Tutorial Hydroxy Compounds

EUNOIA JUNIOR COLLEGE

ORGANIC CHEMISTRY
Hydroxy Compounds
Tutorial
2018 JC2
Self-Attempt Questions
*1. (a) Draw the full structural formulae for all the alcohols with the molecule C5H12O and classify
them into primary, secondary and tertiary alcohols. Indicate the chiral centre(s) in your
structure(s) with an asterisk. There are 8 possible structures.
(b) Name the alcohol(s) which will produce only one possible product upon dehydration.
(c) One of the alcohols in (a) cannot undergo dehydration. Give the name of the alcohol.
(d) Some of the alcohols in (a) produces yellow precipitate when heated with alkaline I2. Name
the alcohols and write equations to explain the observations made.
(e) Name the alcohol(s) in (a) which upon heating under reflux with acidified K2Cr2O7
respectively,
(i) Gives no visible reaction.
(ii) Produces a compound which on adding solid Na2CO3 gives effervescence. Gas evolved
produces white precipitate when bubbled into Ca(OH)2(aq).

*2. Predict the major product of the reactions by balancing the following equations.
Indicate “No Reaction” if the reaction does not occur. State the type of reaction undergone in
each case.

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Discussion Questions

3. Arrange the following in order of increasing acidity and explain how you derive your answer:
phenol, 2-nitrophenol, ethanol, methylpropan-2-ol, water, 2-methylphenol [4]

4. (a) Draw the structural formula of each of the organic

products formed and state the type of reactions
undergone when a compound with the structure on the
right is treated with the following reagents:

(i) sodium metal

(ii) aqueous sodium hydroxide
(iii) phosphorus pentachloride
(iv) aqueous bromine
(v) acidified K2Cr2O7(aq), with immediate distillation
(vi) acidified K2Cr2O7(aq), heat under reflux
(vii) acidified KMnO4(aq), heat under reflux [8]
(b) State the observations for the reaction of the above compound with reagents (iii) to (v). [4]

5. Outline simple chemical tests to distinguish the following pairs of organic compounds and
state what would be observed. When appropriate, write balanced equations to illustrate your
answer.

(a) ethene and ethanol (7 possible tests)

(b) butan–1–ol and butan–2–ol (1 possible test)
(c) cyclohexanol and phenol (4 possible tests)
[15 + 3 + 12]

6. Suggest how the following conversions can be carried out, indicating all necessary
reagents and conditions and showing clearly all the intermediates.

(a) propyl propanoate from propan-1-ol as the only starting material

(b)

from
[5 + 7]

*7. A compound Y has molecular formula C8H10O and exists as a pair of enantiomers. It reacts with
phosphorus pentachloride to give HCl and gives a yellow precipitate when aqueous alkaline
iodine is added. Suggest a possible identity for Y and explain the reactions involved (i.e. state
the type of reactions undergone by the compounds and state the functional groups of the
compounds formed).
[4]
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*8. Alcohol B forms esters which are responsible for the flavours of various fruits and has the
molecular formula C5H12O. Reaction of B with acidified potassium dichromate(VI) produces a
compound C, C5H10O2. Heating B over Al2O3 produces D, C5H10, as the only organic product.
Vigorous oxidation of D forms 2-methylpropanoic acid as one of the products.
Suggest structures for B, C and D and explain the reactions involved (i.e. state the type of
reactions undergone by the compounds and state the functional groups of the compounds
formed).
[6]

