- definite and constant composition throughout the system molecules which upon exhaustive fractionation fails to yield fractions

with different properties - free from other substance (impurities)

Solids melting point, freezing pt, solubility Liquids- refractive index, boiling point, density

PURIFICATION TECHNIQUE: RECRYSTALLIZATION

1. Governed by the solubility of a solid in a solvent increases with increase in temperature and decreases with decrease in temperature.
2. Purification is based on differences in the solubility of the solids and impurities in a given solvent.

Steps of purification through crystallization 1. Choosing the appropriate solvent 2. Dissolving the impure sample in a suitable solvent at or near the boiling point to form a nearly saturated solution. 3. Decolorization: Addition of activated carbon/charcoal is used to absorb all colored impurities. 4. Filtering the hot solution to remove any insoluble impurity. Allowing the hot solution to cool slowly thus causing some of the dissolved substance to crystallize out. Crystals are well formed in slow cooling, whereas at rapid cooling, precipitation occurs. If crystals do not form: Seeding (to serve as nuclei for crystal growth) Scratching (disturb equilibrium of the supersaturated solution) 5. Separating the crystals from the supernatant solution (also called mother liquor) by filtration. 6. Test for purity melting point. If found to be impure, recrystallization can be repeated until pure.

Choice of Solvent
1. Non-reactive with solutes 2. Dissolves most substance to be crystallized in hot solution and crystallize most of the substance when cold. 3. It should dissolve either the substance of interest or only the impurities, but not both. 4. Boils at a temperature below the compounds melting point. 5. It should yield well formed crystals of the desired substance. 6. Easy to separate from the crystals using filtration. Moderately volatile, so crystals can readily be dried. 7. Nontoxic, nonflammable and inexpensive.

1. If the sample dissolved immediately in 1 mL of the solvent or upon slight warming, the solvent is unsuitable.

2. If all solids does not dissolved even on heating, another ml of the solvent is added and heat is again applied. If until after 3 mL of the solvent and is still undissolved even when heated, the solvent is unsuitable.
3. If the solid dissolves in the hot solvent, the test tube is cooled to determine whether crystallization occurs. If no crystals appear, this maybe due to the absence of nuclei for crystal growth. The glassware can be scratched with a glass rod below the surface of the solution or seeded with a few crystals. If no crystals form, the solvent is not suitable. 4.

Synthesis of Acetanilide

(Reaction mechanism: Nucleophilic Acyl Substitution)

Synthesis of Acetanilide

(Reaction mechanism: Nucleophilic Acyl Substitution)

Clear,light red oily liquid with aromatic odor

Clear colorless liquid with strong vinegar odor

White glistening crystals

d= 1.02 g/mL MW= 93.13 g/mole

1.08 g/mL 102.9 g/mole

1.219 g/mL 135.17 g/mole

PURIFICATION TECHNIQUE: SUBLIMATION A purification technique for organic solids using heat to increase the vapor pressure of the solid, to convert it directly to gas without undergoing the liquid phase. Upon cooling, the crystals are of higher purity.

Figure 1. Phase Diagram

Factors affecting sublimation:

1. Desired compounds must have relatively high vapor pressure naphthalene, anthracene, benzoic acid, salicylic acid, beta-naphthol, camphor, iodoform, and acetanilide. 2. Desired compound does not decompose upon heating. 3. Sample must be able to be recondensed.

Advantages of sublimation technique 1. Less tedious and shorter to perform compared to recrystallization. 2. Less contamination in the desired product.

Disadvantages of sublimation technique 1. A considerable amount of solute may be lost while heating. 2. Limited to a few compounds with have relatively high vapor pressure. 3. Impurities may also sublime with the desired substance, even if repeatedly done to purify mixture.

Identification of Substance/Purity Test

Benzoic acid is a weak acid that's used as a preservative. It's naturally ocurring in many fruits in trace amounts. The largest natural source of benzoic acid is from the gum of the Chinese Balsam tree, called gum benzoin. Gum benzoin is typically 13-20% benzoic acid.

Physical properties: Color and Nature Melting Point 122 0 C Specific Gravity 1.321

White, crystalline flakes Boiling Point 2490 C Solubility in water 0.29 g/100 ml

TEST for PURITY using Melting Point Determination 1. Melting point temperature range at which the crystals start to melts and the last crystal disappear. Melting range for pure substances - =/< 0.5 0C. 2. Heat of fusion amount of energy needed to convert the sample from solid to its liquid states, by disrupting the intramolecular forces that are taking place in the crystal lattice. 3. A pure substance has a sharp and narrow melting point. Impurities can lower the melting point (colligative properties) and broaden the melting point range.

Factors to ensure proper melting point determination 1. Well-grounded/pulverized 2. Well-packed 3. No spaces (absence of air/moisture) 4. Dry sample 5. Small amount of sample, to ensure uniform heating
Upon melting, the following phenomenon can take place 1. Decomposition 2. Oxidation 3. Rearrangement 4. Hydration 5. Polymorphs (oxalic acid-118/1210C mpt) Mixed melting point method