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Appendix

APPENDIX 1 Chemical tests for functional groups

Homologous series/ Functional


Chemical tests/Observations
Typical compound group(s)

Alkanes C – C and Add liquid bromine in ultraviolet light (or sunlight):


CH3CH3 C–H White fumes of HBr liberated; decolourisation of bromine
ethane occurs slowly

Alkenes (a) Add Br2 in CCl4 at room temperature:


C=C
CH2 = CH2 Decolourisation of bromine occurs immediately
ethene CH2 = CH2 + Br2 → CH2BrCH2Br

(b) Add acidified KMnO4 at room temperature:


Decolourisation of KMnO4 occurs immediately
CH2 = CH2 + [O] + H2O → CH2 – CH2
⏐ ⏐
OH OH

Aromatic (a) Insert a glowing splint into the hydrocarbon


hydrocarbons hydrocarbons:
Burns with smoky flame

(b) Add concentrated nitric(v) acid and concentrated


benzene sulphuric acid at 55 °C:
Yellow oil with bitter almond smell produced
NO2

H2SO4
+ HNO3 (HONO2) + H2O

Alkylbenzenes – CH3 Add alkaline KMnO4 and boil:


CH3 Decolourisation of KMnO4; brown precipitate of MnO2
formed

⎯ CH3 + 3[O] ⎯ COOH + H2O


methylbenzene

Comment Oxidation of the side chain is more effective in


alkaline than acidic conditions.

Haloalkanes C–X Add silver nitrate in alcohol and warm:


R–X White precipitate for C – Cl group; cream-coloured
where R is an alkyl precipitate for C – Br group; yellow precipitate for C – I
group; X is Cl, Br or I group

Alcohols – OH (a) Add solid PCl5:


CH3CH2OH White fumes of HCl liberated
ethanol C2H5OH + PCl5 → C2H5Cl + POCl3 + HCl(g)

(b) Add glacial ethanoic acid and a few drops of


concentrated sulphuric acid and heat:
Fragrant fruity smell of ester liberated
CH3COOH + C2H5OH → CH3COOC2H5 + H2O

Appendix 1

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Homologous series/ Functional
Chemical tests/Observations
Typical compound group(s)
Aldehydes H (a) Add 2,4-dinitrophenylhydrazine at room temperature:
CH3CHO ⏐ Yellow-orange precipitate formed
ethanal –C=O NO2

CH3CHO + H2NNH ⎯ ⎯ NO2

NO2

CH3CH = NNH ⎯ ⎯ NO2 + H2O

(b) Add ammoniacal silver nitrate (Tollens’ reagent) and


warm:
CH3CHO + 2Ag+ + H2O → CH3COOH + 2Ag + 2H+
(c) Add Fehling’s solution (alkaline copper(II) complex) and
heat:
CH3CHO + 2Cu2+ + 2H2O → CH3COOH + Cu2O + 4H+
Ketones O (a) Add 2,4-dinitrophenylhydrazine at room temperature:
CH3COCH3 储 Yellow-orange precipitate formed
propanone –C–C–C NO2 NO2
CH3 CH3

C = O + H2NNH ⎯ ⎯ NO2 C = NNH ⎯ ⎯ NO2 + H2O

CH3 CH3

(b) Add Tollens’ reagent or Fehling’s solution and heat:


No reaction
Carboxylic acids O (a) Add Na2CO3 solution at room temperature:
CH3COOH 储 Effervescence and carbon dioxide gas liberated
ethanoic acid – C – OH 2CH3COOH + Na2CO3 → 2CH3COONa + CO2 + H2O
(b) Add ethanol and a few drops of concentrated sulphuric
acid and heat:
Fragrant, fruity smell of ester liberated
Ethanoate ions O (a) Add dilute sulphuric acid, then warm:
CH3COO– 储 Vinegar smell liberated
–C–O– CH3COO– + H+ → CH3COOH
(b) Add iron(III) chloride solution:
Dark red solution produced
3CH3COO– + Fe3+ → (CH3COO)3Fe
Methanoate ions O (a) Add ammoniacal silver nitrate solution, then warm:
HCOO– 储 Grey precipitate or silver mirror of metallic silver formed
H–C–O– HCOOH + Ag2O → 2Ag + CO2 + H2O
(b) Add concentrated sulphuric acid and heat:
Carbon monoxide liberated which burns with a blue flame
HCOO– + H+ → H2O + CO
Benzoate ions O (a) Dissolve the organic salt in water, then add dilute
COO– 储 hydrochloric or sulphuric acid to the aqueous solution
C6H5 – C – O – obtained:
White precipitate of benzoic acid formed

