aγ b ) 1/ 2
Φ=
(Vs1/ 3 + Vl1/ 3 )
2
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June 29, 2005
General expression for the interfacial tension
Fowkes has suggested that total free energy at a surface is the sum of contributions
from the different intermolecular forces at the surface.
γ sl = γ s + γ l − 2 (γ γ )
d d 1/ 2
l s γ sl = γ s + γ l − 2 (γ γ )
d d 1/ 2
l s − 2 (γ γ )
a a 1/ 2
l s
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June 29, 2005
General expression for the interfacial tension
2 2
γ 12 = ⎡⎢(γ )
d 1/ 2
− (γ ) ⎤ + ⎡( γ
d 1/ 2
⎥⎦ ⎢⎣ )
a 1/ 2
− (γ ) ⎤
a 1/ 2
⎥⎦
⎣ 1 2 1 2
Liquid γ1 γ 1d γ 1a
n-hexane 18.4 18.4 0
cyclohexane 25.5 25.5 0 γ 12 = ⎡⎢(γ 1d )
1/ 2 2
− (γ 2d ) ⎤⎥ + ⎡⎢ (γ 1a ) − (γ 2a ) ⎤⎥
1/ 2 1/ 2 1/ 2 2
⎣ ⎦ ⎣ ⎦
γ 12 = ⎢⎡ (γ 1d )
⎣
1/ 2
⎣
1/ 2
1/ 2
⎦ ⎣
2 1/ 2
2
− (γ 2d ) ⎤⎥ + ⎡⎢ (γ 1a ) − (γ 2a ) ⎤⎥
1/ 2
⎦ ⎣
− (γ 2d ) ⎥⎤ + ⎢⎡(γ 1a ) − (γ 2a ) ⎥⎤
1/ 2
⎦
1/ 2
2
1/ 2
⎦
2
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June 29, 2005
Calculation of force components of surface tension
Measure the interfacial tension by one of the available methods (γ 12 = 50.2 mJ/m )
2
•
2 2
γ 12 = ⎡⎢(γ )
d 1/ 2
− (γ ) ⎤ + ⎡(γ
d 1/ 2
⎥⎦ ⎢⎣ )
a 1/ 2
− (γ )
a 1/ 2⎤
⎥⎦ γ 1 = γ 1d + γ 1a
⎣ 1 2 1 2
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June 29, 2005
Conclusions
• Rules are given for the estimation of the interfacial tension and the
contact angle of a liquid on a solid
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June 29, 2005
Extra slides: estimation of Φ
∞ ∞ ∞ ∂ε ab
Fab ( z ) = 2π ∫ nbd j ∫ f df ∫ na dr
z j f ∂r
∞ ∞ ∞ ∞ ∂ε ab
−∆Fab ( z ) = 2π ∫ dx∫ nbd j ∫ f df ∫ na dr
z x j f ∂r
A B
Lennnard-Jones ε ab = − 6 + m
ab ab
Carrying out the integrations and equating the net force to 0
when z=dAB (equilibrium distance) potential r r
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June 29, 2005 Girifalco and Good (1956)
1) Floating needles l
(F1+F2) cosθ
θ F
F2 1
W
end view of needle
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June 29, 2005 F1=F2=γl