Post lab discussion 1

MJP

Experiment 1: Solubility 2: Isolation of caffeine 3: Recrystallization and Melting point determination 4: Steam distillation 5: Chromatography

Solubility

Solubility of Organic Compounds

Strong base (Amine) Weak acid (Phenol) Strong Acid (Carboxylic acid) Neutral Substance (Aldehyde, ketone, alcohol, ester)

Solubility category
(1) Solutions in which both the solvent and the solute are covalent (molecular). (2) Ionic solutions in which the solute ionizes and dissociates.

General guidelines covalent bonding

All hydrocarbons are non polar Compounds with electronegative atoms (O, N, S) are generally polar
Check for the presence of C=O, C-O, OH, NH and CN

The presence of electronegative halogens (Cl,I,Br) does not alter the polarity of an organic compound in a significant way (slightly polar)

When comparing compounds of the same family, adding carbon to the chain decreases the polarity
Hydrogen bonding increases solubility in water

Solubility in 5% HCl
The possibility of amine should be considered if a compound is soluble in 5% HCl. R NH2 + HCl R-NH3+ + Cl-

Solubility in 5% NaHCO3 and 5% NaOH Compounds that dissolve in sodium bicarbonate(weak base) are strong acid Compounds that dissolve in sodium hydroxide(strong base) may either be a strong or weak acid.
Strong acids Soluble in both NaOH and NaHCO3 Weak acids Soluble in NaOH but not in NaHCO3

Sulfonic acids R-SO3H Carboxylic acids RCOOH

Phenols ArOH

Solubility in Concentrated sulfuric acid

Alcohols, ketone, aldehydes and esters, alkenes, alkynes, ethers, nitroaromatics and amides Compounds that are soluble in concentrated sulfuric acid but not in dilute acid are extremely weak bases. Almost any compound with N, O or S can be protonated.

Inert compounds
Compounds that are not soluble in concentrated sulfuric acid or any other solvent are INERT. Alkanes, simple aromatics, alkyl halides.

NaHCO3

Acetone

S1

Aniline Benzyl alc

B N

_ _

_ _

+ _

Benzaldehyde

Benzoic acid

A1

Benzamide

Ethyl alcohol

S2

Hexane Phenol

I A2

_ _

_ + _

Isolation of caffeine

Solid Liquid extraction

Solid Liquid Extraction
Caffeine is soluble in hot water as well as tannins and other impurities Tannins are acidic compounds Calcium carbonate (as a base) calcium salts are formed; removed by filtration

Water insoluble compounds: cellulose, proteins and lipid materials Over 200 compounds are extracted in hot water

Liquid liquid extraction

Liquid-Liquid Extraction Caffeine is extracted with chloroform or dimethylchloride The solute (caffeine) distributes itself between two immiscible liquids (Chloroform and water) The equilibrium is: A (aq) A (org) K = [A] org / [A] aq

Why is it advisable to perform liquidliquid extraction using small portions of solvents rather than one large volume?

Good qualities of solvent for liquid-liquid extraction

Immiscible with the first solvent (usually water) Target compound should be soluble in extracting solvent Major impurities should not be soluble should be sufficiently volatile Non toxic

Extraction efficiency
1.0g of organic compound is dissolved in 100.0mL of water. Compare the extraction efficiency with two 30.0mL portions of ether versus one time 60.0mL extraction. The distribution coefficient at 298K is 8.36.

Emulsions
Colloidal suspension of one liquid to another; minute droplets of an organic solvent often are held in suspension in an aqueous solution when the two are mixed vigorously. How to minimize emulsions 1. Add sodium chloride 2. Add water soluble detergent 3. Gentle swirling or shaking of the sep funnel 4. Filter the mixture 5. Separate by using a centrifuge

Steam distillation

Steam distillation is the distillation of a mixture of water (steam) and an organic compound (or mixtures of it)
Criteria for compounds to be steam distillation: 1. Must have a high boiling point 2. Immiscible with water 3. May decompose if direct distillation is attempted

Principle
Raoults Law: = * for miscible liquids

= + for immiscible liquids

During boiling, The total vapor pressure of the mixture is equal to the atmospheric pressure. The temperature boils at a lower temperature than the boiling points of any one components. 0 = 0 The composition of the distillate and the boiling point is constant throughout the process.

BP and composition of distillates

mixture
Boiling point of pure substance Boiling point of mixture Composition (% water)

Benzene-Water

80.1

69.4

8.9

Octane- water

125.7

89.6

25.5

1-Octanol-water

195.0

99.4

90.0

At 760 mmHg, bromobenzene (C6H5Br, bp 155C) steam distills at approximately 95C. Calculate the approximate amount of water needed to steam distill 20 g of bromobenzene.

