7.

6: Solvent Partitioning (Liquid-Liquid Extraction)

This method is often called "extraction". Extraction means drawing a compound out of a mixture using a solvent. Solvent
partitioning is more specific. It means compounds have a "choice" of two solvents that they can dissolve in. Some compounds
dissolve in one solvent. Some compounds dissolve in the other solvent. That way the compounds in the mixture become separated
into two groups.

Figure 7.6.1 : A cartoon showing the basic idea of solvent partitioning.

Solvent partitioning depends on solubility. It depends on the solubility in two different solvents, though. It depends on an
equilibrium: does the compound dissolve more in solvent A, or solvent B?
Solvent partitioning requires two solvents that are not miscible in each other. Usually one of the solvents is water. The other solvent
is a liquid that does not dissolve very well in water, such as diethyl ether (this is the most common type of ether, and it is often
called simply "ether"). If you look closely at a mixture of ether and water, you will see two layers because the two compounds do
not dissolve very well in each other.

Figure 7.6.2 : The next step in solvent partitioning.

It's important that the two solvents are immiscible, because then it is easy to separate them from each other. The top liquid can be
drawn off with a pipet, or the bottom layer can be drained out via a stopcock. The compounds that dissolved in the ether have thus
been separated from the water-soluble compounds. Because ether evaporates very easily, the compounds that dissolved in the ether
can also be separated from the ether (see "distillation"). As a result, purer compounds can be obtained.

Figure 7.6.3 : The end result of solvent partitioning.

Now let's take another look at the whole process and fill in some details. A solvent partitioning almost always involves the use of
water and an organic solvent (based on carbon & hydrogen). In most cases, the organic solvent is not polar enough to dissolve in

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water. The few exceptions are instructive to look at. Methanol, ethanol, and 2-propanol -- that is, CH3OH, CH3CH2OH, and
(CH3)2CHOH -- dissolve very well in water. Butanol does not, and neither does common ether -- CH3CH2CH2CH2OH and
CH3CH2OCH2CH3. That comparison gives rise to a very rough rule of thumb about water solubility. That is, the carbon : oxygen
ratio should be below 4:1 in order for an organic compound to dissolve in water. There are exceptions, but this is a good rule to
keep in mind.
If the two solvents do not dissolve in each other, then when they are mixed together, they will form two different layers. That's
exactly what we want. If we have a mixture of polar and nonpolar compounds, and we mix them together with water and, say,
diethyl ether, then the polar compounds should migrate to the water layer and the nonpolar compound should migrate to the ether
layer.

Figure 7.6.4 : The basic idea of solvent partitioning.

There are a couple of different ways to carry out this step. If we are working with a very small amount of material (such as a couple
of hundred milligrams) and need only a small amount of solvents (maybe a couple of millilitres), we might do all of this in a test
tube. We would use a pipet to mix the two layers up by flushing one layer repeatedly through the other.
On a larger scale, we would use a separatory funnel. It has an opening on each end, with a stopper at the top and a stopcock at the
bottom. We just close the stopcock, pour the stuff in the top, put the stopper on, and shake it up; typically we shake it up three
times, and vent it after each time. To vent, we just open it up to let the air out, because the mixture gets a little gassy. That's because
when we mix two liquids together there are always heat and volume changes as a result; the mixture may get a little warmer, or it
may expand a little, so it needs more room. Most people turn it upside down and open the stopcock to vent it. Usually you can hear
a little hiss when you do this.
After venting for the third time, we wait for the layers to separate.
At this point, we can separate the two layers. We take the stopper off, open the stopcock a little, and carefully drain each layer into
its own flask. Usually we transfer them into two Erlenmeyer flasks (the cone-shaped ones). It's always a good idea to label the
flasks. Alternatively, if we are on a test-tube scale, we can use a pipet to transfer the organic layer into a dry test tube.

