Detect Organic Compounds with Chemistry Experiments

Organic Chemistry
Experiments
Detection of some common organic compounds
Solid samples Page
1. Oxalic acid 11
2. Citric acid 12
3. tartaric acid 13
4. Succinic acid 14
5. Resorcinol 15
6. Hydroquinone (quinol) 16
7. Benzoic acid 17
8. Salicylic acid 18
9. -Naphthol 19
10. Urea 20
11. Glucose 21
12. Lactose 22
13. Sucrose 23
14. Starch 24
Liquid samples:
1. Formic acid 25
2. Acetic acid 26
3. Methanol 27
4. Ethanol 28
5. Acetone 29
6. Glycerol 30
7. Aniline 30
8. Methyl aniline 31
9. Dimethyl aniline 32
10. Benzaldehyde 32
11. Nitrobenzene 33
12. Benzylalcohol 33
85
Common Reagents/Chemicals:
1. Litmus paper 24. Dilute solution of borax

2. Sodium bicarbonate 25. N,N-Dimethyl aniline
3. Mercuric chloride (HgCl2) solution 26. anhydrous Zinc chloride
4. Iodine in potassium iodide solution 27. Lead oxide
5. Sodium hydroxide solution 28. Bromine-water
6. Ammonium hydroxide solution 29. Phthalic anhydride
7. Fehling’s A 30. Sodium nitrite
8. Fehling’s B 31. Phenol
9. Conc. & dil. HCl 32. Potassium permanganate
10. Alkaline -naphthol 33. Zinc dust
11. Potassium ferrocyanide [K4Fe(CN)6] solution 34. Alcoholic solution of -naphthol
12. Ferric chloride solution 35. Lead acetate solution
13. Resorcinol as a reagent 36. Calcium chloride (CaCl2) solution
14. Silver nitrate solution (for Tollen’s test) 37. Cadmium chloride solution
15. Barfoed’s reagent 38. Freshly prepared ferrous sulfate (FeSO4)
16. Denige’s reagent 39. Dil. Hydrogen peroxide
17. Schiff’s reagent 40. Succinic acid
18. Phenyl hydrazine hydrochloride 41. Tartaric acid
19. Copper wire 42. Aniline
20. Sulfuric acid 43. Very dil. Copper sulfate (CuSO4) solution
21. Nitric acid 44. Quinone
22. Salicyclic acid as a reagent 45. Alkaline sodium hypochloride
23. Alcoholic solution of phenolphthalein
86
Experiment No – 1A: Solid sample (Known)
Experiment No – 1B: Solid sample (Unknown)
Flow sheet for solid sample
solubility in water (no heating)
Soluble Sparingly soluble/

Insoluble
Blue litmus
Hot water
Turns to red immediately No change
Acidic Neutral Soluble
Ignition test blue litmus Sparingly Soluble
NaHCO3
Turns to red immediately blue litmus
Brisk Effervescence Acidic
Sooty flame Non-Sooty flame** Turn slowly to red
Oxali c/ Citr ic/ FeCl3 test Mild acidic
Tartari c/ Succinic aci d NaHCO3
NaHCO 3
Permanent violet color Brisk Effervescence
Resorcinol Transient greenish-blue color Benzoic/ Salicyli c acid No effervescence
Qui nol
FeCl3 test FeCl3 test
Denige's test
Pale green coloration
Beta-napht hol
Blue/violet coloration Buff color ppt
White ppt in cold No ppt in cold Sali cyl ic acid Benzoic acid
Oxalic acid succinic acid/citric acid/
tartaric acid
Boil and add KMnO4 (2-3 drops)
Color disappears Color persists

Color disappears Succinic acid
without turbidity
with ppt
Citric acid Tartaric acid
Acidic = Oxalic acid Mild acidic = Resorcinol Neutral = Urea

Tartaric acid Quinol Glucose
Succinic acid Beta-naphthol Sucrose
Citric acid Lactose
Benzoic acid Starch
Salicylic acid
 Cold means at room temperature.

 Succinic acid has less solubity in water at room temperature. Sometimes it may appear under samples
soluble in hot water.
** see next page
87
Solid sample
Non sooty flame**

Heat in a dry tt
Charring and no No charring but smell of ammonia

smell of ammonia
glucose/sucrose/Lactose/Starch Urea
I2 solution
Violet colour No violet colour

Starch Glucose/Sucrose/Lactose
Fehling's test
Positive Negative
Glucose/Lactose Sucrose
Barfoed's reagent
Positive Negative
Glucose Lactose
Preparation of Tollen’s reagent: Add 4 drops of 10% NaOH solution to few drops (4-6) of AgNO3 solution till
grey/black turbidity appears. Slowly add dilute ammonia solution with thorough mixing till clear solution. Remove
excess ammonia on heating in water bath, cool under tap water and use for test.
88
Experiment No – 2A: Liquid sample (Known)
Experiment No – 2B: Liquid sample (Unknown)
*Miscible= Methyl alcohol **Immiscible = Benzaldehyde

Ethyl alcohol Flow sheet for liquid sample
Aniline
Acetone Water Methyl aniline
Glycerol
Formic acid * ** Dimethyl aniline

miscible inmiscible
Nitrobenzene
Acetic acid litmus
Benzylalcohol
Acidic Neutral
Formic acid, Acetic acid Methanol, Ethanol, Acetone,

Glycerol, Acetone
HgCl2 test
Light Viscous
White or grey ppt No ppt
Methyl alcohol, Ethyl alcohol, Glycerol
Formic acid Acetic acid Acetone
Iodoform test in NaOH
Yellow ppt NO yellow ppt

Ethyl alcohol, acetone Methyl alcohol
Iodoform test in NH4OH
Yellow ppt NO yellow pp

Acetone Ethyl alcohol
89
Liquid sample
Inmiscible
dil. HCl
Miscible Immiscible
Aniline, Benzaldehyde,
Methyl aniline Nitrobenzene,
Dimethyl aniline Benzylalcohol
Diazocoupling DNP test
Red dye No response

Yellow ppt No ppt
Aniline Methyl aniline,
Benzaldehyde Nitrobenzene
Dimethyl aniline Benzylalcohol
K4Fe(CN)6 test reduction &
diazocoupling test
White ppt No ppt

Red dye No red dye
Dimethyl aniline Methyl aniline
Nitrobenzene Benzylalcohol
**Important: The above flow sheet is a general guidance to arrive at a

preliminary conclusion. You must do confirmatory tests for final
conclusion.
Note: Organic compounds insoluble / immiscible in water should be

