Rogeni Misaelle M. Petinglay B.S. in Chemistry II
Date performed: April 6, 2017 Date submitted: April 7, 2017
Experiment No. 9 ORGANIC DERIVATIVES OF WATER I.
Summary of Results
Table 1. Solubility Behavior Sample
1-butanol
Solubility Test 10% H20 H2SO4 NaOH S+
-
Observations H20
10% NaOH
+
Colorless with emulsions, oily layer
2 layers, emulsions
2 layers, bubble suspennsions upon shaking
2-butanol
+
-
+
Colorless -> turbid white (upon shaking) -> colorless
t-butyl alcohol
+
-
+
Colorless w/ small white particles
2 layers,
+
2 layers, yellow bubbly upper layer, coloress bottom layer
2 layers, yellow upper layer, colorless bottom layer
Turbid white on top, dirty white on bottom
Gelatinous cloudy white solution w/ small white precipitates
Diethyl ether
S+
Phenol
Legend:
-
+
-
-
= soluble
n/a
S+ = slightly soluble
H2SO4 Colorless, soluble, exothermi c Neon yellow, soluble, exothermi c Yellow, soluble, exothermi c Pale brown, soluble, exothermi c
n/a
- = insoluble
Table 2. Reaction with Potassium Permanganate Sample 1-butanol 2-butanol
Before heating Brown violet solution with dark violet precipitate Brown dark violet solution with
KMnO4 After heating Light brown solution with dark violet precipitate Dark brown solution with
Result + +
violet precipitate t-butyl alcohol Diethyl ether Phenol
Dark violet solution Dark violet solution with violet precipitate Light brown solution with dark brown precipitate
dark brown precipitate Dark violet solution, no changes Dark brown solution with dark brown precipitate Pale yellow -> brown solution with dark red precipitate, light red precipitate on the surface
Table 3. Reaction with Ammoniacal Silver Nitrate Ammoniacal AgNO3 Sample Before heating After heating Colorless liquid, 1-butanol Colorless liquid emulsions 2-butanol Colorless liquid Colorless liquid t-butyl alcohol Colorless liquid Colorless liquid Diethyl ether Colorless liquid Colorless liquid Colorless bottom Pale yellow solution layer with pale yellow Phenol with emulsions, dark upper layer brown precipitate
Table 4. Lucas Test: Reaction with HCl – HCl – ZnCl ZnCl2 Mixture HCl – HCl – ZnCl ZnCl2 Mixture Sample Observations 1-butanol Colorless solution 2-butanol Colorless solution -> Cloudy white solution t-butyl alcohol Colorless solution -> Cloudy white solution Diethyl ether Colorless liquid Phenol Colorless solution
+
+
Result -
Results + + -
Table 5. Reaction with Ferric Chloride Sample 1-butanol 2-butanol t-butyl alcohol Diethyl ether Phenol
Ferric Chloride Observations Colorless solution -> Pale yellow solution Colorless solution -> Pale yellow solution Colorless solution -> Pale yellow solution Colorless solution -> Pale yellow solution Colorless solution -> light violet with emulsion
Result +
Table 6. Iodoform Test: Reaction with I2, NaOH Sample Before addition of NaOH 1-butanol 2-butanol t-butyl alcohol Diethyl ether Phenol
II.
