Professional Documents
Culture Documents
Azeotrope - Wikipedia, The Free Encyclopedia
Azeotrope - Wikipedia, The Free Encyclopedia
Azeotrope
From Wikipedia, the free encyclopedia
Main page
Contents An azeotrope (pronounced /əˈzi.ətroʊp/ ə- ZEE -ə-trope) is
Featured content a mixture of two or more liquids in such a ratio that its
Current events composition cannot be changed by simple distillation. [1]
Random article This occurs because, when an azeotrope is boiled, the
Donate to Wikipedia resulting vapor has the same ratio of constituents as the
original mixture.
Interaction
Help Because their composition is unchanged by distillation,
About Wikipedia azeotropes are also called (especially in older texts)
Community portal constant boiling mixtures. The word azeotrope is
Recent changes derived from the Greek words ζέειν (boil) and τρόπος
Contact Wikipedia (change) combined with the prefix α- (no) to give the
Vapor-liquid equilibrium of 2-
overall meaning, “no change on boiling.”
propanol/water showing azeotropic
Toolbox
Azeotropic mixtures of pairs of compounds have been behavior
Print/export documented. [2] (See Azeotrope (data)). Many azeotropes
of three or more compounds are also known. [citation needed]
Languages
Contents [hide]
Български
1 Types
Català 1.1 Positive and negative azeotropes
Deutsch 1.2 Homogeneous and heterogeneous azeotropes
Español 1.3 Number of constituents
Français 1.4 Zeotropy
Gaeilge
2 Distillation of mixtures
Galego
3 Phase diagrams
3.1 Minimum-boiling or Positive azeotrope
Italiano
3.2 Maximum-boiling or Negative azeotrope
עברית
3.3 Why there are two traces
Kurdî
Latina 4 Heteroazeotropes
http://en.wikipedia.org/wiki/Azeotrope[10-03-2011 17:34:42]
Azeotrope - Wikipedia, the free encyclopedia
Types [edit]
If the constituents of a mixture are not completely miscible an azeotrope can be found inside the
miscibility gap. This type of azeotrope is called heterogeneous azeotrope. If the azeotropic
composition is outside the miscibility gap or the constituents of the mixture are completely miscible
the type of azeotrope is called a homogeneous azeotrope.
Azeotropes consisting of two constituents, such as the two examples above, are called binary
azeotropes. Those consisting of three constituents are called ternary azeotropes. Azeotropes of more
than three constituents are also known.
http://en.wikipedia.org/wiki/Azeotrope[10-03-2011 17:34:42]
Azeotrope - Wikipedia, the free encyclopedia
Zeotropy [edit]
Combinations of solvents that do not form an azeotrope when mixed in any proportion are said to be
zeotropic.
If two solvents can form a positive azeotrope, then distillation of any mixture of those constituents will
result in the distillate being closer in composition to the azeotrope than the starting mixture. For
example, if a 50/50 mixture of ethanol and water is distilled once, the distillate will be 80% ethanol
and 20% water (see ethanol data page), which is closer to the azeotropic mixture than the original.
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 number of distillations, however, 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 slightly
richer than the azeotrope. [5]
If two solvents can form a negative azeotrope, then distillation of any mixture of those constituents
will result in the residue being closer in composition to 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.[6]
The boiling and recondensation of a mixture of two solvents are changes of state. As such, they are
best illustrated with a phase diagram. If pressure is held constant, the two parameters that can vary
are the temperature and the composition. An azeotrope is not the same as an emulsion.
http://en.wikipedia.org/wiki/Azeotrope[10-03-2011 17:34:42]
Azeotrope - Wikipedia, the free encyclopedia
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.
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.
Alternatively, one can view the lower trace as the boundary for the region of the diagram in which
liquids are in equilibrium, and the upper trace as the boundary of the region in which the vapor is in
equilibrium. These two boundaries need not coincide. Indeed, the region between them is a no-
man's-land: attempts to bring the system to the midpoint of line-segment AB will result in a mixture of
liquid A and vapor B, but nothing at the midpoint.
Heteroazeotropes [edit]
http://en.wikipedia.org/wiki/Azeotrope[10-03-2011 17:34:42]
Azeotrope - Wikipedia, the free encyclopedia
Raoult's law predicts the vapor pressures of ideal mixtures as a function of composition ratio. In
general only mixtures of chemically similar solvents, such as n-hexane with n-heptane, form nearly
ideal mixtures that come close to obeying Raoult's law. Solvent combinations that can form
azeotropes are always nonideal, and as such they deviate from Raoult's law.
The diagram on the right 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. 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 Total vapor pressure of mixtures as a
function of composition at a chosen constant
top trace deviates sufficiently that there is a
temperature.
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. [8] 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
http://en.wikipedia.org/wiki/Azeotrope[10-03-2011 17:34:42]
Azeotrope - Wikipedia, the free encyclopedia
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.
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. [2] Indeed this difficulty led some early investigators to believe that azeotropes were actually
compounds of their constituents.[1] 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 of
acetonitrile for each mole of water. [9] 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.
http://en.wikipedia.org/wiki/Azeotrope[10-03-2011 17:34:42]
Azeotrope - Wikipedia, the free encyclopedia
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 was possible to cross over the low pressure azeotrope.
When the solution is boiled at point E, the distillate is poorer in X than point E. This means that the
residue is made richer in X than point E. Indeed, progressive distillation can result in a residue that is
as rich in X as is required.
In summary:
1. Low pressure rectification (A to Rectification: the distillate, or "tops", is retained and exhibits an
B) increasingly lower boiling point.
2. High pressure rectification (C Stripping: the residue, or "bottoms", is retained and exhibits an
to D) increasingly higher boiling point.
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/ethanol azeotrope discussed earlier is not affected enough
by pressure to be easily separated using pressure swings[2] 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.[10]
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. [12]
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
[12]
http://en.wikipedia.org/wiki/Azeotrope[10-03-2011 17:34:42]
Azeotrope - Wikipedia, the free encyclopedia
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. [2]
The pervaporation method uses a membrane that is more permeable to the one constituent than to
the 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.[2]
Sometimes 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. [2]
Azeotropes can only form when a mixture deviates from Raoult's law. Raoult's law applies when the
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 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 sticking together 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 there is more sticking together of the
molecules in the mixture than in the pure constituents, they are more reluctant to escape the stuck-
together liquid phase. [1]
http://en.wikipedia.org/wiki/Azeotrope[10-03-2011 17:34:42]
Azeotrope - Wikipedia, the free encyclopedia
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, and so an azeotrope is the result.
Azeotropic distillation
Azeotrope (data)
Eutectic
Batch Distillation
Heteroazeotrope
http://en.wikipedia.org/wiki/Azeotrope[10-03-2011 17:34:42]
Azeotrope - Wikipedia, the free encyclopedia
Ebulliometer
Bancroft Point
References [edit]
http://en.wikipedia.org/wiki/Azeotrope[10-03-2011 17:34:42]
Azeotrope - Wikipedia, the free encyclopedia
Text is available under the Creative Commons Attribution-ShareAlike License; additional terms may apply. See Terms of
Use for details.
Wikipedia® is a registered trademark of the Wikimedia Foundation, Inc., a non-profit organization.
Contact us
http://en.wikipedia.org/wiki/Azeotrope[10-03-2011 17:34:42]