Reactions of Alcohols and Thiols

Copyright © 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings

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Solubility of Alcohols
 Alcohols with low molar masses (methanol, ethanol, and propanol)
 very soluble in water
 are capable of forming hydrogen bonds with water molecules

2
Solubility of Alcohols
 Alcohols with higher molar masses
 less soluble in water
 the increasing size of the nonpolar chain disrupts the hydrogen
bonding network

 As the number of carbons in the alcohol increases, the solubility

decreases.

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Alcohol Solubility in water Solubility in oil
methanol Yes No
denatured ethanol Yes No
1-propanol Yes No
isopropanol No Yes
1-butanol No Yes
1-pentanol No No
1-hexanol No No
1-0ctanol No No

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denatured alcohol
 alcohol products adulterated with toxic and/or bad tasting
additives 
 (e.g., methanol, benzene, pyridine, castor oil, gasoline, isopropyl alcohol,
and acetone)
 making it unsuitable for human consumption.

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6
Combustion of Alcohols
Combustion is the reaction of an alcohol
with O2 to produce CO2 and H2O.
2CH3OH + 3O2 2CO2 + 4H2O + Heat

Copyright © 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings
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Dehydration of Alcohols
Dehydration of an alcohol occurs
 When heated with an acid catalyst.
 With the loss of —H and —OH from adjacent carbon
atoms.
H OH
| | H+, heat
H—C—C—H H—C=C—H + H2O
| | | |
H H H H

alcohol alkene
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Learning Check
Write the equations for the reactions when
2-propanol undergoes:
1. combustion

2. dehydration

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Formation of Ethers

 Ethers form when dehydration takes place at low

temperature.
H+
CH3—OH + HO—CH3 CH3—O—CH3 + H2O
two methanol dimethyl ether

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Oxidation and Reduction

In the oxidation of an organic compound

 There is an increase in the number of C—O
bonds.
 There is a loss of H.

In the reduction of an organic compound

 There is an decrease in the number of C—O
bonds.
 There is a gain of H.

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Oxidation and Reduction

Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

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Oxidation of Primary (1) Alcohols
When a primary alcohol is oxidized [O],
 One H is removed from the –OH.
 Another H is removed from the carbon bonded to the OH.
 An aldehyde is produced.
[O]
Primary alcohol Aldehyde
OH O
| [O] ||
CH3—C—H CH3—C—H + H2O
|
H
Ethanol Ethanal
(ethyl alcohol) (acetaldehyde)
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Oxidation of Secondary (2) Alcohols
When a secondary alcohol is oxidized [O],
 One H is removed from the –OH.
 Another H is removed from the carbon bonded to the OH.
 A ketone is produced.
[O]
secondary alcohol ketone
OH O
│ [O] ║
CH3—C—CH3 CH3—C—CH3 + H2O
│
H
2-propanol (isopropyl alcohol) 2-propanone(dimethyl ketone,
“acetone”) 14
Oxidation of Tertiary (3)Alcohols
Tertiary alcohols do not readily oxidize.
[O]
Tertiary alcohol no reaction
OH
│ [O]
CH3─C─CH3 no product
│
CH3 no H on the C-OH to oxidize

2-methyl-2-propanol

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Learning Check

Select the compound that would result for each reaction

of CH3—CH2—CH2—OH.
O
||
1) CH3—CH=CH2 2) CO2 + H2O 3) CH3—CH2—C—H
A. H+, heat

B. [O]

C. O2, heat
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Oxidation of Ethanol in the Body

In the body,
 Ethanol is oxidized by enzymes in the liver.
 Aldehyde product impairs coordination.
O O
║ ║
CH3─CH2─OH CH3─C─H CH3─C─OH
ethyl alcohol acetaldehyde acetic acid

2CO2 + H2O

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Ethanol CH3─CH2─OH
Ethanol
 Acts as a depressant.
 Kills or disables more
people than any other drug.
 Is metabolized at a rate of
12-15 mg/dL per hour by a
social drinker.
 Is metabolized at a rate of 30 Copyright © 2007 by Pearson Education, Inc.

mg/dL per hour by an

Publishing as Benjamin Cummings

alcoholic.

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Effect of Alcohol on the Body

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Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings
Learning Check
Select the product for the oxidation of
OH
│ [O]
CH3—CH—CH2—CH3

O
║
1) CH3—CH=CH—CH3 2) CH3—C—CH2 —CH3

OH
│
3) CO2 + H2O 4) CH3—CH—CH2—CH3 20
21
Oxidation of Thiols
When thiols undergo oxidation,
 An H atom is lost from each of two –SH groups.
 The product is a disulfide.
[O]
CH3—SH + HS—CH3 CH3—S—S—CH3 + H2O

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Types of alcohol and their uses
 Ethanol – safe for humans
 Other alcohols – for cleaning and manufacturing but not for making
drinks
 Methanol
 component of fuel for cars and boats
 used to manufacture antifreeze, paint remover, windshield wiper fluid
 poisonous
 Isopropyl alcohol (rubbing alcohol)
 Cleaning and disinfecting
 poisonous

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Ethyl alcohol

 Product of fermentation of yeast, sugars and starches

 Fit for human consumption but in limited quantities
 overconsumption damages the liver, brain and other organs over time
 inhibits the central nervous system, thus imparing coordination and
judgement
 develops addiction

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Categories
 Undistilled – fermented drinks
 Wine and beer
 Wineries - ferment grapes
 Breweries – ferment barley, wheat and other grains

 Distilled – process following fermentation

 Bacteria or yeast chemically convers sugar into ethanol
 Liquors and spirits
 Contain more alcohol by volume (ABV) than undistilled
(mL ethanol /100mL
 Has higher alcohol proof (twice the percentage of ABV)
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50% ABV is 100 proof
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 Alcohol Alcohol conten
Undistilled alcohol content (ABV) Distilled Alcohol (ABV)
 
Gin (wheat or barley) 35% - 55%
Light beer 2% - 4 %
Malt liquor(beer) 6% - 8% Brandy (distilled wine) 35% - 60%
Wine < 14% Cognac 40%
Champagne 10% - 12%
Whiskey (fermented grain) 40% - 50%
Fortified wine ~ 20%
Hard cider (fermented Rum (fermented sugar
apple juice) 5% cane or molasses 40%
Tequila (Mexican agave
Mead (water + fermented plant) 40%
honey) 10% - 14%
sake (Japanese wine - Vodka (fermented grains
fermented rice) 16% and potatoes) 40%
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