Qualitative Analysis Test for and identify organic

functional groups
Functional group Test method Observation Comments
Alkene or Alkyne Bubble gas through or add The orange R2C = CR1→BrR2C –
Bromine solution in hexane or /brown bromine CR2BR
water rapidly
decolourises, as a RC ≡ CR + 2Br2 →Br2RC-
saturated CRBr2
colourless organic Page | 1
bromo-compound Here R is H, alkyl or aryl
is formed Saturated alkane do not reacts
with bromine

Hydroxy group –OH (i) Mix it with a few drops of (i) Litmus turns (i) R–OH + CH3COCl →
chemical test in alcohol ethanoyl chloride, test fumes red and a white CH3COOR + HCl
and phenols ( in dry with litmus and silver nitrate precipitate with
conditions) (* note ethanoyl chloride reacts silver An ester and hydrogen
with water, phenols and amines nitrate(aq)(drop on chloride are formed
too!). end of glass rod),
The first 3 tests (i) (ii) (iii) if the mixture is (ii) R–OH + PCl5 → R–Cl +
given on right are quit poured into water
POCl3 + HCl
general for most alcohol you may detect a
'pleasant' ester
odour, can test for a chloro compound and
HCl but water and hydrogen chloride are
amines produce it formed.
too!
(i) and (ii)
(ii) Mix it with a little (ii) as for (1) but
phosphorus(V) chloride and test no ester smell! Ag+(aq) + Cl–
as above. (aq) →AgCl(s) from the

(iii) You should hydrogen chloride fumes

(iii) Warm with a little ethanoic get a 'pleasant' dissolved in water.
acid and a few drops of conc. characteristic
sulphuric acid. Pour into water. smell of an ester. (iii) CH3COOH + ROH
→CH3COOR + H2O

Primary alcohol (i) Lucas test – shake a few (i) Solution (i) Not usually reactive
chemical test RCH2OH, R drops with cold zinc chloride in remains clear. enough to form a primary
= H, alkyl or aryl (NOT a conc. HCl(aq) halogenoalkane.
phenol). (ii) If product (ii) R–CH2OH + [O] →
(ii) Distil with potassium distilled off R–CHO + H2O or the full
(ii) is not a good test on its dichromate(VI) and mod. conc. immediately an works!
own, since so many other H2SO4(aq) aldehyde odour
readily reducible organic can be detected 3R–CH2OH + Cr2O72– +
compounds will give the and the solution 8H+ → 2Cr3+ + 3R–CHO +
same reaction, though colour changes 7H2O
following it up by testing from orange to
for an aldehyde gives it green. The orange dichromate(VI)
much more validity ion is reduced to thegreen
chromium(III) ion. If the
organic product is collected
you could test for an
aldehyde.
Qualitative Analysis Test for and identify organic
functional groups
Functional group
Secondary
alcohol chemical test
R2CHOH, R = alkyl or
aryl.
(ii) is not a good test on
its own, since so many
other reducible organic
compounds will give the
same reaction, though
following it up by testing
for a ketone gives it
much more validity.
Tertiary alcohol
chemical test
R3COH, R = alkyl or
aryl.
Phenols(OH group is
attached directly to
aromatic ring)chemical
test. R–OH, where R is aryl
e.g. C6H5OH
Carboxylic acids
chemical test
RCOOH
Test method Observation Comments
(i) Lucas test. (i) Solution may (i) May be reactive enough
cloud very to slowly form an
(ii) Distil with slowly or insoluble secondary
K2Cr2O7/H2SO4(aq) remains clear halogenoalkane: R2CHOH Page | 2
(hit and miss) + HCl →R2CHCl + H2O
(ii) If product (ii) R2CHOH + [O] => R–
distilled off CO–R + H2O or the full
immediately works!
ketone odour
can be detected 3R2CHOH + Cr2O72– +
and the solution 8H+ → 2Cr3+ + 3R–CO–
colour changes R + 7H2O
from
orange to green The orange
dichromate(VI) ion is
reduced to thegreen
chromium(III) ion. If the
organic product is
collected you could test for
an aldehyde.
(i) Lucas test. (i) Goes cloudy (i) Reactive enough to
very quickly. immediately form an
(ii) Distil with insoluble tertiary
K2Cr2O7/H2SO4(aq) (ii) No aldehyde halogenoalkane R3COH +
or ketone readily HCl =>R3CCl + H2O
formed
(iii) Stable to modest
oxidation.
Add a few drops of iron(III) Usually gives a ( See also test for primary
chloride solution to little of the purple colour aromatic amines –use it in
phenol in water reverse starting with a known
primary aromatic amine)
Mix the carboxylic acid with Fizzing, RCOOH + NaHCO3 →
water and add a little sodium colourless gas
hydrogencarbonate solid or gives white RCOONa + H2O + CO2
solution precipitate with
lime water (see also salts of aliphatic
carboxylic acids below)
Qualitative Analysis Test for and identify organic
functional groups
Functional group Test method Observation Comments