*9. Alcohol J, CxHyOH, is a volatile fungal metabolite whose presence when detected in air can
indicate hidden fungal attack on the timbers of a house.
When 0.10 cm3 of liquid J was dissolved in an inert solvent and an excess of sodium metal
added, 10.9 cm3 of gas (measured at 298 K) was produced.
When 0.10 cm3 of liquid J was combusted in an excess of oxygen in an enclosed vessel, the
volume of gas (measured at 298 K) was reduced by 54.4 cm3. The addition of an excess of
NaOH(aq) caused a further reduction in gas volume of 109 cm3 (measured at 298 K).
(i) Use these data to calculate values for x and y in the molecular formula CxHyOH for J.
Alcohol J reacts with acidified K2Cr2O7, and can be dehydrated to alkene K. On treating K with
an excess of hot acidified concentrated KMnO4, an equimolar mixture of ethanoic acid and
propanone is produced.
(ii) Use this information to deduce the structural formulae for J and K, explaining your
reasoning.
(iii) Suggest suitable reagents and conditions for the conversion of J into K.
(iv) Explain whether K can show geometrical isomerism.
[8]
N2010/III/3(d)

*10. To determine the structure of compound W (C10H12O2), the following tests were conducted and
the observations noted below. Deduce the structures of W and X (3 possible structures for
both), giving your reasoning:
 1 mole of W reacts with excess sodium metal to produce 1 mole of an explosive gas.
 W reacts to give a yellow precipitate with iodine and aqueous sodium hydroxide.
 W decolourises aqueous bromine in the dark to form X (C10H12O3Br2) as the major product.
[12]
Multiple Choice Questions:

11. N05/II/39 (modified)

C6H5CH2OH and C6H5OH react in a similar way with a reagent Z.
What could Z be?
1. ethanoyl chloride 2. aqueous sodium hydroxide 3. aqueous bromine

A All are correct.

B Only 1 and 2 are correct.
C Only 2 and 3 are correct.
D Only 1 is correct.

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*12. N08/I/20
Which two-stage process will not give a good yield of 1,2-dibromocyclohexane?
A

13. N07/I/26
All the isomeric alcohols with the molecular formula C5H12O are added separately to warm
alkaline aqueous iodine.
How many isomers will give a yellow precipitate? (Ignore stereoisomers)
A 0 B 1 C 2 D 3

14. N09/I/24
Ajulemic acid is a derivative of cannabis which does not have any hallucinogenic properties. It is
being developed as a pain killer.

Which reaction will ajulemic acid undergo?

A It reacts with dilute nitric acid to form an addition product.
B It will form a diester on heating with ethanol under reflux in the presence of a catalytic
amount of concentrated sulphuric acid.
C It will turn a heated acidified solution of potassium dichromate(VI) from orange to green.
D It reacts with Br2(aq) to incorporate up to 4 atoms of bromine in each molecule.

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Suggested Solutions to Self-Attempt Questions

*1. (a)

primary primary primary

primary

secondary
secondary tertiary

secondary
(b) Pentan–1–ol, 3–methylbutan–1–ol, 2–methylbutan–1–ol
Pentan–3–ol is not accepted as it forms an alkene which can exhibit geometrical
isomerism.
(c) 2,2–dimethylpropan–1–ol
(d)

(e) (i) 2–methylbutan–2–ol

(ii) Pentan–1–ol, 3–methylbutan–1–ol, 2–methylbutan–1–ol, 2,2–
dimethylpropan–1–ol

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*2. Predict the major product of the reactions by balancing the following equations.
Indicate “No Reaction” if the reaction does not occur. State the type of reaction undergone in
each case.
(a)

Type of reaction: nucleophilic substitution

(b)

Type of reaction: nucleophilic substitution

(c)

Type of reaction: redox

(d)

(e)

Type of reaction: oxidation

(f)

Type of reaction: oxidation

(g)

Type of reaction: oxidation

(h)

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2* (i)

Type of reaction: electrophilic substitution

(j)

Type of reaction: electrophilic substitution

(k)

Type of reaction: condensation

(l)

Type of reaction: elimination

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Suggested Solutions to Discussion Questions

3. Relative acidity:
methylpropan-2-ol < ethanol < water < 2-methylphenol < phenol < 2-nitrophenol

In general, acidity: alcohol < water < phenol.

The relative acid strength depends on the relative stability of the respective conjugate
bases, namely the phenoxide, the hydroxide and the alkoxide ions. The more stable the
conjugate base, the more acidic the compound.

