The Origins of Surface and Interfacial Tension

The Molecular Origin of Surface Tension

y Imbalance of

intermolecular forces exists at the liquid-air interface y Kla= the surface tension that exists at the liquid-air interface

Surface Tensions of Pure Liquids at 293 K

Substance Acetone Benzene Carbon Tetrachloride

K / (10-3 N/m)
23.7 28.8 27.0

Methylene Iodide 50.8 Water Methanol n-Hexane 72.8 22.6 18.4

Alternative Explanation of Surface Tension

y Suppose we have a thin liquid film suspended

on a wire loop as follows

l = length of wire liquid film dA

expanded liquid film

dx f = force needed to move wire dw = dG = KdA

Measurement of Surface Tension

y Early measurements

even pure liquids has been described as a comedy of errors y Today possible to routinely measure the surface tension of liquids and solutions to an accuracy of + 0.05 mN/m

Capillary Action
y The tendency of

liquids to rise up in narrow tubes capillary action. y Due to the phenomenon of surface tension.

The Complication of Contact Angles

y The balance of

forces that results in a contact angle, Uc. y The contact angle gives information on the wettability of a surface.

Capillary Rise
y The pressure exerted by a column of liquid is balanced by the hydrostatic pressure. y This gives us one of the best ways to measure the surface tension of pure liquids and solutions.

2 r ! Vgh

Vgh ! 2r

The Wilhelmy Plate Method

a) detachment

b) static

The Du Noy Ring Method

y Measure the force required to pull the ring

from the surface of the liquid or an interface by suspending the ring from one arm of a sensitive balance
F R

Wat r

The Correction Factor

y The correction factor takes into account of the small

droplets that are pulled up by the ring when it detaches from the surface

Drop Weight/Drop Volume Method

y A stream of liquid (e.g., H O) falls slowly

from the tip of a glass tube as drops

Drop Weight Method

y The drop weight is found by
y Counting the number of drops for a specified liquid

volume passing through the tip; y Weighing a counted number of drops

VVg= mg = TrVgFK y A correction factor - F F w r/v1/3

Sessile Drop Method

y The surface tension of a liquid may be

obtained from the shape and size of a sessile drop resting on a horizontal surface

Sessile Drop
Ue

h Surface

Sessile Drop Method (Cont d)

y Three techniques for obtaining the surface tension

from the image of the sessile drop

y Measure the height of the top of a large sessile drop

above its maximum diameter. y Estimate the shape factor of the drop from the coordinates of the drop profile. y Fit the drop profile to ones that are generated theoretically.

Drop Profiles
y The sessile drop method may also be used to obtain

the value of the equilibrium contact angle.

Contact angle, Ue < 90 Ue

The Maximum Bubble Pressure Method

y The maximum pressure required to force a

bubble through a tube is related to the surface tension of the liquid.

gas stream

l b

The Bubble Pressure Technique

y The maximum bubble pressure is related to

the surface tension of the liquid as follows P = g l (V + K / b

y (V = the density difference between the liquid and

the vapour y b = radius of curvature at the apex of the bubble y l = hydrostatic height to the bottom of the bubble y g = 9.807 m / s

The Differential Maximum Bubble Pressure Method

y Two probes of different diameters. y A differential pressure is generated, (P.
gas stream

t z1 b1 b2 z2

The Differential Bubble Pressure Equations

y The maximum bubble pressure is related to the

surface tension of the liquid as follows (P = g z1 (V + K / b1 - g z (V + K / b

y (V = the density difference between the liquid and

the vapour of the first bubble y (V = the density difference between the liquid and the vapour of the second bubble y z1 = the distance from the tip to the bottom, of the first bubble y z = the distance from the tip to the bottom, of the second bubble

Methods of Measuring Surface Tension

Method Pure Liquids Solutions

Wilhelmy Plate

quick and easy to operate

Good, suitable when ageing occurs n/a Good when surface ageing occurs Poor when surface ageing occurs n/a if U{ Good when ageing occurs

Du Nuy Ring Satisfactory Sessile Drop Very Good

Drop Weight

Suitable

Capillary Height Bubble pressure

Very Good Very Good

Molecular Contributions to an Oilwater Interfacial Tension

Koil Koil x Kd
1/2 ater)

Oil Phase

= Oil

Koil x Kd

1/2 ater)

= water

Water Phase
ater

The Work of Adhesion

y Ener

required t reversi l ull rt t f r unit surf ce reas f each f the t substances.

Wadh ! K 1  K 2  K 12
K 12 K1 K2

The Work of Cohesion

 Defined in terms of the energy required to reversibly separate a column of a pure liquid to form two (2) new unit surface areas of the liquid.

Wcoh ! 2K 1
K1 K1

The Definition of the Surface Excess

y To obtain a clearer meaning of the surface excess,

let s consider the following system.