dissolved in ethanol for confirmatory test
Identification of organic compounds by special test:
OS = Organic Sample CT = Confirmatory Test
90
Procedure for the flow sheet of solid sample
Take a very minute amount of solid organic sample (OS) in a test tube and fill up to 1/3 rd with water. Shake well the
mixture.
soluble insoluble
If soluble, dip (DON’T DROP) a blue litmus paper to the above If insoluble, heat the suspended mixture in water-bath
solution. with occasional shaking.
If it changes blue to If the solution does not change the If soluble in hot condition, then take little amount solid
red immediately, then blue litmus to red immediately, take sample in test tube and fill up with ethanol (95%
pour solid NaHCO3. a little amount of solid OS on the tip rectified spirit/ethyl alcohol) till 1/4th of test tube.
of a glass rod. Hold it on upper part Shake well to get a clear solution. Add 3-4 drops of
of Bunsen burner and observe the water and dip (DON’T DROP) a blue litmus paper to
top of the flame of burning sample, the above solution.
it is black sooty flame or not.
If it gives brisk If gives sooty flame, take a little If litmus paper changes blue to red immediately, then
effervescence, then amount of sample in a test tube and pour solid NaHCO3 to the above solution.
make FRESH aqueous dissolve it in water (test tube should
solution of OS (1/4th be 1/3rd filled). Slowly Add 2-3
of test tube). Add drops of FeCl3 solution and observe
Denige’s reagent and the color change.
shake well.
If the above gives If non-sooty flame, take a little If it gives brisk effervescence, then make FRESH
white ppt, the sample amount of solid OS in DRY test aqueous alcoholic solution as above (take little amount
may be oxalic acid. tube. Heat the test tube on the top of solid sample in test tube and fill up with ethanol (95%
burner (initially the solid may melt rectified spirit/ethyl alcohol) 1/4th of test tube. Shake
to liquid, heating continue) well to get a clear solution. Add 2-3 drops of water).
Add 2-3 drops of FeCl3 solution and observe the color
change.
If addition of Denige’s If the above charred (produce If insoluble or sparingly soluble even in hot water,
reagent does not give brown/black solid material), but no Make an aqueous alcoholic solution of the solid
white ppt, then heat smell of ammonia, dissolve little sample. Repeat entries 2-4 of column-4 of this sample.
the above solution amount of OS in water and add 2-3 If litmus paperDOES NOT change to red immediately
(entry 4) in water bath drops of diluted I2/KI solution – and no brisk effervescence, then FeCl3 test as above.
and add few drops of violet coloration indicates starch
KMnO4 solution. may be present.
If there is no violet coloration,
make another fresh solution of OS in
water and add Fehling’s A and B
reagent equal amount successively.
Heat the mixture in a water-bath for
5-7 minutes – NO red ppt (blue
color persists) indicates sucrose may
be present.
If brick-red ppt, it may be glucose or
lactose. Take another fresh solution
of OS in water and add 2 mL of
Barfoed’s reagent. Heat the mixture
in water-bath for >10 minutes.
If no charring, but smell of
ammonia, it may be urea.
Preparation of Tollen’s reagent: Add 4 drops of 10% NaOH solution to few drops (4-6) of AgNO3 solution till
grey/black turbidity appears. Slowly add dilute ammonia solution with thorough mixing till clear solution. Remove
excess ammonia on heating in water bath, cool under tap water and use for test.
Preparation of neutral solution: To the aqueous solution/aqueous-alcoholic solution add dil. ammonia dropwise till
smell of ammonia persists. Heat the solution for few minutes till NO smell of ammonia.
91
Procedure for the flow sheet of liquid sample
Take 2-3 drops of liquid organic sample (OS) in a test tube and fill up to 1/3 rd with water. Shake well the mixture.
miscible immscible
If miscible, dip (DON’T DROP) a blue litmus If immiscible in water, take 2-3 drops of liquid sample in test tube
paper to the above solution. and add 2 ml of dil. HCl (1/3rd of test tube). Shake well.
If it changes blue to red immediately, take 4-5 If miscible, cooled the above If immiscible, take 3-4
drops of liquid sample in a test tube and fill solution in an ice bath. Then add 3- drops of sample in test
with water 1/4th of test tube. Add 1.0 mL of 4 drops of ice-cold solution of tube and dissolve in
HgCl2 solution and heat the mixture in water- NaNO2. Take 1 ml of alkaline alcohol (rectified
bath. White or grey ppt indicates formic acid solution of β-naphthol solution in spirit/ethyl alcohol). Add
may be present. No ppt – may be acetic acid. another test tube and cool in ice- 4-5 drops of DNP solution
bath. Add the 1st solution to the β- and shake well.
naphthol solution. (Cooling is
If it gives yellow-orange
very important).
ppt, it may be
benzaldehyde.
If the solution does not change the blue litmus If it gives brilliant red dye, it may If there is no yellow-
to red immediately, check the sample. Is it be aniline. orange ppt, it ma be
light (free flow like water) or viscous (thick nitrobenzene or
liquid)? benzylalcohol.
If viscous, it may be glycerol.
If it is light, take 1.0 ml of sample and 1.0 ml If there is no red dye, Take 3-4 Take 4-5 drops of liquid
of water in test tube (total 1/3rd of test tube). drops of liquid sample and sample in a test tube. Add
Add about 1 ml of a dilute solution (10 per dissolve in dil HCl to get clear pinch of zinc dust and 2
cent) of sodium hydroxide. Add to the solution. Add 3-4 drops of ml of dil. HCl. Keep for 5
mixture, drop by drop, a solution of iodine in K4Fe(CN)6 solution, shake well min. with occasional
potassium iodide until a faint color persists and warm in water-bath. shaking.
after the solution is shaken. Heat the test-tube
Decant the clear solution
until it feels warm to the hand (about 60°;
in a separate test tube and
over heating dissolve the ppt). If a
do diazo coupling test as
precipitate does not separate at once set the
mention for aniline.
tube aside for a few minutes.
If the above gives yellow ppt, it may be ethyl If it gives brilliant red dye,
alcohol or acetone. Then repeat the test with it may be nitrobenzene.
ammonium hydroxide instead of sodium
No red dye – may be
hydroxide.
benzyl alcohol.
92
1. Oxalic acid
O
OH
HO
O
Experiment Observation
1. CaCl2 test: CaCl2 solution is added to an A white ppt. forms immediately.

aqueous neutral solution of OS. The ppt. is
divided into two parts.
a) dil. AcOH is added to one portion

a) The ppt. does not dissolve
b) dil. HCl or dil. HNO3 is added to another
portion b) The ppt. dissolves
2. AgNO3 test: AgNO3 solution is added to an A white crystalline ppt. forms

aqueous solution solution of OS. The ppt. is
divided in three parts.
a) Dil. NH4OH is added to one portion.

a) The ppt. dissolves.
b) dil. HNO3 is added to another potion.
b) The ppt. Dissolves.
c) The third portion is warmed, dried and heated
c) Metallic silver is formed.
strongly in a dry test tube
3. Denige’s test (CT): Denige’s reagent is added to White ppt. in the cold which does not dissolve on
an aqueous solution of OS boiling (Distinction from tartarate, citrate and
succinate).
4. KMnO4 test (CT): A little of dil. H2SO4 is added The pink colour of permanganate disappears.
to an aqueous solution of OS. The solution is
warmed and dil. KMnO4 solution is added
dropwise with shaking.
93
2. Citric acid
1. CaCl2 test: CaCl2 solution is added to aqueous No ppt. appears on shaking and scratching, but
neutral solution of OS. The solution is shaken white ppt appears on boiling for several minutes
vigorously; inner side of the tube is scratched with a (distinction from oxalic and tartaric acid).
glass rod and finally boiled.
2. AgNO3 test: Please vide as described for tartaric A Curdy white ppt. soluble in NH4OH, but no silver
acid mirror is obtained on boiling. (distinction from
tartaric acid)
3. Denige’s test (CT): (a) Denige’s reagent is added a) No ppt. in the cold but the colour of
to neutral solution or aq. solution of OS. (b) The permanganate discharges with appearance of heavy
solution is boiled and then 1-2 drops of KMnO4 white turbidity on boiling (distinction from oxalic,
solution is added tartaric and succinic acid).
4. CdCl2 test: an equal volume of cadmium chloride A gelatinous white ppt. insoluble in hot water but
solution is added to aqueous neutral solution of soluble in hot AcOH.
OS.
94
3. Tartaric acid,
1. Silver-mirror test (CT): A test tube is washed A white crystalline ppt.
with NaOH solution, with dil. HNO3 and finally b) shining silver mirror forms at the inner side of the tube
with distilled water. (distinction from oxalic, citric and succinic acid).
a) Neutral aqueous solution of OS is taken in that
tube and AgNO3 solution is added.
b) addition of AgNO3 solution is continued till the
precipitation is complete. Then dil. NH4OH solution
is added dropwise with constant shaking, till the ppt.
almost dissolved (but not completely). The tube is
then warmed in a water bath for few minutes.
2. Denige’s test (CT): As described under citric acid Permanganate colour disappears immediately without
turbidity (distinction from citric and succinic acid).
4. Fenton’s test: 1-2 drops of freshly prepared A deep violet coloration (distinction from citric and oxalic
FeSO4 solution is added to 2 ml of neutral aqueous acid)
solution of OS taken in a test tube. Then a drop of
dil. H2O2 is added followed by excess NaOH
solution (excess FeSO4 and H2O2 must be avoided)
5. Mohler’s test (CT): 4-5 drops of neutral solution A violet colour appears.
of OS is just heated to dryness without charring. A
small particle of resorcinol and 2-3 drops of conc.
H2SO4 is added and warmed.
95
4. Succinic acid
O
OH
HO
O
1. CaCl2 test: CaCl2 solution is added to neutral A white ppt. soluble in AcOH.
solution of OS. The solution is boiled and inner
wall of test tube is scratched with a glass rod.
2. AgNO3 test: AgNO3 solution is added to solution A white pt. soluble in dil. NH4OH.
of OS.
3. Denige’s test (CT): (a) Denige’s reagent is added a) No ppt.