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 Figure 7.6.5 : Separating the two layers.
How do we know which layer is which? The fact that two layers form depends on differences in intermolecular attractions, but
which layer is on the bottom depends on density. That's something you should look up in a table. However, there are some rough
rules of thumb here, too. Most organic solvents are less dense than water, so they float on the top. A few organic solvents are more
dense than water, so they sink to the bottom. Usually these solvents contain heavy atoms such as halogens, like chlorine.
If you're looking closely at the pictures, you will notice here is something wrong with them. The red molecules were supposed to
go into the yellow solvent and the green molecules were supposed to go into the blue solvent. In reality, it never works out
perfectly. Someone always gets left behind. This isn't because of "human error", the mainstay of high school lab reports. It's
because of nature. When we expect a compound to dissolve in one solvent rather than another, we are seldom rewarded with
perfection. Instead, the compound is more likely to dissolve in one layer; there is an equilibrium constant that governs how much of
the compound goes in one layer and how much goes in the other. Maybe 95% goes in the right layer, and the equilibrium constant
forces the other 5% into the wrong one.
So we go back and try again. We take the water layer and extract with fresh solvent. If we are able to extract 95% of the remaining
5%, that leaves just 0.25% behind this time. That's pretty good.
By the way, that term "extract" is usually used to indicate that we are removing what we want from something we did not want. We
just extracted the remaining compound from the water. Now we need to keep it safe. We combine it with the first fraction that we
extracted so that all of the compound we want is in one place.

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 Figure 7.6.6 : A second extraction: making sure to get every bit.
Now for another practical problem. Usually when we do an extraction, we like to see a good separation between two clear layers.
Sometimes that does not happen. Things are cloudy, they are messy, the laters are not separating well. This is not always about
human error. This could be more nature. Maybe the two layers are not separating because they are not different enough from each
other.
One way to make the layers more different is to add brine (saltwater). That brine takes a polar water layer and makes it even more
polar. Now there is a clearer choice about phase separation.

Figure 7.6.7 : Adding brine to force better separation between layers.

Incidentally, if you are worried that there is polar impurity in the organic layer, we can handle it the same way. Add brine to the
organic layer to coax that polar impurity out. You will get two layers and will need to separate them again but the organic layer may
be purer as a result. This step is called washing; washing is like extraction, but we are removing something we do not want rather
than keeping something we do want.
We are getting close to the end of a successful experiment but there is still another detail we need to deal with. Most organic
solvents can dissolve a little bit of water. Usually it's an amount that is significant enough to contaminate the compound we are
trying to isolate. We need to get that water out.
To remove water, we add a drying agent. A drying agent is just a salt containing a Lewis acidic metal ion; anhydrous sodium
sulfate, magnesium sulfate, or calcium chloride are the most common examples. These salts have been dried to remove any traces
of water, but they have a natural affinity for it, and will sponge it out of solution for us.
The method of using a drying agent is simple. You need to put a very thin layer of it on the bottom of the flask containing your
combined extracts. Stir it up and wait five minutes. That's 5 minutes. Wait until the big hand moves to the next number.

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At the end of that time, swirl the flask and look at the drying agent. The thing you need to know about drying agent is that when it
gets wet the grains stick together in little clumps. Some of them should be stuck together now, because your organic layer came
into contact with water recently and it certainly picked up a little bit of moisture. The question is, are some of the grains free? They
did not stick to anybody else? When you swirl the flask, do they fly up freely like a snow globe? If so, they must be dry. If they are
dry, so is your solution. Good job!
What if all of your grains of drying agent are stuck in little clumps at the bottom of the flask? They all got wet. Maybe all of the
water is gone, but maybe there was too much water for the drying agent that you added. In that case, add another layer of drying
agent. Wait five minutes. You get the idea.

Figure 7.6.8 : Removing traces of moisture from an organic layer ("drying").

If you're a lab genius, you will find a shortcut to this drying business. Forget the little layer. Just add lots. That will get rid of all the
water quickly. And you're right, it will. It will probably get rid of anything else you want, too. The problem is, the drying agent is a
Lewis acid. It sticks to lone pairs on the oxygen atoms in the water molecules. Unless the compound you are trying to extract is a
hydrocarbon, chances are it contains oxygen atoms, too; most compounds in nature do. That means it sticks to the drying agent.
Too much drying agent, and you've lost all of the compound you needed. In science, this could be described as a non-ideal
situation. In layman's terms, it's a complete and utter failure.

Figure 7.6.9 : Drying agent disasters: when you add too much drying agent.
There's another common problem that can appear when you add the drying agent. If the organic layer is really, really wet, and you
add a drying agent, which is a salt, you make saltwater. Now you have an organic layer mixed with brine. The brine layer separates
from the organic layer. This is an easy problem to solve. Just separate the two layers and go back to drying the organic layer. But
wait -- is the TA looking? Maybe you can just add a bunch of drying agent and absorb all of that water. If you think that sounds like
a good idea, go back and read the previous paragraph.