Salts of aliphatic Add a little hydrochloride/ The solid or The stronger acid,
carboxylic acids e.g. sulphuric acid to a suspected solution have no HCl/H2SO4 displaces the
RCOO–Na+or (RCOO– salt of an aliphatic carboxylic stronger odour, weaker aliphatic
)2Mg etc. acid but after adding carboxylic acid which
the mineral acid
have strong–pungent Page | 3
you should get a
pungent odour of characteristic odours e.g.
the original
aliphatic acid. If ethanoic acid from an
it’s the salt of an ethanoate salt (smell of
aromatic acetic acid, vinegar) and
carboxylic acid, butanoates release
you get little butanoic acid(butyric acid,
odour and maybe rancid odour).
white crystalline
precipitate

Acid or Acyl Chloride (i)Add a few drops to (i) Litmus turns (i) RCOCl + H2O →
chemical test water, test with litmus red and a white RCOOH + HCl
and silver nitrate precipitate with
RCOCl solution. silver nitrate. The acid chloride is
hydrolysed to form HCl
Fumes in air forming (ii) As above acid (chloride ions) and
HCl(g) (ii) Add to a little ethanol and you may the original carboxylic
and pour the mixture into detect a acid.
water. 'pleasant' ester
odour. (ii) CH3CH2OH
+ RCOCl → RCOOCH2C
H3 + HCl

an ethyl ester and

hydrogen chloride are
formed
Acid Amide chemical test Boil the suspected amide Ammonia RCONH2 + NaOH →
with dilute sodium evolved on RCOONa + NH3
RCONH2 hydroxide solution, see in boiling (no heat
inorganic for ammonia tests required to form
ammonia, if it
was an ammonia
salt)
Aliphatic amines (i) Lower members soluble (i) A fishy odour (i) Unless its a liquid or
(primary, where R = in water but a very fishy , litmus turns solid, only the more fishy
alkyl) chemical test R– smell! test with red litmus blue, white odour distinguishes it from
NH2 and conc. HCl(aq) fumes. clouds with HCl. ammonia.(ii) The reaction
(ii) If a suspected salt of an is e.g. R–NH3+ + OH– ==>
e.g. CH3CH2CH2–NH2 amine, then add sodium (ii) The above is R–NH2 + H2O
hydroxide solution to free not observed
the amine until after
adding the
alkali.
Qualitative Analysis Test for and identify organic
functional groups
Aliphatic amines Test method Observation Comments

(Primary,secondary and (i)Sub+dil.HCl+NaNO2 cool to Yellow ppt (i) Secondary amine

tertiary) 00-50C
Green ppt (ii)Tertiary amine
(ii) Sub+dil.HCl+NaNO2 cool
to 00-50C+NaOH Page | 4

(iii) Sub+dil.HCl+NaNO2 cool

to 00-50C+ β-naphthol in NaOH Red azo dye (iii)primary amine

Aldehydes chemical (a) Add a few drops of the (a) A yellow – The aldehyde or ketone
test (R–CHO, R = H, suspected carbonyl organge 2,4–
alkyl or aryl) to compound by Brady’s precipitate forms dinitrophenylhydrazone is
distinguish from ketones reagent (2,4- with both types formed
(R2C=O, R = alkyl or dinitrophenylhydrazine of carbonyl
aryl) and also reducing solution) compound R2C=O +
sugars. (NO2)2C6H3NHNH2 ==>

Note (NO2)2C6H3NHN=CR2 +
H2O
(1) Test (b)(i) and
(ii) can be used to (R = H, alkyl or aryl)
distinguish aldehydes
(reaction) and ketones This tells you its an
(no reaction). aldehyde or ketone, but
can't distinguish them,
(2) Aromatic aldehydes read on below!
do NOT give a positive
result
with (b)(ii)Benedict's or (b)(i) warm a few drops of (b) Only the Aldehydes are stronger
Fehling's reagent). the compound withTollens' aldehyde reducing agents than
reagent[ammoniacal silver produces(i) A ketones and reduce the
(3) Reducing sugars may nitrate] silver mirror on metal ion and are oxidised
also give a positive test the side of the in the process
with (b)(i)/(ii)reagent (b)(ii) simmer test tube.
e.g. glucose withFehling's or Benedictsso i.e. RCHO + [O] →
(aldohexose) but not lution [a blue complex of (ii) A brown or RCOOH (i) reduction of
fructose? (ketohexose)? Cu2+(aq)] brick red ppt silver(I) ion to silver metal
RCHO + 2Ag+ + H2O →
RCOOH + 2Ag + 2H+

