Practical Organic Chem by Acme Study Point

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FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 1
Practical Organic
Chemistry
IITJEE Syllabus:
Detection of elements (N, S, Halogens); Detection and identification of the

following functional groups: hydroxyl (alcoholic and phenolic), carbonyl (aldehyde
t
in
and ketone), carboxyl, amino and nitro; Chemical methods of separation of
monofunctional organic compounds from binary mixtures.
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INTRODUCTION
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The identification of organic compounds differs from that of the inorganic salts in the
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respect that inorganic salt analysis is very systematic while there is no such systematic
scheme for the analysis of organic compounds. However, the following operations are
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generally useful for the identification of unknown organic compounds:

(i) Preliminary tests
(a) Physical state
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(b) Colour
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(c) Odour
(d) Ignition test
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(e) Saturation test

(f) Solubility
(ii) Detection of elements
(iii)Detection of functional groups
(iv)Determination of melting or boiling point and
(v) Preparation of derivatives (if any)
DETECTION OF ELEMENTS
Organic compounds consist mainly of carbon, hydrogen and oxygen. Hence, detection of
these elements are not necessary. In addition to the above elements, organic compounds
often contain nitrogen, halogens, and sulphur. Hence identification of organic compounds
means detection of nitrogen, halogens and sulphur only.
(a) Lassaignes test (for nitrogen, sulphur and halogens)
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Nitrogen,
sulphur and halogens are generally detected by this test. Cut a small piece of sodium metal
with a knife, press it between the folds of a filter paper to wipe out the kerosene oil and
transfer to a fusion tube. Add a little of the organic compound. Heat the fusion tube first
gently and then strongly to dullred. Continue heating for some time and then immerse the
hot tube into 1520 ml distilled water. The tube must be broken into pieces. Grind the
whole mass thoroughly and then filter. Use this filterate for testing the presence of
nitrogen, sulphur and halogens in the organic compound.
The following reactions occur when sodium is fused with an organic compound.
Carbon and nitrogen from the organic compound react with sodium to form sodium
cyanide.
Na + C + N NaCN
Halogen and sulphur present in the organic compound react with sodium to form sodium
halide and sodium sulphide respectively.
Na + X NaX (X = Cl, Br, I)
2Na + S Na2S
When nitrogen and sulphur both are present, sodium thiocyanate is formed.
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Na + C + N + S NaCNS
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These substances being soluble are extracted with water and identified.
(i) For Nitrogen: The following reactions take place when the filtrate is treated first with
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ferrous sulphate solution, then with ferric chloride and finally with excess of dilute
sulphuric acid.
2Na + 2H2O 2NaOH + H2
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FeSO4 + 2NaOH Fe(OH)2 + Na2SO4
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Fe(OH)2 + 2NaCN Fe(CN)2 + 2NaOH

Fe(CN)2 + 4NaCN Na4[Fe(CN)6]
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Sodium ferrocyanide
3Na4[Fe(CN)6] + 4FeCl3 Fe4[Fe(CN)6]3 + 12NaCl
ferricferrocyanide
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(prussian blue)
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An intense blue colouration is produced due to the formation of Prussian blue.

Hydrazine (NH2NH2), Benzene diazonium salts do not give Lassiagnes test of
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nitrogen.
(ii) For sulphur

(a) Na2S + Na2[Fe(CN)5NO]
Na4[Fe(CN)5NOS]
sodium sulpho nitroprusside
(violet colour)
(b) Na2S + (CH3COO)2Pb PbS + 2CH3COONa
lead sulphide
(black)
(iii) For halogens:

(a) NaCN + HNO3 NaNO3 + HCN
NaCl + AgNO3 AgCl + NaNO3
Curdy white
NaBr + AgNO3 AgBr + NaNO3
pale yellow
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NaI + AgNO3 AgI + NaNO3

bright yellow
Before adding AgNO3 solution, the filtrate is boiled with conc. HNO3 to
decompose NaCN, if present. Otherwise, a white precipitate will be formed even in
absence of halogen.
(b) In this test acidify a little sodium extract with dil. HNO 3 or dil. H2SO4 and add
CHCl3 or CCl4 and excess of chlorine water. If organic layer becomes yellow or
brown, bromine is present and if violet, iodine is present. Chlorine is not detected
by this test.
2NaBr + Cl2 2NaCl + Br2
CHCl3 + Br2 Yellow or brown layer
2NaI + Cl2 2NaCl + I2
CHCl3 + I2 Violet layer
(iv)For nitrogen and sulphur: (when both are present)
(a) C + N + S Na
NaCNS
3NaCNS + FeCl3 Fe(CNS)3 + 3NaCl
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in
ferric thiocyanate
(red colour)
(b) NaCNS + HCl
4HCNS + Co(NO3)2
HCNS + NaCl
thiocyanic acid Po
H2[Co(SCN)4] + 2HNO3
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cobaltithiocyanic
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acid (blue)
Bielsteins test
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Many organic compounds containing halogens impart a green colour to the Bunsen flame
when heated on a copper wire. The green colour is developed due to the formation of
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volatile halides of copper. However, urea (H2NCONH2) and thiourea (H2NCSNH2) do not
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contain halogens even then they given Bielsteins test. Fluorine is unable to respond this
test as it is volatile.
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Formula used in the determination of empirical, molecular and structural

