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Hydroxy Compounds 12 Candidates should be able to:

17.1 Introduction to hydroxy 1 (a) write the general formula for hydroxy compounds;
compounds (b) name hydroxy compounds according to the IUPAC nomenclature;
(c) describe structural and optical isomerism in hydroxy compounds;
(d) state the physical properties of hydroxy compounds.

17.2 Alcohols 6 Candidates should be able to:

(a) classify alcohols into primary, secondary and tertiary alcohol;
(b) classify the reactions of alcohols whereby the ROH bond is broken: the formation of
an alkoxide with sodium, esterification, acylation, oxidation to carbonyl compounds and
carboxylic acids;
(c) classify the reactions of alcohols whereby the ROH is broken and OH is replaced by
other groups: the formation of haloalkanes and the dehydration to alkenes and ethers;

(d) explain the relative reactivity of primary, secondary and tertiary alcohols as
exemplified by the reaction rate of such alcohols to give haloalkanes, and the reaction
products of KMnO4/K2Cr2O7 oxidation in the presence of sulphuric acid;
(e) explain the reaction of alcohol with the structure CH3CH(OH) with alkaline aqueous
solution of iodine to form triiodomethane;
(f) describe the laboratory and industrial preparation of alcohol as exemplified by
ethanol from the hydration of ethane;
(g) describe the synthesis of ethanol by fermentation process;
(h) state the uses of alcohols as antiseptic, solvent and fuel

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Alcohol

1. Organic compound with at least one hydroxyl group (–OH) which act as functioning group.
2. Alcohol has the general formula of CnH2n+1OH or sometimes CnH2n+2O.
3. The naming of alcohol end with -ol.

Nomenclature of alcohol (naming & classifying alcohol)

The way of naming alcohol is similar to the way of naming alkene
[1] Find the longest carbon chain with –OH in it, and name accordingly
[2] Identify the alkyl group that attached towards the “parent” chain and name the alkyl
[3] Give the prefix of di- ; tri- or tetra based on how many similar alkyl attached toward it
[4] Give the numbering of alkyl based on the carbon number based on alcohol

Exercise 1

1. Name the following alcohol

Isomerism in alcohol.

Alcohol may exhibit structural isomerism and in some case, optical isomerism.
For example, butanol, C4H9OH, may have 5 different isomers

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Physical properties of alcohol

(A) Boiling point of alcohol

1. Similar to other organic compounds, the boiling point of alcohol increased with number of carbon as the weak Van Der Waals
forces increase with ………………………… of the compound.

2. Though, the hydrogen bonding are weaker when goes down to homologous series as the polarity of molecules decrease as
the number of carbon increase.

3. Similar too, to other organic compound, alcohol with more branch has lower boiling point than a straight-chain molecule.

4. Straight chain molecules have higher boiling point compare to branched chain because straight chain molecule has a
………… surface area than a branched chain molecule.

5. The more branches attached to the parent chain, the ……………. the surface area ; …………… the forces of attraction
between molecules ; ………… the boiling point

6. The number of the hydroxyl group in an organic compound is also one of the major factor which contribute to its boiling point

7. The boiling point of the alcohol increase with the number of –OH. This is a result caused by more ………………….. bond
formed between –OH of the molecules. So the more the –OH ; stronger the hydrogen bond ; higher the boiling point.

8. Compare to alkane and haloalkane, alcohol has a higher boiling point

9. Alcohol has the highest boiling point compare to other organic compound because it forms strong ……..…………. bond
between the molecules. Fluoroethane has a higher boiling point than propane as fluoroethane is a ……………………. molecules
and so, the weak ………………………… forces are stronger than propane since propane is a …………………..…. molecule.

Exercise 2

1. Arrange the following compounds in increasing order of boiling point.

(a) 1,2-ethanediol, n-butane, 1-propanol, 1,3-propanediol

(b) (CH3)2CHCH2OH, (CH3)2CH(CH2)2CH2OH, (CH3)2CH(CH2)3CH2OH

2. Arrange the following compounds in order of increasing boiling point.

I HOCH2CH2OH II CH3CH2CH2OH
III CH3CH(OH)CH3 IV HOCH2CH2CH2OH

A. II < III < IV < I B. III < II < I < IV C. I < IV < III < II D. II < III < I < IV
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B)Solubility of alcohol in water

1. Hydrogen bonding occur between alcohol molecules because of the presence of …………..……. group.

2. This bring 2 important consequences toward hydrogen where

a) It cause the boiling points of alcohol higher than those in alkanes and haloalkanes
b) It cause lower alcohol (methanol and ethanol) to be completely miscible with water.

3. Solubility decrease with the increase of number of carbon in alcohol.

4. Butan-1-ol and pentan-1-ol are slightly miscible with water and the rest become more and more insoluble.

5. This is due to the non-polar properties of alkyl which attached to the –OH, directly influence the efficiency of hydrogen bond,
causing the polar bonding to be more obvious than hydrogen bonding.

