SURFACE TENSION OF LIQUIDS

Surface tension is a property that arises from the mismatch in intermolecular forces experienced at a liquid/vapor interface. In the bulk portion of a liquid a molecule experiences intermolecular forces from all directions around it. In water, these forces are predominately strong hydrogen bonds. Since the molecule is surrounded from all directions, all of the pair-wise intermolecular attractive forces cancel each other out and there is no net motion of the molecules other than random thermal motion. At the surface of the liquid, however, a very different situation is present. A water molecule at the surface will experience attractive hydrogen bonds back towards the bulk of the water, but there are no offsetting forces on the air side of the interface (or more accurately, the liquid-air intermolecular forces are much weaker than the liquid-liquid forces). This leads to a pulling in of the surface towards the bulk of the liquid. It also creates a gradient in the Gibbs Free Energy at the surface.
Molecules in Bulk Liquid Molecules on Surface of Liquid

Because of this mismatch between intermolecular forces, energy in the form of work is required to expand the surface. This work is described by: (1)
dw = d ,

= surface tension

where dw = incremental work required to increase the surface area ( ) of the liquid by an incremental amount. The surface tension () is the proportionality constant between the change in surface area and work. has units of energy/area. The SI units for surface tension are N/m (or J/m2). Surface tension is often listed, however, in cgs units of dynes/cm, but this can be translated to SI units according to 1 dyn/cm = 1mN /m. Note that surface tension represents an alternative type of work to the PV work that is the normal focus of attention in our class. Surface tension affects a number of the handling and performance characteristics of a liquid. Examples include capillary action, wetting of surfaces, and drop formation. The latter is the effect that surface tension has on a liquids desire to form spherical droplets in air. Since positive work is required to increase the surface area of a liquid, anything that can be done to reduce the surface area will lead to negative work, i.e. lower free energy. A sphere represents the geometry with the smallest possible surface area for a given volume. Wetting of a support surface is the opposite effect, where lower surface tensions mean that a liquid is more likely to spread and wet the entire surface of a supporting substrate like glass, rather than a high- liquid beading up on the surface.
Gentry, 2008

Surfactants Because of its strong polar and hydrogen bonds, water has a high surface tension. (72 dyn/cm at 20C) Compare this to nonpolar liquids like benzene (28.9 dyn/cm) or olive oil (32.0 dyn/cm) that do not have as large a intermolecular force mismatch at the surface of the liquid due to their much weaker attractive forces. The surface tension of water can be lowered by the addition of surfactant. Surfactants are amphiphilic molecules that can be thought of as hydrophobic/hydrophilic two-ended molecules. One end of the molecule is usually polar in nature, for example a sulfate anion. The other end of the molecule is usually nonpolar, for example a long alkane chain.
Sodium Dodecyl Sulfate (SDS), C12H25OSO3 Na+ O CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2 O-S-O O Nonpolar (Hydrophobic) Polar (Hydrophilic)

Surfactants are effective surface-active agents in that they act to stabilize what would otherwise be incompatible phases at a polar/nonpolar interface. For example, their presence in a dish detergent acts to help disperse grease in water by forming a surfactant layer at the surface of the oil droplets. The hydrophobic (NP) end of the surfactant adsorbs to the oil layer, while the hydrophilic (P) end provides a compatible interaction with the surrounding water thus acting as a bridging layer.
Surfactant
H2O H2O

NP P
H2O

Oil

H2O

Surfactants have a similar effect on water/air surfaces since air is considered to be highly nonpolar. This stabilization of the water/air boundary has the end result of lowering the surface tension of the liquid.
air liquid
H2 O H2O H2 O

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The reduction of surface tension depends on the concentration of surfactant. At very low concentrations, the surface tension will be close to that of the pure liquid. As more surfactant is added, more and more surfactant is able to stabilize the surface, thus continuously lowering the surface tension. A plateau is reached, however, when additional surfactant is no longer able to lower the surface tension. This is because at the Critical Micelle Concentration (CMC), the surfactants reach their saturation point in the liquid and begin to self-associate (form micelles) in the liquid phase. Any additional surfactant that is added after this point will add to the micelles, not to the water phase, and thus will not further increase the surface stabilization. The result is that a graph of surface tension versus surfactant concentration will show two types of behavior above and below the CMC.
Low Concentration << CMC Med. Concentration < CMC High Concentration > CMC

air liquid

air liquid

air liquid

micelle

pure liquid

Surf. Tens.

no micelles

micelles

Gibbs isotherm CMC

ln (Surfactant Concentration)