Alcohols
 contain alkyl groups which are electron donating, intensify negative charge on O
atom
 destabilise the alkoxide ions (compared to hydroxide ions)
 acidity decreases as number of alkyl group increases.
 Acid strength: methylpropan-2-ol < ethanol

Phenols
 phenoxide ions are resonance-stabilised as the negative charge on O atom is
delocalised into the ring due to the overlapping of the p–orbital of the oxygen atom
with the –electron cloud of the benzene ring.
 Acid strength: water < phenol

Phenol containing an electron-donating substituent (e.g. alkyl group)

 less acidic than an unsubstituted phenol
 delocalisation of negative charge into the ring is hindered
 resulting substituted phenoxide ion is destabilized (compared to phenoxide ion)
 Acid strength: 2-methylphenol < phenol

Phenol containing an electron-withdrawing substituent (e.g. nitro group)

 more acidic than an unsubstituted phenol
 delocalisation of negative charge into the ring is enhanced.
 resulting substituted phenoxide ion is destabilized (compared to phenoxide ion)
 Acid strength: phenol < 2-nitrophenol

4. (a) Draw the structural formula of each of the

organic products formed and state the type of
reactions undergone when a compound with
the structure on the right is treated with the
following reagents:

(i) sodium metal

Type of reaction: redox [1]

aqueous
(ii) sodium
hydroxide

Type of reaction: acid-base [1]

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[1]
phosphorus
(iii)
pentachloride

Type of reaction: nucleophilic substitution

Observations: white fumes of HCl evolved [1]

[1]
aqueous
(iv)
bromine
Type of reaction:
electrophilic substitution and electrophilic addition [1]
Observations: Red-brown Br2(aq) decolourises initially and
white ppt if formed. [1]

acidified
K2Cr2O7(aq), [1]
(v)
distil
immediately
Type of reaction: mild oxidation
Observations: orange K2Cr2O7 turns green. [1]

acidified
K2Cr2O7(aq),
(vi)
heat under
reflux
Type of reaction: oxidation [1]

Acidified
KMnO4(aq),
(vii)
heat under
reflux
Type of reaction: oxidation [1]

(b) State the observations for the reaction of the above compound with reagents (iii) to (v).
(see answers in (a)(iii) to (v))

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5. (a) Ethene and ethanol

(Note that ethene is a gas and should be bubbled into the reagents instead.)

Test 1: Add Br2 (in CCl4) to each of the two substances in separate test
tubes at room temperature, in the absence of uv light.

Observation:
For ethene, rapid decolourisation of orange-red Br2 is observed.
CH2=CH2 + Br2  CH2BrCH2Br
For ethanol, no decolourisation of orange-red Br2 observed.

Test 2: Add a small piece of Na(s) to each of the two substances in

separate test tubes at room temperature

Observation:
For ethene, no gas is evolved
For ethanol, bubbles of gas observed. Gas extinguishes a lighted split with a
‘pop’ sound.
CH3CH2OH + Na  CH3CH2O-Na+ + ½ H2

Test 3: Add a small spatula of PCl5(s) to each of the two substances in

separate test tubes at room temperature
Observation:
For ethene, no steamy white fumes evolved.
For ethanol, steamy white fumes of HCl evolved.
CH3CH2OH + PCl5  CH3CH2Cl + POCl3 + HCl

Test 4: Add I2(aq), followed by NaOH(aq) to each of the two substances in

separate test tubes and heat each mixture.

Observation:
For ethene, no yellow ppt formed
For ethanol, yellow ppt of CHI 3 is formed.
CH3CH2OH + 4I2 + 6NaOH  CHI 3 + HCOO–Na+ + 5NaI + 5H2O

Test 5: Add KMnO4(aq) acidified with dilute H2SO4(aq) to each of the two
substances in separate test tubes and heat each mixture.

