Experiments 4 and 5: Extraction and Recrystallization of Unknown Ketone

Lexie E. Kosanovic

SCH 121 02 Organic Chemistry Principles Lab

March 20, 2018

 I. Introduction

A. The Theory of Liquid – Liquid Extraction

Extraction is a physical process in which a compound is transferred from one phase to

another. There are two main types of extraction. First, there is solid-liquid extraction, and there is

also liquid-liquid extraction (“The Theory of Liquid-Liquid Extraction.”). The latter was

accomplished during the experiment. In liquid-liquid extraction, two or more liquids will not

dissolve in each other and form two distinct layers. Polarity and solubility are two contributing

factors to liquid-liquid extraction. Polar solvents like polar solutes as nonpolar solvents like

nonpolar solutes. Immiscible liquids are liquids which are insoluble in one another, thus two

distinct layers will be formed. In the experiment, tert-butylether and water were the two

immiscible liquids used. Water is denser than the tert-butylether, and the unknown ketone bonded

to the tert-butylether to form the top layer while to blue dye bonded to the water layer.

Water tert-butylether

Figure 1: Comparison of two immiscible liquids – water and tert-butylether

There are two types of liquid-liquid extraction. The first is organic solvent extraction. In

this type of extraction, an organic solvent with a high affinity for the desired compound is used to

extract the compound from another (“The Theory of Liquid-Liquid Extraction.”). The second is

acid base extraction. In this type of extraction, an organic acid or an organic base is extracted from

an organic solvent by using a solution of an inorganic base or acid. The combination of the acids

and bases will produce a neutral, ionic, water-soluble salt (“The Theory of Liquid-Liquid
Extraction.”). A phase change from the organic phase to the aqueous phase occurs during the acid

base extraction (“The Theory of Liquid-Liquid Extraction.”).

Organic solvent extraction was utilized in the experiment. When mixed, the two liquids

produced a nonhomogeneous liquid. In this experiment, tert-butylether and water were the two

immiscible liquids. The bottom layer was determined to be the water because it was the denser

solvent and the less dense tert-butylether was the top later. In order to separate the two layers, a

separatory funnel is commonly used in organic solvent liquid-liquid extraction. The separatory

funnel allows the undesired layer to be eliminated by being expelled through the funnel while the

desired layer remains inside of the funnel.

Figure 2: Set Up of the Extraction using a Separatory Funnel and Erlenmeyer flask

B. Recrystallization

Recrystallization is a method for purifying solid organic compounds. Recrystallization allows

soluble, insoluble and colored impurities to be removed, and the purified solid can be reached

(“Recrystallization.”). The extraction product is in a crystalline form. In order to allow the crystals

to form in the desired lattice network, the compound must be a pure substance in a supersaturated

solution.
 The recrystallization process can be understood through solubility behavior. There is a

common statement when speaking about solubility that details “like dissolves like”. This is correct,

but in the context of recrystallization, it is more correctly stated, “compounds having similar

structural features will be soluble in one another” (“Recrystallization.”). From a supersaturated

solution, compounds organize into crystal structures. In the experiment performed, the water and

the ether were insoluble in one another because of their structural differences.

There are general steps to recrystallization. First, a solvent must be picked. The product that is

trying to be purified is soluble at high temperatures and insoluble at low temperatures. The

impurities in the product are very soluble. The solvent used in this experiment was ethanol. Second,

dissolving the product is done using heat. As a temperature is increased, then the solubility is

increased. Conversely, a decrease in temperature will yield a decrease in solubility. In this

experiment, a hot water bath was used. The temperature increase yielded an increase in the

solubility. After the product is heated, then the sample must be allowed to cool. This is important

for one main reason. Transitioning from near boiling to room temperature and then to an ice bath

will allow the crystals to form (“Recrystallization.”). Finally, the last step is a further purification

stage. The crystals are isolated through filtration. The solution is filtered to remove any insoluble

impurities, and the solvent is evaporated to produce the solid compound.

 Figure 3: Filtration Set Up using a rubber stopper, funnel with filter paper and rubber tubing

connecting it to the vacuum hose at the lab station

C. IR Spectrum

Infrared Spectroscopy is commonly used by placing a sample of liquid between two salt plates

and passing infrared light through the salt plates containing the sample. Salt plates are commonly

used because they do not absorb any of the light. For liquid samples, salt plates work very well,

but for solid samples, like the unknown ketone, salt plates are not as desired.

Attenuated Total Reflectance or ATR is utilized for solid samples. A small amount of the solid

sample is placed on top of the crystal surface. The crystal works in a similar way to the salt plate

in that the crystal does not absorb any of the light passing through the sample. The ATR takes a

measurement of the reflection of the solid on the crystal surface. The light passing through the

sample will record the various wavenumbers (cm-1), and these wavenumbers are associated with

various functional groups. In any IR spectrum, the desired outcome is a graph with frequencies on

the y-axis. If there are unknown functional groups found on the IR spectrum, then two things may

have happened.