to an aqueous solution of OS. (b) The solution is
b) The colour of permanganate persists
boiled and then 1-2 drops of KMnO4 solution is
added
4. Fluorescein test (CT): A small amount of OS and

twice of its weight resorcinol are mixed thoroughly
and taken in a dry test tube. A few drops of conc.
H2SO4 is added and
a) The mixture is heated gently on burner (1 min).

a) A deep red solution.
b) The deep red solution is poured into a large
volume of water in a beaker. b) Deep red colour changes to orange yellow solution which
emits an intense green fluorescence.
c) The solution of beaker is made alkaline with
NaOH solution. c) The solution changes to bright red and fluorescence
intensified.
96
5. Resorcinol (1,3-dihydroxybenzene)
HO OH
1. FeCl3 test (CT): 1-2 drop of freshly prepared solution Bluish-violet coloration appears.
of FeCl3 is added to aq. solution of OS.
2. Fluoroscein test (CT): A small quantity of OS is An intense green fluorescence.

mixed with succinic acid and the test is performed as
described under succinic acid.
3. Tartaric acid test (CT): A small amount of OS is A violet-red coloration.

dissolved in 1% H2SO4 solution. 2-3 drops of the
solution is added to 2-3 ml of C. H2SO4 and then 2-3
drops of neutral tartaric acid solution is added and
warmed for few minutes.
97
6. Hydroquinone (Quinol):
HO
OH
1. FeCl3 test (CT): 1-2 drop of freshly prepared solution Transient blue coloration, then turns to yellow
of FeCl3 is added to aq. solution of OS. (coloration should be followed while a drop of FeCl3 is
going deep inside the solution of OS, coloration don’t
persist more than 1-2 seconds)
2. Mix equal volume of aqueous solution of OS and Dark needle shaped crystals of quinhydrone comes
freshly prepared para-quinone solution. Shake well and out.
stand for couple of minutes.
Preparation of fresh para-quinone solution: Dissolve little amount of quinol (from reagent rack) in minimum amount
of water. Slowly add FeCl3 solution with shaking till NO transient greenish-blue color appear.
98
7. Benzoic acid
CO2H
1. FeCl3 test (CT): a) 1-2 drop of freshly prepared a) A buff coloured ppt (distinction from salicylic
solution of FeCl3 is added to an aqueous alcoholic
acid).
neutral solution of OS
b) ppt. dissolved with appearance of white ppt.
b) dil. HCl is added to the ppt.
2. Esterification test (CT): About 0.1 g of OS and 2 Fruity smell of ester appears.
ml of dehydrated ethanol are taken in dry tube and
shaken well, then a few drops of conc. H2SO4 are
added and the test tube is warmed in a hot water
bath. The test tube is cooled and contents of the
tube are poured in a beaker containing 50 ml dil.
Na2CO3 solution.
Preparation of neutral solution: To the aqueous solution/aqueous-alcoholic solution add dil. ammonia dropwise
till smell of ammonia persists. Heat the solution for few minutes till NO smell of ammonia.
99
8. Salicylic acid (ortho-hydroxybenzoic acid)
CO2H
OH
1. FeCl3 test (CT): 1-2 drop of freshly prepared An intense violet coloration occurs
solution of FeCl3 is added to aqueous alcoholic
neutral solution of OS, and the coloured solution is
divided into two parts,
a) The colour discharges
a) dil. HCl is added to one part
b) the colour persists (color given by phenol is
b) AcOH is added to another part
discharged by acetic acid)
2. Oil of wintergreen test (CT): About 0.1 g of OS, Characteristic smell appears which intensifies on pouring
1ml of MeOH and few drops of C. H2SO4 are into dil. Na2CO3 solution.
warmed in a clean dry test tube
3. Br2-Water test: An excess of Br2-water is added to Light yellow crystalline ppt. appears.
aqueous alcoholic solution of OS
100
9. β-Naphthol
OH
1. FeCl3 test (CT): 1-2 drop of freshly prepared Green coloration changes to a flocculant ppt. after
solution of FeCl3 is added to aq. solution of OS. sometime.
2. Back-dye test (CT): 2-3 drops of aniline is A brilliant red coloration or ppt.
dissolved in dil. HCl and cooled in ice-water. A
cold dil. NaNO2 solution is then added to it and the
resulting solution is added to cold alkaline solution
of OS.
Make sure that all the reagents are cooled to 0-

50C with the help of ice.
101
10. Urea.
H2N NH2
Biuret test (CT): About 0.5 g of OS is heated A pink or violet coloration.

gently to melt. The heating is continued till the
molten mass solidifies at once then test tube is
taken out of the flame. If there is no solidification,
the process is repeated. The residue is cooled and
dissolved in 1ml. of NaOH solution by warming
and shaking. The solution is cooled again and 1-2
drop of very dil. CuSO4 solution is added.
Urea and sodium hypochlorite: Add 3-4 drops of