Observation:
For ethene, decolourisation of purple KMnO4 observed. Effervescence seen. Gas
evolved forms white ppt when bubbled into Ca(OH)2(aq).
CH2=CH2 + 6[O]  2CO2 + 2H2O
For ethanol, decolourisation of purple KMnO4 observed. No effervescence seen.

Test 6: Add cold KMnO4(aq) with dilute NaOH(aq) to each of the two
substances in separate test tubes.

Observation:
For ethene, decolourisation of purple KMnO4 observed with the formation of
black MnO2(s).
CH2=CH2 + [O] + H2O  CH2(OH)CH2OH
For ethanol, no decolourisation of purple KMnO4 observed.

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Test 7: Add K2Cr2O7(aq) acidified with dilute H2SO4(aq) to each of the two
substances in separate test tubes and heat each mixture.

Observation:
For ethene, solution remains orange.
For ethanol, orange K2Cr2O7(aq) turns green.
CH3CH2OH + 2[O]  CH3COOH + H2O
(b) butan–1–ol and butan–2–ol

Test: Add I2(aq), followed by NaOH(aq) to each of the two substances in

separate test tubes and heat each mixture.

Observation:
For butan–1–ol, no yellow ppt formed
For butan–2–ol, yellow ppt of CHI 3 is formed.
CH3CH2CH(OH)CH + 4I2 + 6NaOH  CHI 3 + CH3CH2COO–Na+ + 5NaI + 5H2O
(c) cyclohexanol and phenol

Test 1: Add neutral FeCl3(aq) to each of the two substances in separate

test tubes at room temperature.

Observation:
For cyclohexanol, no violet colouration observed.
For phenol, violet colouration observed.
3
3+ +
Fe (aq) + 6 OH Fe O + 6H
6

Test 2: Add a small spatula of PCl5(s) to each of the two substances in

separate test tubes at room temperature

Observation:
For cyclohexanol, steamy white fumes of HCl evolved.

For phenol, no steamy white fumes evolved.

Test 3: Add Br2(aq) to each of the two substances in separate test tubes
at room temperature.

Observation:
For cyclohexanol, no decolourisation of orange Br2 and no white ppt observed.
For phenol, decolourisation of orange Br2 observed with the formation of a white
ppt.

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Test 4: Add K2Cr2O7(aq) acidified with dilute H2SO4(aq) to each of the two
substances in separate test tubes and heat each mixture.

Observation:
For cyclohexanol, orange acidified K2Cr2O7 turns green.

For phenol, orange acidified K2Cr2O7 remains.

6. (a)

(b)

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7.

C:H  1:1

6 () – [3]
4-5 () – [2]
2-3 () – [1]

8. Evidence Conclusion
Oxidation occurred.
Note:  in 1O,  in 2H  B is a primary alcohol and C is a
carboxylic acid.
Elimination of water occurred.
 D is an alkene OR D has one C=C.
Oxidative cleavage of C=C occurred.
 C=C in D is present at the terminal C.
Upon oxidation, one carbon atom is lost as
Note:  in 1C CO2.

Structure of D is

Structure of B is

Structure of C is

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9. (i) CxHyOH(l) + Na(s)  ½H2(g) + CxHyONa+( l)

10.9
Amount of H2 (g)   4.54  104 mol
24000
Amount of Cx Hy OH  2  4.54  104  9.08  104 mol

4x  y  1 y 1
CxHyOH(l) + O2(g)  xCO2(g) + H2O(l)
4 2
Change in volume  Final volume of gases  Initial volume of gases
54.4   Vol. of O2 left  Vol. of CO 2 produced   Initial vol. of O2
54.4  Initial vol. of O 2   Vol. of O 2 left  Vol. of CO2 produced 
54.4  Initial vol. of O2  Vol. of O 2 left   Vol. of CO 2 produced
54.4  Vol. of O2 reacted  Vol. of CO 2 produced
Vol. of O2 reacted  54.4  Vol. of CO 2 produced
 54.4  109
 163.4 cm3
163.4
Amount of O2 (g)   6.81 103 mol
24000
109
Amount of CO2 (g)   4.54  103 mol
24000

