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Kelly
INTRODUCTION
H
R C OH
R'
R''
R C OH
R'
Alcohols have a much higher boiling point than ethers or alkanes of similar
molecular weight. This is due to the association of alcohols in the liquid phase through
hydrogen bonding. For example, the boiling point of butyl alcohol is118C whereas the
boiling point of the isomeric diethyl ether is 36C.
Hydrogen Bonds
R
-
O
+ H
II.
H +
O
-
Procedure
I.
Solubility of Alcohols
Because of the hydrogen bonding possible between the polar hydroxyl group of
an alcohol and water, many alcohols are soluble in water. However as the carbon
content of an alcohol goes up, the solubility decreases. This is often described as the 5Carbon Rule, since the point at which an alcohol is no longer soluble in water is often
(but not always) reached when it contains 5 or more carbons. However, alcohol
structure (either 1, 2 or 3) also has an effect on solubility.
PROCEDURE
1. Add each of the following alcohols dropwise to 1 mL of water. Count the
number of drops needed to cause a phase separation, but do not use more than 10
drops. If you have added 10 drops of alcohol, and no phase separation has been
observed, the alcohol should be classified as completely miscible in water.
Record your observations as very soluble(6-9 drops), soluble (2-5 drops), or
insoluble (1-drop)
1. absolute ethyl alcohol
2. n-butyl alcohol
3. sec-butyl alcohol
4. tert-butyl alcohol
5. cyclohexanol
6. Unknown
II.
alcohol that reacts fastest. DO NOT POUR THE ALCOHOL DOWN THE
DRAIN UNTIL YOU ARE SURE NO SODIUM REMAINS.
1. absolute ethyl alcohol
2. n-butyl alcohol
3. sec-butyl alcohol
4. tert-butyl alcohol
5. cyclohexanol
6. Unknown
III.
The hydroxyl (OH) group of an alcohol is a poor leaving group and is not
redily displaced by nucleophiles. However, in strongly acidic solutions, protonation of
the -OH can occur to give -OH2+ and water may be displaced. The alcohol may,
depending on its structure, give substitution by either Sn1 or Sn2 mechanisms.
PROCEDURE
1. Add 5-7 drops of each of the following alcohols to each of 6-inch test tubes
and add to each test tube 2-3 mL of Lucas Reagent prepared by dissolving 16 g of
test to be valid, the alcohol must be initially soluble in the Lucas Reagent. The
formation of a milky or opaque solution is evidence for formation of the
insoluble alkyl chloride. Note the time required for the mixture to become
cloudy or to separate into two layers. Place test tubes that have not reacted after
10 minutes in a beaker of boiling water for 15 minutes. Observe any changes.
Write an equation to describe the reaction, if any.
1.
2.
3.
4.
IV.
n-butyl alcohol
sec-butyl alcohol
tert-butyl alcohol
Unknown
Oxidation of Alcohols
Primary and secondary alcohols are oxidized rapidly to acids and ketones,
respectively, by Cr and Mn oxidizing agents. Tertiary alcohols are not easliy oxidized,
however, over time in an acidic environment, they are dehydrated to alkenes.
Oxidation of Primary, Secondary and Tertiary Alcohols with the Jones Reagent :
CrO 3/H2SO4
PROCEDURE
1. Prepare the Jones Reagent by adding 2 grams of sodium dichromate to 10 mL
of water. Then add, slowly, with stirring, 2 mL of Conc. sulfuric acid. Pour 2
mL each of this solution into four 6-inch test tubes and add 2 mL of the following
alcohols to different test tubes.
1. n-butyl alcohol
2. sec-butyl alcohol
3. tert-butyl alcohol
4. Unknown
2. Stir each tube and note any rise in temperature(use you hand as a guide) or
change in color. Report your observations. In an acidic solution, the dichromate
ion, which is usually an orange-red color, is oxidized to the Cr+3 ion. This ion is
usually a dark green color but may form a dark precipitate with the carboxylate
group.
V.
I2 as
oxidising
agent
-
OH / I2
OH / I2
OH / I2
-
OH
O
R C CH3 + 2 HI Oxidation to methyl ketone
O
R C CH2I
O
R C CHI2
O
R C CI3
O
R C O + CHI3 Formation of iodoform
PROCEDURE
1. Add 4 drops of isopropyl alcohol to 5 mL of dioxane in a test tube and shake
until all the sample has gone into solution. You may need to stopper the test tube to get
adequate shaking. Add 1 mL of 10% sodium hydroxide solution, and then iodinepotassium iodide solution, with shaking, until a slight excess yields a definite dark color
of iodine. If less than 2 mL of the iodine solution is decolorized, place the test tube in a
water bath maintained at a temperature of 60. If the slight excess of iodine already
present is decolorized, continue the addition of iodine solution with shaking until a
slight excess of iodine solution again yields a definite dark color. The addition of
iodine is continued until the dark color is not discharged by 2 minutes heating at 60.
This excess of iodine is removed by the addition of a few drops of 10% sodium
hydroxide solution with shaking. Now fill the test tube with water and allow to stand
for 15 minutes. Observe the results. Iodoform is a light yellow solid.
The iodine-potassium iodide solution has been prepared by adding 200 g of
potassium iodide with 100 g of iodine to 800 mL of distilled water and stirring until
solution is complete
H+
RCH2OCOR' + H2O
R'CO2-Na+ + H2O
(a)
(b)
DATA SHEETS
Include these Data Sheets in with your report
I.
SOLUBILITY TESTS
Alcohol
ethyl alcohol
n-butyl alcohol
sec-butyl alcohol
tert-butyl alcohol
Cyclohexanol
Unknown
A.
Drops of H 2 O
II.
A.
Show below the general reactions of the sodium with water and the various
alcohols (except the unknown).
B.
III.
A.
Show, below, the complete mechanism for the reaction of Lucas Reagent with the
various alcohols(except the unknown).
B.
Offer an explanation of the relative rate of reaction for each of the alcohols.
IV.
OXIDATION OF ALCOHOLS
Alcohol
Rate of Reaction with Jones Reagent
n-butyl alcohol
sec-butyl alcohol
tert-butyl alcohol
Unknown
A.
Show a balanced equation for the reaction of the Jones Reagent with each of the
alcohols.
V.
IODOFORM TEST
A.
Show a balanced equation for the reaction of isopropyl alcohol with iodine in a
base solution.
VI.
FORMATION OF ESTERS
ACID
Acetic acid
Butyric acid
Salicylic acid
A.
ALCOHOL
amyl alcohol
ethyl alcohol
methyl alcohol
SMELL
Show the reactions for the formation of ester for each of the following.
a. Acetic acid + amyl alcohol