Scribd
Upload
19 views4 pages

AnswersOttoChapter5 Part1 2023

Uploaded by

baggie.baggie.bags
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
19 views4 pages

AnswersOttoChapter5 Part1 2023

Uploaded by

baggie.baggie.bags
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 4

Let´s suppose that the oil (in this case:n-hexanol) forms a drop at the air-water interphase.

Defining
the contact angle 𝜃, the force balance derived from the surface tension of the different phases:

𝛾𝑊𝐴 = 𝛾𝑂𝑊 + 𝛾𝑂𝐴 cos 𝜃.

As cos 𝜃 ≤ 1, one gets

𝛾𝑊𝐴 ≤ 𝛾𝑂𝑊 + 𝛾𝑂𝐴 .

Defining the wetting parameter S as

𝑆 = 𝛾𝑊𝐴 − 𝛾𝑂𝑊 − 𝛾𝑂𝐴 ,

one can conclude that if a droplet forms, 𝑆 ≤ 0, while if a film is formed, 𝑆 ≥ 0.

Initially,

𝑆0 = 𝛾𝑊𝐴 − 𝛾𝑂𝑊 − 𝛾𝑂𝐴 = (72.8 − 6.8 − 24.8) mN m−1 = 41.2 mN m−1 ≥ 0.

That is, a film is formed. However, after a while, water gets saturated with hexanol. Thus, instead of
water a new phase is present in the system, with a surface tension (at its interface with water) of
𝛾𝑊(𝑂)𝐴 = 28.5 mN m−1 , hence

𝑆0 = 𝛾𝑊(𝑂)𝐴 − 𝛾𝑂𝑊 − 𝛾𝑂𝐴 = (28.5 − 6.8 − 24.8) mN m−1 = −3.1 mN m−1 ≤ 0,

That is, finally a droplet is formed .

Note: in the above analysis, several factors were neglected. First, not only water gets saturated with
hexanol, but hexanol gets saturated with water as well. Second, these mixed phases have not only a
different surface tension at their interface with water, but on their interface with each other as well,
which also have to be determined.
Two processes occur simultaneously: first, as the concentration of the surfactant is well below the
critical micellar concentration, it steadily increases and accordingly some of the surfactant molecules
will be at the water-air interface. After reaching the critical micellar concentration, the concentration
of the surfactant monomer does not increase any more, thus neither does its concentration on the
surface.

Note: understanding the following derivation of the used Equation (1) is not obligatory. If you do
not have enough time/energy, you can directly proceed after Equation(1).

The Gibbs adsorption isotherm, which describes the surface tension change as a function of the
change of the corresponding chemical potentials, is as follows:
𝑛

� ΓiS 𝑑µ𝑖 + 𝑑γ = 0.
𝑖=1

(The derivation of this equation can be found e.g. on the Wikipedia page
nSi
http://en.wikipedia.org/wiki/Gibbs_isotherm). Here ΓiS =
𝐴
, the surface concentration of the ith
compound, 𝑑µ𝑖 is the change of the chemical potential of the the ith compound, and 𝑑γ is the change
in surface tension.

If only one solute is present in the system, two compounds have to be regarded (the solute and the
solvent):

Γ1S 𝑑µ1 + Γ2S 𝑑µ2 + 𝑑γ = 0.

Now, if the spatial starting point of the air-water interphase is chosen in a way that the concentration
of the solvent is zero at this interface (the borders of the interface can be chosen arbitrarily), one can
abandon the indexes and write:

𝑑γ = −Γ𝑑µ .

The chemical potential depends on the activity of the corresponding compound as follows:

µ = µ0 + 𝑅𝑇ln𝑎 ,

where µ0 is the chemical potential at standard conditions and a is the activity.


𝑑γ = −Γ𝑅𝑇𝑑ln𝑎 .

In case of diluted solutions, the activity is approximately equal to the concentration in the bulk
phase. In the case of an ionic surfactant, the dissolution of 1 equivalent of surfactant results in the
presence of 2 equivalents of ions (1 eq cation and 1 eq anion) in solution, thus:

𝑑γ𝑐𝑎𝑡 = −Γ𝑅𝑇𝑑ln𝑐𝑐𝑎𝑡 = −Γ𝑅𝑇𝑑ln𝑐

𝑑γ𝑎𝑛 = −Γ𝑅𝑇𝑑ln𝑐𝑎𝑛 = −Γ𝑅𝑇𝑑ln𝑐

, where 𝑑γ𝑐𝑎𝑡 and 𝑑γ𝑎𝑛 are the the change in surface tension due to the change in cation and anion
concentration, respectively. Adding up these two equations, one finally gets:

𝑑γ = 𝑑γ𝑐𝑎𝑡 + 𝑑γ𝑎𝑛 = −2 Γ𝑅𝑇𝑑ln𝑐 𝐄𝐪𝐮𝐚𝐭𝐢𝐨𝐧(𝟏)

a) Determination of the CMC

As seen from Eq (1), the surface tension decreases with increasing surfactant concentration. For the
sake of simplicity, we use here a linear and not a logarithmical fit (of course, on the data points which
are still in the region of decreasing surface tension):

In the case of the last 4 data points, the surface tension does not change any more, the average value
is 39.72 mN.m-1, so the equation to be solved is:
𝑐
70.43 − 4.08 × = 39.72,
𝑚𝑀

which gives cCMC =7.53 mM.

b) Determination of the area of one SDS molecule on the interface


Equation (1) can be re-written as:
1 𝑑γ
Γ=−
2 𝑅𝑇 𝑑ln𝑐
Performing now a linear fit on the lnc values (in the region where the surface tension still decreases):

The slope of the line is -16.22 mN.m-1, which gives:

1 𝑑γ 1
Γ=− = − × −16.22𝑚𝑁 𝑚−1
2 𝑅𝑇 𝑑ln𝑐 2 × 8.314 𝐽 𝑚𝑜𝑙−1 𝐾−1 × 293 𝐾
= 3.33 × 10−6 𝑚𝑜𝑙 𝑚−2 = 3.33 × 10−6 𝑚𝑜𝑙 𝑚−2 × 6.02 × 1023 𝑚𝑜𝑙 −1
= 2 × 1018 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑚−2 .

The reciprocal value of the result gives the area of one molecule at the interface:

𝐴 = Γ −1 = 5 × 10−19 𝑚2 = 50 Å2 .

You might also like