formulae
12 weight of CO 2 formed
Percentage of carbon = 100
44 weight of organic compound
2 weight of CO 2 formed
Percentage of hydrogen = 100
Percentage of nitrogen
28 volume of Nitrogen at NTP evolved
= 100 (Duma's method)
1.4 volume of acid Normality of acid
= (Kjeldal's method)
weight of organic compound
35.5 weight of AgCl formed
Percentage of chlorine= 100
143.5 weight of organic compound
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Percentage
80 weight of AgBr formed
of bromine = 100
127 weight of AgI formed
Percentage of iodine = 100
32 weight of BaSO 4 formed
Percentage of Sulphur = 100
Percentage of oxygen = 100 Sum of percentage of all other elements percent in the
compound.
Molecular formula = n Empirical formula
Molecular weight
n=
Empirical formula weight
Molecular weight of acid = Equivalent weight Basicity
weight of silver salt
Molecular weight of acid = Basicity 107
weight of silver
1 weight of platinum salt 195
t
Molecular weight of base= acidity 410
in
2 weight of platinium
Molecular weight = 2 Vapour density
Molecular weight =
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2 weight of compound 22400
volume of vapour given by subs tan ce at NTP
100 K f weight of subs tan ce
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Molecular weight =
Tf weight of solvent
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where Kf = Molal freezing point depression constant

Tf = Depression in freezing point
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100 K b weight of compound

Molecular weight =
Tb weight of solvent
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where Kb = Molal boiling point elevation constant

Tb = Elevation of boiling point
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DETECTION OF FUNCTIONAL GROUPS

Detection of functional groups is an important step in the analysis of organic compounds.
It largely depends on the correct determination of the constituent elements.
(a) Tests for carboxylic group
(i) Litmus test: Place a small quantity of the organic compound or its aqueous solution
on a piece of moist blue litmus paper. If the paper turns red, carboxylic group may be
present.
(ii) Sodium bicarbonate test: Add a small quantity of the organic compound to about
5 ml sodium bicarbonate solution taken in a testcube. Compound dissolves with brisk
effervescences.
RCOOH + NaHCO3 RCOONa + H2O + CO2
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(iii)Take a
small quantity of the organic compound and add 45 ml of alcohol in a testtube. Add
a few drops of conc. sulphuric acid and warm on a water bath. A fruity smell indicates
the presence of an ester.
RCOOH + R OH H RCOOR + H2O
2SO 4
Ester
(b) Tests for aldehyde group
(i) Schiff test: Take 5 ml of Schiffs reagent in a testtube and shake with organic
compound (do not heat). A pink colour is formed within two minutes.
Cl NH2 Cl NHSO2H

H2N C H2N C CHO
H
2SO 3
R

or SO 2 gas HO3S
2 H 2O
NH2 NHSO2H
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pRosaniline hydrochloride Schiffs reagent (colourless)
Cl

NHSO2H Po
H2N C
+ RCHO.H2SO3
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NHSO2H
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(Pink colour)
(ii) Fehlings test: Mix equal volumes of Fehlings (A) and Fehlings (B) solution in a
testtube. Add a small amount of the organic compound and boil for some time. A red
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precipitate of Cu2O is obtained.

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RCHO + 2CuO RCOOH + Cu2O

Red
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(iii)Tollens test: Take about 5 ml of Tollens reagent in a testtube. Add a small quantity
of the organic compound and heat on a water bath. A shining silver mirror is formed
on inner walls of the testtube.
RCHO + 2[Ag(NH3)2]OH + H2O RCOONH4 + NH3 + 2NH4OH + 2Ag
Tollens reagent Silver mirror
(iv)Benedicts test: Take 45 ml of Benedicts reagent in a testtube. Add a few ml of the

organic compound (or a solution prepared in alcohol or water). Heat the mixture to
boiling. Formation of red precipitate indicates the presence of aldehydes.
RCHO + 2Cu(OH)2 + NaOH Cu2O + RCOONa+ + 3H2O
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(c) Tests for
ketonic group
(i) Ketones, unlike aldehydes, do not restore the pink colour of Schiffs reagent nor do
they reduce Fehlings solution or ammoniacal silver nitrate solution. However, they
form crystalline precipitate with 2,4dinitro phenylhydrazine and also with sodium
bisulphite reagent.
NO2 NO2
R R
C = O + H2NHN NO2 C = NHN NO2
R R
R R OH
C = O + NaHSO3 C
R R SO3Na
(Bisulphite addition
compound)
(ii) Sodium nitroprusside test: Treat 1 ml of the organic compound with 1 ml of freshly
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prepared solution of sodium nitroprusside followed by excess of NaOH solution. A
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winered colour is obtained.
(d) Tests for phenolic group Po

(i) Litmus test: Place a trace of the organic compound on the moist blue litmus paper. It
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turns red.
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(ii) Neutral FeCl3 test: When phenols are treated with neutral ferric chloride solution,
they form coloured complexes. The colour of the complex may be violet, red, blue or
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green. This is a characteristic reaction of compounds having enolic group. (=COH).

All enols respond to this test.
With relatively milder oxidizing agents such as ferric chloride (Fe3+) a resonance
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stabilized phenoxyl radical is formed. This radical soon undergoes dimerization which
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may take place by orthoortho, orthopara, parapara coupling reaction.

