ALCOHOLS,

EATERS AND
CARBOXYLIC ACIDS
Alcohols
The homologous series of alcohols

— C — OH Functional group: hydroxyl group

—

General formula ： CnH2n+1OH

Name: alkane stem + -anol e.g.

methanol
ethanol
propanol
Classifying alcohols

H H R3

—
—

R1 — C — OH R1 — C — OH R1 — C — X

—
—

H R2 R2

Primary alcohol Secondary alcohol Tertiary alcohol

1 alkyl group 2 alkyl groups 3 alkyl groups
 Alcohols with more than one ─OH group

Secondary alcohol
OH
Primary alcohol Primary alcohol Primary alcohol

—
HO—CH2CH2—OH HO—CH2CHCH3

ethane-1,2-diol propane-1,2-diol
Properties of alcohols

● Alcohols have higher boiling points than alkanes of the same chain length. Because
alcohols have hydrogen bond.

● Small alcohol molecules are miscible (mix and dissolve well) in water. This can also
be explained by having hydrogen bond.
The following table describes the chemical formula of five alcohols.

name methanol ethanol Propan-1-ol Butan-1-ol Pentan-1-ol

formula CH3OH CH3CH2OH CH3(CH2)2OH CH3(CH2)3OH CH3(CH2)4OH

Which of these alcohols should be the least soluble in water?

The longer the carbon chain length, the less the solubility of the alcohol in water.
Comparing the acidity of alcohols and water

K1 ＜ K2
 δ- δ-
CH3-CH2-O-H H-O-H

Electron-donating group ：
has the effect of concentrating
more negative charge on O
atom, so the ethoxide ion more
readily accept H+ than OH-.
Question
1 a. Explain how hydrogen bonds arise:
i. between ethanol molecules
ii. between ethanol and water molecules.

b. Explain why ethanol mixes with water in all proportions but hexan-1-ol is less
miscible with water.

c. Give the structural formula of 2-methylbutan-2-ol, and classify it as a primary,

secondary or tertiary alcohol.
d.
i. Give the structural difference that makes an alcohol a weaker acid than
water.

ii. Suggest which type of alcohol is the weakest acid:

A. a primary alcohol
B. a secondary alcohol
C. a tertiary alcohol
D. no difference
Reactions to make alcohols

1. electrophilic addition of steam, H2O(g),

using concentrated phosphoric(V) acid, H3PO4, as catalyst
2. oxidation of alkenes with cold, dilute, acidified potassium manganate(VII)
form a diol
3. nucleophilic substitution (hydrolysis in this case) of a halogenoalkane
heating with NaOH (aq)
4. reduction of an aldehyde (to form a primary alcohol) or of a ketone (to form
a secondary alcohol)
using a reducing agent, such as NaBH4 or LiAlH4 （ a stronger reductant ）
5. reduction of a carboxylic acid using NaBH4 or LiAlH4
or H2 (g) / Ni and heat
6. hydrolysis of an ester by heating with a dilute acid or alkali
Reactions of the alcohols

1. Combustion

Completely combustion:

alcohol + oxygen → carbon dioxide + water

a clean blue flame in a good supply of air

2.1 Nucleophilic Substitution to form a halogenoalkane
using hydrogen halide

alcohol + hydrogen halide → halogenoalkane + water

HCl: dry HCl gas be made in the reaction vessel using the reaction NaCl + H 2SO4 → NaHSO4 + HCl
 δ+ δ-
CH3CH2 — OH
CH3CH2 — Cl + H2O

:Cl δ-
_

H δ+
2.2 Nucleophilic Substitution to form a halogenoalkane
using Sulfur dichloride oxide, SOCl2

C2H5—OH + SOCl2 → C2H5—Cl + HCl + SO2

Both are gases, can escape from the reaction mixture.

NO NEED to heat the reaction.

2.3 Nucleophilic Substitution to form a halogenoalkane
using phosphorus halides

• Solid phosphorus(V) chloride, PCl5

C2H5—OH + PCl5 → C2H5—Cl + HCl + POCl3

Observation: white steamy fumes, HCl gas.
HCl gas can be used as a test for the hydroxyl group.

• Phosphorus(III) chloride, PCl3, does require heating.

heat
3C2H5—OH + PCl3 3C2H5—Cl + H3PO3
For bromoalkanes and iodoalkanes:
red phosphorus and bromine or iodine are warmed with the alcohol.

heat
3C2H5—OH + PBr3 3C2H5—Br + H3PO3

heat
3C2H5—OH + PI3 3C2H5—I + H3PO3
Question
2 a. Starting with an alkene, give the reactants and conditions needed to produce:
i. propanol
ii. propane-1,2-diol

b. Write a balanced equation for the complete combustion of

i. propan-1-ol
ii. butan-1-ol

c. Write a balanced equation to show the reaction between ethanol and hydrogen
bromide.
i. What are the reagents and conditions used for this reaction?
ii. What do we call this type of reaction?
3. Reaction of sodium metal

alcohol + sodium → sodium alkoxide + hydrogen

2C2H5 O — H + 2Na → 2C2H5O- Na+ + H2 less vigorous

ethoxide

2HO — H + 2Na → 2Na+ OH- + H2 more vigorous

basic ionic compound H2 gas

Other alcohols react in a similar way with sodium.
Which alcohol react with sodium more vigorous, ethanol or butanol? Why?