⎯ COO– + H+ ⎯ COOH

2 Appendix

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Homologous series/ Functional
Chemical tests/Observations
Typical compound group(s)

(b) Add iron(III) chloride solution:


Buff-coloured precipitate formed

3 ⎯ COO– + Fe3+ ( ⎯ COO)3Fe

Amides – CONH2 Add aqueous sodium hydroxide, then warm:


CH3CONH2 Ammonia gas liberated; it forms white fumes with hydrogen
ethanamide chloride gas
CH3CONH2 + NaOH(aq) → CH3COONa + NH3

Aliphatic primary – NH2 Add sodium nitrite (NaNO2), followed by dilute hydrochloric
amines acid, then warm:
C2H5NH2 Effervescence occurs
ethylamine NaNO2/HCl
RNH2 + O = N – OH ⎯⎯⎯⎯⎯→ ROH + N2 + H2O
(HNO2)
nitrous acid

Acyl chloride O (a) Add ethanol and shake:


CH3COCl 储 White fumes of HCl liberated
ethanoyl chloride – C – Cl On pouring reaction mixture into a beaker of water,
fragrant smell of ester produced
CH3COCl + C2H5OH → CH3COOC2H5 + HCl

(b) Add aqueous silver nitrate at room temperature:


White precipitate of silver chloride formed
CH3COCl + AgNO3 + H2O → CH3COOH + AgCl + HNO3

Amino acids – CHCOOH Add copper(II) sulphate solution:


H2NCH2COOH ⏐ Dark blue solution of copper(II) complex formed
aminoethanoic acid NH2

Phenols OH (a) Add bromine water at room temperature:


OH Decolourisation of bromine water and white precipitate
formed
OH OH
Br Br
phenol
+ 3Br2 + 3HBr

Br

(b) Add iron(III) chloride solution at room temperature:


Purple solution produced

Arylamines NH2 (a) Add bromine water at room temperature:


NH2 Decolourisation of bromine water and white precipitate
formed
NH2 NH2
Br Br
phenylamine
+ 3Br2 + 3HBr

Br

(b) Add sodium chlorate(I) solution:


Purple solution produced

Appendix 3

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APPENDIX 2 Tests to distinguish between organic compounds

(A) Aliphatic Organic Compounds

To distinguish between Chemical tests Observations


Alkene and alkane Add Br2 in CCl4 Alkene: Immediate decolourisation
(or cycloalkane) Alkane (or cycloalkane): No reaction

Alcohol and ether Add PCl5 Alcohol: White fumes of HCl


Ether: No reaction

CH3CH2OH and CH3OH Iodoform C2H5OH: Yellow precipitate of iodoform


(triiodomethane) (CHI3) formed (positive test)
test: Add I2 in CH3OH: No visible reaction
NaOH(aq), then
warm

CH3CH2OH and CH3CH2CH2OH Iodoform test C2H5OH: Positive iodoform test


CH3CH2CH2OH: No reaction

CH3CHCH3 and CH3CH2CH2OH Iodoform test CH3CH(OH)CH3: Positive iodoform test


⏐ CH3CH2CH2OH: No reaction
OH

Aldehyde (RCHO) and (a) Silver mirror test: Aldehyde: Silver mirror formed
ketone (RCOR') Add Tollens’ Ketone: No reaction
reagent, then
warm