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OH O O O O
H H
+ Fe3+

H Fe2+ + H+
O O O
H H H
O O O
+ H +
H H
The phenoxyl radicals are highly coloured and therefore, products are also coloured.
(iii) Anilne Dye test: Dissolve a little aniline in dilute hydrochloric acid, cool in icecold
water and add aqueous solution of sodium nitrite dropwise. To this cold solution, add
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organic
compound already dissolved in sodium hydroxide solution. A red or orange precipitate
is obtained.
NaNO2 + HCl HNO2 + NaCl
Cl
0C

NH2 + HNO2 + HCl N N + 2H2O
Cl

NN + OH N=N OH
NaOH

NaCl
Benzenediazonium Phenol H 2O
phydroxy azobenzene (dye)
chloride
(iv)Phthalein test (Fluorescein test): Heat gently some organic compound and phthalic
anhydride with a few ml of conc. sulphuric acid in a testtube. Pour the heated mixture
to about 50 ml of water taken in a beaker and then add sodium hydroxide solution till it
became alkaline. A beautiful pink or purple colour appears.
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OH OH
C + H2O
O=CO
C=O
+
OH
H
2SO 4
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O=CO OH
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ONa+
2NaOH
C
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O
O=CONa+
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(pink or purple)
(v) Bromine water test: Take aqueous or alcoholic solution of the organic compound in a
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testtube. Add excess of bromine water. A yellowish white precipitate is obtained.

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OH OH
Br Br
+ 3Br2

Phenol
Br
(2,4,6tribromophenol)
(vi)Ceric ammonium nitrate test: Treat a few drops of the ceric ammonium nitrate with
34 ml hot aqueous solution of the organic compound. A green or brown precipitate is
obtained.
(NH4)2[Ce(NO3)6] + 2C6H5OH [Ce(NO3)4(C6H5OH)2] + 2NH4NO3
phenol green or brown ppt.
(vii) Liebermanns test: Take a little amount of the compound and fuse with a few
crystals of NaNO2 in a testtube. Cool the testtube and add 1 ml conc. H2SO4. A deep
green colour is obtained which changes to pruple, to blue and finally, when poured
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into large excess
of water, to red. When a little NaOH solution is added to the aqueous solution, the
same green, purple or blue colour reappears.
Tauto
merize
NaNO2 H 2SO 4
HO
HO N=O O NOH
(green colour)
Phenol
O OH O ONa+
NaOH
N N
H 2SO 4
Indophenol (red) Indophenol (blue)
(e) Tests for alcoholic group

Alcohols may be considered as neutral compounds. They are soluble in water or dioxane.
(i) Sodium test: Take 34 ml of the organic compound in a testtube. Add a thin slice of
sodium metal. A brisk effervescence due to the evolution of hydrogen takes place.
(Organic compound should be free from water).
2ROH + 2Na 2RONa + H2
t
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(ii) Ester test: Warm the given liquid with acetic acid in presence of sulphuric acid. A
fragrant smell indicates the formation of ester.
ROH + CH3COOH H Po
RCOOCH3 + H2O
2SO 4
Alcohols give crystalline esters with 3,5dinitrobenzoyl chloride. These esters have
sharp melting points and can be used for testing a given alcohol.
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NO2 NO2
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R OH + Cl C R O C
+ HCl
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O O
NO2 NO2
(iii) Oxidation test: Take some organic compound, 5 ml of K2Cr2O7 solution and 23 ml
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of conc. H2SO4 in a testtube. Heat the testtube after fitting a delivery tube. The
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distillate is passed into another testtube containing water. Test the aqueous solution
of the distilalte for aldehyde group. A positive test indicates the presence of primary
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alcoholic group in the given compound.

RCH2OH RCHO + H2O
[O]
(iv)Ceric ammonium nitrate test: Shake a few drops of ceric ammonium nitrate with
1 ml of the organic compound. A red colour is produced (Phenols give a green or
brown colour).
2ROH + (NH4)2[Ce(NO3)6] [Ce(NO3)4(ROH)2] + 2NH4NO3
Distinction between primary, secondary and tertiary alcohols

Lucas test: Add 34 drops of alcohol to 2 ml of Lucas reagent (anhydrous ZnCl2 + conc.
HCl) in a testtube. Shake the mixture and allow to stand at room temperature. If a cloudy
precipitate is obtained immediately then it is a tertiary alcohol, if obtained after 23
minutes then it is a secondary alcohol, while no cloudy precipitate even after long standing
means it is a primary alcohol.
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+
R OH + ZnCl2 R O ZnCl2
R Cl
RCl
+
H [Zn(OH)Cl2]
(f) Tests for primary amines(NH2)
(i) Carbylamine test: Heat the organic compound with alcoholic KOH and chloroform in
a testtube. A highly offensive smell is evolved due to formation of isocyanides.
RNH2 + CHCl3 + 3KOH R N C + 3KCl + 3H2O
This test is applicable to aliphatic and aromatic primary amines.
(ii) Dye test: This test is applicable only for aromatic primary amines. Dissolve a small
amount of the organic compound in dil. HCl. Cool it in icecold water. Add cold
solution of sodium nitrite with constant shaking and then add naphthol prepared in
NaOH solution. An orangered dye is obtained.
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Cl
NH2 + HNO2 + HCl Po
N N + 2H2O
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OH OH
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Cl

NN + N=N
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+ HCl
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naphthol (Orangered dye)

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(g) Tests for secondary amines (NH)