Effervescences is noticed
sodium hypochlorite solution to a dilute solution of urea
and shake well.
102
OH
11. Glucose
HO O
HO OH
OH
1. Fehling’s test: To 2ml of Fehling’s reagent (I + II) is A yellow ppt of cuprous hydroxide forms initially
added 2ml of aq. solution of OS and then warmed gently in which turns to red cuprous oxide on further heating
water bath for 5 minutes
2. Tollen’s test: 5 ml of aq. solution of OS is added to equal Shinning mirror of silver appears on the inner wall
volume of Tollen’s reagent taken in a clean test tube and of the test tube.
the tube is placed in a water bath for 2 minutes.
3. Molisch’s test: 2 ml of the aq. Solution of OS and 2-3 A red colored ring gradually changing to blue or
drops of 15% alcoholic solution of α-napthol are mixed violet appears at the junction of the two layers.
together in a tube. Then the test tube is carefully inclined
and 2-3 drops of C. H2SO4 is added so that two layer
between OS and C. H2SO4 forms at the bottom of the test
tube.
4. Barfoed’s test: 2ml of Barfoed’s reagent is added to 1ml Red ppt. of Cu2O appears.
aq. solution of OS taken in a tube and the tube is boiled in
water bath for 10 minutes.
5. Lead acetate test (CT): Lead acetate solution is added to The white ppt. turns Salomon-pink in colour.
an aq. solution of OS and the mixture is boiled for few
seconds. Then dil. NH4OH solution is added dropwise till
just sufficient to produce a permanent white ppt appears.
The mixture is boiled again.
103
12. Lactose or milk sugar,
1. Fehling’s test: Same as glucose Same as glucose
2. Tollen’s test: same as glucose Same as glucose
3. Molisch’s test: same as glucose Same as glucose
4. Barofoed’s test (CT): Same as glucose No red ppt. of Cu2O is obtained (distinction from
glucose)
104
13. Sucrose or cane sugar,
1. Fehling’s test: To 2ml of Fehling’s reagent (I + II) is No red ppt. (Distinction from Glucose)
added 2ml of aq. solution of OS and then warmed
gently
2. Tollen’s test: 5 ml of aq. solution of OS is added to No silver mirror*. (Distinction from Glucose)
equal volume of Tollen’s reagent taken in a clean test
tube and the tube is placed in a water bath for few
minutes.
3. Molisch’s test: same as glucose Same as glucose
4. Seliwanoff’s test (CT): 1ml of conc. HCl is added to A deep wine-red colour followed by formation of
1 ml of aq. solution of OS and the solution is heated on brown ppt. the ppt. gives dark red solution when
a water bath until it turns red. Then few crystals of dissolved in ethanol. (Distinction from Glucose and
resorcinol is added to it and warmed again. lactose)
5. Lead acetate test (CT): Lead acetate solution is added The white ppt. does not change colour.
to an aq. solution of OS and the mixture is boiled for
few seconds. Then dil. NH4OH solution is added
dropwise till just sufficient to produce a permanent
white ppt appears. The mixture is boiled again.
* It sometimes gives positive test for Tollen’s test due to in situ hydrolysis.
105
14. Starch
1. Fehling’s test: Same as glucose No red ppt.
2. Tollen’s test: same as glucose No silver mirror
3. Molisclh’s test: same as glucose Same as glucose
4. Barofoed’s test (CT): Same as glucose No red ppt. of Cu2O is obtained (distinction from
glucose)
5. Starch-iodide test (CT): 1-2 drops of dilute I2 in A deep blue colour. The colour disappears on
KI solution is added to 2ml aq. solution of OS. boiling and reappears on cooling.
Starch is sparingly soluble in cold water, hence it

is advised to heat the solution and then cool it
prior to addition of I2 in KI.
106
Liquid Samples
1. Formic acid, HCO2H.
1. Silver mirror test: AgNO3 is added to the OS White ppt. of silver formate, blackens on warming
due to reduction to metallic silver
2. FeCl3 Test: A few drops of freshly prepared A red colour develops

FeCl3 solution as added to the neutral aqueous
solution of OS. The resulting solution is divided
into two parts.
a) The red colour is discharged and yellow
a) dilute HCl is added to one part
colour of FeCl3 appears.
b) another part is boiled
b) A brown ppt of basic ferric formate
appears.
3. HgCl2 test (CT): Take 4-5 drops of HgCl2 White ppt. of mercurous formate forms.
solution in a test tiube. Add 2-3 drops of neutral
aqueous solution of the sample and warm in water-
bath.
Then an excess of neutral solution is added and

warmed. Grey ppt. of metallic mercury.
2. Acetic acid, CH3CO2H.
1. FeCl3 Test: A few drops of freshly prepared A red colour develops

FeCl3 solution as added to neutral solution of OS.
The resulting solution is divided into two parts.
a) dilute HCl is added to one part

a) The red colour is discharged and yellow colour
of FeCl3 appears.
b) another part is boiled
b) A brown ppt of basic ferric formate appears.
2. HgCl2 test (CT): Same as formic acid No ppt forms (Distinction from Formic acid)
107
3. Methanol, CH3OH
1. Oxidation test: A Cu-spiral is made repeatedly

red hot and immersed into 2ml of OS kept in a test
tube dipped in a beaker containing cold water. The
solution is then divided into two parts:
a) Tollen’s test: One part is added to Tollen’s
a) Bright silver mirror appears on the side of the
reagent and heated in a water bath.
tube.
b) Resorcinol test: A mixture of 0.5 ml of oxidized

b) A reddish-violet ring appears at the junction of
liquid and a drop of 0.5% aq. solution of resorcinol
two liquid layers. A white ppt. changing to reddish
is added carefully down the side of the test tube held
violet appears in the aq. layer above the ring after a
in an inclined position containing 2ml of C. H2SO4
little while.
Oil of wintergreen test (CT): 0.5 ml of OS and 3 Characteristic smell of methyl salicylate.
drops of conc. H2SO4 are added to 0.5 gm of
salicylic acid and heated for one minute the reaction
mixture is poured into 50 ml of water in a beaker
4. Ethyl alcohol, CH3CH2OH
1. Oxidation test: Similar like MeOH
a) Tollen’s test: One part is added to Tollen’s a) Bright silver mirror appears on the side of the
reagent and heated in a water bath. tube.
2. Iodoform test (CT): Take 1.0 ml of sample and

1.0 ml of water in test tube (total 1/3 rd of test tube).
a) Yellow crystalline ppt. of CHI3 having
Add about 1 ml of a dilute solution (10%) of sodium
characteristic sweet smell.
hydroxide. Add to the mixture, drop by drop, a
solution of iodine in potassium iodide until a faint
color persists after the solution is shaken. Heat the
test-tube until it feels warm to the hand (about 60°;
over heating dissolve the ppt). If a precipitate does
not separate at once set the tube aside for a few
minutes.
b) The iodoform test is repeated by adding NH 4OH

instead of NaOH
b) No ppt. of iodoform.
108
5. Acetone, MeCOMe
1. 2,4-DNP test: alcoholic solution of OS is added Reddish yellow ppt. forms immediately.
to 2,4-DNP solution
2. a) Iodoform test (CT): Iodoform test is performed a) Yellow crystalline ppt. of CHI3 having characteristic
following the procedure as in the case of EtOH. sweet smell.
b) The iodoform test is repeated by adding NH 4OH

instead of NaOH
b) Yellow crystalline ppt. of CHI3 having characteristic
sweet smell.
109
6. Glycerol; HO-CH2-CHOH-CH2OH
1. Dunstan’s test: Aq. solution of OS is added to Pink colour discharges; reappears on warming but
borax-phenolphthalein (few drops of alcoholic vanishes on cooling.
solution of phenolphthalein is added to very dilute
solution of borax).
2. Acrolein test (CT): OS is heated with KHSO4 in a Characteristic pungent smell of acrolein
test tube. With the resulting solution the following
tests are performed.
a) Tollen’s test
a) Silver mirror formed
7. Aniline, Ph-NH2
1. Bromine-water test: Few drops of Br2-water is A white ppt. of 2,4,6-tribromoaniline forms.