(b) Add Fehling’s Aldehyde: Reddish-brown precipitate of


solution, then Cu2O formed
heat Ketone: No reaction
CH3COCH2CH2CH3 and Iodoform test CH3COCH2CH2CH3: Positive iodoform test
CH3CH2COCH2CH3 CH3CH2COCH2CH3: No reaction
HCOOH (or its salts) and Acidified KMnO4 HCOOH (or its salts): Decolourisation of
CH3COOH (or its salts) and heat KMnO4
CH3COOH (or its salts): No reaction
COOH (or its salts) and Acidified KMnO4 COOH (or its salts): Decolourisation of
⏐ and heat ⏐ KMnO4
COOH COOH
CH3COOH (or its salts) CH3COOH (or its salts): No reaction
COOH and HCOOH Add concentrated COOH: Gives CO(g) and CO2(g)
⏐ sulphuric acid, then ⏐ (limewater turns milky)
COOH heat COOH

HCOOH: Only CO(g) liberated which has


no effect on limewater

CH3COONH4 and CH3CONH2 Add FeCl3 solution CH3COONH4: Dark red colouration due
to formation of
(CH3COO)3Fe
CH3CONH2: No visible reaction

H2NCH2COOH and ClCH2COOH Add copper(II) H2NCH2COOH: Deep blue colouration


sulphate solution formed
ClCH2COOH: No reaction

4 Appendix

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To distinguish between Chemical tests Observations
COOC2H5 and CH3COOC2H5 Reflux with COOC2H5: KMnO4 decolourised
⏐ NaOH(aq); distill ⏐
COOC2H5 off the ethanol COOC2H5
produced; acidify the
CH3COOC2H5: No reaction
residual solution; add
KMnO4 solution

CH3CH2Br and CH3CH2Cl Add silver nitrate in CH3CH2Br: Yellow precipitate formed
ethanol and warm CH3CH2Cl: White precipitate formed

(B) Aromatic Compounds

To distinguish between Chemical tests Observations


C6H5CH3 and benzene Add KMnO4 in C6H5CH3: KMnO4 decolourised and brown
alkaline solution, precipitate formed
then boil Benzene: No reaction

CH3C6H4OH and C6H5CH2OH (a) Bromine water CH3C6H4OH: Decolourisation and white
precipitate formed
C6H5CH2OH: No reaction

(b) PCl5 C6H5CH2OH: White fumes


CH3C6H4OH: No reaction

C6H5CHO and C6H5COCH3 Add Tollens’ reagent, C6H5CHO: Silver mirror formed
then warm C6H5COCH3: No reaction
Comment Fehling’s
solution cannot be
used, as C6H5CHO
has no effect on
Fehling’s solution

C6H5CH2CHO and CH3C6H4CHO Add Fehling’s C6H5CH2CHO: Yellow-orange precipitate


solution, then heat of Cu2O formed
CH3C6H4CHO: No reaction

C6H5CH2Cl and C6H5Cl Add AgNO3 in C6H5CH2Cl: White precipitate


ethanol, then heat C6H5Cl: No reaction

CH3C6H4COOH and CH3C6H4OH Add Na2CO3 solution CH3C6H4COOH: Effervescence, CO2


at room temperature liberated
CH3C6H4OH: No reaction

CH3C6H4NH2 (or C6H5NH2) and Add bromine water CH3C6H4NH2 (or C6H5NH2): Bromine
C6H5CH2NH2 decolourised and white precipitate formed
C6H5CH2NH2: No reaction

(C) Aliphatic and Aromatic Compounds

To distinguish between Chemical tests Observations


Benzene and hexane Add nitrating Benzene: Yellow oil formed
mixture Hexane: No visible reaction
(concentrated HNO3
+ concentrated
H2SO4) at 55 °C

Appendix 5

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To distinguish between Chemical tests Observations

Cyclohexene and benzene (a) Br2 in CCl4 (or Cyclohexene: Bromine decolourised
bromine water) Benzene: No reaction