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Liebermanns nitroso test: Dissolve some organic compound in 3 ml of conc. HCl

and then add 23 ml of water. Cool the solution in icecold water and then add 34 ml
of cold dilute NaNO2 solution. A white or yellow emulsion is produced. Take 45
drops of the above emulsion in a test tube. Add 45 drops of phenol and conc. H2SO4.
A blue colour develops. Addition of water changes blue colour to red which again
changes to blue on adding NaOH solution.
(h) Tests for nitro group
(i) Reduction test: Take a small amount of the organic compound in a testtube. Add a
few ml of conc. hydrochloric acid and one or two pieces of granulated zinc or tin. Heat
the mixture gently for few minutes. Decant the clear liquid into a testtube. Cool it in
icecold water and then add cold dilute solution of sodium nitrite. Pour this cold
solution into an alkaline solution of naphthol. An orangered dye is obtained. This
test is applicable only to aromatic nitro compounds.
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Zn
+ 2HCl
ZnCl2 + 2[H]
C6H5NO2 + 6[H]
C6H5NH2 + 2H2O
C6H5NH2 + HNO2 + HCl
C H N Cl + 2H2O
6 5 2
OH OH
Cl

NN + N=N
+ HCl
naphthol (Phenyl azo naphthol dye)
(ii) Mullikens test: Take a small amount of the organic compound in a testtube. Add a
few ml of water or alcohol, 1 ml of calcium chloride or ammonium chloride solution
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and then a pinch of zinc dust. Boil the mixture for few minutes. Cool and then filter.
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Treat this filtrate with ammoniacal silver nitrate solution. A grey or black precipitate is
obtained.
Zn + 2H2O
C6H5NO2 + 4[H]
Zn(OH)2 + 2[H]
C6H5NHOH + H2O
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C6H5NHOH + Ag2O C6H5NO + H2O + 2Ag
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Grey
This test is also applicable for aromatic nitro compounds.
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QUANTITATIVE ELEMENTAL ANALYSIS

After determining the constituent elements of an organic compound, the next step is to
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determine their amounts by quantitative methods. The methods usually involve

combustion, oxidation etc. of an organic compound so that they may change into such
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inorganic compounds as can be estimated either by volumetric or gravimetric method.

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ESTIMATION OF CARBON AND HYDROGEN

Liebigs Combustion Method: A weighed amount of the compound is heated in a current
of dry air free from carbon dioxide or pure oxygen till the carbon of the compound
changes to CO2 and hydrogen into water. Carbon dioxide and water thus formed are
trapped in a suitable apparatus and weighed.
C + 2CuO CO2 + 2Cu
2H + CuO H2O + Cu
The percentage composition is then calculated.
Calculation
Let the weight of the sample = W g
Let the weight of water formed = x g
(Increase in weight of CaCl2 tube)
and let the weight of CO2 formed = y g
(Increase in weight of potash bulb)
Since 44 g of CO2 are formed from 12 g of carbon,
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y g of
12
CO2 are formed from y g of carbon
44
Since 18 g of water are formed from 2 g of hydrogen,
2 1
x g of water are formed from x g of hydrogen = x g of hydrogen
18 9
12
Now, W g of the substance contains y g of carbon
44
12 100 y
100 g of the substance contains g carbon
44 W
x
Again W g of the substance contain g of hydrogen
9
100x
100 g of the substance contain g of hydrogen
9W
12 100y
Percentage of carbon =
44 W
t
100x
in
and percentage of hydrogen =
9W
ESTIMATION OF NITROGEN Po
(i) Dumas Method: In this method the organic compound is heated with copper oxide
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strongly. Carbon, hydrogen and sulphur are oxidized to CO2, H2O and SO2 respectively,
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while nitrogen is set free. These gases are passed through a nitrometer containing 30%
KOH solution. Carbon dioxide and sulphur dioxide are absorbed, steam condenses and
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nitrogen collects by the displacement of KOH solution. From the volume of the collected
nitrogen, the percentage of nitrogen is calculated.
y z
CxHyNz + CuO xCO2 + H2O + N2 + Cu
e
2 2
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Calculation
Let the weight of the sample = W g
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Volume of moist N2 = V cc
Room temperature = tC
Barometric pressure = P mm
Aqueous tension at tC = f mm
PV PV
We know, 1 1 2 2
T1 T2
(P f ) V 760 V2
or (V2 = Volume of N2 at NTP)
(273 t ) 273
(P f ) 273 V
V2 = cc
760 (273 t )
(P f ) 273 V
Volume of N2 at NTP in cc =
760 (273 t )
Now, 22400 cc of N2 at NTP weigh 28 g.
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(P f ) 273 V 28(P f ) 273 V
at NTP weigh g
760 (273 t ) 760 22400(273 t )
28(P f ) 273 V
W g of the substance contain g N2
760 22400(273 t )
28(P f ) 273 V 100
100 g of the substance contains
760 22400 W (273 t )
28 Volume of N 2 at NTP
Percentage of Nitrogen = 100
22400 Weight of substance
(ii) Kjeldahls Method: The principle of this method is that when an organic compound
containing nitrogen is heated with concentrated sulphuric acid, the nitrogen is converted
into ammonium sulphate. The resulting solution on treatment with excess of sodium
hydroxide solution gives off ammonia. Ammonia is then absorbed in excess of standard
sulphuric acid. The amount of ammonia and hence the amount of nitrogen is determined
by finding the amount of acid neutralized by back titration of the residual acid with a
t
in
standard alkali solution. From this the percentage of nitrogen is calculated.
Calculation:
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Let the weight of the substance = W g and let V cc of N acid is required to neutralize the
ammonia evolved.
V cc of N acid = V cc of N NH3
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1000 cc of N NH3 = 17 g of NH3 = 14 g of nitrogen
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14
V cc of N NH3 = V N = 0.014 NV g
1000
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100
Percentage of nitrogen = Weight of nitrogen
Weight of subs tan ce
0.014 N V 100
e
=
m
W
Kjeldahls method fails to detect nitrogen from azo compounds (N = N),
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Azoxy (N = N) , nitroso (NO) compounds and nitrogen present in pyridine ring.
ESTIMATION OF HALOGEN
(i) Carius Method: The compound containing halogen is heated with fuming nitric acid
in a sealed tube (Carius tube) in presence of silver nitrate. Carbon and hydrogen present
are oxidized to carbon dioxide and water. The halogens react with silver nitrate to give the
precipitate of silver halide. The precipitate is collected, washed, dried and weighed.
Calculation
Let the weight of the substance be W g.
Weight of the silver halide be y g.
Atomic weight of ha log en
Weight of halogen = y g
Molecular weight of silver halide
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Atomic weight of halogen 100
Percentage of halogen = y
Molecular weight of silver halide W
ESTIMATION OF SULPHUR
The compound is heated with fuming nitric acid. Sulphur present is oxidized to sulphuric
acid. Barium chloride solution is added. The precipitate of barium sulphate is obtained. It
is collected, washed, dried and weighed.
Weight of BaSO 4 Atomic weight of Sulphur
% of Sulphur = 100
Molecular weight of BaSO 4 Weight of Organic compound
Silver salt method for determining molecular weight of organic acids
This method is based on the fact that organic acids form insoluble silver salts which on
ignition leave a residue to metallic silver.
A small quantity of organic acid is treated with water or a suitable solvent and then a slight
excess of ammonia solution added. The solution is boiled to expel excess of ammonia.
Excess of silver nitrate solution is added to this solution when a white precipitate of
t
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insoluble silver salt is obtained. The precipitate is filtered and washed successively with
water, alcohol and ether and then dried in an air oven.
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A known weight of the silver salt is taken in a weighed crucible and ignited till
decomposition is complete. The crucible is cooled and then weighed. Heating, cooling and
weighing is continued till the final weight is constant.
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Calculation
Weight of crucible + lid = W g
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Weight of crucible + lid + silver salt = W1 g