D. Melting Point

Melting point is a physical property of compounds to assess their purity. The melting point of

a solid is the temperature at which the solid exists in equilibrium with its liquid under pressure

(“Melting Point of an Organic Compound.”). In the instance of the extraction and recrystallization

experiment, pure crystalline solids possess a sharp melting point range. The presence of a small

range details that little impurities were present (“Melting Point of an Organic Compound.”). In
this experiment, a pure sample of the ketone (9 Fluronene) is compared to the sold unknown

ketone. The pure sample of the ketone should possess a sharp melting point range since this is a

pure sample with very few or no impurities. The unknown ketone sample that was extracted and

recrystallized should possess a sharp melting point similar to the 9-Fluronene. If there is a longer

melting point range, then the unknown ketone sample possesses undesired impurities.

Figure 4: Structure of the 9-Fluronene

E. Crystalline Solids

A crystalline solid is a solid with molecules stacked up in an organized fashion which leads to

a three-dimensional shaped solid. Comparing the unknown ketone that has been extracted and

recrystallized and the beginning green powder leads to several important inferences. First, simple

observation can be a key aspect to assessing the purity of the crystalline solid. High purity will

lead to more consistent crystal structure.

II. Results

A. Data

Table 1: Mass of the Mixed Ketone

Mass of Mixed Ketone 0.48g

 Table 2: Mass of Extracted Ketone

Mass of the Empty Beaker 49.38g

Mass of Beaker with Unknown Ketone 49.66g

Mass of the Unknown Ketone (49.66g-49.38g) = 0.28g

Table 3: Mass of Ethanol Used

Mass of Unknown Ketone 0.28g

Ethanol: 5mL per 1g unknown ketone (0.28g) x 5 = 1.4mL ethanol

Table 4: Mass of Recrystallized Ketone

Empty Vial Mass 16.26g

Full Vial Mass (February 27, 16.56g

2018)

Full Vial Mass (March 13, 17.34g

2018)

Mass of Recrystallized Option 1 (February 27)

Ketone 16.56g-16.26g = 0.30g

Option 2 (March 13)

17.34g-16.26g = 1.08g

o Note: the vial was in the lab drawer, uncapped, for two weeks

B. Percent Recovered
Steps for Calculation

mass of isolated product

Percent Recovered = mass of mixture to start (g) x 100%

Calculation 1: Extraction

- Mass of the Mixture to Start: 0.48g

- Mass of the Isolated Product: 0.28g

Calculation

0.28g
x 100% = 58.3%
0.48g

Calculation 2: Recrystallization (February 27)

- Mass of isolated product: 0.30g

- Mass of mixture to start: 0.48g

Calculation

0.30g
x 100% = 62.5%
0.48g

Calculation 3: Recrystallization (March 13)

- Mass of isolated product: 1.08g

- Mass of mixture to start: 0.48g

Calculation

1.08g
x 100% = 225%
0.48g
 C. Melting Point

Table 5: Melting Points from class (March 13, 2018)

Pure (9-Fluronene) Product (Unknown Mixture

Ketone)

Initial 85 ºC 58ºC - 82ºC 83ºC

*Began to see the

lack of shine and
structure loss at 58ºC,
but liquefaction
began at 82ºC
Final 88ºC 87ºC 87ºC

Difference 3ºC 29ºC - 5ºC 4ºC

D. IR Spectrum

Table 6: Most Notable Functional Groups Determined from IR Spectrum

Wavenumbers (cm-1) Description Functional Group

1711.40 cm-1 C=O stretch Ketone

1597.12 cm-1 C-C stretch in ring Aromatics

1471.44 cm-1 C-C stretch in ring Aromatic

743.87 cm-1 C-H oop Aromatics

 Figure 5: IR Spectrum taken in Class (March 13, 2018)

Possible sources of error for Extraction and Recrystallization of Unknown Ketone

For the IR spectrum, the substance being analyzed may not be as pure as desired. Undesired

functional groups can determine how impure a substance is. In addition, the over 100% recovered

indicates that there were unwanted groups present in the recrystallized ketone. Second, the surface

in which the solid substance was tested on was commonly cleaned with hexene. In the case of the

unknown ketone, hexene is not completely soluble when the unknown ketone is added. When the

IR spectrum is performed, the hexene and the unknown ketone are analyzed together because the

hexene did not completely neutralize the previous samples. In short, acetone should be used in this

case because of its ability to neutralize any unwanted samples left behind. Finally, the dramatic

increase in the second weighing of the unknown ketone (225% recovered) could be from not

utilizing the same balance when weighing the samples. If the same balance is not used, then the

masses of the dried ketone may be altered. Another source of error for the increase in the percent

recovered could simply be that the number was recorded incorrectly.

 References

“Melting Point of an Organic Compound.” OnlineLabs, Ministry of Electronics and

Informational Technology, 2013,

http://www.amrita.olabs.edu.in/?sub=73&brch=7&sim=33&cnt=1 .

“Recrystallization.” University of Massachusetts, University of Massachusetts,

http://www.people.chem.umass.edu/samal/267/owl/owlrecryst.pdf .

“The Theory of Liquid-Liquid Extraction.” Extraction Theory, ChemLab, 2002,

www.thevespiary.org/rhodium/Rhodium/chemistry/extraction_theory.html .