Ci

CJ(1) + zo z CJ(2)

The Spreading Coefficient

y Substance (usually liquid) already in contact with

another liquid (or solid) spreads

y increases the interfacial contact between the first and

second liquid (or the liquid and the solid) y decreases the liquid-vapour interfacial area

Three Cases of Spreading

y Place a drop of oil on a clean water surface y Define the spreading coefficient
dG ! Kwa  ( Kwo  K oa ) S=dAwo
S = dG ! Ww o  Wo o d Aw o
Koa Oil Kwa Kow Water Air

y The spreading coefficient (to be defined later) is

indicative of the difference in the adhesive forces between liquid 1 and liquid (or the solid), and the cohesive forces that exist in liquid 1

y S > 0, spreading occurs spontaneously

K ow K oa
Air Water Oil

y S < 0, formation of oil lenses on surface

Oil
K wa K oa K ow

Ue
Water

Air

y A third possibility is the a monolayer spreads until

spreading is not favourable; excess oil is left in equilibrium with the spread monolayer

Oil

Koa Kow Koa

Air

Kwo

Koa

Kwo

Water

Wetting Ability and Contact Angles

y Wetting - the displacement of a fluid (e.G., A gas

or a liquid) from one surface by another fluid y Wetting agent - a surfactant which promotes wetting y Three types of wetting
 Spreading wetting  Immersional wetting  Adhesional wetting

Spreading Wetting
y Liquid already in contact with another liquid (or solid) wets

the surface of the second component (liquid or solid) by spreading across the surface of the second component y Using the spreading coefficient defined earlier, we find that the liquid spreads spontaneously over the surface when S >0

S =
Ksl

dG ! dAwo

wa

(

wo

oa

)
Liquid

K la

Air

Solid

Solid Surfaces
y Consider the case of a liquid drop placed on a

solid surface (non-spreading)

K

la

Liquid
K

sl

sa

C s Ue

Ue
K

sa
Solid

Air

y For a liquid drop making a contact angle U with

the solid surface

Cos Ue =

sa


la

sl

Solid Surfaces/Different Contact Angles

y Examine the following two surfaces.

A spreading drop p Ue < 90

Ue

y A drop with a contact angle << 90r

Ue

The Derivation of Young s Equation

Kla Ue Ksa Kls Ue

dA change in the liquid-solid interfacial area = dA change in the solid-air interfacial area = - dA change in the liquid-air interfacial area = dA Cos Ue

Young s Equation
y For a liquid (as a drop or at at the surface of a

capillary) making a contact angle Uc with the solid surface

K sa ! K sl  K la os Uc
os U c

K sa K la

K sl

Adhesional Wetting
y The ability of the liquid to wet the solid will be

dependent on its ability to stick to the solid

liquid droplets
Kla Ksl

Solid Surface

droplets adhering to solid surface

from the Young Equation

 (G A WA ! ! K sa  K la  K sl A

K sa ! K sl  K la Cos Ue
W A ! K la (1  CosUe )

Note: the solid is completely wetted if Ue = 0; it is partially wetted for finite values of Ue.

Immersional Wetting
y Immerse a solid substance in a pure liquid or

solution
y area of the solid-air interface decreases y interfacial contact between solid and liquid is

increased

Ksa

solid particle

Water

Ksl

immersed solid particle

y Work required to immerse the solid in the liquid y Examine the difference ion the solid-air surface tension and the solid-liquid interfacial tension

( W ! A

! K sa  K sl

y Applying young s equation

 (G A

la

os U e

If sa > sl, spontaneous wetting while if sa < sl, work must be done to wet the surface

Degrees of Liquid-solid Interaction

Wadh adh > coh adh < coh adh < coh

(wetG <0 <0 >0

S spont. non-spont. non-spont.

Cos Ueq 1 0 -1

Ueq 0 90r 180r

Surfactants
y What is a surfactant?

Surface active agent

Headgroup

Tail

Heads or Tails?
y Headgroup

hydrophilic functional group(s) y Tail hydrocarbon or fluorocarbon chain y Typical headgroups (charged or uncharged)
y Sulfate y Sulfonate y Trimethylammonium y Ethylene oxide y carboxybetaine

Properties of Surfactant Molecules

y Aggregate at various interfaces due to the

hydrophobic effect
y Air-water interface y Oil-water interface

y Form aggregates in solution called micelles at a

specific concentration of surfactant called the critical micelle concentration (the cmc)
y Micellar aggregates are known as association colloids

Applications of Surfactants
y Surfactants are an integral part of everyday life;

they are formulated into a wide variety of consumer products

y Shampoos y Dish detergents y Laundry detergents y Conditioners y Fabric softeners y Diapers y Contact lens cleaners

Applications of Surfactants (Cont d)

y Surfactants are also widely used in industry due

to their ability to lower surface and interfacial tensions and act as wetting agents and detergents
y Heavy and tertiary oil recovery y Ore flotation y Dry cleaning y Pesticide and herbicide applications y Water repellency

Interfacial Properties of Surfactant Molecules

y Surfactants

used in a large number of applications due to their ability to lower the surface and interfacial tension y Gibbs energy change to create a surface of area dA

dG = KdA

y Using the Gibbs adsorption equation for a 1:1

ionic surfactant

dK ! 2RT +surf d lnCsurf

Where +surf = nWsurf / A

Plot of K vs. Log Csurf for Sodium Dodecylsulfate at 298.2 K



K dyne/cm  cmc     log Csurf 

Surfactants and Detergents

y Detergency - the theory and practice of soil

removal from solid surfaces by chemical means y Early detergents

y Ancient Egypt - boiled animal fat and wood ashes to

make soap

y Past thirty years

y Made significant progress in our understanding of

detergency on a molecular level