Weight of crucible + lid + residual silver = W2 g
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Weight of silver salt = (W1 W) g

And weight of silver = (W2 W) g
(W2 W) g of silver is obtained from (W1 W) g of silver salt.
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( W W ) 108
108 g of silver is obtained from 1
m
g of silver salt.
( W2 W )
( W1 W ) 108
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Equivalent weight of silver salt =

( W2 W )
But equivalent weight of acid = Equivalent weight of Ag salt 108 + 1
= Equivalent weight of Ag salt 107
( W W ) 108
Molecular weight of the acid = 1 107 n
( W2 W )
(where n = basicity of the acid)
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Pla
tinichloride method for determining molecular weight of organic bases
Organic bases (e.g. amines) form insoluble salts known as platinichlorides when treated
with hydrochloroplatinic acid [H2PtCl6]. These salts are represented by the general
formula B2H2PtCl6, where B is one equivalent of the base. These salts on ignition leave a
residue of metallic platinum.
The base is dissolved in HCl and a solution of platinic chloride PtCl4 is added. The yellow
crystalline salt that separates out is filtered, washed and dried. A known weight of the
dried salt is ignited is a crucible.
Calculation
Let X1 g of the platinichloride leave on ignition X2 g of platinum.
X2 g of Pt is left by X1 g of the salt on ignition.
X 195
195 g (At. weight of Pt) is left by 1 g of the salt on ignition.
X 2
X1
Molecular weight of the salt = 195
X2
t
in
Molecular weight of H2PtCl6 = 410
X1
Equivalent weight of base B = 2 2

2
Po

B H PtCl 6 H 2 PtCl 6 X 2
195 410
If the acidity of the base is n, then

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X n
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Molecular weight of base = 1 195 410

X 2 2
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e
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SOLVED
SUBJECTIVE EXAMPLES
EXAMPLE 1
0.25 g of an organic compound on combustion gave 0.495 g of CO2 and 0.2025 g of
H2O. Calculate the percentage of carbon and hydrogen in the compound.
SOLUTION
Given weight of the substance = 0.25 g
Weight of CO2 formed = 0.495 g
Weight of H2O formed = 0.2025 g
44 g of CO2 are formed from 12 g of carbon.
12
0.495 g are formed from 0.495 of carbon
44
12 0.495
Now 0.25 g of the substance contains g carbon.
44
12 0.495 100
100 g of the substance contains = 54.55 g
44 0.25
Since 18 g of H2O are formed from 2 g of hydrogen.
t
in
2
0.2025 g H2O are formed from 0.2025 g hydrogen
18
Now, 0.25 g of the substance contains Po
2 0.2025
18
g hydrogen
2 0.2025 100
100 g of the substance contains
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= 9.09 g hydrogen
0.25 18
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% of carbon = 54.55
% of hydrogen = 9.09
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EXAMPLE 2
0.159 g of an organic compound gave 14.01 cc of nitrogen at 19C and 719.5 mm
pressure by Dumas method. Calculate % of nitrogen in the organic compound.
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Given: Aqueous tension of water = 11.5 mm of Hg at 19C.

