Lab 5 - seperation (fall 2023)
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Dec 6, 2023
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Experiment 5: Separation of a mixture
1
SEPARATION OF A MIXTURE: EXTRACTION
(Adapted from
http://wwwchem.uwimona.edu.jm/lab_manuals/c1901exp8.html
)
Purpose: Use pH dependent solubility to separate (aka extract) organic compounds from a
mixture.
Background Information
: Extraction is a particularly useful means of separating organic
compounds if one compound in the mixture can be chemically converted to an ionic form. The
ionic form is soluble in an aqueous layer and can be extracted into it. Other, non-ionic organic
compounds in the mixture will remain dissolved in the organic solvent layer. Separation of the
two layers results in the separation of the two compounds.
The extent to which an acid-base reaction proceeds to completion depends upon the relative
acidity of the reactants and products.
Reactions occur so that stronger acids and bases are
converted into weaker conjugate base and conjugate acids, respectively.
The p
K
a value of the
acids gives a measure of the acidity of each compound. Stronger acids have smaller p
K
a values
and their conjugate bases are weaker. The position of an acid-base equilibrium can then be
predicted from knowledge of the p
K
a values of the acids involved.
Look at the following acid-base reactions in Figure 1, paying particular attention to the position
of the equilibrium and its relationship to the p
K
a values given.
Figure 1:
The reactions of a carboxylic acid and a phenol with bicarbonate ion. Note that the carboxylic
acid has a lower pKa than the conjugate acid of bicarbonate ion (carbonic acid). The reaction,
Experiment 5: Separation of a mixture
2
therefore, proceeds to products. The reaction of a phenol, however, favors the reactants since the
pKa of phenol (10) is larger than that of the carbonic acid (6.4). Acid-base reactions favor the
side with the weaker acid (that is, they favor the side with the larger pKa). So, extracting a
mixture of these two compounds with bicarbonate results in the ionization and extraction of a
carboxylic acid in the presence of phenol thus separating the two compounds from one another.
Now, look at the reaction in Figure 2 where we use a stronger base to do the reaction:
Figure 2:
The reactions of a carboxylic acid and a phenol with hydroxide ion. Note that in both cases, the
reactions favor the formation of products. Therefore, extracting with hydroxide ion would result
in the ionization and extraction of both compounds at the same time.
A close look at these two figures indicates that separating a mixture of a carboxylic acid and a
phenol would best be done using bicarbonate ion since only the carboxylic acid is converted into
its conjugate base by bicarbonate. The conjugate base of the carboxylic acid, being an ionic
species, is soluble in the aqueous layer while the phenol (left unionized) would remain dissolved
in the organic layer. However, if we were to extract with hydroxide ion, both the carboxylic acid
and the phenol would be converted into their conjugate bases (see figure2). The conjugate bases
again are both ionic species and therefore soluble in the aqueous layer. This means that both
compounds would be extracted at the same time, resulting in no separation.
A neutral compound will not react with either bicarbonate ion or hydroxide ion since a neutral
compound does not have protons acidic enough to be removed by these bases. Therefore, such a
compound will remain dissolved in the organic layer, no matter which base is added. For
Experiment 5: Separation of a mixture
3
example, a mixture of neutral compound and carboxylic acid can be separated using bicarbonate
ion since only carboxylic acid will be ionized by the bicarbonate ion.
Once extracted, the carboxylic acid and phenol can both be recovered by adding HCl to the
aqueous solutions. The carboxylate ion and phenoxide will both be protonated by HCl, resulting
in the formation of the original carboxylic acid and phenol, neither of which is soluble in water,
so they precipitate from solution. The solid can then be isolated by filtration. Figure 3 shows this
chemistry for you.
Figure 3:
The reactions of a carboxylate ion and a phenoxide ion with HCl. Since HCl is a stronger acid
than either of the conjugate acids, the products are favored in both cases. The products, a
carboxylic acid and a phenol, are insoluble in aqueous solutions and precipitate from solution.
The resulting solids can be isolated, and their melting points determined.
(Note: melting point
analysis is not employed in this lab.)
The procedure you will use in this experiment exploits the differences in acidity and solubility as
described previously.
(a)
you will dissolve your unknown in ethyl acetate (an organic solvent). All the possible
compounds are soluble in ethyl acetate.
(b)
you will extract with sodium bicarbonate to remove any carboxylic acid that is present.
(c)
you will extract with sodium hydroxide to remove any phenol that is present.
(d)
you will acidify both resulting aqueous solutions to cause any compounds that were
extracted to precipitate.
Experiment 5: Separation of a mixture
4
These solids will be isolated by filtration and dried. You will weigh each solid you obtain to
determine the percent recovery of your procedure. If a neutral compound was present in your
unknown, it will remain in the organic layer throughout the extraction procedure. To isolate it,
you will simply evaporate the ethyl acetate to leave a solid.
Remember, though, that you only have two compounds in your unknown mixture so that you
should not isolate solids from all the extracts.
Possible compounds in the unknown mixture.
Look up the structures of these compounds and include them in your prelab question 1.
benzoic acid, 4-tertbutylphenol, 1,4-dimethoxybenzene
Experiment 5: Separation of a mixture
5
Safety
Concentrated NaOH and HCl will cause burns!
Gloves must be worn at all times.
Notify your TA immediately of any spills!
Pressure can build up in the separatory funnel. Handle carefully
and vent the gas frequently - as demonstrated by the TA
Procedure:
Read the entire section of the procedure before starting the corresponding
experiment.
1.
Label 3 Erlenmeyer flasks:
125 ml flask 1: bicarbonate
125-ml flask 2: hydroxide
50-ml round-bottom flask: ethyl acetate
2.
Collect an unknown and record the unknown number. (Without this number, we cannot
grade your report.)
3.
Dissolve approximately
1.0 g of your unknown mixture
in 10 mL of ethyl acetate.
Unknown: ________
Mass of unknown: ______________
Mass of mixture: ______________
Extraction 1 – Bicarbonate extraction
Prediction: Which compound(s) would be extracted in this step? Show the reaction that occurs that
results in the compound(s) becoming water soluble.
1.
Pour the solution into a clean separatory funnel.
2.
Add
10 mL of 10% aqueous sodium bicarbonate
found on the solutions bench.
3.
Stopper the funnel, properly grip the neck and stopper to prevent leaks, and invert it.
Slowly open the stopcock to release any built-up pressure, then close the stopcock
(
Figure 4
).
Don’t lose track of which
is which!!
A
1
.
099
9
,
409
Beaker
=
35
.
259
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