Critical Analysis of a Scientific Paper

“Interfacial Thermodynamics of Surfactants at the CO2-

Water Interface” Sandro R. P. da Rocha and Keith P.
Johnston, Langmuir 16, 3690-3695 (2000)

Olaleye Oladiran,
CHEN 568A
9/28/2010

1
 Motivation
The principle of interfacial tension,
surfactant adsorption, and the
thermodynamics of the formation of
microemulsion based on the structure
of surfactants is useful in the design of
surfactants for processes involving
water-CO2 interface.

Examples of such processes are

cleaning, wetting, fabric softener,
paints, adhesives and cosmetics.

http://www.acmite.com/market-reports/chemicals/world-surfactant-market.html 2
The principle of Interfacial Tension

The property of the surface of a liquid that allows it to resist an

external force is termed surface tension. It is revealed, for example, in
floating of some objects on the surface of water. When this tension is
observed between dissimilar liquids e.g. oil and water, it is called
interfacial tension.
http://www.acmite.com/market-reports/chemicals/world-surfactant-market.html 3
Surfactant adsorption

Surfactants are compounds that lower the surface tension of a liquid, allowing
easier spreading, and lowering of the interfacial tension between two liquids, or
between a liquid and a solid.
Surfactants are made up of two parts: the hydrophilic and the hydrophobic
part. They reduce the surface tension of water by adsorbing at the liquid-gas
interface.
Surfactant used: PerfluoropolyetherCOO-NH4
http://www.acmite.com/market-reports/chemicals/world-surfactant-market.html 4
 Interfacial Tension Measurement
No detailed
experimental
procedure

Laplace Equation:
2
P     gz
R0
Where,
ΔP = Interfacial Pressure drop
R0 = Radius of curvature at the
apex of the drop,
z = Vertical distance from apex.

γ = Surface Tension
Figure 1:Schematic diagram of the tandem high-pressure
variable-volume pendant drop tensiometer. 5
Interfacial Thermodynamics
Determination of Surface excess concentration (Γ):

d   RT d ln x -----(1) Gibbs Adsorption Equation

Where, x = Surfactant mole fraction

Determination of the Surface Pressure versus Area Isotherms:

   RT ln(1  C S / a) -----(2) Surface Equation of State

Where,
Γ∞ = Limiting adsorption at the saturated interface,
a = Surfactant concentration required to reach half Γ∞,
∏ = γ0 – γ; γ0 = Binary CO2-water interfacial tension.

Determination of the Maximum Saturation of Surfactant

Monolayer (Γm) and the Critical Microemulsion Concentration
(cμc) by Graphical Analysis:
The above parameters were determined from the curve of interfacial
tension (mN/m) versus log [Cs(M)]
6
Main Points
1. Based on experimental results and molecular surface equation of state,
the area per surfactant at the critical microemulsion concentration is much
larger at the water-CO2 vs water-oil interface for two primary reasons:
a. The first reason is that γ0 (without surfactant) is much smaller for the
water-CO2 interface; thus, less surfactant is required to lower γ to a
typical value for microemulsion, 1 mN/m.
b. The second reason is the larger entropic contribution to the free
energy of the monolayer, due to greater penetration of the small CO2
molecules in the tail region relative to larger oils.

2. The value of the critical microemulsion concentration, using the the

surfactant perfluoropolyetherCOO-NH4+, varies from 0.26 to 1.5mM for a
temperature range of 25-65 °C.

3. The enthalpy of microemulsion formation is -37.6 kJ/mol.

7
 Abstract

The author’s abstract

(on the front page of the paper).

8
 Abstract

The author’s abstract

(on the front page of the paper).

Ambiguous statement
(At 20oC, γ0, water = 72.8 mN/m while γ0, hydrocarbon oil = 20-25 mN/m.

9
 Abstract

The author’s abstract

(on the front page of the paper).

Ambiguous statement
(At 20oC, γ0, water = 72.8 mN/m while γ0, hydrocarbon oil = 20-25 mN/m.

No experimental values for the water-oil interface.

10
Graph of Interfacial Tension versus log of Surfactant
Concentration

Graphical
Analysis
(On page 3 of
the Paper)

11
Graph of Interfacial Tension versus log of Surfactant
Concentration

Graphical
Analysis
(On page 3 of
the Paper)

Values obtained at 45 and 65oC are of relatively high correlation

12
Graph of Interfacial Tension versus log of Surfactant
Concentration

Graphical
Analysis
(On page 3 of
the Paper)

Values obtained at 45 and 65oC are of relatively high correlation.

Values obtained at 25oC have low correlation.

13
Graph of Interfacial Tension versus log of Surfactant
Concentration

Graphical
Analysis
(On page 3 of
the Paper)

Values obtained at 45 and 65oC are of relatively high correlation.

Values obtained at 25oC have low correlation.

The post-cμc line is generally horizontal.

It does not slope towards the x-axis.
14
 Results

Calculated
values
(Page 3)

Insufficient temperature range for surfactant

characterisation

15
 Results

Calculated
values
(Page 3)

Values cannot be trusted especially at 25oC

16
 Results

Calculated
values
(Page 3)

Determination of area is not explicit enough in the paper

17
 Results

Calculated
values
(Page 3)

Values cannot be trusted due to low correlation

18
 Results

Calculated
values
(Page 3)

Values cannot be trusted due to low correlation

19
Results

Calculated
values
(Page 3)

No mention of how enthalpy change was determined

20
Critical Analysis Summary
STRENGTHS
Addressed an important subject
matter in the chemical industry
Applied a good number of
chemical engineering principles to
deal with the subject matter
Explicit historical background
Adopted both experimental,
theoretical and graphical analysis
Worked with an ideal range of
temperature values.
WEAKNESSES
Absence of theory background
Absence of required mathematical
model
No explicit experimental procedure
Unjustified experimental values
Ambiguity of statement
Inadequate assumptions
No new model
21
Citation Report

The paper has been cited 61 time since 2000.

It was cited 13 times in 2003.
Average citations per year is 5.55

22
23
24
Classification of Surfactants

25
Theoretical Background
-- (1)

--- (2)

--- (3)

--- (4)

--- (5)

--- (7)

chemweb.calpoly.edu/dgragson/Teaching/.../SurfTens_New.pdf 26
 Surface tension vs Concentration

chemweb.calpoly.edu/dgragson/Teaching/.../SurfTens_New.pdf 27
Surface tension vs Natural Logarithm of
Concentration

chemweb.calpoly.edu/dgragson/Teaching/.../SurfTens_New.pdf 28
29
 Methods of Measuring Surface Tension
Du Noüy Ring method: measures maximum pull exerted on the ring by the
surface.
Wilhelmy plate method: Measures force due to wetting
Spinning drop method: The diameter of a drop within a heavy phase is
measured
Pendant drop method: Geometry of a drop is analyzed optically.
Bubble pressure method: Maximum pressure of each bubble is measured.
Drop volume method: Measures time between drops produced
Capillary rise method: Measures capillary height
Stalagmometric method: A method of weighting and reading a drop of liquid.
Sessile drop method: Measures the contact angle
Test ink method: A method for measuring surface tension of substrates using
test ink
30