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 Figure 7.6.10 : Drying agent disasters: when you form a briny layer.
If all goes well, and you have a nice, clear organic layer, you can just filter out the drying agent and evaporate the solvent. Finished.

Figure 7.6.11: The end result of solvent partitioning.

Exercise 7.6.1

List reasons why ether and water SHOULD and SHOULD NOT dissolve in each other. In this case, what factors prevail in
determining whether these two compounds are miscible?

Answer
Both water and ether (a common nickname for diethyl ether) contain electronegative oxygen atoms. Because both oxygens
are bonded to less electronegative hydrogen or carbon atoms, each molecule will have a dipole. We may expect dipole-
dipole interactions and miscibility.
Both oxygen atoms have lone pairs. Either one could act as a hydrogen bond acceptor. Because ether also contains a very
polar O-H bond (remember, hydrogen bonding involves F,O,N), we may expect hydrogen bonding interactions and
miscibility.
However, a C-O bond in ether is less polar than a H-O bond in water. In order for the two liquids to be miscible, stronger
dipole-dipole interactions between the water molecules would have to be given up and traded in for weaker dipole-dipole
interactions between the water and the ether molecules. The two liquids might not mix.
Ether has an oxygen atom with a lone pair, but it does not have a very polar O-H bond. The possibility for hydrogen
bonding between water and ether is lower than between water molecules alone. The two liquids might not mix.
Ether has two hydrophobic hydrocarbon chains, although they are rather short. When mixing, these chains must be
accommodated between neighbouring water molecules, which are thereby prevented from hydrogen bonding with each
other. The two liquids might not mix.

Exercise 7.6.2

Ether and water have different densities. Water has a density of 1.000 g/mL and specific gravity of 1.000. Specific gravity is
the ratio of a compound's density to that of water. It is no surprise that water has a specific gravity of 1.000. If ether has a
specific gravity of 0.977, which compound is heavier? Which compound will float to the top and which will sink to the
bottom?

Answer

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 The lighter ether would be on the top. The heavier water would sink to the bottom.

Exercise 7.6.3
a. Methanol has a specific gravity of 0.980. When methanol and water are mixed, which compound should float to the top?
b. However, only one layer of liquid is observed, not two. Why?

Answer
Answer a
Given two separate layers, the lighter methanol would be on the top. The heavier water would sink to the bottom.
Answer b
Methanol and water are miscible. Both are fully capable of hydrogen bonding; they are each hydrogen-bond donors and
acceptors. Although the methanol has a non-polar hydrocarbon component, the methyl groups are not large enough to
significantly disrupt hydrogen bonding between neighbouring water molecules.

Exercise 7.6.4

a) Draw three compounds that you think will dissolve better in water than in ether. Explain your answer.
b) Draw three compounds that you think will dissolve better in ether than in water. Explain your answer.

Answer
Answer a
Maybe the compounds are salts, containing an anion and a cation. The anions and cations could be simple inorganic ones
such as Li+ and F-, but either the anion or the cation could also be organic (containing hydrocarbon portions). If the
compounds are organic and not ionic, either the molecules would be fully capable of hydrogen bonding (containing O-H or
N-H bonds), or they would contain highly polar bonds such as C=O. Also, the compounds should not contain too great a
proportion of hydrocarbon compared to the polar part; for neutral compounds, that means a carbon:oxygen ratio below
about 4:1, although the ratio can be significantly higher for ionic compounds.
Answer b
The compounds should be neutral, not ionic. Although they may contain polar bonds, the compound should be mostly non-
polar; a rough rule is that the carbon:oxygen ratio should be greater than 4:1.

Exercise 7.6.5

State whether the following organc solvents would be form the top or bottom layer when mixed with water (d = 1.0 g/mL).
a) dichloromethane, d = 1.33 g/mL b) hexane, d = 0.66 g/mL c) toluene, d = 0.87 g/mL
d) tert-butyl methyl ether, d = 0.7404 g/mL e) chlorobenzene, d = 1.11 g/mL
f) ethyl acetate, d = 0.902 g/mL g) chloroform, d = 1.489 g/mL h) cycopentane, d = 0.75

Answer
Answer a
bottom
Answer b
top
Answer c
top
Answer d

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 top
Answer e
bottom
Answer f
top
Answer g
bottom
Answer h
top

Exercise 7.6.6

In general, most neutral, organic compounds will dissolve better in ether than in water. Most ionic compounds dissolve better
in water than in ether. Benzoic acid dissolves better in ether than in water, but sodium benzoate dissolves better in water than in
ether. Why do you think this is true?