C2H5 O — H + Na →

C4H9 O — H + Na →

NOTE:
the longer the hydrocarbon chain in the alcohol,
the less vigorous the reaction with sodium metal
alcohol + sodium → sodium alkoxide + hydrogen

Sodium ethoxide

Sodium propoxide

Sodium butoxide
Question
3 Lithium reacts with alcohols in a similar way to sodium.
A small piece of lithium metal is dropped onto a watch-glass containing propan-1-ol.
a. Describe what you would observe.
b. Name the products of the reaction.
c. Suggest what difference you would see if you used sodium instead of lithium in this
reaction.
4. Esterification: condensation reaction

strong acid
carboxylic acid + alcohol ⇄ ester + water

O O
strong acid
=

=
CH3 C —OH + H—OC2H5 ⇄ CH3C —OC2H5 + H2O

ethanoic acid ethanol ethyl ethanoate water

● Condition: heated under reflux with a strong acid catalyst

(usually concentrated H2SO4 or H3PO4).
● The reaction is reversible.
● The esters formed usually have sweet, fruity smells
 formula name

acid part + alcohol part alcohol part + acid part

H O

H C C H H
ethyl ethanoate
Name of ester H O C C H

H H
O

H C H H H
propyl methanoate
O C C C H

H H H
 Heating under reflux with acid, usually dilute H2SO4

Hydrolysis of esters

Heating under reflux with alkali, eg. NaOH

Question

4. a. Name the ester formed in each of the following reactions :

i. butan-1-ol + ethanoic acid
ii. ethanol + hexanoic acid
iii. pentan-1-ol and methanoic acid.

b. Write the structural formula of each ester formed in part a.

5. Dehydration: elimination reactions

Condition:
alcohol vapour passed over hot Al2O3 powder.

Pieces of porous pot or pumice, as well as a

concentrated acid, also catalyse the reaction
pumice
Question

5 Concentrated sulfuric acid or phosphoric acid can be used to catalyse the dehydration of
an alcohol.
The alcohol and concentrated acid are heated to about 170 °C. The concentrated acid
does not change chemically during the reaction.
a. Write an equation showing the dehydration of ethanol using concentrated sulfuric acid.

b. If propan-1-ol was used instead of ethanol, name the organic product formed.
6. Oxidation

H H R3
—

—
R1 — C — OH R1 — C — OH R1 — C — X
—

—
H R2 R2

Condition:
be oxidized by potassium dichromate(VI) solution, K2Cr2O7 , acidified
with dilute sulfuric acid / acidified K2Cr2O7 solution
 H
—

R1 — C — OH + acidified K2Cr2O7 solution → R1 — C = O + Cr3+ (aq)

—
—

R2 orange color R2 green color

secondary alcohol ketone

use [O] to represent the oxidising agent
 H
—

R1 — C — OH + acidified K2Cr2O7 solution → R1 — C = O + Cr3+ (aq)

—
—

H orange color H green color

primary alcohol aldehyde

R1 — C = O refluxing with
+ → R1 — C = O
excess acidified K2Cr2O7 solution
—

—
H OH

aldehyde carboxylic acid

Question
6 Propan-1-ol can be oxidised to propanal, CH3CH2CHO, and then further oxidised to
propanoic acid, CH3CH2COOH.
a. Give the reagents and conditions that should be used to oxidise propan-1-ol to propanal.

b. Write a balanced chemical equation for this oxidation.

c. Give the reagents and conditions that should be used to oxidise propan-1-ol to
propanoic acid.

d. Write a balanced chemical equation for this oxidation.

Question
7 Given three unknown alcohols, one primary, one secondary and one tertiary, state
the method of distinguishing the tertiary alcohol.
Before warming with the labelled alcohol, each of these tubes contained orange acidified K2Cr2O7 solution.
After warming, the orange Cr2O7 2- have been reduced to green Cr3+ by the primary and secondary alcohols.
This is because both the primary and secondary alcohols have been oxidised, but the tertiary alcohol has not.
Functional Group: -OH, hydroxyl
General formula: CnH2n+2O
diol: CnH2n+2O2
Name and classification: 1°, 2°, 3°
Structure: saturated
Physical property:
1. High m.p.: H bonding
2. Soluble in water: the longer the carbon
chain, the less soluble in water
3. Low acidity: lower than H2O & 3°-ol has
R-OH the weakest acidity

Preparation method:
Carboxylic acid
 Reactions that form carboxylic acids

1. Oxidation of primary alcohol Condition: reflux with excess acidified

K2Cr2O7 solution / KMnO4 solution

H
—

R1 — C — OH + [O] → R1 — C = O + [O] → R1 — C = O

—
—
—

H H OH

primary alcohol aldehyde carboxylic acid

2. Hydrolysis of nitriles, R-C≡N Condition: reflux with dilute HCl

CH3CH2 - CN + HCl + 2H2O → CH3CH2 - COOH + NH4Cl

Reactions as typical acids

CH3COOH(aq) ⇄ CH3COO- + H+
ethanoic acid ethanoate

Weak acid: partially dissociated in water

Reduction of carboxylic acids

Condition: LiAlH4 in dry ether at room temperature

CH3COOH + 4[H] → CH3CH2OH + H2O

• LiAlH4: lithium tetrahydridoaluminate

• The liquid ether is dried because LiAlH4 reacts violently with any water present