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SOLUTION
Aqueous tension at 19C = 11.5 mm
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We know,
P1V1 P2 V2

T1 T2
(719.5 11.5) 14.01 760 VN at NTP
or
(273 19) 273
708 14.01 273
VN 2 at NTP = cc
760 292
Now, 22400 cc of N2 at NTP weigh 28 g
28
1 cc of N2 at NTP weigh g
22400
708 14.01 273 28 708 14.01 273
cc = g
760 292 22400 760 292
28 708 14.01 273
0.159 g of the compound contains g N2
22400 760 292
Acme Study Point

100 g
28 708 14.01 273 100
of the compound contains = 9.60 g of nitrogen
22400 760 292 0.159
Percentage of nitrogen = 9.6%
EXAMPLE 3
0.69 g of an organic compound after heating with concentrated sulphuric acid was
distilled with excess of NaOH. Ammonia liberated was passed into 100 cc of N HCl
solution. The excess of the acid neutralized 80 cc of N NaOH. Calculate the percentage
of nitrogen in the compound.
SOLUTION
80 cc of N NaOH = 80 cc of N HCl = Volume of residual acid
Volume of acid neutralized = (10080) cc N = 20 cc of N HCl = 20 cc of N NH3
Now, 1000 cc N NH3 = 14 g of nitrogen
14 20
20 cc N NH3 = g of nitrogen
1000
14 20
0.69 g of the substance contains g of nitrogen.
t
1000
in
14 20 100
100 g of the substance contains = 40
Percentage of nitrogen = 40% Po
0.69 1000
EXAMPLE 4
y
0.26 g of an organic compound on heating with fuming nitric acid and silver nitrate
ud
give 0.31 g of silver bromide. Calculate the percentage of bromine in the compound.
SOLUTION
St
Now, AgBr Br
or (108+80) g = 80 g
188 g of AgBr give 80 g of bromine.
e
80
0.31 g of AgBr give 0.31 = 0.1319 g bromine
m
188
Now, 0.26 g of the substance give 0.1319 g bromine.
Ac
0.1319 100
100 g of the substance gave = 50.7
0.26
Percentage of bromine = 50.7
EXAMPLE 5
40 g of an organic compound gave 0.60 g of barium sulphate after Carius method. Find
out the percentage of sulphur in the compound.
SOLUTION
Since, BaSO4 S
233 g 32 g
233 g of BaSO4 gives 32 g of sulphur.

32
0.60 g of BaSO4 gives 0.60 g of sulphur = 0.082 g sulphur
233
Acme Study Point

0.082
Percentage of sulphur = 100 = 0.205%
40
EXAMPLE 6
0.167 g of the silver salt of a monobasic organic acid left on ignition 0.108 g of silver.
Calculate the molecular weight of the acid.
SOLUTION
Weight of Ag salt = 0.167 g and weight of Ag left = 0.108 g.
0.167
The weight of Ag salt that would leave 108 g of silver = 108 = 167 g
0.108
Equivalent weight of acid = 167 108 + 1 = 167 107 = 60
Molecular weight of the acid = 60 1 (basicity) = 60
EXAMPLE 7
Calculate the molecular weight of a monobasic base, 0.298 g of whose platinichloride
left 0.0975 g of platinum on ignition.
t
SOLUTION
in
Weight of the platinichloride = 0.298 g (X1) and weight of platinum = 0.0975 g (X2).
0.298
Equivalent weight of the base = 0 . 0975
2
Po
195 410
=
596 410 186
2

2
= 93
Molecular weight of the base = 93 1 (acidity) = 93
y
ud
EXAMPLE 8
A mono acid organic base on analysis gave the following results: 0.10 g of the base gave
St
0.28 g of CO2 and 0.075 g of water and 0.20 g of the base gave 31.32 ml N2 measured at
15C and 760 mm, 0.30 g of the platonic chloride left on ignition 0.093 g of platinum.
What is the molecular formula of the base?
e
SOLUTION
The molecular formula is derived as follows
m
(a) Calculation of % of elements

Ac
12 0.28
% of carbon = 100 = 76.36%
44 0.10
2 0.075
% of hydrogen = 100 = 8.33%
18 0.10
28 Volume of N 2 at NTP 100
% of nitrogen =
22400 Weight of organic compound
28 31.32 100
% of nitrogen = = 13.05%
22400 0.3
(b) Calculation of relative number of each atom:
76.36 8.33 13.05
C= = 6.36; H = =8.33 and N = =0.90
12 1 14
(c) Calculation of simplest ratio:
6.35 8.33 0.90
C= 7; H= = 9 and N = 1
0.90 0.90 0.90
(d) Determination of empirical formula:
Acme Study Point

It
comes to be C7H9N, its empirical formula weight = 84 + 9 + 14 = 107
(e) Determination of molecular weight:
The molecular weight of the base is given by,
1 Weight % hexachloroplatinate salt
B = 195 410
2 Weight % pt
1 195 0.3 1
B= 410 [629 410] 109.5
2 0.093 2
B = 109.5
Molecular weight 109.5
n= 1
Empirical weight 107
Hence, molecular formula = empirical formula = C7H9N
EXAMPLE 9
A sample of a gaseous hydrocarbon occupying 1.12 litre at NTP was completely burnt in
air and gave 2.2 g of CO2 and 1.8 g of H2O. Calculate the weight of compound taken
t
and volume of O2 at NTP required for its burning. Also calculate the molecular formula
in
of the hydrocarbon.
SOLUTION
Molecular of compound = Po
Volume evolved at NTP
22400 ml or 22.4 litres is occupied
by each subs tan ce
y
ud
1.12
= = 0.05 mol
22.4
2 .2
St
Moles of CO2 produced = = 0.05 mol

