IV. Experimental E. Tests for Alcohols and Phenols 1. Reaction of Alcohols 1.

1 Reaction with Sodium Metal Twenty drops of n-butyl alcohol were placed in a 5mL test tube. A tiny piece of Na metal was added. The rate of evolution of bubbles were observed and recorded. Repeat the same procedure using sec-butyl alcohol and tert-butyl alcohol. 1.2 Lucas Test Twenty drops of Lucas reagent and 10 drops of n-butyl alcohol were placed in a 5mL test tube. With a stopper, the test tube was shaken vigorously. A formation of an insoluble layer was observed and timed. Repeat the same procedure using sec-butyl alcohol and tert-butyl alcohol. 1.3 Reactions with Potassium Twenty drops of n-butyl alcohol were placed in a 5mL test tube. The solution was acidified with the addition of 2M H2SO4. Five drops of 3% K2Cr2O7 was added. Observations were recorded. Repeat the same procedure using sec-butyl alcohol and tert-butyl alcohol. V. Results E. Tests for Alcohols and Phenols 1. Reaction of Alcohols Table 1: Reaction with Na metal Sample Visible Rate of Result Reaction n-butyl evolution of most rapid alcohol gas/bubbles bubbling sec-butyl evolution of mild alcohol gas/bubbles bubbling tert-butyl evolution of Very mild alcohol gas/bubbles bubbling Table 2: Lucas Test Sample Visible Rate of Result Formtation n-butyl No Slow alcohol change secFormation Moderate butyl of layers alcohol tertClear to Fast butyl light blue alcohol Table 3: Reaction with Potassium

Sample n-butyl alcohol

Visible Result

Formula 3+ Cr

sec-butyl alcohol tert-butyl alcohol

Cr

3+

Cr2O7

2-

VI. Discussion E. Tests for Alcohols and Phenols 1. Reaction of Alcohols Reaction with Na Metal: The reaction of alcohol with sodium metal form salts called alkoxides. It is a test for reactive hydrogen, hydrogens which are acidic will react with a sodium metal by the following equation: The hydrogen gas diffuses out of the liquid as a series of bubbles. It is based on the rate in which the sodium metal replaces the OH- group and reduces it to hydrogen gas. The order of reactivity of alcohol to sodium metal is known to decrease with the increasing size of the alkyl portion of the alcohol. The rate of bubbling measures the acidity of the alcohol. It has been observed that the faster rate of bubbling, the more acidic the compound is. With this, it is possible to differentiate primary, secondary and tertiary alcohols from each other. Thus, n-butylalcohol is the most acidic and has the fastest rate of evolution of H2 gas, followed by sec-butylalcohol then tert-butylalcohol being the least acidic. Lucas Test: This test also determines the primary, secondary and tertiary alcohols from each other. The Lucas reagent is composed of zinc chloride in concentrated hydrochloric acid. Its reaction with alcohols produces alkyl chlorides as its products. This test focuses on the rate of formation of an insoluble layer. An insoluble layer shows that the alcohol is soluble in the reagent and the alkyl chloride is not; forming a second layer or an emulsion in the solution. The solubility of alcohol

Formula H2 H2 H2

Formula none

in the reagent limits the test to alcohols with less than seven carbons only. The reaction goes as H from HCl protonates the hydroxyl group (-OH) of the alcohol and leaves as water. Then, the nucleophile Cl will replace the hydroxyl group producing the insoluble alkyl chloride. This is a substitution reaction, specifically a halogenation process.
+

this, since tertiary alcohols do not have this H atom, they dont have any reaction with the dichromate ion. Primary and secondary alcohols could react with potassium dichromate and can also be distinguished from each other for they will produce different products during oxidation.

Tertiary and secondary alcohols form the insoluble alkyl chloride layer that is observed in the solution. The alcohol that forms the most stable carbocation will react to form the alkyl chloride at a faster rate. When the carbocation intermediate is more stabilized by a greater number of electron-donating alkyl group bonded to the carbon atom, the formation of the insoluble layer is much faster. Thus, primary alcohols do not give a reaction with HCl because the primary carbonium ion is too unstable to serve as an intermediate for the mechanism. While, the reactivity of secondary and tertiary alcohols to the Lucas reagent gives form to the insoluble layer as its intermediate carbonium ion is stable. Theoretically, the order of rate of formation of the insoluble layer would be Tertbutylalcohol>sec-butyl alcohol>n-butylalcohol. Sec-butyl would react in 5 minutes while n-butyl alcohol does not have a reaction with Lucas reagent at room temperature. Secondary alcohols will react slowly,while tertiary, benzylic and allyl alcohols react instantly.

Primary alcohols are the most reactive with potassium dichromate. Primary alcohols form aldehydes on its first oxidation and forms carboxylic acids upon further oxidation when there is excess of the oxidizing agent. On the other hand, secondary alcohols form up until ketones only. Tertiary alcohols are generally unreactive with potassium dichromate because the oxidizing agent has nothing to remove.

Primary Alcohol: Reaction with Potassium/Jones Test: This test also distinguishes between primary, secondary and tertiary alcohols. Their reactivity with potassium dichromate, or Jones reagent, would be the basis for this test. Jones reagent is a solution of chromic acid (H2Cr2O7) prepared by dissolving CrO3 in concentrated H2SO4. The chromic acid is the oxidizing agent. Unlike Lucas Test, this test is not limited in the solubility of alcohols thus scientists rely on it the most. The reaction with potassium dichromate + would require the alcohol to have H attached to the hydroxide group to be able to oxidize it. With Secondary alcohol:

Tertiary alcohol: No reaction Change in color from orange to green would indicate a secondary or primary alcohol. A change in color implies that a reductionoxidation reaction took place. Dichromate ion is reduced causing chromium ions to be released. These chromium ions cause the change in color from orange to green of the primary and secondary alcohols.

References: Cady, S.S. (2012). Qualitative Analysis of Alcohols, Aldehydes, and Ketones. Retrieved from: http://www.esu.edu/~scady/Experiments /Alcohols(summer).pdf Chem 4563: Organic Qualitative Analysis Alcohols-Functional Group. Retrieved from: Testshttp://faculty.swosu.edu/william.kell y/pdf/qo4.pdf Clark, J. (2003). Oxidation of Alcohols. Retrieved from: http://www.chemguide.co.uk/organicpro ps/alcohols/oxidation.html Lucas Test. Retrieved from: http://www.organicchem.org/oc2web/lab /exp/oxid/lucas.pdf