Bondoc, Kristopher Jayson C.

27 June 2012
CH 45 A: Physical Chemistry 1, Laboratory Instructor: Erwin P. Enriquez, Ph.D.

Experiment 1: Surface Tension and Size of Surfactant Molecules

Derived Data Tables

Vol
Total Surface
Added C of C of Average Density Density Capillary
ln C Mass of Tension
n-buOH Solution Solution Height ρ ρ Radius
Solution γ
Stock

mL mol/L mol/m3 m g g/mL kg/m3 m N/m

0.00 0.00 0.0E+00 n/a 0.0382 49.79 0.9958 995.8 0.000381 0.0721
0.50 0.11 1.1E+02 4.69 0.0333 49.69 0.9938 993.8 0.000381 0.0620
0.90 0.20 2.0E+02 5.28 0.0307 49.61 0.9922 992.2 0.000381 0.0569
1.85 0.40 4.0E+02 6.00 0.0289 49.42 0.9885 988.5 0.000381 0.0534
2.75 0.60 6.0E+02 6.39 0.0280 49.25 0.9849 984.9 0.000381 0.0516
3.70 0.80 8.0E+02 6.69 0.0262 49.06 0.9812 981.2 0.000381 0.0481

Vol
Ad-
Uncertainty Uncertainty
ded Uncertainty Uncertainty Uncertainty
for mass Uncertainty Uncertainty for
n- for mass for Total for Surface
n-butanol for Density for Radius Average
buta- water Mass Tension
stock Height
nol
Stock

mL g g g kg/m3 m m N/m
0.00 0.0076 n/a n/a n/a 0.0012 0.000012 0.0001
0.50 0.0077 0.016 0.018 1.06 0.0012 0.000013 0.0031
0.90 0.0077 0.016 0.018 1.05 0.0012 0.000015 0.0031
1.85 0.0078 0.016 0.018 1.05 0.0012 0.000015 0.0031
2.75 0.0078 0.016 0.018 1.05 0.0012 0.000016 0.0031
3.70 0.0079 0.016 0.018 1.04 0.0012 0.000017 0.0030

Parameters for ln C vs. γ graph:

Equation: y = -0.0064x + 0.0915
Linearity: R² = 0.9798
Slope: -0.0064
-
Radius of surfactant molecule: m
Results and Discussion

At the surface of a liquid, its molecules experience an imbalance in forces due to its unbalanced
intermolecular forces as opposed to the balanced intermolecular forces experienced by its molecules
in the bulk. Hence, the molecules above the liquid (at the surface) tend to become pulled by the bulk,
an thu , a “ten i n” due t unba anced f rce happen hi phen en n can be exp ained by the
idea of surface tension. Surface tension is defined to be the force per unit length needed to increase
the surface area of the liquid to oppose the formation of a smaller surface area due to the pull
produced by the bulk. This term can also be called surface energy since increasing the surface area of
the liquid requires energy input.

Surface tension is computed using a formula derived from the Laplace Equation. The derived
formula is:

ρ hr
γ here ρ den ity, acce erati n due t ra ity, h hei ht, r radiu

It is important to take note that Eq. 1 was derived by linking surface tension with pressure
associated when a liquid rises in a capillary with radius r.

In the experiment, several standard solutions were prepared by mixing water and n-butanol. N-
butanol is a surfactant: it forms a layer above the liquid (in this case, water) due to its molecular
structure. It contains a hydrophilic head (-OH, in this case) that layers itself along the surface of the
liquid and it has a hydrophobic tail (alkyl chain) that may extend out of the bulk water phase, into
the air or into the bulk phase. This characteristic of a surfactant therefore modifies the surface
tension of the liquid, and the relationship of the increasing concentration of surfactant with the
surface tension is observed for this experiment. Also, the size of the surfactant molecule was
-
determined to be m as computed using the excess concentration value obtained. Excess
concentration is defined to be the concentration of surfactant molecules on the surface of the liquid
(surfactants generally go mostly on the surface of the liquid).

Assumptions
Several assumptions were made along the course of the experiment. To obtain the mass of the
standard solutions at a particular temperature value, their density were obtained (either by literature
or by experiment). See Calculations for specific examples.

Also, the value for the surface tension of water at 29.5 degrees Celsius is not available, so what was
used for the calculations is the surface tension value of water at 30.0 degrees Celsius.

On the other hand, it is assumed that the surfactant molecules are spherical and closely packed on
the surface. This approximation is done to simplify rigorous calculations. However, it is important to
know that the surfactant used in the experiment is short chained: the short tail of the surfactant
might affect the order of the molecules, and hence, packing efficiency may not be achieved wholly.