44
1.8
Moles of H2O produced = = 0.10 mol
e
18
m
Suppose the hydrocarbon is CxHy

Then
Ac
y
CxHy + x O2 xCO2 + y/2 H2O
4
1 mole of CxHy gives = 0.05 a mol of CO2
0.05 x = 0.05
0.05
x= 1
0.05
y
Now, 1 mole of CxHy gives = mol of H2O
2
y
0.05 mol of CxHy will give = 0.05 mol of H2O
2
y
0.05 = 0.10
2
y=4
Hence, the hydrocarbon is CH4
Acme Study Point

Weight of
16 1.12
1.12 litre CH4 at STP = = 0.8 g
22.4
Also, CH4 + 2O2
CO2 + 2H2O
1 mol of CH4 requires 2 32 g oxygen
0.05 mol of CH4 requires 2 32 0.05 = 3.2 g CO2
CH4 requires O2 = 3.2 g
EXAMPLE 10
An organic compound, A containing C, H, N and O, on analysis gives 40.32% carbon,
9.59% hydrogen and 19.18% nitrogen. A on boiling with NaOH gives off NH 3 and a salt
which on acidification gives a monobasic nitrogen free acid B. The silver salt of B
contains 59.67% silver. Deduce the structures of A and B.
SOLUTION
Percentage of oxygen = 100 (49.2 + 9.59 + 19.18) = 21.91
Percentage Relative No. of

Elements Atomic weight Simplest ratio
t
composition atoms
in
49.12 4.11
C 49.32 12 = 4.11 =3
12 1.37
H 9.59 1 Po 9.59
1
= 9.59
9.59
1.37
=7
19.18 1.37
y
N 19.18 14 = 1.37 =1
14 1.37
ud
21.91 1.37
O 21.91 16 = 1.37 =1
1.37 1.37
St
Hence empirical formula of A = C3H7NO

Because A, gives NH3 on boiling with NaOH, it can be an amide.
e
Now, silver salt of B, has 59.67% silver.

m
100 108
Hence equivalent weight of acid = 107 = 74
59.67
Ac
Molecular weight of monobasic acid = 74 1 = 74

Molecular formula of acid = C3H6O2
Structural formula of acid B is C2H5COOH.
Molecular formula of amide = C3H7NO.
Hence structural formula of amide (A) is C2H5CONH2.
Acme Study Point

STRAIGHT OBJECT
O - Level
1. Nitrogen in an organic compound can be estimated by
(a) Kjeldahls method (b) Dumas method
(c) both (a) and (b) (d) None of the above
2. Which of the following compounds is of violet colour

(a) Na4[Fe(CN)5NSO3]3 (b) Na3[Fe(CN)6NSO]2
(c) Na2[Fe(CN)5NSO]3 (d) Na4[Fe(CN)5NOS]
3. A compound containing 80% carbon and 20% hydrogen is likely to be

(a) C6H6 (b) C2H5OH
(c) C2H6 (d) CHI3
4. Aniline, chloroform and alc. KOH on heating gives

(a) Phenyl isocyanide (b) Phenyl cyanide
t
in
(c) Chlorobenzene (d) Phenol
5.
(a) Tollens test
(c) Schiff test
Po
Methyl ketones are usually characterized through
(b) Iodoform test
(d) Benedicts test
y
6. Which of the following is used for separating aniline from nitrobenzene?
ud
(a) Na2CO3 (b) HCl

(c) NaHCO3 (d) NaCl
St
7. The compound that does not give a blue colour in Lassaignes test is
(a) Aniline (b) Glycine
e
(c) Hydrazine (d) Urea

m
8. 0.2 g of an organic compound on complete combustion produces 0.18 g of water, then the
Ac
percentage of hydrogen in the compound is

(a) 5 (b) 10
(c) 15 (d) 20
9. In which of the following compounds, nitrogen cannot be tested by Lassaignes test?

(a) C6H5NH2 (b) NH2.NH2.H2O
(c) CH3CONH2 (d) C6H5NO2
10. When a nitrogen containing organic compound is strongly heated with conc. H2SO4, the
product is
(a) HNO3 (b) (NH4)2SO4
(c) NH3 (d) N2
Acme Study Point

11. To
determine the weight of a halogen in organic compound, the compound is heated with
fuming HNO3 in presence of
(a) Ag (b) AgNO3
(c) Ag2CO3 (d) Ag2SO4
12. A mixture of onitrophenol and pnitrophenol can be separated by

(a) Sublimation (b) Steam distillation
(c) Fractional crystallization (d) Distillation
13. In Lassaignes test for nitrogen the blue colour is due to the formation of
(a) FerricFerro cyanide (b) K4[Fe(CN)6]
(c) Na4[Fe(CN)6] (d) NaCN
14. Nitrogen is estimated by

(a) Liebig method (b) Carius method
(c) Dumas method (d) None of these
t
in
15. An organic compound is found to contain C = 39.9%, H = 6.7%, O = 53.4%. Its empirical
formula is
(a) CHO
(c) CH2O2 Po
(b) CHO2
(d) CH2O
16. Which of the following compounds will give blood red colour in the Lassaignes test for
y
nitrogen?
ud
(a) (NH2)2C = O (b) H2N(C6H4)SO3H

(c) C6H5SO3H (d) CHCl3
St
17. In Kjeldahls method, nitrogen element is estimated as

(a) N2 (b) NO
(c) NH3 (d) NO2
e
m
18. 0.10 g of an organic compound containing phosphorus gave 0.222 g of Mg2P2O7. Then the
percentage of phosphorus in it is
Ac
(a) 62 (b) 6.2