(b) Acidified Cyclohexene: KMnO4 decolourised


KMnO4 at room Benzene: No reaction
temperature

C6H5COOC2H5 and Reflux the esters C6H5COOC2H5: White precipitate of


CH3COOC2H5 with aqueous NaOH, C6H5COOH formed
distill off the ethanol CH3COOC2H5: No precipitate formed
produced, add
excess sulphuric acid
to the residual liquid

C6H5CHO and CH3COCH3 (a) Add Tollens’ C6H5CHO: Silver mirror formed
reagent, then CH3COCH3: No reaction
warm

(b) Iodoform C6H5CHO: No reaction


(triiodomethane) CH3COCH3: Yellow precipitate of CHI3
test formed (positive test)

CH3COOH and C6H5OH (a) Na2CO3 solution CH3COOH: Effervescence; CO2 liberated
at room C6H5OH: No reaction
temperature

(b) Bromine CH3COOH: No reaction


water at room C6H5OH: White precipitate of
temperature 2,4,6-tribromophenol formed

C6H5OH and C2H5OH (a) Bromine C6H5OH: White precipitate of 2,4,6-


water at room tribromophenol formed
temperature C2H5OH: No reaction

(b) Iodoform test C6H5OH: No reaction


C2H5OH: Positive iodoform test

C6H5NH2 and C2H5NH2 Add bromine water C6H5NH2: White precipitate of


at room temperature 2,4,6-tribromophenylamine
formed
C2H5NH2: No reaction

C6H5CONH2 and C2H5NH2 Add NaOH(aq) and C6H5CONH2: Ammonia gas liberated
heat C2H5NH2: No reaction

C6H5CONH2 and C2H5CONH2 Add NaOH(aq), C6H5CONH2: Ammonia gas liberated;


then boil; add excess on acidification, white
sulphuric acid to the precipitate of C6H5COOH
reaction mixture on formed
cooling C2H5CONH2: Ammonia gas liberated; on
acidification, no precipitate
formed

6 Appendix

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K2Cr2O7/H+ K2Cr2O7/H+ PCl5 NH3
C2H4Br2 C2H6 (CH2)n C2H5OH CH3CHO CH3COOH CH3COCl CH3CONH2
APPENDIX

O
4
OH

2
H
SO
LiAlH4 COOH

Ace Ahead Chem (Appendix) 3rd (11/11/08).indd 7


2
Na

Br 2
+

H
H2SO4

0
3

H2,Ni


30
/H

20 atm
4
200 °C OCOCH3
C2H5HSO4 C2H5ONa

SO
O4

2
H 2S COOH

H
CH2 CH3COOH
O O2/Ag C

CH3COOH
180 °

HN
CH2 C2H4 , C2H5OH

NaOH, reflux
SO 4 aspirin

NaOH, reflux
250 °C

HX
O2
H2

OH 5
C

4
H
P/I2 C2H5OH

2

H2O

C
OH

nO
CH3COOC2H5 CH3CN CH3OH CH3I CH3COOC2H5

14
5
H
NaOH

KM
/C
CH2OH KCN

Na
alc. reflux
CH2OH NH3 Li
C2H5OC2H5 C2H5X C2H5NH2 CH3Li
ether
H+
KCN alloy Na/Pb
alcohol O K2Cr2O7/H+ (CH3)3Pb
+ H– heat

N
K2Cr2O7/H

a/
Na/C2H5OH C2H5NH3+

Pb
C2H5CH2NH2 C2H5CN C2H5MgX
Mg
HS Grignard
2 O ether
HNO2 4 reagent

COOH
refl
COOH K2Cr2O7/H+ ux
CH3CH2COOH HCHO
C2H5CH2OH CH3CH2CHO
COOH LiAlH4
H2SO4 Cr2O72–/H+
KMnO4/H+ (CH3CH2)4Pb
180 °C HCHO R
R’ C O