Orange solution, 2 layers Orange solution, 2 layers, oily upper layer 2 layers, yellow orange upper layer, orange bottom layer 2 layers, orange upper layer, yellow orange bottom layer 2 layers, orange upper layer, gelatinous pink bottom layer
After addition of NaOH 2 layers, pale yellow upper layer, la yer, colorless lower layer 2 layers, pale yellow upper layer, la yer, colorless lower layer
Result
Soluble, pale yellow solution
-
2 layers, yellow upper layer with some yellow immiscible liquid
-
2 layers, colorless upper layer, oily white turbid lower layer
-
-
Discussion
Solubility Behavior This part of the experiment examined the solubility of the each sample in water, 10% NaOH and H2SO4 if insoluble in the basic solvent. solvent. The samples used were 1-butanol, 2-butanol, t-butyl alcohol, diethyl ether, and phenol. Solubility in Water. The presence of a polar functional group in a sample will be soluble in water following the rule “like dissolves like”. Alcohols are insoluble in water except if they are in Carbon-6. The more branching is present in a compound, the more it will be soluble because branching lowers intermolecular forces and deceases intermolecular attraction. The higher the number of carbon atoms, the more nonpolar the compound making it insoluble in water. Diethyl ether is a diprotic solvent which means that it has limited solubility in water. In the experiment, results showed that phenol was insoluble in water while 1-butanol and diethyl ether are slightly soluble. Samples soluble in water are 2 -butanol and t-butyl alcohol. Solubility in 10% NaOH. A compound is deemed soluble in NaOH if it is significantly soluble in water. Insoluble compounds in this solvent are some sodium salts with highly substituted phenols. In In the experiment, all of the samples were were insoluble in this solvent. Alcohols are insoluble in NaOH solution because it is the hydroxide reacting with the alcohol, not the sodium ions (Rxn: NaOH + R-OH -> R-ONa + H2O). The free energy difference between the products and reactants side of the equation is not very large, however, so there will be some equilibrium between hydroxide ions (OH-) and alkoxide ions (R-O-) in solution, which will depend on the pKa of the alcohol (Net ionic equation: OH- + R-OH -> R-O - + H2O). The reaction of phenol with NaOH gave a gelatinous cloudy white solution w/ small white precipitates. Theoretically, it should give a colorless solution containing sodium phenoxide. Phenol behaves as an acid and gives up its proton to the OH- which is a base that is why it dissolves in NaOH solution. Solubility in H2SO4. Sulfuric acid protonates all organic compounds that contains oxygen and/or nitrogen, as well as few aromatic carbons and alkenes. The reaction of the compound with
this solvent may produce color changes and heat. In the experiment all the samples tested as observed to have an exothermic reaction. Some color changes were observed in 2-butanol (colorless to neon yellow solution), t-butyl alcohol (colorless to yellow solution), diethyl ether (yellowish to pale brown solution). In 1-butanol, no color change was observed.
Reaction with Potassium Permanganate Baeyer's reagent is an alkaline solution of cold potassium permanganate, which is a powerful oxidant making this a redox reaction. Reaction with double or triple bonds in an organic material gives a positive test which includes the disappearance of purple color and appearance of brown precipitate. In the experiment, all of the samples turned into a brown colored solution with the appearance of precipitates except for t-butyl alcohol which had no changes. Tertiary alcohols cannot be oxidized for the reason that all the hydrogen atoms are already filled or occupied by the remaining 3 spaces needed and there are no hydrogen atoms attached to the alcohol carbon. KMnO4 oxidizes phenol to para-benzoquinone while alcohols will be oxidized to carbonyls.
R eaction eaction with Tollen’s reagent (Ammoniacal (Ammoniacal Silver Nitrate) Tollens' reagent is a chemical reagent used to determine the presence of an aldehyde, aromatic aldehyde and alpha-hydroxy ketone functional groups and not for alcohols. The reagent consists of a solution of silver nitrate and ammonia. It can oxidize aldehydes into corresponding carboxylate ion, while it reduces itself to metallic silver. The aldehyde itself is oxidised to a salt of the corresponding carboxylic acid because the solution is alkaline. Only phenol reacted to the reagent but it was not a positive result. The solution turned pale yellow instead of a silver mirror” solution. The rest of the samples remained colorless.
Lucas Test: Reaction with HCl – HCl – ZnCl ZnCl2 Mixture Lucas test distinguishes tertiary, secondary and primary alcohols from each other by using zinc chloride as the reagent in concentrated hydrochloric acid. It is based on the rate of formation of insoluble alkyl chloride. An emulsion is formed. This test is reliable only for alcohols that are fairly soluble in water. The rate of reaction of the alcohols is determined by the ease of formation of the carbocation intermediate. Tertiary alcohols react quickly because they form a relatively stable tertiary carbocation while secondary alcohols react more slowly because the secondary carbocation is less stabilized than the tertiary carbocation. Primary alcohols generally take to react, about an hour. The reaction of a tertiary alcohol, involves a Lewis acid- base reaction between zinc