(ii) reduction of copper(II)

to copper(I) i.e. the blue
solution of the
Cu2+ complex changes to
the brown/brick red colour
Qualitative Analysis Test for and identify organic
functional groups
Aromatic amines
chemical test (where R =
aryl with the amine or
amino group directly
attached to an aromatic
ring) R–NH2
e.g. C6H5–NH2
Halogenoalkanes
(haloalkanes)chemical
test R–X where R =
alkyl, X = Cl, Br or I
. increases the solubility of
The halide is covalently
bound (C–X bond), so
the halogen X cannot
react with the silver ion
to form the ionic Ag+X–
(s)precipitate until it is
converted to the 'free' X–
ionic form. Note that
aromatic halogen
compounds where the X
is directly attached to the
ring, do NOT readily
hydrolyse in this way
and no AgX ppt. will be
seen. Aromatic C–X is a
stronger bond than
aliphatic C–X.
(i) Dissolve the primary
aromatic amine in dilute
hydrochloric acid at 5oC and
mix with sodium nitrite
solution.
(ii) Add a phenol dissolved
in dilute sodium hydroxide.
(i) Warm a few drops of the
haloalkane with aqueous
ethanolic silver nitrate
solution, the ethanol
the immiscible haloalkanes.
(ii) Gently simmering a few
drops with aqueous NaOH
(may need to add ethanol to
increase solubility and
reaction rate). Add dilute
nitric acid followed by
aqueous silver nitrate
solution.
of insoluble copper(I)
oxide Cu2O.
RCHO + 2Cu2+ + 2H2O →
RCOOH + Cu2O + 4H+
With (b)(i)/(ii) no Page | 5
reactions with ketones.
(i) It should be a (i) If a primary aromatic
clear solution amine, a 'stable' diazonium
with few, if any, salt is formed. Diazonium
brown fumes. salts from aliphatic amines
decompose rapidly
(ii) A coloured evolving colourless
precipitate [red nitrogen.
– brown –
yellow etc.] (ii) An azo dyestuff
molecule is formed in a
coupling reaction e.g.
C6H5–N=N–C6H4–OH
(i) Observe i) AgNO3 + RX ==> R–
colour of NO3? + AgX(s)
precipitate and
the effect of (ii) The sodium hydroxide
ammonia converts the halogen atom
solution on it into the ionic halide ion in
(for rest of a hydrolysis reaction.
details see the (i)
notes RX(aq) + NaOH(aq) ==>
for chloride ROH(aq) + NaX(aq)
bromide and
diodide tests then
above in
inorganic)
Ag+(aq) + X–(aq) → AgX(s)
(ii) see the (i)
The addition of dilute
notes
nitric acid prevents the
as above for
precipitation of other silver
more details.
salts or silver oxide (e.g.
Ag2O forms if solution
alkaline)
Qualitative Analysis Test for and identify organic
functional groups
Functional group Test method
Esters chemical The ester can be reacted with
test RCOOR' saturated ethanolic
hydroxylamine
R = H, alkyl or aryl hydrochloride + 20%
methanolic KOH and gently
R' = alkyl or aryl heated until boiling. Then
mixture acidified with 1M
There is no simple test HCl(aq) and FeCl3 (aq) added
for an ester. Usually a dropwise.
colourless liquid with a
pleasant 'odour'.
Iodoform test NaOH(aq) is added to a
solution of iodine in
The formation of CHI3, postassium iodide solution
triiodomethane(or old until most of the colour has
name 'iodoform'. gone. The organic
compound is warmed with
this solution
Observation Comments
Deep read or The reaction is also given
purple colour by acid chlorides and acid
formed. The test anhydrides and phenols
depends on the gives a purple colour with
Page | 6
formation of a iron(III) chloride, so
hydroxamic acid frankly, the test is not that
R-C(=NOH)OH good. This test is not to be
which forms expected .
coloured salts
with Fe3+(aq) ion
A yellow solid is This reaction is given by
formed with the the alcohol ethanol
smell of an CH3CH2OH and all
antiseptic CHI3, alcohols with the 2–ol
tri-iodomethane structure –CHOH–
melting point CH3 and
119oC
the aldehyde ethanal
CH3CHO and all ketones
with the 2–one structure
R–CO–CH3 ('methyl
ketones')
It’s a combination of
halogenation and oxidation
and is not a definitive test
for anything, it just
indicates a possible part of
a molecules structure.