6. Ethanol is a good solvent for both polar and non polar solute because it contain non polar alkyl group and a polar hydroxyl
group in it. As a result, ethanol is used as solvent in many industries.

Exercise 3

1. Arrange the compounds in each set in decreasing order of solubility in water.

(a) ethanol, 1-pentanol, 1-hexanol
(b) hexane, 1-hexanol, 1,2-ethanediol

2. Classify the following compounds as primary, secondary or tertiary

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(C) Acidity of alcohol

1. Alcohols are generally a weak acid. Table below shows the pKa value of some alcohols and water.

pka = - log [H+] where the lower the pka value the stronger the acid

electron donating group make the compound become less acidic while electron withdrawing make it more acidic.

2. As shown in the table above, alkyl-alcohol is weaker than phenylalcohol. This is a result of the different effect of the group that
attached to hydroxyl group –OH.
3. Alkyl is an electron …………..…….. group whereas phenyl is an electron …………..……… group.

Alcohol Explanation

Ethanol dissociate in water according to the equation

CH3CH2–OH + H2O ⇋ CH3CH2–O- + H3O+
Alkyl group, which is an electron donating group, donate electron to O and caused the electron
density of O in R–OH increase. As a result, O is more readily to accept proton, which makes
the equilibrium favors to left.
Phenol dissociate in water according to the equation
C6H5–OH + H2O⇋C6H5–O- + H3O+
The phenyl group is an electron-withdrawing group, which withdrawn the electron density from
partially negative charge,δ−, from O making O less readily to accept proton. As a
result, O is more readily to donate proton which makes equilibrium favour more to right.

Quiz 1

Draw all possible structural isomers of alcohol with the molecular formula, C4H10O. Arrange these isomers in the order of
decreasing boiling point. Explain

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5.3 Chemical properties of alcohol

5.3.1 Preparation of alcohol in industries.

Alcohol can be prepared by a few methods in industries / laboratory

1. Fermentation
2. Hydration of alkene
3. Hydrolysis of haloalkane
4. Grignard reagent

Name of reaction Reagent used and condition Equation

Fermentation of glucose Zymase enzyme C6H12O6 → 2 CH3CH2OH + 2 CO2

Hydration of alkene Steam (H2O)

---------
Phosphoric acid, (H3PO4 )
At 300oC ; 60 atm
@
Concentrated
H2SO4 at 800C

Hydrolysis of haloalkane NaOH (aq) under reflux

Reaction of Grignard Aldehyde /ketone with H2SO4

reagent

Exercise 4

Draw the structural formulae of A to D in the following equations.

1. Which of the folowing reactions would not produce

alcohol?

A. Hydration of alkene
B. Alkaline hydrolysis of haloalkane
C. Fermentation of starch by yeast
D. Ozonolysis of alkene

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2. Pick the TRUE statement for the following reaction: CH3CH2Br + OH- →CH3CH2OH + Br-
A. The reaction mechanism is Sn1.
B. Reaction occur in a single step
C. The rate determining step involves CH3CH2Br.
D. The transition state involves the formation of CH3CH2+ ion

5.4 Chemical reaction of alcohol

Aliphatic alcohol undergoes 2 types of reaction which involve R–O–H where :

Fission of O – H Fission of C – O
• Formation of alkoxide • Dehydration of alcohol
• Formation of ester • Reaction with hydrogen halide
• Oxidation of alcohol • Reaction with phosphorous halide
(PX5) or thionyl chloride, SOCl2

Name of reaction Reagent used and Equation

condition
Formation of Sodium (Na)
alkoxide

Esterification Carboxylic acid

(R–COOH)
catalysed by
conc.sulphuric acid
(H2SO4)
Oxidation of Acidified KMnO4
alcohol or acidified
K2Cr2O7 + heat

Dehydration Excess conc. H2SO4

at 1800C
or
Alumina (Al2O3)
at 350oC

Halogenation Phosphorous
of alcohol pentachloride
(PCl5)

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Question

The structural formula of alcohol A is given below:

(a) Is A optically active? Explain your answer.

(b) Classify alcohol A as 10, 20 or 30
(c) Give the major product of the dehydration of A.

(1) Reaction with sodium metal

When sodium is added to alcohol, a white solid (sodium alkoxide) formed and effervescences occur and hydrogen is released.

Example :
2 CH3CH2CH2OH + 2 Na → 2 CH3CH2CH2O-Na+ + H2
Propan-1-ol sodium propoxide

Sodium alkoxide formed dissolve readily in water to form back alcohol + sodium hydroxide

The reaction is slower than when sodium reacts with water.