In the region below the CMC where adding surfactant still lowers the surface tension, the relationship between concentration and surface tension () is given by the Gibbs Isotherm.1 The equation calculates , which is the excess solute concentration at the surface as compared to what the concentration would have been if the bulk concentration had been maintained at the surface. can be either positive or negative, with = 0 corresponding to a solute having intermolecular forces the same as the solvent. For materials with a nonpolar component, is positive since there is a shift of the material towards the nonpolar surface and away from the polar solvent. This in turn weakens the surface tension by reducing the mismatch in hydrogen bonding at the surface. (2)

1 d 2 = excess surface-area concentration of solute (moles/m ) RT d ln( C ) T ,P

with R = Gas Constant (J/molK), T = temperature, and C = bulk concentration (moles/m3). This equation assumes dilute, ideal solutions. is constant under these conditions, therefore ln(C) vs. should give a linear relationship below CMC.

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EXPERIMENTAL METHODOLOGY DU NOUY TENSIOMETER We will use a DuNouy tensiometer (also known as a ring tensiometer) to measure surface tension in our samples. It operates by measuring the force needed to pull a platinum-iridium ring away from the surface of a liquid. The metal is easily wet by most liquids. The ring starts at the surface of the liquid. As the ring is slowly pulled out of the liquid in the vertical direction, the liquid attempts to keep contact with the metal. As the ring continues to be pulled further from the initial surface, the liquid continues to maintain contact until the amount of increased surface area becomes too much to be maintained under the surface tension of the liquid. At that point it catastrophically breaks away from the ring and restores back to a normal flat liquid surface.

Top View

Side View

The surface tension in the ring tensiometer is given by the expression:2 (3)

F 4 R

Cf

where F = maximum force (at breaking), R = radius of the ring. Cf is a correction factor based on the shape of the liquid being held in the air, and is normally close to 1.0. The DuNouy tensiometer that we will be using has already been calibrated to compensate for this factor in dilute water solutions, and thus gives a direct read on the surface tension of the liquid (in mN/m).

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EXPERIMENTAL METHODOLOGY SPECTROSCOPIC DETERMINATION In addition to using the DuNuoy tensiometer to measure the physical properties of the solution, we will also use a spectroscopic technique to look at how analyte molecules interact with surfactant solutions.3-5 Acridine orange is an organic dye molecule that is used to stain nucleic acids in biological samples. It can also be used, however, to probe whether or not micelles are present, and hence determine the critical micelle concentration.

(CH3)2 N

N Acridine Orange (AO)

N(CH3)2

Its usefulness stems from the inclination of the hydrophobic dye molecules to self-associate and form dimer aggregates when only limited surfactant is available in the aqueous solution. If surfactant micelles are present in the solution, however, the dimers break apart and the dye goes back to being single molecules dispersed in separate micelles.4
Dimer Acridine Orange (AO) Limited Surfactant Present Monomeric Acridine Orange Surfactant > CMC air liquid
AO AO AO AO AO AO AO AO AO

micelle

The dimers are usually constructed of two AO molecules stacked one on top of the other.
N N

What is important for the technique is that the optical absorption and emission properties for monomic-AO and dimerized-AO are different. One can monitor the fluorescence intensity as a function of surfactant concentration to find at what point micelles begin to form and alter the optical properties. This occurs at the CMC. It will manifest as the point at which the intensity begins to rapidly increase although there still is a stoichiometric effect from whether enough micelles are present near the CMC to absorb all of the AO present.
Fluorescence Intensity Monomer Dye Dimerized Dye

CMC

Surfactant Concentration

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SAMPLES: A stock solution of 0.0100M SDS has been prepared. a) Accurately pipet 10 ml of 1*10-4 M acridine orange into each of eight 100 mL flasks b) Add stock SDS solution in amounts necessary to reach final SDS concentrations of 2*10-5, 4*10-5, 6*10-5, 8*10-5, 1*10-4, and 2*10-4 M SDS, unless otherwise instructed by your professor. c) Dilute to the mark with water. TENSIOMETER PROCEDURE: The DuNouy tensiometer (CSC Scientific Inc., Model 70535) is a sensitive instrument and needs to be treated with care. - Do not touch the circular part of the ring ! The ring is expensive and easily distorted. - Slowly turn the dial and watch to insure that you do not take the instrument outside of its range it has a thin wire that it twists to provide the force and the wire can break under too much tension. 1) Zero the instrument by hanging the ring in air. Turn the dial slowly until the lever arm is horizontal relative to the leveling mirror. Loosen the thumbscrew on the pointer at the bottom of the dial and set pointer to zero. 2) Fill clean 50ml beaker with sample to within 1 of top. Adjust height of sample platform so that lever arm is approximately horizontal when the ring is at the surface of the liquid. Ring should be located in center of beaker, well away from sides. 3) Begin to slowly raise the arm. You must continually readjust the height of the beaker so that the arm remains horizontal. 4) Continue raising the arm until the ring suddenly breaks free of the liquid. 5) The surface tension can be measured directly off of the dial, with the instrument providing surface tension in units of mN/m (or dyn/cm). 6) Take a total of 3 replicates for each sample. The numbers should all be clustered within 1 unit of each other. 7) Water should have a surface tension of 72.8 dyn/cm. You can use the theoretical number to correct for any minor inaccuracies in instrument calibration by calculating a linear correction value, Cf. Use this correction factor for the rest of your results. (4)

