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Chapter 27: Separation, Purification, and Analysis

Extraction
 Simple extraction – the mixing of the organic solution with water in a separating funnel
o Thorough mixing of the 2 phases (organic and aqueous) is done, and then the mixture is allowed to settle for some time until the 2
phases separate
o Then the lower layer can be poured into another flask
o This method can separate water soluble impurities such as inorganic salts, low molecular weight carboxylic acids, and alcohols
o Extraction can be done with dilute aqueous acids to remove organic bases, and with dilute aqueous bases to remove organic acids
Crystallization
 Crystallization – dissolving the material to be purifies in a solvent under hot conditions, followed by slow cooling of the solution, and
collection of the crystals by vacuum filtration
 Quantities of the Solvent Used for Crystallization
o The compound that is purified should be soluble in the selected solvent, only at high temperatures; at low temperatures, the
compound should be insoluble
o The solvent used should have a relatively low boiling point; the boiling points of the selected solvent should not be higher than the
melting point of the compound to be purified
o Some solvents commonly used for crystallization are: acetone, chloroform, methanol, benzene, diethyl ether, carbon tetrachloride,
and water
Distillation
 Boiling of the mixture to vaporize it, followed by condensation to get the distillate, and then collected in order of their condensation
 Simple distillation – used to separate compounds, which have boiling points that sufficiently differ
 Vacuum distillation – used to separate compounds that have very high boiling points or are heat sensitive
 Fractional distillation – used for the separation of compounds that have very close boiling points
Chromatography
 Chromatography – based on the differences in the adsorption and the solubility of the compounds to be separated
o Involves 2 phases: stationary and moving phases
o The moving phase actually carries the compounds along the stationary phase
 Thin Layer Chromatography (TLC) – Used for the separation of small quantities of the desired compound, especially for qualitative
analysis
o The liquid mobile phase is allowed to run along a layer of adsorbent; this thin layer—usually alumina or silica gel—is usually coated on
a plate, and the plate is then held vertically with a small amount of the solvent just touching the bottom of the plate
o Capillary action allows for the solvent to ascend up the plate
o The sample is separated amongst the various phases
o The greater the polarity of the compound, the lesser rate of upward mobility of that compound
o Also used to monitor the progression of reactions, and to test the authenticity of the effectiveness of other separation techniques
 Gas Chromatography (GC) – Usually employed for the separation of volatile compounds
o The maintenance of the correct temperature of the column is extremely important for an efficient separation of the components
o Highly sensitive technique
o Can be used to detect compounds even if very little of the compound is present
IR Spectroscopy
 In order to analyze organic compounds, certain properties at the molecular level are put to use in the infrared spectroscopy
 The infrared light is passed thru organic compound samples, so that some of the frequencies are absorbed by the sample and the other
frequencies simply pass thru
 The percentage absorbance or transmittance is plotted against the frequency—the wave number—which is the reciprocal of wavelength
expressed in centimeters
 Vibrational Modes
o The bonds present in the molecules of the sample vibrate when they absorb characteristic frequencies
o Stretching vibrations: symmetric or asymmetric
o Bending vibrations: scissoring, rocking, wagging, or twisting
 Absorbencies
Type of Bond Absorbance (cm-1) Type of Bond Absorbance (cm-1)
OH 3200 – 3600 Ethers 1000,1300
COOH 2500 – 3300 Amines 3300 – 3500
Aromatic Ring 1500, 1600 C=O (Carbonyl) 1640 – 1750
Aromatic CH 3000 – 3100 C=O (Ketone) 1665 –1725
– CH (sp3) 2850 – 3000 C=O (Aldehyde 1660 – 1740
= CH (sp2) 3300 C=O (Amide) 1630 – 1690
 CH (sp) 2720, 2820 C=O (Ester) 1735 – 1750
Aldehyde 2210 – 2260 C=O (Acid) 1700 – 1730
CN 2210 – 2260 C=C (Alkene) 1620 – 1680
NMR
 Nuclear Magnetic Resonance Spectroscopy – type of analysis with which we can identify the positions of certain atoms in a compound
 Only those atoms which possess non-zero nuclear spins can exhibit NMR behavior
 Based on the magnetic properties exhibited by the nuclei of certain atoms
 Proton NMR – can be used to find or recognize the characteristic groups in the unknown compound, to which the specific protons are
attached and identify the number of different types of equivalent protons in a compound
o The neutrons and protons that make up atomic nuclei have an intrinsic quantum mechanical property referred to as spin
o A non-zero nuclear spin gives rise to a non-zero magnetic moment
o Protons in different regions of a molecule have different shifts
Type of Proton Chemical shift, ppm
R-CH3 (Primary) 0.9
R-CH2 (Secondary) 1.3
R2-CH (Tertiary) 1.5
HC=CH (Vinyl) 4.5 – 6
CCH (Acetylenic) 2–3
Ar-H (Aromatic) 6 – 8.5
Ar-CH (Benzylic) 2–3
C=CHCH3 (Allylic) 1.6
CHX (Halides) 2 – 4.5
CHOH (Alcohol) 3.4 – 4
CHOR (Ether) 3.4 – 4
CHCOOH (Carboxylic) 2 – 2.6
CHCOOR (Ester) 2 – 2.2
RCH=O (Aldehyde) 9 – 10
CHOH (Hydroxyl) 1 – 5.6
Ar-OH (Phenolic Hydroxylic) 4 – 12
CHCOOH (Carboxylic Acid) 10 – 12
R-NH2 (Amino) 1-5