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Surface tension lowering effect of surfactant

The surface tension () of a liquid is often defined as the force, which acts at right
angles to any line of unit length on the liquid surface. The most frequently used method for
surface tension determination is the drop-volume or drop-weight method.
Drops of a liquid are allowed to detach themselves slowly from the tip of a vertically
mounted narrow tube, and they are weighed. At the point of detachment, the weight of a drop
is equal to the surface force acting on the circular rim of the tube: mg = 2 r , where m is
the mass of the drop, g is the acceleration due to gravity (g = 9.81 m s-2), r is the radius of the
tube and is the surface tension. In practice, this can be used as a relative method to estimate
the surface tension of dilute solutions. For surfactant solutions, weigh the mass of x water
drops and the same amount of surfactant solution drops. If the same dropper was used, we
can write (mwater/x) g = 2r water
(msolution/x) g = 2r solution
Dividing the 2 equation by the 1st one and arrange the equation, we get
nd

solution = water msolution / mwater

Surface tension of solutions (solution) can be calculated with the knowledge of the surface
tension of water (water = 72 mN/m at 25oC).

Exercise 1.

Surface tension lowering effect of dilute surfactant solutions

Means: a dropper, 4 pieces of vial, 4 pieces of 25-ml baker, 2 pieces of 10-ml measuring
pipet, balance (+0,01 g)
Materials: surfactant solutions, e.g. 100 mmol/l NaDS, 50 mmol/l Na-oleate, 10 mmol/l
HDPCl or HDPBr. Choose one of the solutions and use that in the Exercise 2, too.

Weigh the vials on the balance with accuracy 0.01 g! Dilute a surfactant solution so that the
concentration reaches the critical micelle formation concentration (cM). E.g., dilute the 100
mmol/l NaDS solution to ten times, i.e., to 10 mmol/l, since the cM of NaDS is 6-8 mmol/l;
the 50 mmol/l Na-oleate to 20 times, i.e., to 2,5 mmol/l, since the cM of Na-oleate is 1
mmol/l; 10 mmol/l HDPCl or HDPBr solutions to ten times, i.e., to 1 mmol/l, since their cM
is about 0.6 mmol/l. Make dilution series (e.g., 10x, 5x, 2x) from the dilute surfactant
solutions into the beakers. Rinse the dropper with distilled water at least 10 times. Drop 20
drops distilled water into one of the vials and close it, then rinse the dropper with the most
dilute surfactant solution, and drop its 20 drops into the next vial and close it. Repeat this
process with the more concentrate solutions, too. Weigh the vials containing the 20 drops of
distilled water and surfactant solutions, respectively. Determine the mass of liquids!
IMPORTANT: Do not use detergent to washing-up! Start dropping with distilled water and
proceed it in the direction from dilute to concentrate solutions.

Calculate the surface tensions of solutions. Summarize the data into a Table:
Surfactant solution Mass of 20 drops Estimated surface
concentration, mmol/l liquid, g tension, mN/m
0 72.0 (25oC)
Evaluate the change in surface tension with increasing surfactant concentration!
 d

Skip over this part!

funnels, filter papers,

between 2 and 6 g of the

 Erlenmayer
0.5 - 0.5 g of salicylic

5
During ultrasonication, solutions get warm and turbid; therefore each has to be cooled
down in an ice bath. This needs about 10 minutes. Then filter the solutions and use the
clear filtrates for further quantitative analysis.

1-2
Standardize

Summarize the data in a table below!

3
cTween 20 0.1 M NaOH consumption, cm Amount of salicylic acid solubilized
3 3 3 3
Dilution g/100 cm 1 2 3 Average mol in 10 cm g in 10 cm g/100 cm
no
2x
4x
8x

Plot the amount of salicylic acid solubilized (g/100 cm3) in the function of the Tween 20 concentration (g/100 cm3)!
Calculate the MAC value (g benzoic acid solubilized by 1 g of surfactant) of Tween 20!
Questions:
1. Explain the molecular structure of association colloids! What are the molecular structural
criteria of association?
2. Explain the amphiphilic character!
3. Classify the surfactants according to the molecular structure! Write 1-1 expample, too!
4. Write some examples of natural amphiphatic compounds!
5. What does micelle mean? What are the conditions under which micelles form in
surfactant solutions?
6. What does HLB mean? Explain the HLB scale!
7. How does the solubility of ionic and non-ionic surfactants change with temperature?
8. List the most important properties of surfactants!
9. How can you simply measure and calculate the surface tension lowering effect?
10. What is the cM? And how can it be determined?
11. What kinds of physical properties as a function of concentration are suitable for cM
determination?
12. Explain the concentration dependence of surface tension of surfactant solutions!
13. Explain the concentration dependence of specific conductivity of surfactant solutions!
14. What is solubilization? How can you determine the solubilized amounts? What does
MAC value mean?
15. Explain the possible locations of different solubilizates in the micelles of ionic and non-
ionic surfactants?