added to the aq. solution of OS.
2. Diazo coupling test (CT): 4 to 5 drops of OS is Brilliant scarlet red dye appears.
dissolved in dil. HCl in a test tube and cooled in an
ice bath. Then 3-4 drops of dilute ice-cold solution
of NaNO2 is added to it. Then the solution is
added to 1 ml of ice-cold alkaline solution of β-
naphthol.
8. Methylaniline, PhNHMe
1. Liebermann’s test (CT):
a) About 0.5 ml of the OS is dissolved in dil HCl a) A light yellow oil separates.
until a clear solution is obtained and the test tube is
cooled in ice water. To this cooled solution add 1ml
of aq. NaNO2 solution.
b) The light yellow oil is extracted with ether and

the ethereal solution is evaporated on a watch glass. b) A blue colour develops which turns red on
Then the liquid is taken in a test tube and warmed addition of water and changes to blue again on
on water bath with 0.5 ml of phenol and 2 drops of addition of NaOH solution.
conc. H2SO4
110
9. Dimethyl aniline, PhNMe2
1. K4Fe(CN)6 test: To a clear HCl solution of OS White ppt appears

add 3-4 drops of K4Fe(CN)6 solution and warm in
water bath.
2. Diazo-coupling test (CT): A cold dilute solution

of benzene-diazonium chloride (prepared by aniline
Rose-red colour develops
+ dil. HCl + aq. NaNO2) is added to cold solution of
OS in dil HCl and allowed to stand.
3. Malachite green test (CT): 1 ml of OS is heated Same as benzaldehyde

with 0.5 ml of benzaldehyde and 2-3 drops of conc.
H2SO4 in a dry test tube for a minute. The leucobase
is oxidized with lead oxide in a solution of AcOH
and excess conc. HCl is then added.
Note: If necessary, please use anhydrous ZnCl2 to

get better result.
10. Benzaldehyde; Ph-CHO
1. Tollen’s test: Same as earlier A brilliant silver mirror formed
2. 2,4-DNP test: alcoholic solution of OS is added Reddish yellow ppt. forms immediately.
to 2,4-DNP solution
3. Malachite green test (CT): Same as An intense green coloration appears.

dimethylaniline
N.B. Take dimethylaniline instead of

benzaldehyde.
111
11. Nitrobenzene, PhNO2
1. Reduction and diazocoupling test (CT): 0.5 ml of OS

is reduced by pinch of Zn dust and dil. HCl for 5 mins.
Brilliant scarlet-red dye forms.
The decanted solution is cooled and performed the red-
dye test like aniline
2. Mullikan-Barker test (CT):).1 g of OS is dissolved in A silver mirror or black grey ppt appears.
3 ml of ethanol and 3 ml of water, a little solid NH 4Cl
and a pinch of Zn-dust are added to it. The mixture is
boiled for few mins and cooled and then decanted. To
the decanted solution add freshly prepared Tollen’s
reagent.
12. Benzyl alcohol, PhCH2OH
1. Oxidation test: To 0.5 ml of hot alkaline The pink colour of KMnO4 disappears
solution of KMnO4, OS is added dropwise and the
solution is boiled.
112
Chemical reactions used in this manual
1. Oxalic acid
(a) CaCl2 test
O O
CO2NH4 +
CO2NH4
CaCl2 Ca2+ + 2NH4Cl
O O
white ppt
(b) AgNO3 test
O OAg
CO2NH4 + 2NH4NO3
+ 2AgNO3
CO2NH4
O OAg
white ppt
heat
2Ag + CO2
black
shining residue
(c) KMnO4 test: Pink color disappears due to reduction of KMnO4
CO2H
+ 2KMnO4 + 3H2SO4 K2SO4 + MnSO4 + 2H2O + 10CO2
CO2H
(d) Denige’s test:

O O
CO2H
+ HgSO4 + HgO Hg.HgSO4. HgO + Na2SO4
CO2H
O O
2. Tartaric acid
(a) CaCl2 test
HO CO2 NH4 HO CO2
+ CaCl2 Ca2+ + 2NH4Cl
HO CO2 NH4 HO CO2
(b) Ag mirror test
HO CO2 NH4 HO CO2Ag

+ AgNO3 + 2NH4Cl
HO CO2 NH4 HO CO2Ag
heat
Ag
shinning silver mirror
(c) Fenton’s test
113
O
OH OH HO O
Fe2+
CO2H CO2H Fe
HO2C HO2C
OH OH HO O
O
Dihydroxy maleic acid Deep violet color
(d) Mohler’s test
OH OH
HO OH OH
OH heat HO OH
OH [O] HO OH
CO2H HO CHO
HO2C
conc. H2SO4 H+
OH
OH OH
violet color
3. Succinic acid
(a) AgNO3 test
CO2Ag + 2NH4NO3
CO2 NH4 + 2AgNO3 AgO2C
NH4 O2C
(b) FeCl3 test
O
O
CO2 NH4 + 2FeCl3 + 2H2O Fe OH + 6NH4Cl
NH4 O2C
O
O
Reddish brown ppt
114
(c) Fluorescence test:
HO OH HO O OH
CO2H conc. H2SO4
+ 2
CO2H
H
O
Red color
CO
NaOH
O O O
CO2
Green fluorescent
4. Citric acid
(a) CaCl2 test
2C6H5O7(NH4)3 + 3 CaCl2  Ca3(C6H5O7)2 + 6 NH4Cl
(b) CdCl2 test

2C6H5O7NH4 + 3 CdCl2  Cd3(C6H5O7)2 + 6 NH4Cl
(c) AgNO3 test
C3H4(OH).(CO2NH4)3 + 3AgNO3 C3H4(OH)(CO2Ag)3 + 3 NH4NO3
(d) Denige’s test

O
OH O HgSO4 O
oxidation O + H2SO4
HO2C CO2H HO2C CO2H Hg
CO2H O
acetone dicarboxylic acid
O
Mercuric acetone-dicarboxylate
The final product is white ppt, which is a double salt of basic mercuric sulphate with
mercuric acetone dicarboxylate
O O
Hg
O
Hg O
SO4 Hg
Hg O
O 2
O
115
5. Resorcinol
(a) FeCl3 test

OH O
FeCl3
Fe2
OH O
3
(b) Br-water test
OH OH
Br Br
Br-water
OH OH
Br
(c) Fluorescence test: Similar as described for succinic acid
(d) Mohler’s test: Same as described for tartaric acid
6. Hydroquinone
FeCl3 test
OH O O
FeCl3
Fe2
3
OH O O
7. Benzoic acid
FeCl3 test
CO2H FeCl CO2 CO2H

3 Fe. Fe(OH)3 HCl
3
Buff color
Esterification test
CO2H conc. H2SO4 CO2Et
EtOH
fruity smell
116
8. Salicylic acid
(a) FeCl3 test

CO2H CO2
OH FeCl3 O
Fe
n
Violet color
(b) Br-water test
CO2H Br
OH Br-water OH
Br Br
(c) Oil of wintergreen test: same as MeOH
9. -Naphthol
(a) FeCl3 test
OH O
FeCl3 Fe OH
OH
3
Green
Binaphthol (flocculant ppt)
(b) Back dye test: Same as aniline
10. Urea
Biuret test
H2N NH2
O O
O heat O O N Cu2+ N
2 CuSO4 SO42-
H2N NH2 H2N N NH2 O O
-NH3
H H2N NH2
Biuret
H
yprochlorite test
H2NCONH2 + 3NaOCl + 2NaOH  N2  + Na2CO3 + 3NaCl + 3H2O
117
11. Glucose
(a) Reducing properties such as reduction of Fehling’s, Tollen’s and Barfoed’s test are due
to conversion of glucose to gluconic acid (Red ppt of Cu2O for Fehling and Barfoed.
Black mirror of Ag for Tollen).
OH OH OH OH
OHC OH HO2C OH
OH OH OH OH
Gluconic acid
(b) Molisch test (applicable to all carbohydrates)