theor = exp tl Cf

Notes: When switching between liquids, make sure to carefully clean the sample beaker so that there is no carryover contamination. It does not take much stray surfactant to affect your results, and surfactant tends to remain attached to hydrophobic surfaces like glass. Measure your samples from most dilute to most concentrated in order to minimize carry-over contamination. The ring can be cleaned by holding in a flame. Measure the surface tension for pure water and for each solution. *** For the SDS samples, if all of your samples have plateaued at 30-35 dynes/cm or if none of your samples have reached the plateau, then you will need to adjust to new concentrations.

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FLUORESCENCE PROCEDURE We will use the Hitachi fluorescence spectrometer to measure the absorbance spectrum for the mixed solutions. 1) Turn the instrument on by first using Power switch all the way in front left corner of instrument, then push green lamp button to the right, then on/off Main switch further to the right. After the instrument has been turned on, and only then, turn the computer on and start the FL Solutions software program. 2) Set Method by going to software button on right side of display: General Tab: Wavelength Mode Instrument Tab: Emission Scan Excitation (Ex) Wavelength = 470nm Emission (Em) Wavelengths = 480 800nm Excitation and Emission Slits = 5nm Scan speed = 240nm/min Report Tab: Wavelength range = 480-800nm 3) To record a spectrum a) Go to Sample (on right side of panel) to name the spectrum b) Do a Pre-Scan to allow instrument to select appropriate sensitivity settings c) Hit the Measure button to collect data 4) To save the spectrum a) Go to Save As b) Select .txt as file type so that will be able to open data later with Excel. 5) Close spectrum window Collect spectra for each of your samples. You will need to determine the maximum peak intensity for each of the samples. Do this by selecting the wavelength where the intensity reaches a peak for samples above CMC. Then determine the intensity at this wavelength for all of the other samples. Plot the intensity as a function of SDS concentration. Include representative spectra in your report for at least one sample above the CMC and one sample below the CMC.

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DATA ANALYSIS: Recalculate concentrations in units of molarity.

AO For DuNuoy Data micelle Acridine Orange A) Plot the surface energy results on a vs. ln(conc.) graph. (AO) Draw separate straight lines through your data above and below the CMC. Surfactant No B) Based on the intersection of interpolated lines, what is the value for the critical Surfactant > CMC micelle concentration? Report this tensiometer CMC value. C) Determine the slope of the straight line for data having concentrations less than the CMC. Use this slope to calculate .

For Spectroscopic Data A) Plot intensity at 530nm as a function of ln(SDS conc.) Draw separate straight lines through the data above and below the CMC. Do not include the most dilute sample if higher intensity the system needs a small amount of SDS present to form dimers in solution. B) Determine the transition point on the plot. Report this concentration as the spectroscopic CMC. Compare and contrast the CMC numbers that you obtained using the two different procedures.

C.W. Garland, J.W. Nibler, D.P. Shoemaker, Experiments in Physical Chemistry, 7th ed., McGraw Hill (New York, 2003). 2 F. Daniels, JW Williams, P Bender, RA Alberty, CD Cornwell, JE Harriman, Experimental Physical Chemistry, 7th Ed., McGraw-Hill Book Company (New York, 1970). 3 Miyoshi, N., Hara, K. Yokoyama, I., Tomita, G. Fududa, M., Photochem. and Photobiol. 47, 1988, 685. 4 Encyclopedia of Surface and Colloid Science, ed. P. Somasundaran, (CRC Press), 2006, pp 391-394. 5 CHM 317H1 Molecular Fluorescence, /www.chem.utoronto.ca/coursenotes/CHM317/pages/D_fluor.pdf (accessed Aug, 2008).

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