Miscibility

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Diesel fuel is immiscible in water. The bright rainbow pattern is the result of thin-film interference.

Miscibility (/mɪsɪˈbɪlɪti/) is the property of two substances to mix in all proportions (that

is, to fully dissolve in each other at any concentration), forming
a homogeneous mixture (a solution). The term is most often applied to liquids but also
applies to solids and gases. For example, water and ethanol are miscible because they
mix in all proportions.[1]
By contrast, substances are said to be immiscible if there are certain proportions in
which the mixture does not form a solution. For one example, oil is not soluble in water,
so these two solvents are immiscible. As another example, butanone (methyl ethyl
ketone) is significantly soluble in water, but these two solvents are also immiscible
because they are not soluble in all proportions. [2]

Contents

 1Organic compounds
 2Metals
 3Effect of entropy
 4Determination
 5See also
 6References

Organic compounds[edit]
In organic compounds, the weight percent of hydrocarbon chain often determines the
compound's miscibility with water. For example, among the alcohols, ethanol has
two carbon atoms and is miscible with water, whereas 1-butanol with four carbons is
not.[3] 1-Octanol, with eight carbons, is practically insoluble in water, and its immiscibility
leads it to be used as a standard for partition equilibria.[4] The straight-chain carboxylic
acids up to butanoic acid (with four carbon atoms) are miscible with water, pentanoic
acid (with five carbons) is partly soluble, and hexanoic acid (with six) is practically
insoluble,[5] as are longer fatty acids and other lipids; the very long carbon chains of
lipids cause them almost always to be immiscible with water. Analogous situations
occur for other functional groups such as aldehydes and ketones.

Metals[edit]
Immiscible metals are unable to form alloys with each other. Typically, a mixture will be
possible in the molten state, but upon freezing, the metals separate into layers. This
property allows solid precipitates to be formed by rapidly freezing a molten mixture of
immiscible metals. One example of immiscibility in metals is copper and cobalt, where
rapid freezing to form solid precipitates has been used to create granular
GMR materials.[6]
There also exist metals that are immiscible in the liquid state. One with industrial
importance is that liquid zinc and liquid silver are immiscible in liquid lead, while silver is
miscible in zinc. This leads to the Parkes process, an example of liquid-liquid extraction,
whereby lead containing any amount of silver is melted with zinc. The silver migrates to
the zinc, which is skimmed off the top of the two-phase liquid, and the zinc is then boiled
away, leaving nearly pure silver.[7]

Effect of entropy[edit]
Main article: Hydrophobic effect
If a mixture of polymers has lower configurational entropy than the components, they
are likely to be immiscible in one another even in the liquid state. [8][9]

Determination[edit]
Miscibility of two materials is often determined optically. When the two miscible liquids
are combined, the resulting liquid is clear. If the mixture is cloudy the two materials are
immiscible. Care must be taken with this determination. If the indices of refraction of the
two materials are similar, an immiscible mixture may be clear and give an incorrect
determination that the two liquids are miscible. [10]

See also[edit]
 Miscibility gap
 Emulsion
 Heteroazeotrope
 ITIES
 Multiphasic liquid

References[edit]
 Wikimedia Commons has
media related to Immiscible
liquids.

1. ^ Wade, Leroy G. (2003).  Organic Chemistry. Pearson

Education. p. 412.  ISBN  0-13-033832-X.
2. ^ Stephen, H.; Stephen, T. (2013-10-22).  Binary Systems:
Solubilities of Inorganic and Organic Compounds, Volume
1P1. Elsevier.  ISBN  9781483147123.
3. ^ Barber, Jill; Rostron, Chris (2013-07-25).  Pharmaceutical
Chemistry. OUP Oxford.  ISBN  9780199655304.
4. ^ Sangster, J. (1997-05-28).  Octanol-Water Partition
Coefficients: Fundamentals and Physical Chemistry. John
Wiley & Sons. ISBN 9780471973973.
5. ^ Gilbert, John C.; Martin, Stephen F. (2010-01-
19).  Experimental Organic Chemistry: A Miniscale and
Microscale Approach. Cengage Learning. p. 841.  ISBN  978-
1439049143.
6. ^ Mallinson, John C. (2001-09-27). Magneto-Resistive and
Spin Valve Heads: Fundamentals and Applications. Academic
Press. p.  47. ISBN 9780080510637.
7. ^ Rich, Vincent (2014-03-14).  The International Lead Trade.
Woodhead Publishing. pp.  51–52.  ISBN  9780857099945.
8. ^ Webb, G. A. (2007).  Nuclear Magnetic Resonance. Royal
Society of Chemistry. p. 328.  ISBN  9780854043620.
9. ^ Knoll, Wolfgang; Advincula, Rigoberto C. (2013-02-
12).  Functional Polymer Films, 2 Volume Set. John Wiley &
Sons. p. 690.  ISBN  9783527638499.
10. ^ Olabisi, Olagoke; Adewale, Kolapo (1997-03-
19).  Handbook of Thermoplastics. CRC Press.
p. 170.  ISBN  9780824797973.

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Multiphasic liquid
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A multiphasic liquid is a mixture consisting of more than two immiscible liquid phases.
Biphasic mixtures consisting of two immiscible phases are very common and usually
consist of an organic solvent and an aqueous phase ("oil and water").
Multiphasic liquids can be used for selective liquid-liquid extractions or for decorative
purposes, e.g. in cosmetics.
While it is possible to get multilayered phases by layering nonpolar and aqueous
phases of decreasing densities on top of each other, these phases will not separate
after mixing like true multiphasic liquids.

Contents

 1Compositions
o 1.1Triphasic systems
o 1.2Tetraphasic systems
o 1.3Higher order multiphasic systems
 2See also
 3References
 4External links

Compositions[edit]
The following types of multiphasic liquids exist:
Triphasic systems[edit]
 Nonpolar solvent / aqueous biphasic mixture
e.g. using hexane, heptane, cyclohexane, or mineral
oil as the nonpolar solvent
o Nonpolar solvent / polar solvent / salt /
water
e.g. 100 ml mineral oil, 100 ml isopropanol,
75 ml water, 35 g calcium chloride
 o Nonpolar solvent / water-
soluble polymer A, water-soluble
polymer B, water
e.g. hexane, polyethylene oxide, dextran, water
o Nonpolar solvent / water-soluble
polymer / salt / water
e.g. hexane, polyethylene oxide, sodium sulfate, water
o Nonpolar solvent A / solvent B /
polymer soluble in solvent B and water
/ water
e.g. heptane, dichloromethane, polyethylene oxide,
water
 Nonpolar solvent A / solvent B / polymer soluble in
solvent B and water / salt / water
e.g. 16.3% heptane, 21.7% dichloromethane, 9.5%
polyethylene oxide, 51.5% water, 0.1% sodium sulfate
 Nonpolar solvent / hydrophobic salt / water
e.g. iso-octane, Aliquat 336 (methyltrioctylammonium
chloride, a phase transfer catalyst), water [1]
o or: cyclohexane,  bmim-PF6 (an ionic liquid), water [2]
 Hydrophobic ionic liquid – water – hydrocarbon
systems
o e.g. 1-butyl-3-methylimidazolium
hexafluorophosphate – water –
cyclohexane
Tetraphasic systems[edit]
 Nonpolar solvent A / solvent B / polymer soluble in
solvent B and water / salt / water
e.g. 10.9% heptane, 15.5% dichloromethane, 7.1%
polyethylene oxide, 66.5% sodium sulfate (> 0.1%) in
water

 Nonpolar solvent / Polar solvent / salt / water /

Fluorinated solvent
o e.g. Hexane, isopropanol, brine,
perfluoromethylcyclohexane
Higher order multiphasic systems[edit]
A system with eight phases is known. In addition to a hydrocarbon and an aqueous
phase, it includes a silicone oil, an aniline and a fluorous phase, and
molten phosphorus, gallium and mercury.[1]
See also[edit]
 Separating funnel

References[edit]
1. ^ Reichardt, C. (2006). Solvents and Solvent Effects in Organic
Chemistry. Wiley-VCH. pp. 9–10. ISBN 3-527-60567-3.

External links[edit]
 Chem. Commun. 1998, 787 Polymer induced
multiphase generation in water/organic solvent
mixtures. Strategies towards the design of triphasic
and tetraphasic liquid systems (pdf)
 US patent application 20050215443 Multiphase
aqueous cleansing composition
 (Movie) Oil and water separation by molecular
dynamics simulation
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ITIES
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In electrochemistry, ITIES (interface between two immiscible electrolyte solutions)[1]
[2][3]
 is an electrochemical interface that is either polarisable or polarised. An ITIES is
polarisable if one can change the Galvani potential difference, or in other words the
difference of inner potentials between the two adjacent phases, without noticeably
changing the chemical composition of the respective phases (i.e. without noticeable
electrochemical reactions taking place at the interface). An ITIES system is polarised if
the distribution of the different charges and redox species between the two phases
determines the Galvani potential difference.
Usually, one electrolyte is an aqueous electrolyte composed of hydrophilic ions such
as NaCl dissolved in water and the other electrolyte is a lipophilic salt such
as tetrabutylammonium tetraphenylborate dissolved in an organic
solvent immiscible with water such as nitrobenzene, or 1,2-dichloroethane.

Contents
  1Charge transfer reactions of an ITIES
 2Four-Electrode cell
 3Ion partition coefficient and ion distribution coefficient
 4Distribution potential
 5See also
 6References

Charge transfer reactions of an ITIES[edit]

Three major classes of charge transfer reactions can be studied at an ITIES:

 Ion transfer reactions

 Assisted ion transfer reactions
 Heterogeneous electron transfer reactions

The Nernst equation for an ion transfer reaction reads

,
where  is the standard transfer potential defined as the
Gibbs energy of transfer expressed in a voltage scale.
The Nernst equation for a single heterogeneous
electron transfer reaction reads
,
where  is the standard redox potential for the
interfacial transfer of electrons defined as the
difference the standard redox potentials of the two
redox couples but referred to the aqueous standard
hydrogen electrode (SHE).

Four-Electrode cell[edit]
To study charge transfer reactions of an ITIES, a
four-electrode cell is used.
Two reference electrodes are used to control the
polarisation of the interface, and two counter
electrodes made of noble metals are used to
pass the current. The aqueous supporting
electrolyte must be hydrophilic, such as LiCl,
and the organic electrolyte must be lipophilic,
such as tetraheptylammonium tetra-
pentafluorophenyl borate.

Ion partition coefficient and ion

distribution coefficient[edit]
Contrary to a neutral solute, the partition
coefficient of an ion depends on the Galvani
potential difference between the two phases:

Distribution potential[edit]
When a salt is distributed between two
phases, the Galvani potential difference is
called the distribution potential and is
obtained from the respective Nernst
equations for the cation C+ and the anion
A– to read
where γ represents the activity
coefficient.

See also[edit]
 Ionic partition diagram
 Distribution law
  Ion transport number

References[edit]
1. ^ Hung, Le Quoc (1980-12-23).
"Electrochemical properties of the
interface between two immiscible
electrolyte solutions: Part I.
Equilibrium situation and galvani
potential difference". Journal of
Electroanalytical Chemistry. 115 (2):
159–174. doi:10.1016/S0022-
0728(80)80323-8. ISSN 0022-
0728.
2. ^ Hung, Le Quoc (1983-07-08).
"Electrochemical properties of the
interface between two immiscible
electrolyte solutions: Part III. The
general case of the galvani potential
difference at the interface and of the
distribution of an arbitrary number of
components interacting in both
phases". Journal of Electroanalytical
Chemistry. 149 (1–2): 1–
14. doi:10.1016/S0022-
0728(83)80553-1. ISSN 0022-
0728.
3. ^ Samec, Zdenek (1988-06-01).
"Electrical double layer at the
interface between two immiscible
electrolyte solutions". Chemical
Reviews. 88 (4): 617–
632. doi:10.1021/cr00086a003.

Categories: 
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 Phases of matter
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