HOOC
Br2 H2SO4 +
HCOOH acid RCHO
CO2 + H2O CH3CH=CH2 CH3CHBrCH2Br CO + H2O
heat +
H C2H5CH2OH acid R
Terylene r 2 SO
R ’ C—OH
HB H 4 MnO4–/H+
2O C2H5
Routes for the synthesis of aliphatic compounds

R
NaOH K2Cr2O7 CHOH
CH3CHBrCH3 CH3CH(OH)CH3 CH3COCH3 CO2 + H2O C2H5
reflux H2SO4

Appendix
7

11/13/08 12:36:38 PM
8
Appendix
OH
APPENDIX

CH3
CrO2Cl2 LiAlH4 HNO3
CHO —CH2OH HOOC(CH2)4COOH

Ace Ahead Chem (Appendix) 3rd (11/11/08).indd 8


KM
4

KMn nO
O4 /H + 4 /H + Cl
O LiAlH4 K2Cr2O7/H+
NH2(CH2)6NH2
C—CH3
H2, Ni

15
O H, COOH 200 °C
C 2H 5O

Na
nylon

atm
eat

Cl
C—OC2H5 H C l, h

CH3Cl/AlCl3
OH

CO
, 30

3
COCl, NaOH O

20
,N
i

0
CH
0 °C

H 2 °C
OH heat C—O
H O—OH
250 °C, 25 atm, H3PO4 O2, 120 °C H2SO4
C—CH3 C—CH3 + CH3COCH3 NaOH (aq)
CH3CH=CH2 100 °C reflux
CH3 CH3

e
2 5
H

,F
cumene

0
4

2
Cl
C 2 °C,
4
l3
—N 2
+
Cl

/A 0 at
H H CO2Na + O–Na+

lC m
Fe2O3 polymerisation
C2H5 CH=CH2 —C—C—
( )n
600 °C N=N OH
H

55 °C

u.v.
HNO3/H2SO4

2
Cl ,
NO2 OH
NH2 N2+Cl– OH Br Br
Sn/HCl HNO2 H2O Br2
5 °C 70 °C
l H
2, N
Cl HC 20 Br
Cl Cl CH3COCl OH 0° i
OH O
C
NH3+Cl– NHCOCH3 K2Cr2O7/H+
Cl Cl
Routes for the synthesis of aromatic compounds

Cl N=N OH heat

11/13/08 12:36:38 PM
APPENDIX 5 Reactions of bromine with organic compounds

Organic compound Observations Reaction type/Equations

Alkene, cycloalkene or Immediate decolourisation Electrophilic addition reaction


alkyne CH2 = CH2 + Br2 → CH2BrCH2Br

Br
+ Br2
Br

H – C ≡ C – H + 2Br2 → CHBr2CHBr2

Phenol or Decolourisation and white Electrophilic substitution reaction


phenylamine precipitate formed OH
Br Br

– OH + 3Br2 + 3HBr

Br
NH2
Br Br

– NH2 + 3Br2 + 3HBr

Br

Aldehyde or ketone No reaction with bromine Substitution reaction


alone; decolourisation CH3COCH3 + Br2 → BrCH2COCH3 +HBr
occurs only in the presence
of a dilute acid

Alkanes or Decolourisation occurs Free radical substitution reaction


cycloalkanes slowly in uv light or RH + Br2 → RBr + HBr
sunlight; no reaction in the
dark at room temperature

Benzene or No reaction with bromine Electrophilic substitution reaction


alkylbenzene alone; decolourisation
occurs only in the presence
+ Br2 ⎯ Br + HBr
of a halogen carrier such as
iron filings
CH3 CH3 CH3
Br

+ 2Br2 + + 2HBr

Br

Appendix 9

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Reactions of aqueous sodium hydroxide with organic
APPENDIX 6 compounds

Reaction type Organic compound(s) Equation(s)

