Cohesion, Adhesion, Spreading, and Surfactants

Work of Cohesion and Adhesion

Lets imagine that we have a tube of water or some other pure liquid whose crosssectional area is one cm2. We apply a force to the liquid such that it separates. The work we have done is called the work of cohesion. It is defined as the surface tension times the amount of new area created. Since we have created 2 cm2 of new area the work can be written as:

Wc=2
Let's now imagine that our tube of liquid is made up of two liquids which do not dissolve in each other (oil & water). If we again apply a force along the tube to cause the liquids to separate, we have done three things and the work we have done is called the work of adhesion ( Wa). We have created a one cm2 surface of water, a one cm2 surface of oil and have destroyed a one cm2 interface between water and oil. Work of adhesion is then:

Wa = oil + water - oil/water

The coefficient of each term is one because we either created or destroyed one cm 2 of surface or interface.

Spreading
We can use the two concepts we have just defined to help us understand the spreading of one liquid on another and predict if it would spread spontaneously or not. REMEMBER that if the reaction has a net loss in free energy it will be spontaneous. Spreading can be observed by adding one liquid to the surface of another liquid. The supporting liquid is usually designated with an "s", while the liquid being added to the top by an "l" since it initially forms a lens. Lets examine what happens when benzene is added to the surface of water. There are two possibilities. (One) the benzene can spread over the surface of the water or (two) the benzene will contract into a small lens on the surface of the water. How can we predict which will happen?? We can determine if there is a net loss in free energy and use that result as a way of predicting the outcome of our experiment. Some facts you will need to have to do this are: Water has a surface tension of 72.8 dynes/cm; benzene has a surface tension of 28.9 dynes/cm and the interfacial tension between water and benzene is 35.0 dynes/cm.

Let's ask ourselves some questions. What happens to the water surface when/if the benzene spreads? What happens to the interface between water and benzene if/when the benzene spreads? What happens to the surface of benzene that faces the air if/when the benzene were to spread over the surface of the water? Be prepared to discuss this in class. There is a mathematical relationship which can be used to predict the outcome. It is called the Spreading Coefficient "S" and is defined as;

S = Wa - Wc = s - l - ls
A positive number means that the material will spread, a negative means it will contract, and zero means it will sit there and look at you. Can you emperically derive this expression??? This is not the end of the story. Will benzene spread on water?? After some time, the benzene will begin to saturate the water and the surface tension of water saturated with benzene will change to 62.2 dynes/cm. Now what happens??

SURFACTANTS
Substances which have a tendency to concentrate at the surface or interface are called surface active agents. They can have a number of effects on the nature of the surface. Gibbs (same guy as the Gibbs free energy) observed this and developed a relationship between the surface tension lowering and the excess concentration of surfactants at the surface. This is called the Gibbs adsorption isotherm. The symbol for excess surface concentration is "" and has units of moles/cm2 The equation is: = - c/RT X d/dc Where R is the gas constant, T is the temperature in degrees K, c is the average concentration, and d/dc is the change in surface tension with the addition of a small amount of surfactant. The excess concentration of surfactant at the surface causes some interesting changes in the way the interface or surface acts.

For example, in 1757 Ben Franklin was on a ship going to Europe when he observed that the sea behind the ship calmed when the cook dumped cooking grease on the water. This was a well known fact to those who went to sea, but Franklin(who was the first great american scientist) did something about this observation. He took the second step in the scientific method, he performed an experiment. He found a small lake in England

with a known surface area (1/2 acre) and he placed a small amount of cooking oil on it. He learned that it took only one teaspoonful to calm the entire lake. What can we learn from this story? Can you calculate the cross sectional area of the molecules of cooking oil ? What additional information would you need to know? If we assumed that the cooking oil was made of hydrocarbons with an average molecular weight of 300 and the oil had a density of 0.9g/ml what would be the cross sectional area of the molecules? Agnes Pockels an uneducated woman from lower Saxony, Germany, developed an instrument which allows us to examine the nature of the film that is formed on the surface of water by surfactants. It is called a surface balance. With it she measured surface pressure. We use the symbol "" to represent surface pressure. Surface pressure() = Surface Tension of the pure liquid ()o - the surface tension of the liquid with the surfactant added ()1 If we combine this concept with the Gibbs adsorption isotherm, we come up with the following equation: () A = n R T, where A is the surface area, R is the gas constant and T is temperature in absolute degrees and n is the molar concentration of the surfactant in the surface. What does that equation look like?? Does it help to remember we are working in two dimensions here?? As we compress a gas, we can cause a phase change from gas to liquid. Do you think the same thing can happen with a flim???