Reactivity decrease with the class increase 30 alcohol < 20 alcohol < 10 alcohol (more reactive)

Sodium hydroxide (NaOH) cannot react with aliphatic alcohol.

(2) Esterification : Formation of ester

When excess alcohol (R–OH) react with carboxylic acid (R”COOH) and catalysed by a few drops of concentrated sulphuric acid
and heat under reflux.
R–OH + R”COOH →R”COO–R + H2O

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Esterification can also be achieved by replacing carboxylic acid with alkanoyl chloride

Example:

Note that in the reaction above, no acidic medium is required.

Compare to carboxylic acid, alkanoyl chloride is more reactive than carboxylic acid. Also, the reaction produces a white fume of
hydrogen chloride as side product.

(3) Oxidation of alcohol

1. Using strong oxidising agent such as acidified potassium dichromate [K2Cr2O7 / H+], alcohol can be oxidise to form carbonyl
compound and even to carboxylic acid.
2. Using different categories of alcohol, different type of carbonyl compounds are formed.

Note the following changes occur in the oxidation of alcohol

1. Oxidation of primary (10) alcohol will yield an aldehyde while oxidation of secondary (20) alcohol will yield a ketone.
2. Aldehyde formed from 10 alcohol can be further oxidised to form carboxylic acid.
3. For the case of methanal, further oxidation of methanal will yield carbon dioxide and water.
4. Tertiary (30) alcohol is not oxidised when react with strong oxidising agent as it does not have H attached to the C–OH.
5. The differences in behaviour of alcohols toward oxidising agents may be used to distinguish
between 10 alcohol, 20 alcohol and 30 alcohol. So, this is consider a basic test to distinguish between the class of alcohol
used.

Quiz 2

1. Which of the following alcohol gives 2-methylpropanoic acid when it is oxidized?

A. 1-Butanol B. 2-Butanol C. 2-Methyl-1-propanol D. 2-Methyl-2-propanol

2. Reagent that can be used to differentiate between propan-2-ol from propan-1-ol is

A. FeCI3 B. Hot KMnO4 C. Alkaline iodine solution D. Aqueos NaOH
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3. Which of the following alcohols will produce (CH3)2CHCO2H when oxidized?

A. Butan-1-ol B. 2-methylpropan-2-ol C. Butan -2-ol D. 2-methylpropan-1-ol

4. Which of the following reagents can react with CH3CH2CH2CH2OH but not (CH3)3C-OH?
A. acidified K2Cr2O7 B. PCI3 C. Potassium D. C H3COCI

5. Reagent that can be used to differentiate between 2-propanol from 1-propanol is

A. FeCI3 B . hot KMnO4 C. ZnCI2/ conc HCI D. Aqueous NaOH

6. What is the product formed when 2-methyl-1-propanol is oxidized by acidified sodiumdichromate?

A. CH3CH2COCH3 B. CH3CH (CH3) CHO C. (CH3)CHCOOH D. CH3CH (COOH) COOH

In industries, oxidation of alcohol is carried under catalytic dehydrogenation, where hydrogen is removed from the alcohol,
forming aldehyde, ketone and even an alkene

Note that, unlike oxidation using acidified potassium manganate (VII), here, the side product is hydrogen gas. Furthermore,
aldehyde and ketone formed are not further oxidised.

(4) Dehydration of alcohol

1. Dehydration of alcohol is an elimination reaction where water is removed from organic compound.
2. Dehydration of alcohol can be carried out under these conditions :
3. Heating mixture of excess concentrated acid such as H2SO4 or H3PO4 at 1800C
4. Passing alcohol vapour over aluminium oxide (Al2O3) as catalyst at 3000C.
5. Dehydrating 1o alcohol will yield only 1 product whereas dehydrating 2o alcohol will yield 2 products

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The major/minor products of the alkene formed followed Saytzeff ’s

1. Rule where alkene containing the greater alkyl is predominant. (H atom from a lesser C–H is preferably to be eliminated)
2. However, if excess alcohol react with alcohol, ether is given off.

2 CH3CH2CH2OH  CH3CH2CH2–O–CH2CH2CH3 + H2O

Propan-1-ol dipropyl ether

3. Same result is given off by using aluminium oxide (Al2O3). The ease ofdehydration increase in order from
10 alcohol < 20 alcohol < 30 alcohol.

Example : Write out the possible products for dehydration of these

a) CH3CH2CH2CH2OH
b) CH3CH(OH)CH2CH3
c)C(CH3)3OH

Question
1. The following equation shows the dehydration of an alcohol forming an alkene.

Illustrate with reaction mechanism how the major product could be formed. Draw another possible product and name the rule
applied in determining the major product.