(at 95C, the vapor pressure of water is 634mmHg)

Recrystallization and Melting point determination

Crystallization vs precipitation
Precipitation rapid formation of an amorphous solid - occurs when a hot saturated solution is cooled too quickly Crystallization slow formation of crystalline solid - impurities tend to be excluded from the growing crystal structure (why?)

Crystallization a purification technique for impurities that have a different solubility with your target compound. Recrystallization further crystallization to obtain a purer compounds. Steps in crystallization: 1. Choose the best solvent 2. Dissolving the compound in a minimum amount of hot solvent. 3. Filter to remove impurities 4. Cool the crystal slowly.

What is the best solvent?

(C)
(A) Grams Soluble

(B)
temperature

Solvent for crystallization

Ideal solvent:

1. Does not react with the compound 2. Boils at a temperature below the compounds melting point 3. Dissolves a large amount of compound when hot and small amount at room temperature 4. Moderately volatile 5. Non toxic, non flammable and inexpensive

Supersaturated solution
A hot solution cools to room temperature yet there is no crystal formation. What will you do?

1. Is the solution supersaturated? 2. Too much solvent?

Melting point
Primary index of purity for crystalline compounds MP is a physical property of that substances. MP can be used to identify a substance The purer the material, the higher is the melting point The purer the material, the more narrow is the melting point range

Effect of impurities
*pure organic compounds has a sharp melting point (range of 1.0C or less) *impure compound a broader range (3.0C or more)

Chromatography

Chromatography
Mikhail Tsweet coined the term CHROMATOGRAPHY, from the Greek words chroma color and graphein writing.

Chromatography is a physical method of separation in which the components to be separated are distributed between two phases, one which is stationary (stationary phase), while the other (the mobile phase) moves in a definite direction. IUPAC

 Mobile phase: moving fluid liquid or gas or supercritical fluid carries the components of the sample through volume or layer of particles of solid materials Stationary phase: solid support, sorbent, static phase, packing material

Classification
Based on the physical means by which the stationary and mobile phases are brought into contact 1. Column chromatography = stationary phase is held in a narrow tube through which the mobile phase is forced under pressure/gravity

2. Planar chromatography = stationary phase is supported on a flat plate or in the interstices of paper; here, the mobile phase moves thru the stationary phase by capillary action or under the influence of gravity

Based on the types of mobile and stationary phases and the kinds of equilibria involved in the transfer of solutes between phases.

Distribution constant

Kc = distribution constant; partition ratio; partition coefficient

If the stationary phase is POLAR: the least polar substance moves out of the column last (Column Chrom) or the spot is on top of the paper (Paper Chrom)

If the stationary phase is NON-POLAR: the most polar subtances moves out of the column first (Column Chrom)

Paper chromatography liquid-liquid partitioning technique

Stationary phase adsorbed water molecules cellulose Mobile phase Solvent 1: pet ether:diethyl etheracetone - Solvent 2: pet ether:acetone (which of the two solvent system is able to separate many pigments in the leaf?)

- AA: 1:2 2% ammonium hydroxide: isopropyl alcohol * Solvent moves through capillary action*

Cellulose absorbs 22% water.

Most polar substance is strongly held, least polar substance moves up the top of paper Paper chromatography is applied to the separation of highly polar substance or those that are polyfunctional. (sugars, amino acids, natural pigments)

Rf value (paper chrom)

Rf values (ratio to front or retention factor) Rf = distance travel by substance/distance travelled by solvent Low Rf value ---- strongly bonded to the stationary phase High Rf value ------strong attraction to the solvent (least bonded to the stationary phase)

Thin layer chromatography- solid-liquid partitioning technique

Stationary phase silica or alumina on a support (polar) Mobile phase ------- solvent system 6:2:2 (v/v/v) n-butanol-ethanol-NH3

Important uses of TLC in organic chemistry

1. To establish if two compounds are identical 2. To determine the number of components in a mixture 3. To determine the appropriate solvent for column chromatography 4. To monitor column chromatography separation 5. To check the effectiveness of separation 6. To monitor the progress of reaction

Rf value for TLC

1. 2. 3. 4. The solvent system Adsorbent Thickness of the adsorbent layer Relative amount of material spotted

Rf values can be used to identify the unknown only when the conditions are completely specified.

Techniques and problems encountered 1. Spotting --- the smaller the spot, the better the separation 2. Development ---- the chamber should be lined with filter paper to saturate the air with solvent vapors for speedy development 3. Solvent System --- trial and error