HLB - Hydrophilic - Lipophilic Balance

It is useful to correlate the characteristics of surfactants with the properties that are needed to make various heterogenous systems. A common system which is used to do this is the HLB system. The HLB value for a given surfactant is the relative degree to which the surfactant is water soluble or oil soluble. The lower the HLB, value the more lipophilic. The higher the HLB value, the more hydrophilic. I will not go over how these numbers are derived. You can look it up if you like. The range is usually between 1 and 20. Please note the one exception at the bottom of the table.>

HLB Values and the use for those surfactants

HLB VALUE 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 40 USE Antifoaming Agent Antifoaming Agent Antifoaming Agent Emulsifying Agent W/O Emulsifying Agent W/O Emulsifying Agent W/O Emulsifying Agent W/O; Wetting ans Spreading Agents Emulsifying Agent W/O; Wetting and Spreading Agents Emulsifying Agent O/W; Wetting and Spreading Agents Emulsifying Agents O/W Emulsifying Agents O/W Emulsifying Agents O/W Emulsifying Agents O/W ; Detergents Emulsifying Agents O/W ; Detergents Emulsifying Agents O/W ; Detergents Emulsifying Agent O/W ; Detergents: Solubilizing Agents Solubilizing Agents Solubilizing Agents Solubilizing Agents Solubilizing Agents Everything EXAMPLE Oleic Acid Sorbitan Tristearate Glyceryl Monostearate Sorbitan mono-oleate (Span 80) Glyceryl Monostearate Diethylene glycol monolaurate {none} Sorbitan monolaurate (Span 20) Polyethylene lauryl ether(Brij 30) Methyl Cellulose(Methocel15 cps) Polyoxyethylene monostearate (Myrj 45) Triethanolamine oleate Polyethylene glycol 400 monolaurate (none) Polyoxyethylene sorbitan monooleate(Tween 80) Polyoxyethylene sorbitan monolaurate (Tween 20) Polyoxylene lauryl ether(Brij 35) Sodium oleate None Potassium oleate Sodium Lauryl Sulfate (Tide)

In laboratory we used Sodium Lauryl Sulfate for most experiments. It dissolves in water very well and is a common additive to most heterogeneous systems and to almost all common detergents, shampoo etc. However, when we made the 1% surfactant in mineral oil we used Span 80. Why?? The blending of Surfactants with HLB vaules to get a desired HLB mixture is very easy. The HLB values are additive. See page 275 of Ansel.

For example if we want a surfactant mixture with an HLB value of 9 we can blend

surfactants with HLB values of 3 and 11. We use alligation and we now know that we need 6 parts of the HLB 11 surfactant with 3 parts of the HLB 3 surfactant to get our mixture with an HLB value of 9. We can use that mixture to make an oil in water emulsion.

Solid Interfaces
Adsorption at a solid/gas or solid/liquid interface is another important consideration. One use of this property is to remove poisonous levels of drugs and other toxins from the body. We often use activated charcoal as an antidote to poisons. Activated charcoal is fine particles, thus there is a very large surface in a small amount of powder. This powder is not wet by water but has a high affinity for some types of drugs. As an example, the sulfonylureas such as tolbutamide will concentrate on the surface of the activated charcoal. Another example is the common OTC analgesic acetaminophen (what is the trade name?). An overdose of this drug can cause severe liver complications leading to death. A dose of 15 g can kill an adult. (How many tablets would someone have to take to kill themselves?) By administering activated charcoal we can reduce the amount of the dose that is absorbed into the body and some researches have shown that some of the drug will actually cross from the blood supply into the gut. Can you develop a theory that explains this observation??

Wetting Agents
A wetting agent is a surfactant that, when dissolved in water lowers the advancing contact angle and aids in displacing an air phase at the surface and replacing it with a liquid phase. We used the 1% SDS solution in lab to wet sulfur. Try an experiment at home. Find a Teflon (polytetrafluoroethylene) coated fry pan. Place a drop of different liquids on it and observe the shape of the drop. The lower the surface tension of the liquid the smaller the angle between the liquid and the pan. Some examples are listed below Liquid Contact Angle Water 63 degrees Glycerin 55 degrees Ethylene Glycol 40 degrees Mineral Oil 14 degrees Surfactants also have some direct therapeutic effects. They can act as antibacterials. How does a surfactant kill a microb??

Other Interesting Properties of Surfactants

Surfactants often carry a charge and thus they impart a charge to the surface that they attach to. What effect will this have on the properties of the particles with a film of surfactant on it?. Zeta potential is defined as the electrical potential between two charged particles. Its strength of attraction or repulsion varies with distance between the charge and size of the charge as well as the nature of the fluid the particle is suspended in. What use is that to our understanding of how a heterogeneous system is stabilized?.

What do you expect will happen if we used two surfactants in combination instead of just one?. What is the impact of the size of the polar head group?. What would be the benefit of a mixed film of both positively charged surfactants and negatively charged surfactants?? What would be the downside to that type of a film?