Answer
The ionic compounds can form strong ion-dipole interactions with the water molecules. That interaction enhances their
solubility in water.

Exercise 7.6.7

Describe a series of steps you could take in the lab to separate sodium benzoate from benzoic acid via solvent partitioning. By
the end, you should have a sample of pure benzoic acid in one labeled vial and a sample of sodium benzoate in another.

Answer
Water and ether should be added to the mixture and the mixture should be shaken until it dissolves. The layers should be
separated. The water should be extracted with additional ether and the combined ether layers should be washed with brine.
The ether layers should be dried with sodium sulfate, filtered, and evaporated under vacuum.

Exercise 7.6.8

In the question above about separation of benzoic acid from sodium benzoate, why is washing the solid possibly an inadequate
method?

Answer
The water molecules would have to come into contact with the sodium benzoate in order to dissolve it. If some sodium
benzoate is completely surrounded by benzoic acid, it would remain undissolved.

Exercise 7.6.9

There are exceptions to the rule that most neutral, organic compounds dissolve better in ether than water. Acetic acid dissolves
well in water. Why?

Answer
Acetic acid, CH3CO2H, contains a polar C=O bond, a hydrogen-bonding O-H group, and a carbon:oxygen ratio of 1:1. All
of these factors render it relatively polar.

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Exercise 7.6.10

Some organic compounds will dissolve in ether under some circumstances and water in others. For example, suppose THF is
mixed with equal volumes of ether and water, and the water layer gets bigger.
In what layer is the THF? If salt is added, the water layer gets smaller and the ether layer gets bigger. In what layer is the THF
now? Why does the solubility of THF vary in this way?

Answer
Answer a
The THF is in the water layer.
Answer b
The THF is in the ether layer.
Answer c
The brine makes the water layer even more polar. The THF is already on the edge of being water-soluble, because it has a
carbon:oxygen ratio of 4:1. The added water polarity pushes it past the tipping point.

Exercise 7.6.11

It is useful to remember that solvent partitioning always involves an equilibrium between two solvents; compounds often do
not dissolve entirely in one solvent or the other. Suppose perfluorobutanoic acid, a member of a class of compounds used for
stain-resistant carpeting, is taken up in a mixture of equal parts water and ether. Imagine half the perfluorobutanoic acid
(C3F9CO2H) dissolves in the water and half in the ether (this is just a made-up number for argument's sake). What would you
have to do in order to get all the perfluorobutanoic acid out of the water?

Answer
After one extraction, half the perfluorobutanoic acid would remain in the water. A second extraction would remove half the
remainder, leaving only a quarter of the original amount still in the water. A third extraction would leave 12% of the
original in the water; a fourth extraction would leave 6%; a fifth extraction would leave 3%; a sixth extraction would leave
1.5% a seventh extraction would leave less than 1%.
The idea here is that multiple extractions are usually necessary. However, it would be pretty unusual to choose solvent
partitioning as a purification method if a compound is this soluble in water.

Exercise 7.6.12

Suppose you have a mixture of benzoic acid and sodium benzoate. You add 2 mL of ether and 2 mL of water to the mixture
and it all dissolves. You forget what to do next, so you go to read Zubrick's Organic Chem Lab Survival Manual for a while.
When you come back, you notice the top layer of liquid is only half as big as the bottom layer. There are also white floaties in
between the two layers.
a. What has happened?
b. What are the white floaties?
c. What should you do next?

Answer
Answer a
It looks like half the ether has evaporated.
Answer b
The white floaties are probably the bezoic acid that used to be dissolved in the ether. You don't have enough ether to keep it
dissolved anymore.
Answer c

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 You should add more ether before this experiment gets any worse.

Attribution
Chris P Schaller, Ph.D., (College of Saint Benedict / Saint John's University)

7.6: Solvent Partitioning (Liquid-Liquid Extraction) is shared under a CC BY-NC license and was authored, remixed, and/or curated by Chris
Schaller.

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