The red violet color appears due to the formation of an unstable condensation product
between hydroxyl methyl furfural and 1-napthol.
OH OH
OH
HO O HO HO
HO CHO
OH O -naphthol O
OH
OH
OH
[O]
HO
O
Purple color dye OH
12. Lactose
(a) One of the reducing group is free in lactose, hence it reduces Fehling’s and Tollen’s
reagent. But it fails to reduce Barfoed’ s reagent (it is good for monosaccharides).
118
13. Sucrose
(a) Sucrose does not respond to Fehling’s or Tollen’s test as it is a non-reducing sugar.
(b) Seliwanoff’ test: Seliwanoff’s test is a chemical test which distinguishes between aldose
and ketose sugars. Ketoses are distinguished from aldoses via their ketone/aldehyde
functionality. If the sugar contains a ketone group, it is a ketose and if it contains an
aldehyde group, it is an aldose. This test is based on the fact that, when heated, ketoses
are more rapidly dehydrated than aldoses.
HCl
HOH2C O CH2OH
sucrose HOH2C O CHO
D-glucose + HO
heat OH
OH
5-(hydroxymethyl)-furfural
fructose
H+ HO OH
O2
HO O OH
CH2OH
wine-red color
14. Starch
Starch is dehydrated product of several glucose units. It is a non reducing sugar but on
hydrolysis it is converted to dextrin and finally to glucose.
119
Reaction for liquid samples
1. Formic acid
(a) AgNO3 test
HCOOH + AgNO3  HCO2Ag + HNO3
HCO2Ag (heat)  HCO2H + CO2 + Ag (black or grey ppt)
(b) FeCl3 test (you need neutral solution of formic acid)

HCO2NH4 + FeCl3  (HCO2)3Fe [red color] + 3 NH4Cl
(HCO2)3Fe + 2H2O  (HCO2)Fe(OH)2 [ brown ppt] + 2HCO2H
(c) HgCl2 test

2HCO2 NH4 + 2HgCl2  Hg2Cl2 + 2 NH4Cl + CO + CO2 + H2O
Hg2Cl2 + 2HCO2 NH4  2Hg + 2 NH4Cl + CO + CO2
2. Acetic acid
(a) FeCl3 test
3CH3CO2 NH4 + FeCl3  (CH3CO2)3Fe [red color] + 3 NH4Cl
(CH3CO2)3Fe + 2H2O  (CH3CO2)Fe(OH)2 + 2CH3CO2H
Brown color
(b) AgNO3 test
CH3CO2 NH4 + AgNO3  CH3CO2Ag + NH4NO3
3. Methyl alcohol
(a) Oxidation test: Copper coil oxidation, MeOH is oxidized to formaldehyde
2Cu + O2  2CuO
MeOH + CuO  HCHO + H2O + Cu
Subsequent tests are given by formaldehyde such as Tollen’s and Fehling’s test.
2 C6H4(OH)2 + HCHO ----> [(HO)C6H3(O)]2•CH2 +H2O
[methylene diresorcin]
(b) Oil of wintergreen test: Methyl salicylate is formed by esterification
OH OH
CO2H conc. H2SO4 CO2Me
MeOH
120
4. Ethyl alcohol
(a) Oxidation test: EtOH is oxidized to acetaldehyde, and reactions are similar to that of
MeOH.
(b) Iodoform test:
EtOH + 4I2 + 6NaOH  CHI3 + HCOONa + 5NaI + 5H2O
Yellow ppt of iodoform is obtained.
(c) Ester formation (acid catalyzed)
EtOH + PhCO2H  PhCO2Et (Fruity smell)
5. Glycerol
(a) Acrolein test:
OH KHSO4 Tollen's reagent
HO OH CHO Ag + CO2
heat
(b) Borax-phenolpthalein test: Borax in aqueous solution hydrolyses to NaOH and boric
acid. NaOH being strong alkali turns phenolphthalein to pink coloration. Boric acid form
boro spiramic acid which has higher electrical conductivity than boric acid and destroys
the pink color of phenolphthalein.
Na2B4O7 + 7H2O 2NaOH + 4H3BO3
OH HO O O
HO OH + H3BO3 B H+
O O OH
Borospiramic acid
6. Acetone
(a) DNP test
Me
H2N N
NH NH
Me
O NO2 NO2
+
Me Me
NO2 NO2
DNP Reddish yellow
(b) Iodoform test

O O
+ 3I2 + 4NaOH + CHI3 + 3NaI + 3H2O
ONa
121
7. Aniline
(a) Bromine-water test
NH2 NH2
Bromine-water Br Br
Br
white ppt
(b) Diazocoupling test
O N
NH2 +
N2 Cl - N
NaNO2, HCl O
0-5 oC
Scarlet red dye
8. Methyl aniline
Libermann test
OH
ON
NHMe NMe NHMe
NaNO2, HCl
ON OH +
conc. H2SO4
yellow oil p-nitroso phenol
OH
conc. H2SO4
water
O N OH HO N OH+ HSO4-
red
blue
NaOH
O N O-Na+
blue
122
9. Dimethyl aniline
(a) Potassium ferrocyanide test
PhNMe2 + HCl  PhNMe2.HCl
2 PhNMe2.HCl + 2HCl + K4[Fe(CN)6]  [PhNMe2]2.H4Fe(CN)6 + 4KCl
White ppt
(b) Diazocoupling test
NH2 N2+Cl-
NMe2
NaNO2, HCl
N N NMe2
rose red dye
(c) Malachite green test:

NMe2 NMe2
CHO NMe2
ZnCl2 [O]
+ 2 OH
or
H2SO4
NMe2 NMe2
HCl
NMe2
NMe2
Malachite green
10. Benzaldehyde
(a) Tollen’s and DNP tests are analogous to any other aldehyde (reluctant to Fehling’s test).
(b) Malachite green test: same as dimethylaniline
11. Nitrobenzene
(a) Reduction in acid-medium and diazocoupling test
O
NO2 NH2 N2+Cl- N
N
Sn/HCl NaNO2, HCl O
red dye
(b) Mulliken-Barker test
NO2 NHOH NO
H AgNO3/NH4OH
Ag +
black
123
Experiment No
Name Roll No:
Sample no: Date:
Physical Characteristics:
Flow Sheet
Preliminary Conclusion:
125
Confirmatory Test/s
Chemical reactions
Final Conclusion:
Signature of the Investigator: Mark:
127
Experiment No
Name Roll No:
Sample no: Date:
Flow Sheet
129
Confirmatory Test/s
Chemical reactions
Final Conclusion:
131
Experiment No
Name Roll No:
Sample no: Date:
Flow Sheet
133
Confirmatory Test/s
Chemical reactions
Final Conclusion:
135
Experiment No
Name Roll No:
Sample no: Date:
Flow Sheet
137
Confirmatory Test/s
Chemical reactions
Final Conclusion:
139
Experiment No
Name Roll No:
Sample no: Date:
Flow Sheet
141
Confirmatory Test/s
Chemical reactions
Final Conclusion:
143
EXPERIMENT 3
Synthesis of Benzoic Acid Using Household Bleach

The aim of this experiment is to synthesise benzoic acid from acetophenone by using haloform reaction.
This experiment will make you familiar with the general procedures used in the organic synthesis
laboratory.
Chemicals required: Acetophenone, household bleach, diethyl ether, sodium sulphite, 1N sulphuric
acid solution, 10% NaOH solution, distilled water, ice
Apparatus required: One 20 mL test tube, one test tube holder, one glass funnel, filter paper, one 100
mL separating funnel, one 100 mL separatory funnel ring, one separatory funnel ring stand, two 100
mL Erlenmeyer flask, one 100 mL beaker, butter paper.
Safety: You are going to deal with hazardous chemicals so never try to smell, taste or let it come in
contact with your skin. There is no danger if you use it cautiously.
Introduction: Haloform reaction is a confirmatory test for methyl ketone, methyl aldehyde or
secondary alcohol with an alpha methyl group. When methyl ketones are treated with the halogen in
basic solution, polyhalogenaton followed by cleavage of the methyl group occurs. The products are the
corresponding carboxylic acid and trihalomethane, commonly known as haloform (Scheme 1). Here we
will be using acetophenone as a substrate for haloform reaction in presence of household bleach.
Household bleach contain NaOCl, which will be reacting with acetophenone to afford benzoic acid and
chloroform. The mechanism of this reaction is given below.
Chemicals Molecular Amount Density Millimole Equivalent