Amount of J : Amount of CO 2 (g) : Amount of O 2 (g)

9.08  10 4 : 4.54  10 3 : 6.81  10 3
1 : 5.00 : 7.50
4x  y  1
1 : x :
4
4x  y  1
 7.5
x = 5 and 4 J is C5H11OH
y  11
(ii) Alcohol J reacts with acidified K2Cr2O7.
 Oxidation occurred of alcohol occurred
 J is either a primary or secondary alcohol.

 Oxidative occurred. C=C is broken.

 K is and J is .
(iii) Excess concentrated H2SO4, 170C
(iv) K cannot exhibit geometric isomerism due to two identical –CH3 groups that are
bonded to one of the carbon atom in the carbon–carbon double (C=C) bond.

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10. Evidence Conclusion

High C:H ratio
 W has a benzene ring.
Redox reaction occurred. Explosive gas is
H2(g).
 W has –OH group.
1 mole of W reacts to give 1 mole of H2(g)
 W has 2 –OH groups.
Oxidation occurred. Yellow ppt is CHI3.

 W has the following structure:

Electrophilic addition across C=C occurred

Note:  in 2 Br,  in 1 O
to form a bromohydrin.
 W has one C=C bond.
(Note:  in 1 Br,  in 1 O,  in 1 H)
Electrophilic substitution occurred.
 W is a phenol.
(Note:  in 1 Br,  in 1 H)
Only one Br was substituted onto the
benzene ring
 W is either 2,4– or 2,6–disubstituted
phenol.

Possible structures of W Possible structures of X

[8 marking points, max 6 + 6 marks for structures. Total = 12]

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Suggested Solutions to Multiple Choice Questions

11. N05/II/39 (modified)

C6H5CH2OH (phenylmethanol) and C6H5OH (phenol) react in a similar way with a reagent Z.
What could Z be?
1. ethanoyl chloride
Both undergo condensation reaction with ethanoyl chloride (CH3COCl) to form ester.
2. aqueous sodium hydroxide
Only phenol is acidic enough to under acid-base reaction with NaOH(aq).
3. aqueous bromine
Only phenol with undergo electrophilic substitution with Br2(aq) to form
2,4,6-tribromophenol.

A All are correct.

B Only 1 and 2 are correct.
C Only 2 and 3 are correct.
D Only 1 is correct.

*12. N08/I/20
Which two-stage process will not give a good yield of 1,2-dibromocyclohexane?
A

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13. N07/I/26
All the isomeric alcohols with the molecular formula C5H12O are added separately to warm
alkaline aqueous iodine.
How many isomers will give a yellow precipitate? (Ignore stereoisomers)

A 0 B 1 C 2 D 3

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14. N09/I/24
Ajulemic acid is a derivative of cannabis which does not have any hallucinogenic properties. It is
being developed as a pain killer.

Which reaction will ajulemic acid undergo?

A It reacts with dilute nitric acid to form an addition product.
Phenol undergoes electrophilic substitution to form a substituted product.
B It will form a diester on heating with ethanol under reflux in the presence of a catalytic
amount of concentrated sulphuric acid.
Only the carboxylic acid group undergoes condensation with ethanol to form one
ester group.
C It will turn a heated acidified solution of potassium dichromate(VI) from orange to green.
All three functional groups present are resistant to oxidation with K2Cr2O7, hence
K2Cr2O7(aq) will remain orange.
D It reacts with Br2(aq) to incorporate up to 4 atoms of bromine in each molecule.
The alkene undergoes electrophilic addition with Br2(aq) and will incorporate 2 Br
atoms to form the minor product.
The phenol undergoes electrophilic substitution with Br2(aq) and will incorporate 2 Br
atoms to from the substituted product (only two of the three substitution positions
are available for substitution)

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