Alkaline hydrolysis Haloalkane (alkyl halide) RX + NaOH → ROH + NaX


CH2XCH2X + 2NaOH → CH2OHCH2OH + 2NaX

Ester RCOOR' + NaOH → RCOONa + R'OH

Amide RCONH2 + NaOH → RCOONa + NH3


C6H5NHCOCH3 + NaOH → C6H5NH2 + CH3COONa

Nitrile RCN + H2O + NaOH → RCOONa + NH3

NaOH as a base Ammonium salt RCOONH4 + NaOH → RCOONa + NH3 + H2O

Amine salt RNH3+Cl– + NaOH → RNH2 + NaCl + H2O

APPENDIX 7 Reactions of sulphuric acid with organic compounds

Role of sulphuric acid Organic compound(s) Reaction(s)/Equation(s)

As a catalyst for acid Ester RCOOR' + H2O RCOOH + R'OH


hydrolysis

As a strong acid Carboxylate Strong acid displaces weaker acid from its salt
RCOONa + H – HSO4 → RCOOH + NaHSO4

Amine Amines react with acids to form salts


RNH2 + H – HSO4 → RNH3+HSO4–

As a dehydrating agent Methanoic acid and Concentrated H2SO4 removes water molecules
ethanedioic acid from HCOOH and H2C2O4 (ethanedioic acid) or
their salts on heating
H2SO4
HCOOH ⎯⎯→ CO + H2O
H2SO4
H2C2O4 ⎯⎯→ CO + CO2 + H2O

As an electrophile in Alkenes Concentrated H2SO4 reacts with alkenes to form


electrophilic addition addition products
reactions with alkenes RCH = CH2 + H – OSO3H → RCHCH3
(H2SO4) ⏐
OSO3H

10 Appendix

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APPENDIX 8 Reactions of iron(III) chloride with organic compounds

Organic compound(s) Observation


Salts of carboxylic acid, for example, methanoate Red solution formed; brown precipitate obtained
(HCOO–) or ethanoate (CH3COO–) when boiled
Benzoate
COO–
Buff-coloured precipitate formed

benzoate ion

Phenol, phenoxide ion and 2-hydroxybenzoic acid


OH O– COOH
OH
Purple solution formed

phenol phenoxide 2-hydroxybenzoic


ion acid

APPENDIX 9 Uses of potassium manganate(VII) in organic chemistry

(a) To distinguish alkenes from alkanes or cycloalkanes


Alkenes decolourise acidified KMnO4 at room temperature or on heating. Alkanes and cycloalkanes do
not react with KMnO4.
(b) To distinguish between alkenes
• Alkenes with a terminal = CH2 group not only decolourise hot, acidified KMnO4, but also liberate
carbon dioxide. This is because a terminal = CH2 group is completely oxidised to carbon dioxide and
water by hot KMnO4. The remaining RCH = group is oxidised to RCOOH.
• Alkenes without a terminal = CH2 group decolourise hot, acidified KMnO4 but do not liberate carbon
dioxide.
(c) To identify the position of the double bond in an alkene
The oxidation products obtained when an alkene reacts with hot, acidified KMnO4 are often used to
determine the position of the double bond of an unknown alkene.
(d) To distinguish aldehydes from ketones
Aldehydes are oxidised by acidified KMnO4 on heating to form carboxylic acids. Thus aldehydes
decolourise acidified KMnO4 on heating. In contrast, ketones do not decolourise hot, acidified
KMnO4.
(e) To distinguish alkylbenzenes from benzene
Alkylbenzenes such as ethylbenzene decolourise acidified or alkaline KMnO4 on heating. The alkyl
group is oxidised to – COOH, for example,

⎯ CH2CH3 + 6[O] ⎯ COOH + CO2 + 2H2O

ethylbenzene

Benzene does not decolourise hot, acidified or alkaline KMnO4.


(f) To distinguish primary or secondary alcohols from tertiary alcohols
Primary and secondary alcohols can be oxidised to aldehydes and ketones respectively. Hence, primary
and secondary alcohols decolourise hot, acidified KMnO4. Tertiary alcohols are resistant to oxidation
and hence do not decolourise hot, acidified KMnO4.

Appendix 11

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