Cloud Point Extraction

Cloud point extraction
Dr. K. P. Shadangi
Assistant Profesor
Department of Chemical Engineering
VSSUT,Burla.
2/23/2019 1
Definition
• The cloud-point temperature (CPT), or equivalently the
lower critical con solute temperature, is the specific
temperature at which the clear micellar solution of a
weekly polar surfactant, such as nonionic or zwitterionic
surfactant, becomes turbid upon heating or cooling
• Every non ionic surfactant will be having its own

characteristic cloud point temperature.
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• It is the temperature beyond which the aqueous solution
of a non ionic surfactant separates into two phases,
• one is surfactant rich phase,
• another is surfactant lean phase or the aqueous phase,
• this particular temperature is known as the cloud point

corresponding to that particular non ionic surfactant.
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Mechanism of Phase separation
• Phase change about CPT is reversible. The possible
mechanisms of phase separation are as follows:
• (i) For non-ionic surfactant, dielectric constant of water
decreases as temperature increases. This reduces
interaction between hydrophilic part of surfactant and
water. Thus, above CPT, dehydration occurs in the
external layer of micelle of non-ionic surfactants.
• (ii) At lower temperature, intermicellar repulsive force
is dominant and beyond CPT, it becomes attractive.
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Mechanism of solubilization of
solutes in coacervate phase
• For non ionic surfactants, the hydrophilic core is
surrounded by a mantle of aqueous hydrophilic
chain.
• Non polar solutes are solubilized within
hydrophobic core.
• Hydrophobicity increases beyond CPT as
extensive dehydration of polyoxyethylene chains
occurs.
• Thus, the organic solutes are solubilized within
micelles core to a large extent beyond CPT.
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Applications:
• Removal of polycyclic aromatic hydrocarbon,
polychlorinated compounds, vitamins dyes,
concentration of dilute solutions of heavy
metals, etc. In fact, this method is utilized
quite frequently for analysing extremely dilute
solutions by concentration them.
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Typical non-ionic surfactants
• Triton X-100 (Iso octyl phenoxy polyethoxy
ethanol): molecular weight (Mw): 628; CMC=
2.8*10-4 (M); CPT= 640C.
• Triton X-114(Octyl phenol poly ethylene glycol
ether): Molecular weight: 537; CMC= 2.1*10-4
(M); CPT= 370C.
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Removal of chrysoidine dye
• A typical concentration of 100 ppm of the dye is
selected. Both, TX-114 and TX-100 are employed
for removal of dye. Depending on their cloud
point temperature, the operating temperature for
TX-114 is selected as 400C and that for TX-100 is
700C. Thus, the operating temperature of the
former surfactant is lower. It is observed that
surfactant concentration about 0.25 (M) is able to
remove more than 95% of dye. In fact, the dye
extraction is about 95% for TX-100 and that for
TX-114 is about 100%.
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Variation of extraction of dye with
surfactant concentration
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Surfactant partition coefficient (m)
• The partition coefficient is defined as the ratio of
concentration of surfactant in coacervate and dilute phase
• More micelles are formed in rich phase so that more
extraction will takes place.
• At constant temperature, surfactant concentration in dilute
phase is nearly constant (near CMC).
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operating conditions
• surfactant concentration
• operating temperature
• operating pH
• operating electrolyte concentration
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Effect of temperature on extraction
(i) At high temperature, CMC of non-ionic surfactant decreases.
(ii) At high temperature, non-ionic surfactant becomes hydrophobic due to
dehydration of ether oxygen.
So, number of micelles increases and solubilization capacity increases with
temperature.
Therefore, the extraction efficiency of the system increases with temperature
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Effect of pH
• At higher pH means greater than 6, the dye is deprotonated.
• The dye looses its ionic character, it becomes more hydrophobic and gets
more solubilized in the micelles at higher pH value, the extraction is more;
• Extraction increases significantly at higher pH values.
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Effect of added salt or the electrolyte
concentration
• Salts decease the cloud point of surfactants due to salting out effect and it
promotes dehydration of ethoxy group on the outer surface of micelles
• if the temperature increase slightly, more solubilization will occur in the
micelles
• extent of extraction or extent of solubilization in the micelle is favored at
high salt concentration.
• So, since the extent of solubilization is more, extent of extraction is also
more.
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Solubilization isotherm
• Moles of solute solubilized per mole of surfactant can be
expressed in terms of solubilization isotherm.
• Solubilization isotherm of chrysoidine dye at various
temperature for TX-100 is shown here
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Design of Cloud Point Extractor
• The isotherm can be expressed using the following Langmuir type

expression
• Where, both m and n are functions of temperature.

• For chrysoidine- TX100 system
• Ce is final solute concentration in dilute phase
• Fc is the Variation of fractional coacervate volume

• V0 is initial volume of the extractor
• C0 is initial concentration of solute
• Vd is the volume of dilute phase
• Cs is the molar concentration of feed surfactant
Or Cs is the initial feed concentration of surfactant
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• Fractional coacervate volume is a function of surfactant concentration
• The parameters a and b in above equation are functions of temperature.

• These variations are generally linear as
• The parameters P, Q, R and S are functions of feed concentration of the

surfactants ond they are almost constant.
• Knowing the variation of various process parameters with the operating
variables, it is possible to design a cloud point extractor.
• For TX-100
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Uses
• Cloud point extractions can be utilized to

remove all these pollutants selectively from
the aqua stream
• Removal of polycyclic aromatic hydrocarbon,
poly chlorinated compounds, dyes, heavy
metals
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Cloud point extraction

• Every non ionic surfactant will be having its own

• one is surfactant rich phase,

• another is surfactant lean phase or the aqueous phase,

• this particular temperature is known as the cloud point

• Extraction increases significantly at higher pH values.

• The isotherm can be expressed using the following Langmuir type

• Where, both m and n are functions of temperature.

• Fc is the Variation of fractional coacervate volume

• The parameters a and b in above equation are functions of temperature.

• The parameters P, Q, R and S are functions of feed concentration of the

• Cloud point extractions can be utilized to

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