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2. Give a chemical test to distinguish between

(a) 2-methyl-1-propanol and 2-methyl-2-propanol
(b) 1-butanol and 2-propanol
(c) benzene and cyclohexanol
(d) 2-methyl-2-butanol and 2-butanol

(5) Halogenation of alcohol – formation of haloalkane

1. As introduced in the earlier chapter, haloalkane can be prepared by adding conc. hydrochloric acid (HCl) with
the aid of zinc chloride,ZnCl2 to alkene. This mixture is called as Lucas reagent.
2. Halogenation can also be carried out using halogen rich compound, such as phosphorous (V) pentachloride
(PCl5) or thionyl chloride (SOCl2).

To prepare a bromoalkane, reagent used is concentrated hydrobromic acid, HBr, catalysed by concentrated sulphuric
Acid

Question

1. Pick the suitable Grignard reagent that can be used to prepare 2-methyl-3- pentanol from propanal.
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A. ( CH3)CMgBr
B. CH3CH2MgBr
C. (CH3)2CHCHMgBr
D. CH3CH2 CH2MgBr

2. Write the complete equation for each of the following reactions.

(a) 2-butanol heated with acidified KMnO 4 solution
(b) 2-propanol heated with concentrated H 2SO4
(c) 2-methyl-1-propanol heated with acidified K 2Cr2O7 solution
(d) methanol reacts with PCl5
(e) 1,2-ethanediol with potassium
(f) glacial ethanoic acid heated with 2-propanol in the presence of concentrated H 2SO4

17.3 Phenols 5 Candidates should be able to:

(a) explain the relative acidity of water, phenol and ethanol with particular
reference to the inductive and resonance effects;
(b) describe the reactions of phenol with sodium hydroxide, sodium, acyl
chlorides and electrophilic substitution in the benzene ring;
(c) describe the use of bromine water and aqueous iron(III) chloride as tests for
phenol;
(d) describe the cumene process in the manufacture of phenol;
(e) explain the use of phenol in the manufacture of cyclohexanol, and hence,
nylon-6,6.

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5.4 Phenol and Aromatic alcohol

5.4.1 Manufacturing of phenol
There are 3 methods of making phenol.
1. The cumene process
2. The hydrolysis of chlorobenzene / diazoniumsalt
3. Alkali fusion with sodium benzenesulphonate

(1) Synthesising phenol – cumene reaction

Step 3 : Decomposition by sulphuric acid : Migration of phenyl group

(2) Hydrolysis of chlorobenzene : Dow Process

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Phenol has been process using Dow process widely in chemical industries. It generally involve 2 steps

(3) Hydrolysis of diazoniumsalt

In laboratory, phenol is prepared by hydrolysis of diazoniumsalt.
Effervescence occur and a colourless gas is given out, along with the white fume of hydrogen chloride

5.5 Chemical reaction of phenol

The –OH act as ring activating groups when attached to benzene. As a result, it activates the rings and cause benzene to
be more reactive. Consequently, phenol is more reactive toward electrophilic substitution than benzene.

(1) Halogenation of phenol

When bromine water is added to phenol at room temperature, brown colour of bromine water decolourised and formed a
white precipitate of 2,4,6- tribromophenol.

(2) Nitration of phenol

When concentrated nitric acid (HNO 3) is used to react with phenol, it formed a yellow crystalline solid of 2,4,6-
trinitrophenol. This yellow crystal is used in dyeing industries and make explosive

(3) Reaction with iron (III) chloride, FeCl3

When a few drops of iron (III) chloride solution is added to phenol, a violet-blue colouration produced. A methylphenol
produce blue colour.

5.5 Chemical Test to distinguish between alcohols

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Question

1. The structural formula of X is shown below

Draw the structural formula of the product formed when X reacts with
(a) sodium
(b) aqueous sodium hydroxide
(c) phosphorus pentachloride
(d) propanoic acid refluxed with traces of concentrated sulfuric acid

2. An alcohol C4H10O which has several isomers gave the following observations:
I Isomer L gives negative result with Lucas reagent and forms butanoic acid when oxidised with acidified potassium
dichromate solution.
II Isomer M is optically active and gives positive result with I 2/NaOH.
III Isomer N reacts instantly with Lucas reagent but does not decolourise acidified solution of potassium dichromate.
Explain the above observations and suggest the structural formulae of isomers L, M and N

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3. If bromine water is added to phenol, a white precipitate (2,4,6-tribromo phenol) is formed.

The reaction mechanism involved is
A. Electrophilic substitution
B. Free radical substitution
C. Electrophilic addition
D. Nuclephilic substitution

4. Phenol can be distinguished from ethanol by using

I. Iron (III) chloride solution
II. Bromine water
III. Iodoform test
A. I only
B. I and II
C. II and III
D. I, II and III

5. Phenol can be differentiate from 1-propanol by using

A. Bromine water
B. Fehling ‘s solution
C. Tollen’s reagents
D. potassium manganate (VII) solution

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