Theory/Principle
As the objective of this experiment requires, a graph of ln C versus surface tension was constructed:
 0.0650

0.0600

Surface Tension (N/m) 0.0550

0.0500 y = -0.0064x + 0.0915

R² = 0.9798
0.0450

0.0400
4.00 4.50 5.00 5.50 6.00 6.50 7.00
ln C (mol/m^3)

Looking on what the graph shows, it can be seen that generally, increasing the concentration of a
surfactant in a liquid decreases its surface tension. By virtue of thinking at a molecular level, the
observed trend is quite reasonable since surfactant molecules tend to layer on the surface, and hence,
the intermolecular forces between the surface molecules of the liquid are disrupted. H-bonds
between those molecules on the surface are interfered by the surfactant molecules, and thus they
tend to lose interaction with each other. As a result, they are pulled towards the bulk, and the
surfactant replaces the surface molecules of the liquid. When the surface molecules become attracted
to bulk, the forces they now experience become more and more balanced and stable since they now
become part of the bulk.

The size of the surfactant molecule is also computed using excess concentration (mol/m^2).
-
Assuming that it is spherical, its radius is equal to m.

Errors and their sources

Uncertainties involved in measurements due to the “ ea urin capacity” f the in tru ent u ed,
propagated uncertainties in derived data due to calculations involving measurements with
uncertainties, and problem with equilibriation (unstability) are some sources of errors for this
experiment. When it comes to equilibriation, stable height difference is difficult to achieve due to the
limitations of the capillary itself. It was observed that the height differences are not constant at times.
To compensate with that problem, what was done was the height differences were measured for
several times until some values agree with one another.

Applications
The concept of lowering the surface tension of a liquid by the use of surfactants are very helpful in a
lot of ways. The most common use of surfactants as surface tension lowering agents is very apparent
in washing our clothes since soap solutions (soap are surfactants) can spread over larger areas due to
decreased surface tension. This helps us wash our clothes efficiently. In soldering, addition of flux
reduces the surface tension of molten tin so it can spread. Surface tension lowering can also be seen
in ducks as they secrete oil from their feathers to help them float on water.
Conclusions
Results have shown that surfactants generally lower the surface tension of the liquid by
interfering with the H-b nd f ater ecu e n the i uid’ urface Due t thi b er ed
interference, water molecules then experience the pull of the bulk molecules and as they become
absorbed by the bulk, the intermolecular forces they experience become balanced.

Calculations

▪▪▪ Calculating the amount of A% n-butanol solution needed to obtain stock solutions in various concentrations:

Note: The reported molar mass of n-butanol in the prelaboratory report is 74.12 g/mol. Apparently,
this value should be 74.14 g/mol (true n-butanol molar mass). Calculations were done for both of
these values and the difference (0.0029) is outside the absolute uncertainty of the measuring
instrument used (±0.02); hence, the error is not significant. Furthermore, the concentrations used in
getting the values for ln C were calculated using the volume added as measured by the pipet.

Assume that A% (v/v) n-butanol solution will be used.

Converting % v/v to mol/L (M1), we get:

For 74.12 g/mol,

n bu n bu n bu n bu
n bu n n bu n bu n bu n

For 74.14 g/mol,

n bu n bu n bu n bu
n bu n n bu n bu n bu n

Using this molar concentration value above (M1), compute for the volume (V1) of the stock needed
to get a V2 mL of M2 mol/L of standard solution.

Here, A=99.4 (as found in the label of the bottle of n-butanol reagent)

▪▪▪ Calculating the actual C (mol/L) of the standard solutions:

Let B = volume (mL) of n-butanol stock added

n bu n bu n bu
n bu t c n bu t c n bu n bu
n
n n

▪▪▪ Calculating for the mean height h in meters:

Given h1, h2, h3 (for trial 1, trial 2, and trial 3, respectively), mean height h in meters can be
calculated as:

h h h de ree c
h in eter
de ree c

▪▪▪ Converting C (mol/L) to mol/m3:

c
c

▪▪▪ Calculating the density ρ of the standard solutions:

a n bu t c a ater
ρ
u e tandard n
n bu t c
a n bu t c n bu t c
n bu t c
ater
a ater n bu t c
ater
n bu t c ater
n bu t c n bu t c
ρ n bu t c ater

▪▪▪ Converting ρ (g/mL) to kg/m3:

ρ c
c

▪▪▪ Calculating the radius r of the glass capillary: