Heteroazeotrope

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A heteroazeotrope is an azeotrope where the vapour phase coexists with two liquid
phases. Sketch of a T-x/y equilibrium curve of a typical heteroazeotropic mixture

Phase diagram of a heteroazeotrope.

Contents

 1Examples of heteroazeotropes
 2Continuous heteroazeotropic distillation
 3Batch heteroazeotropic distillation
 4References
 5See also

Examples of heteroazeotropes[edit]
 Benzene - Water NBP 69.2 °C
 Dichloromethane - Water NBP 38.5 °C
 n-Butanol - Water NBP 93.5 °C
 Toluene - Water NBP 82 °C

Continuous heteroazeotropic distillation[edit]

Heterogeneous distillation means that during the distillation the liquid phase of the
mixture is immiscible. In this case on the plates can be two liquid phases and the top
vapour condensate splits in two liquid phases, which can be separated in a decanter.
The simplest case of continuous heteroazeotropic distillation is the separation of a
binary heterogeneous azeotropic mixture. In this case the system contains two columns
and a decanter. The fresh feed (A-B) is added into the first column. (The feed may also
be added into the decanter directly or into the second column depending on the
composition of the mixture). From the decanter the A-rich phase is withdrawn as reflux
into the first column while the B-rich phase is withdrawn as reflux into the second
column. This mean the first column produces "A" and the second column produces "B"
as a bottoms product. In industry the butanol-water mixture is separated with this
technique.

At the previous case the binary system forms already a heterogeneous azeotrope. The
other application of the heteroazeotropic distillation is the separation of a binary system
(A-B) forming a homogeneous azeotrope. In this case an entrainer or solvent is added
to the mixture in order to form an heteroazeotrope with one or both of the components
in order to help the separation of the original A-B mixture.

Batch heteroazeotropic distillation[edit]

Batch heteroazeotropic distillation is an efficient method for the separation of azeotropic
and low relative volatility (low α) mixtures. A third component (entrainer, E) is added to
the binary A-B mixture, which makes the separation of A and B possible. The entrainer
forms a heteroazeotrope with at least one (and preferably with only one (selective
entrainer)) of the original components. The main parts of the conventional batch
distillation columns are the following: - pot (include reboiler) - column - condenser to
condense the top vapour - product receivers - (entrainer fed) In case of the
heteroazeotropic distillation the equipment is completed with a decanter, where the two
liquid phases are split.

Three different cases are possible for the addition of the entrainer:
1, Batch Addition of the Entrainer: The total quantity of the entrainer is added to the
charge before the start of the procedure.
2, Continuous Entrainer Feeding: The total quantity of the entrainer is introduced
continuously to the column.
3, Mixed Addition of the Entrainer: The combination of the batch addition and
continuous feeding of the entrainer. We added one part of the entrainer to the charge
before the start of the distillation and the other part continuously during distillation.
In the last years the batch heteroazeotropic distillation has come into prominence so
several studies have been published. The heteroazeotropic batch distillation was
investigated by feasibility studies, rigorous simulation calculations and laboratory
experiments. Feasibility analysis is conducted in Modla et al. [1][2] and Rodriguez-Donis et
al.[3] for the separation of low-relative-volatility and azeotropic mixtures by
heterogeneous batch distillation in a batch rectifier. Rodriguez-Donis et al. [4] were the
first to provide the entrainer selection rules. The feasibility methods was extended and
modified by Rodriguez-Donis et al., [5] Rodriguez-Donis et al., (2005), Skouras et al., [6]
[7]
 and Lang and Modla.[8] Varga [9] applied these feasibility studies in her thesis.
Experimental result was published by Rodriguez-Donis et al., [10] Xu and Wand,[11] Van
Kaam [12] and others.

References[edit]
1. ^ Modla G., P. Lang, K. Molnar, ”Batch Heteroazeotropic
Rectification of a Low Relative Volatility Mixture under
Continuous Entrainer Feeding”, 6-th World Congress of
Chemical Engineering, Melbourne, Australia, (2001).
 2. ^ Modla G., P. Lang, B. Kotai and K. Molnar, ”Batch
Heteroazeotropic Rectification of a Low Relative Volatility
Mixture under Continuous Entrainer Feeding”, AICHE J., 49.,
2533-2552 (2003).
3. ^ Rodríguez-Donis I., V. Gerbaud, and X. Joulia, ”Feasibility
of Heterogeneous Batch Distillation”, AIChE J., 48, 1168-
1178, (2002).
4. ^ Rodríguez-Donis I., E. Pardillo-Fontdevila, V. Gerbaud, and
X. Joulia, ”Synthesis, experiments and simulation of
heterogeneous batch distillation processes”, Comp. Chem.
Eng. 4-6, 799, (2001a).
5. ^ Rodríguez-Donis I., A. J. Esquijarosa, V. Gerbaud, and X.
Joulia, ”Separation of minimum boiling azeotropoc mixtures
by extractive batch distillation processes with heterogeneous
entrainers”, AIChE J., 49, 3074-3083, (2003).
6. ^ Skouras S., V. Kiva and S. Skogestad, “Feasible
separations and entrainer selection rules for heteroazeotropic
batch distillation”, Chemical Engineering Science, 60, 2895.
(2005).
7. ^ Skouras S., S. Skogestad and V. Kiva, “Analysis and
Control of Heteroazeotropic Batch Distillation”, AIChE Journal,
51 (4), 1144-1157. (2005).
8. ^ Lang P., G. Modla: „Generalised method for the
determination of heterogeneous batch distillation regions”,
Chem. Eng. Sci., 61, 4262-4270 (2006)
9. ^ Varga V. "Distillation extractive discontinue dans une
colonne de rectification et dans une colonne inverse". Ph.D.
thesis, INP-Toulouse, France. http://ethesis.inp-
toulouse.fr (2006).
10. ^ Rodríguez-Donis, I., Acosta-Esquijarosa I., Gerbaud V.,
Pardillo-Fondevila E., Joulia, X., "Separation of n hexane –
ethyl acetate mixture by azeotropic batch distillation with
heterogeneous entrainers". Chemical Engineering and
Processing. 44, 131-137. (2005)
11. ^ Xu, S. L. and H. Y. Wand, “Separation of tert-butyl alcohol-
water mixtures by a heterogeneous azeotropic batch
distillation process,” Chem. Eng. Tech., 29, 113 (2006).
12. ^ R. Van Kaam, Rodríguez-Donis I., V. Gerbaud,
"Heterogeneous Extractive Batch Distillation of Chloroform -
Methanol - Water: Feasibility and Experiments", Chem. Eng.
Sci., 63, 78-94, (2008).

See also[edit]
 Azeotrope
 Batch distillation
 Distillation
 Steam distillation
Categories: 
 Phase transitions
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Azeotrope
From Wikipedia, the free encyclopedia
Jump to navigationJump to search
Not to be confused with Allotrope.

Vapour–liquid equilibrium of 2-propanol/water showing azeotropic behaviour

An azeotrope (/əˈziːəˌtroʊp/)[1] or a constant boiling point mixture is a mixture of two or more

liquids whose proportions cannot be altered or changed by simple distillation.[2] This happens
because when an azeotrope is boiled, the vapour has the same proportions of constituents as the
unboiled mixture. Because their composition is unchanged by distillation, azeotropes are also
called (especially in older texts) constant boiling point mixtures.
Some azeotropic mixtures of pairs of compounds are known,[3] and many azeotropes of three or
more compounds are also known.[4] In such a case it is not possible to separate the components by
fractional distillation. There are two types of azeotropes: minimum boiling azeotrope and
maximum boiling azeotrope. A solution that shows greater positive deviation from Raoult's
law forms a minimum boiling azeotrope at a specific composition. For example, an ethanol–
water mixture (obtained by fermentation of sugars) on fractional distillation yields a solution
containing at most 97.2% (by volume) of ethanol. Once this composition has been achieved, the
liquid and vapour have the same composition, and no further separation occurs. A solution that
shows large negative deviation from Raoult's law forms a maximum boiling azeotrope at a
specific composition. Nitric acid and water is an example of this class of azeotrope. This
azeotrope has an approximate composition of 68% nitric acid and 32% water by mass, with
a boiling point of 393.5 K (120.4 °C).

Contents
  1Etymology
 2Types
o 2.1Positive and negative azeotropes
o 2.2Homogeneous and heterogeneous azeotropes
o 2.3Number of constituents
o 2.4Zeotropy
 3Mechanism
o 3.1Condition of existence
o 3.2Minimum-boiling or Positive azeotrope
o 3.3Maximum-boiling or Negative azeotrope
o 3.4Traces
o 3.5Temperature-pressure dependence
 4Separation of constituents
o 4.1Pressure swing distillation
o 4.2Azeotropic distillation
o 4.3Chemical action separation
o 4.4Distillation using a dissolved salt
o 4.5Extractive distillation
o 4.6Pervaporation and other membrane methods
 5Complex systems
 6See also
 7References
 8External links

Etymology[edit]
The term azeotrope is derived from the Greek words ζέειν (boil) and τρόπος (turning) with the
prefix α- (no) to give the overall meaning, "no change on boiling". The term was coined in 1911
by English chemist John Wade[5] and Richard William Merriman.[6]

Types[edit]
Positive and negative azeotropes[edit]

Positive azeotrope – mixture of chloroform and methanol

Negative azeotrope – mixture of formic acid and water

Each azeotrope has a characteristic boiling point. The boiling point of an azeotrope is either less
than the boiling point temperatures of any of its constituents (a positive azeotrope), or greater
than the boiling point of any of its constituents (a negative azeotrope).
A well-known example of a positive azeotrope is 95.63% ethanol and 4.37% water (by mass),
which boils at 78.2 °C.[7] Ethanol boils at 78.4 °C, water boils at 100 °C, but the azeotrope boils at
78.2 °C, which is lower than either of its constituents.[8] Indeed, 78.2 °C is the minimum
temperature at which any ethanol/water solution can boil at atmospheric pressure. In general, a
positive azeotrope boils at a lower temperature than any other ratio of its constituents. Positive
azeotropes are also called minimum boiling mixtures or pressure maximum azeotropes.
In general, a negative azeotrope boils at a higher temperature than any other ratio of its
constituents. Negative azeotropes are also called maximum boiling mixtures or pressure
minimum azeotropes. An example of a negative azeotrope is hydrochloric acid at a concentration
of 20.2% and 79.8% water (by mass). Hydrogen chloride boils at −84 °C and water at 100 °C,
but the azeotrope boils at 110 °C, which is higher than either of its constituents. The maximum
temperature at which any hydrochloric acid solution can boil is 110 °C. Other examples:

 hydrofluoric acid (35.6%) / water, boils at 111.35 °C

 nitric acid (68%) / water, boils at 120.2 °C at 1 atm
 perchloric acid (71.6%) / water, boils at 203 °C
 sulfuric acid (98.3%) / water, boils at 338 °C
Homogeneous and heterogeneous azeotropes[edit]
If the constituents of a mixture are completely miscible in all proportions with each other, the
type of azeotrope is called a homogeneous azeotrope. For example, any amount of ethanol can be
mixed with any amount of water to form a homogeneous solution.
Phase diagram of a heteroazeotrope. Vertical axis is temperature, horizontal axis is composition. The dotted vertical line
indicates the composition of the combined layers of the distillate whenever both layers are present in the original mixture.

If the constituents are not completely miscible, an azeotrope can be found inside the miscibility
gap. This type of azeotrope is called heterogeneous azeotrope or heteroazeotrope. A
heteroazeotropic distillation will have two liquid phases. For
example, acetone / methanol / chloroform form an intermediate boiling (saddle) azeotrope.
For example, if equal volumes of chloroform (water solubility 0.8 g/100 ml at 20 °C) and water
are shaken together and then left to stand, the liquid will separate into two layers. Analysis of the
layers shows that the top layer is mostly water with a small amount of chloroform dissolved in it,
and the bottom layer is mostly chloroform with a small amount of water dissolved in it. If the
two layers are heated together, the system of layers will boil at 53.3 °C, which is lower than
either the boiling point of chloroform (61.2 °C) or the boiling point of water (100 °C). The vapor
will consist of 97.0% chloroform and 3.0% water regardless of how much of each liquid layer is
present provided both layers are indeed present. If the vapor is re-condensed, the layers will
reform in the condensate, and will do so in a fixed ratio, which in this case is 4.4% of the volume
in the top layer and 95.6% in the bottom layer.[9] Such a system of solvents is known as
a heteroazeotrope. Heteroazeotropes are always minimum boiling mixtures.
The diagram illustrates how the various phases of a heteroazeotrope are related.[2][3]

Double azeotrope of benzene and hexafluorobenzene. Proportions are by weight.

Number of constituents[edit]
Azeotropes consisting of two constituents are called binary azeotropes such as diethyl
ether (33%) / halothane (66%) a mixture once commonly used in anesthesia. For
example, benzene and hexafluorobenzene form a double binary azeotrope.
Azeotropes consisting of three constituents are called ternary azeotropes,
e.g. acetone / methanol / chloroform. Azeotropes of more than three constituents are also known.
Zeotropy[edit]
Combinations of solvents that do not form an azeotrope when mixed in any proportion are said to
be zeotropic. Azeotropes are useful in separating zeotropic mixtures. An example is acetic
acid and water, which do not form an azeotrope. Despite this, it is very difficult to separate pure
acetic acid (boiling point: 118.1 °C) from a solution of acetic acid and water by distillation alone.
As progressive distillations produce solutions with less and less water, each further distillation
becomes less effective at removing the remaining water. Distilling the solution to dry acetic acid
is therefore economically impractical. But ethyl acetate forms an azeotrope with water that boils
at 70.4 °C. By adding ethyl acetate as an entrainer, it is possible to distill away the azeotrope and
leave nearly pure acetic acid as the residue.

Mechanism[edit]
Condition of existence[edit]
The condition relates activity coefficients in liquid phase to total pressure and the vapour
pressures of pure components.

Total vapor pressure of mixtures as a function of composition at a chosen constant temperature

Azeotropes can form only when a mixture deviates from Raoult's law, the equality of
compositions in liquid phase and vapor phases, in vapour-liquid equilibrium and Dalton's law the
equality of pressures for total pressure being equal to the sum of the partial pressures in real
mixtures.
In other words: Raoult's law predicts the vapor pressures of ideal mixtures as a function of
composition ratio. More simply: per Raoult's law molecules of the constituents stick to each
other to the same degree as they do to themselves. For example, if the constituents are X and Y,
then X sticks to Y with roughly equal energy as X does with X and Y does with Y. A so-
called positive deviation from Raoult's law results when the constituents have a disaffinity for
each other – that is X sticks to X and Y to Y better than X sticks to Y. Because this results in the
mixture having less total affinity of the molecules than the pure constituents, they more readily
escape from the stuck-together phase, which is to say the liquid phase, and into the vapor phase.
When X sticks to Y more aggressively than X does to X and Y does to Y, the result is a negative
deviation from Raoult's law. In this case because the molecules in the mixture are sticking
together more than in the pure constituents, they are more reluctant to escape the stuck-together
liquid phase.[2]
When the deviation is great enough to cause a maximum or minimum in the vapor pressure
versus composition function, it is a mathematical consequence that at that point, the vapor will
have the same composition as the liquid, resulting in an azeotrope.
The adjacent diagram illustrates total vapor pressure of three hypothetical mixtures of
constituents, X, and Y. The temperature throughout the plot is assumed to be constant.
The center trace is a straight line, which is what Raoult's law predicts for an ideal mixture. In
general solely mixtures of chemically similar solvents, such as n-hexane with n-heptane, form
nearly ideal mixtures that come close to obeying Raoult's law. The top trace illustrates a nonideal
mixture that has a positive deviation from Raoult's law, where the total combined vapor pressure
of constituents, X and Y, is greater than what is predicted by Raoult's law. The top trace deviates
sufficiently that there is a point on the curve where its tangent is horizontal. Whenever a mixture
has a positive deviation and has a point at which the tangent is horizontal, the composition at that
point is a positive azeotrope.[10] At that point the total vapor pressure is at a maximum. Likewise
the bottom trace illustrates a nonideal mixture that has a negative deviation from Raoult's law,
and at the composition where tangent to the trace is horizontal there is a negative azeotrope. This
is also the point where total vapor pressure is minimum.[10]
Minimum-boiling or Positive azeotrope[edit]

Phase diagram of a positive azeotrope. Vertical axis is temperature, horizontal axis is composition.

The boiling and recondensation of a mixture of two solvents are changes of chemical state; as
such, they are best illustrated with a phase diagram. If the pressure is held constant, the two
variable parameters are the temperature and the composition.
The phase diagram on the right shows a positive azeotrope of hypothetical constituents, X and Y.
The bottom trace illustrates the boiling temperature of various compositions. Below the bottom
trace, only the liquid phase is in equilibrium. The top trace illustrates the vapor composition
above the liquid at a given temperature. Above the top trace, only the vapor is in equilibrium.
Between the two traces, liquid and vapor phases exist simultaneously in equilibrium: for
example, heating a 25% X : 75% Y mixture to temperature AB would generate vapor of
composition B over liquid of composition A. The azeotrope is the point on the diagram where
the two curves touch. The horizontal and vertical steps show the path of repeated distillations.
Point A is the boiling point of a nonazeotropic mixture. The vapor that separates at that
temperature has composition B. The shape of the curves requires that the vapor at B be richer in
constituent X than the liquid at point A.[2] The vapor is physically separated from the VLE
(vapor-liquid equilibrium) system and is cooled to point C, where it condenses. The resulting
liquid (point C) is now richer in X than it was at point A. If the collected liquid is boiled again, it
progresses to point D, and so on. The stepwise progression shows how repeated distillation can
never produce a distillate that is richer in constituent X than the azeotrope. Note that starting to
the right of the azeotrope point results in the same stepwise process closing in on the azeotrope
point from the other direction.
Maximum-boiling or Negative azeotrope[edit]

Phase diagram of a negative azeotrope. Vertical axis is temperature, horizontal axis is composition.

The phase diagram on the right shows a negative azeotrope of ideal constituents, X and Y. Again
the bottom trace illustrates the boiling temperature at various compositions, and again, below the
bottom trace the mixture must be entirely liquid phase. The top trace again illustrates the
condensation temperature of various compositions, and again, above the top trace the mixture
must be entirely vapor phase. The point, A, shown here is a boiling point with a composition
chosen very near to the azeotrope. The vapor is collected at the same temperature at point B.
That vapor is cooled, condensed, and collected at point C. Because this example is a negative
azeotrope rather than a positive one, the distillate is farther from the azeotrope than the original
liquid mixture at point A was. So the distillate is poorer in constituent X and richer in constituent
Y than the original mixture. Because this process has removed a greater fraction of Y from the
liquid than it had originally, the residue must be poorer in Y and richer in X after distillation than
before.
If the point, A had been chosen to the right of the azeotrope rather than to the left, the distillate at
point C would be farther to the right than A, which is to say that the distillate would be richer in
X and poorer in Y than the original mixture. So in this case too, the distillate moves away from
the azeotrope and the residue moves toward it. This is characteristic of negative azeotropes. No
amount of distillation, however, can make either the distillate or the residue arrive on the
opposite side of the azeotrope from the original mixture. This is characteristic of all azeotropes.
Traces[edit]
The traces in the phase diagrams separate whenever the composition of the vapor differs from
the composition of the liquid at the same temperature. Suppose the total composition were
50/50%. You could make this composition using 50% of 50/50% vapor and 50% of 50/50%
liquid, but you could also make it from 83.33% of 45/55% vapor and 16.67% of 75%/25%
liquid, as well as from many other combinations. The separation of the two traces represents the
range of combinations of liquid and vapor that can make each total composition.
Temperature-pressure dependence[edit]
For both the top and bottom traces, the temperature point of the azeotrope is the constant
temperature chosen for the graph. If the ambient pressure is controlled to be equal to the total
vapor pressure at the azeotropic mixture, then the mixture will boil at this fixed temperature.
Vapor pressure of both pure liquids as well as mixtures is a sensitive function of temperature. As
a rule, vapor pressure of a liquid increases nearly exponentially as a function of temperature. If
the graph were replotted for a different fixed temperature, then the total vapor pressure at the
azeotropic composition will certainly change, but it is also possible that the composition at which
the azeotrope occurs will change. This implies that the composition of an azeotrope is affected
by the pressure chosen at which to boil the mixture. Ordinarily distillation is done at atmospheric
pressure, but with proper equipment it is possible to carry out distillation at a wide variety of
pressures, both above and below atmospheric pressure.

Separation of constituents[edit]
If the two solvents can form a negative azeotrope, then distillation of any mixture of those
constituents will result in the residue being closer to the composition at the azeotrope than the
original mixture. For example, if a hydrochloric acid solution contains less than 20.2% hydrogen
chloride, boiling the mixture will leave behind a solution that is richer in hydrogen chloride than
the original. If the solution initially contains more than 20.2% hydrogen chloride, then boiling
will leave behind a solution that is poorer in hydrogen chloride than the original. Boiling of any
hydrochloric acid solution long enough will cause the solution left behind to approach the
azeotropic ratio.[11] On the other hand, if two solvents can form a positive azeotrope, then
distillation of any mixture of those constituents will result in the residue away from the
composition at the azeotrope than the original mixture. For example, if a 50/50 mixture of
ethanol and water is distilled once, the distillate will be 80% ethanol and 20% water, which is
closer to the azeotropic mixture than the original, which means the solution left behind will be
poorer in ethanol.[12] Distilling the 80/20% mixture produces a distillate that is 87% ethanol and
13% water. Further repeated distillations will produce mixtures that are progressively closer to
the azeotropic ratio of 95.5/4.5%. No numbers of distillations will ever result in a distillate that
exceeds the azeotropic ratio. Likewise, when distilling a mixture of ethanol and water that is
richer in ethanol than the azeotrope, the distillate (contrary to intuition) will be poorer in ethanol
than the original but still richer than the azeotrope.[13]
Distillation is one of the primary tools that chemists and chemical engineers use to separate
mixtures into their constituents. Because distillation cannot separate the constituents of an
azeotrope, the separation of azeotropic mixtures (also called azeotrope breaking) is a topic of
considerable interest.[3] Indeed, this difficulty led some early investigators to believe that
azeotropes were actually compounds of their constituents.[2] But there are two reasons for
believing that this is not the case. One is that the molar ratio of the constituents of an azeotrope is
not generally the ratio of small integers. For example, the azeotrope formed by water
and acetonitrile contains 2.253 moles (or 9/4 with a relative error of just 2%) of acetonitrile for
each mole of water.[14] A more compelling reason for believing that azeotropes are not compounds
is, as discussed in the last section, that the composition of an azeotrope can be affected by
pressure. Contrast that with a true compound, carbon dioxide for example, which is two moles of
oxygen for each mole of carbon no matter what pressure the gas is observed at. That azeotropic
composition can be affected by pressure suggests a means by which such a mixture can be
separated.
Pressure swing distillation[edit]

Azeotrope composition shift due to pressure swing.

A hypothetical azeotrope of constituents X and Y is shown in the adjacent diagram. Two sets of
curves on a phase diagram one at an arbitrarily chosen low pressure and another at an arbitrarily
chosen, but higher, pressure. The composition of the azeotrope is substantially different between
the high- and low-pressure plots – higher in X for the high-pressure system. The goal is to
separate X in as high a concentration as possible starting from point A. At the low pressure, it is
possible by progressive distillation to reach a distillate at the point, B, which is on the same side
of the azeotrope as A. Note that successive distillation steps near the azeotropic composition
exhibit very little difference in boiling temperature. If this distillate is now exposed to the high
pressure, it boils at point C. From C, by progressive distillation it is possible to reach a distillate
at the point D, which is on the same side of the high-pressure azeotrope as C. If that distillate is
then exposed again to the low pressure, it boils at point E, which is on the opposite side of the
low-pressure azeotrope to A. So, by means of the pressure swing, it is possible to cross over the
low-pressure azeotrope.
When the solution is boiled at point E, the distillate is poorer in X than the residue at point E.
This means that the residue is richer in X than the distillate at point E. Indeed, progressive
distillation can produce a residue as rich in X as is required.
In summary:

1. Low-pressure rectification (A to B)  Rectification: the distillate, or "tops", is retained and

2. High-pressure rectification (C to D)  Stripping: the residue, or "bottoms", is retained and e
3. Low-pressure stripping (E to target purity)
Note that both azeotropes above are of the positive, or minimum boiling type; care must be taken
to ensure that the correct component of the separation step is retained, i.e. the binary phase-
envelope diagram (boiling-point curve) must be correctly read.
A mixture of 5% water with 95% tetrahydrofuran is an example of an azeotrope that can be
economically separated using a pressure swing – a swing in this case between 1 atm and 8 atm.
By contrast the composition of the water to ethanol azeotrope discussed earlier is not affected
enough by pressure to be easily separated using pressure swings[3] and instead, an entrainer may
be added that either modifies the azeotropic composition and exhibits immiscibility with one of
the components, or extractive distillation may be used.[15]
Azeotropic distillation[edit]
Main article: Azeotropic distillation
Other methods of separation involve introducing an additional agent, called an entrainer, that
will affect the volatility of one of the azeotrope constituents more than another. When an
entrainer is added to a binary azeotrope to form a ternary azeotrope, and the resulting mixture
distilled, the method is called azeotropic distillation. The best known example is
adding benzene or cyclohexane to the water/ethanol azeotrope. With cyclohexane as the
entrainer, the ternary azeotrope is 7% water, 17% ethanol, and 76% cyclohexane, and boils at
62.1 °C.[16] Just enough cyclohexane is added to the water/ethanol azeotrope to engage all of the
water into the ternary azeotrope. When the mixture is then boiled, the azeotrope vaporizes
leaving a residue composed almost entirely of the excess ethanol.[3]
Chemical action separation[edit]
Another type of entrainer is one that has a strong chemical affinity for one of the constituents.
Using again the example of the water/ethanol azeotrope, the liquid can be shaken with calcium
oxide, which reacts strongly with water to form the nonvolatile compound, calcium hydroxide.
Nearly all of the calcium hydroxide can be separated by filtration and the filtrate redistilled to
obtain 100% pure ethanol.
A more extreme example is the azeotrope of 1.2% water with 98.8% diethyl ether. Ether holds
the last bit of water so tenaciously that only a very powerful desiccant such as sodium metal
added to the liquid phase can result in completely dry ether.[17]
Anhydrous calcium chloride is used as a desiccant for drying a wide variety of solvents since it is
inexpensive and does not react with most nonaqueous solvents. Chloroform is an example of a
solvent that can be effectively dried using calcium chloride.[17]
Distillation using a dissolved salt[edit]
Main article: Salt-effect distillation
When a salt is dissolved in a solvent, it always has the effect of raising the boiling point of that
solvent – that is it decreases the volatility of the solvent. When the salt is readily soluble in one
constituent of a mixture but not in another, the volatility of the constituent in which it is soluble
is decreased and the other constituent is unaffected. In this way, for example, it is possible to
break the water/ethanol azeotrope by dissolving potassium acetate in it and distilling the result.[3]
Extractive distillation[edit]
Extractive distillation is similar to azeotropic distillation, except in this case the entrainer is less
volatile than any of the azeotrope's constituents. For example, the azeotrope of 20% acetone with
80% chloroform can be broken by adding water and distilling the result. The water forms a
separate layer in which the acetone preferentially dissolves. The result is that the distillate is
richer in chloroform than the original azeotrope.[3]
Pervaporation and other membrane methods[edit]
The pervaporation method uses a membrane that is more permeable to the one constituent than to
another to separate the constituents of an azeotrope as it passes from liquid to vapor phase. The
membrane is rigged to lie between the liquid and vapor phases. Another membrane method
is vapor permeation, where the constituents pass through the membrane entirely in the vapor
phase. In all membrane methods, the membrane separates the fluid passing through it into
a permeate (that which passes through) and a retentate (that which is left behind). When the
membrane is chosen so that is it more permeable to one constituent than another, then the
permeate will be richer in that first constituent than the retentate.[3]

Complex systems[edit]

Saddle azeotropic system Methanol/Acetone/Chloroform calculated with mod. UNIFAC

The rules for positive and negative azeotropes apply to all the examples discussed so far, but
there are some examples that don't fit into the categories of positive or negative azeotropes. The
best known of these is the ternary azeotrope formed by 30% acetone, 47% chloroform, and
23% methanol, which boils at 57.5 °C. Each pair of these constituents forms a binary azeotrope,
but chloroform/methanol and acetone/methanol both form positive azeotropes while
chloroform/acetone forms a negative azeotrope. The resulting ternary azeotrope is neither
positive nor negative. Its boiling point falls between the boiling points of acetone and
chloroform, so it is neither a maximum nor a minimum boiling point. This type of system is
called a saddle azeotrope.[3] Only systems of three or more constituents can form saddle
azeotropes.
A rare type of complex binary azeotrope is one where the boiling point and condensation point
curves touch at two points in the phase diagram. Such a system is called a double azeotrope, and
will have two azeotropic compositions and boiling points. An example is water and N-
methylethylenediamine.[18]
See also[edit]
 Azeotrope tables
 Azeotropic distillation
 Bancroft point
 Batch distillation
 Ebulliometer
 Eutectic
 Heteroazeotrope
 Zeotrope

References[edit]
1. ^ "Azeotrope definition and meaning - Collins English
Dictionary". www.collinsdictionary.com.
2. ^ Jump up to:a b c d e Moore, Walter J. Physical Chemistry, 3rd e Prentice-
Hall 1962, pp. 140–142
3. ^ Jump up to:a b c d e f g h i Hilmen, Eva-Katrine (November
2000). "Separation of Azeotropic Mixtures: Tools for Analysis and
Studies on Batch Distillation Operation"  (PDF). Norwegian
University of Science and Technology, Dept. of Chemical
Engineering. Archived from the original  (PDF) on 15 June 2007.
Retrieved 24 March 2007.
4. ^ Department of Chemical Engineering University of
Alicante. "Numerical Determination of Distillation Boundaries for
Multicomponent Homogeneous and Heterogeneous Azeotropic
Systems"  (PDF). Archived from the original  (PDF) on 1 October
2011.
5. ^ F. Gowland Hopkins (1913) "Obituary Notices: John
Wade," Journal of the Chemical Society Transactions, 103 : 767-
774.
6. ^ Wade, John; Merriman, Richard William (1911). "Influence of
water on the boiling point of ethyl alcohol at pressures above and
below the atmospheric pressure". Journal of the Chemical Society,
Transactions. 99: 997–1011. doi:10.1039/CT9119900997. From p.
1004: " … it is proposed, in order to avoid the cumbrous periphrase
"mixtures having a minimum (or maximum) boiling point," to
designate them as azeotropic mixtures (α, privative; ζέω, to boil)."
7. ^ National Institute of Standards and Technology. "Standard
Reference Material 1828: Ethanol-Water Solutions"  (PDF).
Archived from the original  (PDF) on 8 June 2011.
8. ^ Rousseau, Ronald W.; James R. Fair (1987). Handbook of
separation process technology. Wiley-IEEE. pp. 261–
262. ISBN 978-0-471-89558-9.
9. ^ CRC Handbook of Chemistry and Physics, 44th ed., p. 2156.
10. ^ Jump up to:    Jim Clark. "Nonideal Mixtures of Liquids".
a b

Chemguide.co.uk. Archived from the original on 20 February 2008.

Retrieved 5 March 2008.
11. ^ Merck Index of Chemicals and Drugs, 9th ed., monograph 4667
 12. ^ Clark, Jim (February 2014). "Non-Ideal Mixtures of
Liquids". chemguide.co.uk.
13. ^ Morrison, Robert Thornton; Boyd, Robert Neilson, Organic
Chemistry, 2nd ed., Allyn and Bacon, 1972, p. 508
14. ^ Ponton, Jack (September 2001). "Azeotrope Databank". The
Edinburgh Collection of Open Software for Simulation and
Education, University of Edinburgh. Archived from the
original  (Queriable database) on 24 April 2007. Retrieved 14
April 2007.
15. ^ Perry's Chemical Engineer's Handbook – 7th Ed. 1997
16. ^ CRC Handbook of Chemistry and Physics, 44th ed., p. 2181
17. ^ Jump up to:    Cohen, Julius B. Practical Organic
a b

Chemistry MacMillan 1930
18. ^ Olson, John D. "Thermodynamics of Hydrogen Bonding Mixtures
4"  (PDF). Archived from the original  (PDF) on 16 September 2008.
Retrieved 27 January 2008.

External links[edit]
 "Publications about the separation of the azeotropes".
BUTE Department of Process Engineering, Hungary.
Retrieved 9 April 2007.
 "What is an Azeotrope?". B/R
Corporation. Archived from the original on 24 April
2007. Retrieved 24 March  2007.
 Azeotrope defined with a limerick.
 Dr G. A. Busato; Professor G. Bashein (2004). "The
halothane/ether azeotrope – A reconsideration". Update
in Anaesthesia. 18. Archived from the original  (PDF)  on
2 February 2016. Retrieved 26 September  2014.
 Ponton, Jack (September 2001). "Azeotrope Databank".
The Edinburgh Collection of Open Software for
Simulation and Education, University of Edinburgh.
Archived from the original  (Queriable database) on 24 April
2007. Retrieved 9 April 2007.
 Prediction of azeotropic behaviour by the inversion of
functions from the plane to the plane
show

Separation processes

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