Weight
Acetophenone 120.15 185.4 mg/ 1.03 1.54 1
180 µL g/cm3
Household 74.44 6 mL 5.39 3.5
Bleach
(contain 6.6%
NaOCl)
EXPERIMENT 3
10% NaOH 40 0.5 mL 12.32 8

Solution
Na2SO3 126.04 50 mg 0.4 0.25
Diethyl Ether 2.5 mL
Reaction Procedure: Using a dispensing pipet, carefully add 180 µL of acetophenone into a clean 20
mL test tube (TA will help you to use dispensing pipet). Measure 6 mL of household bleach in a 10 mL
graduated cylinder and carefully add it to the same test tube, followed by 0.5 mL of 10% NaOH. Heat
the reaction mixture in a water bath (around 75 °C) for 30 minutes. You should note the starting and
ending time in your notebook. During the heating, frequently shake the test tube to ensure proper mixing
of the reagents. While the solution is being heated, weigh out about 50 mg of sodium sulphite in butter
paper.
Caution: you are not supposed to leave the test tube for heating without observation
After 30 minutes the solution colour will change from yellow to colourless. Now, you should cool down
the reaction mixture for 10 minutes to reach room temperature. In the meantime, make the set up ready
for extraction (get separating funnel, funnel, glass stopper, separatory funnel ring, separatory funnel
ring stand, Note: Please find the picture for the extraction set up below). Extraction is a procedure used
to separate compounds based on their solubility in two immiscible liquids.
Caution: Before you transfer reaction mixture to the separating funnel make sure the separating funnel
is closed and there will be a beaker placed below separatory funnel.
Transfer the reaction mixture into the separating funnel using funnel, wash the test tube with 2.5 mL of
diethyl ether and add to the separating funnel. Stopper the separating funnel and take it out from the
stand and shake it for 10 sec. Carefully remove the cork and allow the layers to separate. You will
observe formation of two layers, the top layer contains diethyl ether and the bottom contains water
(water is heavier than diethyl ether). Now, carefully drain the water layer and collect into an Erlenmeyer
flask. Discard the ether extracts in the organic waste bottle.
Solvent extraction set-up Gravity Filtration set-up
EXPERIMENT 3
Step by step guide to fold the filter paper
The aqueous layer in the Erlenmeyer flask is cooled in an ice bath and acidified by the dropwise addition
of 1N H2SO4. After the addition of 5-6 drops check the pH using a glass rod. You should stop addition
as soon as pH is below 3. You will observe formation of white solid precipitation during addition of 1N
H2SO4. At, this point you should get ready for gravity filtration using funnel, filter paper, and stand.
Collect the thick white precipitate on a filter paper. Wash the solid with 1 mL of ice-cold water. Allow
the crystals to dry, and determine the actual yield, and the percentage yield.
Analysis: Now you will check the melting point of the solid sample and perform one confirmatory test
for benzoic acid (go through the confirmatory test for benzoic acid from the list of solid samples in you
book).
Pre-lab Quiz:
1. Which are the following compounds will participate in haloform reaction and why?
(a) Ethanol (b) Benzophenone (c) Benzyl alcohol (d) Acetaldehyde (e) Benzaldehyde
2. What is the role of base in haloform reaction?

3. Draw the mechanism of haloform reaction with acetone in presence of household bleach and
sodium hydroxide.
4. What is the principle of solvent extraction?
5. Why do you choose ditheyl ether for extraction with water not methanol?
6. What is the purpose for addition of 1N H2SO4?
EXPERIMENT 3
Name: ……………………………… Lab Partner………………………………..
EXPERIMENT 3
Section……………………………..
Name: ……………………………… Date:…………………………………….
Lab Partner………………………………..
Section…………………………….. Date:…………………………………….
REPORT SHEET
REPORT SHEET
Chemicals Molecular Amount Density Millimole Equivalent

Weight
Chemicals
Acetophenone Molecular
120.15 Amount
185.4 mg/ Density
1.03 Millimole
1.54 Equivalent
1
Weight 180 µL g/cm3
Acetophenone
Household 120.15
74.44 185.4
6 mL mg/ 1.03 1.54
5.39 13.5
Bleach 180 µL g/cm3
Household
(contain 6.6% 74.44 6 mL 5.39 3.5
Bleach
NaOCl)
(contain 6.6%
NaOCl)
10% NaOH 40 0.5 mL 12.32 8
Solution
10%
Na2SONaOH
3
40
126.04 0.5 mL
50 mg 12.32
0.4 80.25
Solution
Na2SO3 126.04 50 mg 0.4 0.25
Calculation of percent yield
A. Yield
Calculation of percent of benzoic acid obtained…………………mg
yield
B. Expected yield of benzoic acid………………….mg
A. Yield of benzoic acid obtained…………………mg
Percent Chemical
B. yield = (A/B)×
Expected yield 100 = ……….%
of benzoic acid………………….mg
Percent Chemical yield = (A/B)× 100 = ……….%
Melting point of the benzoic acid obtained……………………..
Melting point of the benzoic acid obtained……………………..

Confirmatory test for benzoic acid
Name of the test for benzoic acid Observation
Confirmatory
Name of the test Observation
Conclusion:
Conclusion:
EXPERIMENT 4
Reaction Rate Comparison for Nucleophilic Substitution Reaction of Organic Halides

You will be investigating eight organic halides for their reactivity under SN2 and SN1 conditions.
Chemicals required: n-Butyl Chloride, n-Butyl Bromide, sec-Butyl Bromide, Isobutyl Bromide, tert-
Butyl Chloride, Benzyl Chloride, Allyl Bromide, Bromobenzene, NaI, Distilled water, Acetone,
Ethanol, silver nitrate
Apparatus required:
Test tubes; Stop Watch/Timer; Water bath (45 °C); Thermometer
Investigation of the rate of SN2 substitution of Organic Halides
SN2 reactions work best when a polar aprotic solvent, we will use acetone for the study. In your
investigation, sodium iodide (NaI) will be reacted with a variety of alkyl halides. When using NaI, the
iodide ion (I−) acts as the nucleophile. The combination of sodium iodide with the solvent acetone
proves especially useful in this investigation because the NaCl or NaBr byproducts are not soluble in
acetone, thus the appearance of the precipitate can be used to monitor the progress of the reaction. By
comparing the precipitate formation versus time for the various organic halides you will be able to
organize them by their relative reactivities.
Organic Halides we will use for this study:
CH3CH2CH2CH2Cl CH3CH2CH2CH2Br CH3CHBrCH2CH3 (CH3)2CHCH2Br
n-Butyl Chloride n-Butyl Bromide sec-Butyl Bromide Isobutyl Bromide
(CH3)3CCl C6H5CH2Cl CH2=CHCH2Br PhBr
tert-Butyl Chloride Benzyl Chloride Allyl Bromide Bromobenzene
Experimental Procedure
Caution: Organic halides are toxic, never try to smell, taste or let it come in contact with your skin.
There is no danger if you use it cautiously. Do not use your finger to cover the test tube.
Take 8 test tubes and number them 1-8. These numbers will correspond to the organic halides listed in
table 1. Place approximately 0.5 mL of 10% NaI in acetone in each test tube. Next, add 5 drops of each
organic halide to the test tube. Start the stopwatch and shake it to mix the reagents thoroughly. Record
whether a precipitate forms and the amount of time elapsed between addition of the halide and the
definitive formation of a precipitate.
Be cautious of false positives. Impurities present with the organic halides can result in the formation
of a small amount of initial precipitate. If you observe a small amount of precipitate, but the amount
does not steadily increase, then you likely have a false positive.
If no precipitation is observed after 5 min at room temperature (Record the current room temperature
from a thermometer in the lab), restart the timer and heat the sample in a 45 °C (or 60 °C) in water bath
and record the precipitation time at the specific temperature.
If no precipitation is observed after 5 min, record as no reaction.
EXPERIMENT 4
Name: ……………………………………… Lab Partner:…………………………….

Section:…………………………….. Date: ……………………………
Observations for the rate of SN2 substitution of Organic Halides
Room Temperature: ______ ⁰ C
Table 1.
Rank according to
Organic Halide Temperature Time
rate
CH3CH2CH2CH2Cl
n-Butyl Chloride
CH3CH2CH2CH2Br
n-Butyl Bromide
CH3CHBrCH2CH3
sec-Butyl Bromide
(CH3)2CHCH2Br
Isobutyl Bromide
(CH3)3CCl
tert-Butyl Chloride
C6H5CH2Cl
Benzyl Chloride
CH2=CHCH2Br
Allyl Bromide
PhBr
Bromobenzene
Quiz:
1. Draw the product with (R)-sec-Butyl Bromide under the above conditions and comment on
the stereochemistry and optical purity of the product.
2. Comment on the rate of the reaction if you used 1% NaI (equimolar with organic halide)
instead of 10% NaI.
3. Comment on the effect of leaving group on the reaction rate.
4. Compare the effect of substrate structure (primary, secondary, tertiary) under SN2
conditions.
EXPERIMENT 4
Investigation of the rate of SN1 substitution of Organic Halides

In the second part of this experiment, you will be investigating the SN1 reactivity of the same eight alkyl
halides. The solvent (ethanol) will be the nucleophile. For this reason, SN1 reactions are often referred
to as solvolysis reactions. We will add silver nitrate (AgNO3) to the reaction mixture. The use of AgNO3
benefits in twofold. First, the silver ion will coordinate with the halogen, helping to pull the halogen off
the molecule resulting in carbocationic species. Second, the AgX by-products are insoluble in the
reaction solvent and precipitation can be observed allowing for the qualitative assessment of the reaction
rate.
Experimental Procedure
Clean your Test tubes from your previous experiments, (you may get AgI precipitate if not washed
thoroughly!!) rinsing with water thoroughly, and then rinsing them 3 times with ethanol.
To eight clean and labeled test tubes, add 0.5 mL of 1% AgNO3 in ethanol. Next, add 5 drops of the
appropriate halide to each test tube. Start the timer and shake the tubes for thorough mixing and watch
for formation of a precipitate. Record the time in table 2. Just as in the SN2 reaction, if precipitation is
not observed, you should restart the timer and heat the solution in a 45 °C water bath.
EXPERIMENT 4
Name: ……………………………………… Lab Partner:…………………………….

Section:…………………………….. Date: ……………………………
Observations for the rate of SN1 substitution of Organic Halides
Room Temperature: ______ ⁰ C
Table 2.
Rank according to
Organic Halide Temperature Time
Rate
CH3CH2CH2CH2Cl
n-Butyl Chloride
CH3CH2CH2CH2Br
n-Butyl Bromide
CH3CHBrCH2CH3
sec-Butyl Bromide
(CH3)2CHCH2Br
Isobutyl Bromide
(CH3)3CCl
tert-Butyl Chloride
C6H5CH2Cl
Benzyl Chloride
CH2=CHCH2Br
Allyl Bromide
PhBr
Bromobenzene
Quiz
1. Draw the product with (R)-sec-Butyl Bromide under the above conditions and comment on
the stereochemistry and optical purity of the product.
2. Comment on the effect of leaving group on the reaction rate.
3. Compare the effect of substrate structure (primary, secondary, tertiary) under SN1
conditions.

Detect Organic Compounds with Chemistry Experiments

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Detect Organic Compounds with Chemistry Experiments

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Organic Chemistry

Solid samples Page

1. Litmus paper 24. Dilute solution of borax

Experiment No – 1B: Solid sample (Unknown)

Flow sheet for solid sample

solubility in water (no heating)

Soluble Sparingly soluble/

Boil and add KMnO4 (2-3 drops)

Color disappears Color persists

Acidic = Oxalic acid Mild acidic = Resorcinol Neutral = Urea

 Cold means at room temperature.

** see next page

Non sooty flame**

Charring and no No charring but smell of ammonia

Violet colour No violet colour

Experiment No – 2B: Liquid sample (Unknown)

*Miscible= Methyl alcohol **Immiscible = Benzaldehyde

Formic acid * ** Dimethyl aniline

Formic acid, Acetic acid Methanol, Ethanol, Acetone,

Yellow ppt NO yellow ppt

Yellow ppt NO yellow pp

Red dye No response

White ppt No ppt

**Important: The above flow sheet is a general guidance to arrive at a

Note: Organic compounds insoluble / immiscible in water should be

OS = Organic Sample CT = Confirmatory Test

1. CaCl2 test: CaCl2 solution is added to an A white ppt. forms immediately.

a) dil. AcOH is added to one portion

2. AgNO3 test: AgNO3 solution is added to an A white crystalline ppt. forms

a) Dil. NH4OH is added to one portion.

3. Denige’s test (CT): (a) Denige’s reagent is added a) No ppt.

4. Fluorescein test (CT): A small amount of OS and

a) The mixture is heated gently on burner (1 min).

2. Fluoroscein test (CT): A small quantity of OS is An intense green fluorescence.

3. Tartaric acid test (CT): A small amount of OS is A violet-red coloration.

Make sure that all the reagents are cooled to 0-

Biuret test (CT): About 0.5 g of OS is heated A pink or violet coloration.

Urea and sodium hypochlorite: Add 3-4 drops of

1. Fehling’s test: Same as glucose Same as glucose

2. Tollen’s test: same as glucose Same as glucose

3. Molisch’s test: same as glucose Same as glucose

3. Molisch’s test: same as glucose Same as glucose

1. Fehling’s test: Same as glucose No red ppt.

2. Tollen’s test: same as glucose No silver mirror

3. Molisclh’s test: same as glucose Same as glucose

Starch is sparingly soluble in cold water, hence it

2. FeCl3 Test: A few drops of freshly prepared A red colour develops

Then an excess of neutral solution is added and

2. Acetic acid, CH3CO2H.

1. FeCl3 Test: A few drops of freshly prepared A red colour develops

a) dilute HCl is added to one part

b) A brown ppt of basic ferric formate appears.

1. Oxidation test: A Cu-spiral is made repeatedly

b) Resorcinol test: A mixture of 0.5 ml of oxidized

4. Ethyl alcohol, CH3CH2OH

1. Oxidation test: Similar like MeOH

2. Iodoform test (CT): Take 1.0 ml of sample and

b) The iodoform test is repeated by adding NH 4OH

b) The iodoform test is repeated by adding NH 4OH

1. Bromine-water test: Few drops of Br2-water is A white ppt. of 2,4,6-tribromoaniline forms.

1. Liebermann’s test (CT):

b) The light yellow oil is extracted with ether and

1. K4Fe(CN)6 test: To a clear HCl solution of OS White ppt appears