(c) 31 (d) 13
19. A gaseous hydrocarbon has 85% carbon and vapour density of 28. The possible formula of
the hydrocarbon will be
(a) C3H6 (b) C2H4
(c) C2H2 (d) C4H8
20. If empirical formula of an organic compound is CH2O and its 6.02 1023 molecules
weight 60 g, then it can be
(a) CH3OH (b) C2H5OH
(c) HCOOH (d) HCOOCH3
Acme Study Point

I-
Level
1. In the estimation by Dumas method 0.59 g of an organic compound gave 112 ml nitrogen
at NTP. The percentage of nitrogen in the compound is about
(a) 23.7 (b) 11.8
(c) 20 (d) 47.5
2. If 0.2 g of an organic compound containing C, H and O on combustion yields 0.147 g CO 2
and 0.12 g water, the percentage of oxygen in it is
(a) 73.29% (b) 78.45%
(c) 83.23% (d) 89.50%
3. A dibasic acid containing C, H and O was found to contain C = 26.7% and H = 2.2%. The
vapour density of diethyl ester of the acid was found to be 73. What is molecular formula
of the acid
(a) CH2O2 (b) C2H2O4
(c) C3H3O4 (d) C4H4O4
4. The percentage of sulphur in the organic compound, when 0.2595 g of a sulphur
containing organic compound in a quantitative analysis by Carius method yielded 0.35 g
t
in
of barium sulphate is
(a) 14.52% (b) 16.52%
5.
(c) 18.52%
Po
(d) 19.52%
If 0.228 g of silver salt of dibasic acid gave a residue of 0.162 g of silver on ignition, then
molecular weight of the acid is
y
(a) 70 (b) 80
(c) 90 (d) 100
ud
6. ClCH2COOH is heated with fuming nitric acid in the presence of AgNO3 in a Carius tube.
After filtration and washing a white precipitate is obtained. The precipitate is
St
(a) AgNO3 (b) Ag2O

(c) AgCl (d) ClCH2COOAg
7. The Lassaignes extract is boiled with dil. HNO3 before testing for halogens because
e
(a) Silver halides are soluble in HNO3.

m
(b) Na2S and NaCN are decomposed by HNO3.

(c) Ag2S is soluble in HNO3.
Ac
(d) AgCN is soluble in HNO3.

8. The silver salt of a monobasic acid on ignition gave 60% of Ag. The molecular weight of
the acid is
(a) 37 (b) 33
(c) 73 (d) 77
9. 0.1914 g of an organic acid is dissolved in about 20 ml of water. 25 ml of 0.12 N NaOH is
required for the complete neutralization of the acid solution. The equivalent weight of the
acid is
(a) 65 (b) 64
(c) 63.8 (d) 62.5
10. If the percentage of nitrogen in an organic compound is 12.5% then how much of the
organic compound should be taken so as to produce 50 ml of N2 at 300 K and 715 mm
pressure (Aqueous tension = 15 mm)?
(a) 0.419 g (b) 0.149 g
(c) 0.914 g (d) 0.941 g
Acme Study Point

E-
Level
1. Which of the following is a technique most suitable for purification of cyclohexanone
from a mixture containing benzoic acid, isoamyl alcohol, cyclohexane and
cyclohexanone?
(a) crystallization (b) I.R. spectroscopy
(c) sublimation (d) gas chromatography
2. Absolute alcohol is prepared by

(a) Fractional distillation (b) Kolbes method
(c) Vaccum distillation (d) Azeotropic distillation
3. 0.24 g of a volatile liquid on vaporization gives 45 ml of vapours at STP. What will be the
vapour density of the substance? (Density of H2=0.089 g L-1)
(a) 99.39 (b) 39.95
(c) 95.53 (d) 59.93
t
in
4. If a compound on analysis was found to contain C = 18.5%, H = 1.55%, Cl = 55.04% and
O = 24.81% then its empirical formula is
(a) CHClO
(c) C2H5OCl
Po
(b) CH2ClO
(d) ClC2H5O
y
5. A liquid decomposes at its normal pressure. It can be purified by
ud
(a) sublimation (b) fractional distillation

(c) vacuum distillation (d) steam distillation
St
6. The best solvent to remove butter stain from cloth is

(a) CHCl3 (b) C2H5OH
(c) C2H5OC2H5 (d) H2O
e
m
7. In peroxidase anhydrase enzyme the percentage of selenium (Se) by mass is 0.5%. If

atomic mass of Se is 78.4U, then minimum molecular mass of peroxidase anhydrase
Ac
enzyme is
(a) 1.568 103 U (b) 1.568 104 U
(c) 1.568 U (d) 2.136 104 U
8. In a hydrocarbon, mass ratio of hydrogen and carbon is 1 : 3, the empirical formula of

hydrocarbon is
(a) CH2 (b) CH4
(c) CH3 (d) CH
9. If we want to study the relative arrangement of atoms in a molecule, we study

(a) empirical formula (b) molecular formula
(c) structural formula (d) none of these
Acme Study Point

10. Which of
the following statements is wrong?
(a) In the estimation of carbon, an organic compound is heated with CaO in a combustion
tube.
(b) Using Lassaignes test nitrogen and sulphur present in an organic compound can be
tested.
(c) Using Beilsteins test the presence of halogen in a compound can be tested.
(d) Lassagines test fails to identify nitrogen in diazo compound.
11. 0.833 mole of a carbohydrate with empirical formula CH2O has 10 g of hydrogen. What is
its molecular formula?
(a) C5H10O5 (b) C6H12O6
(c) C3H4O3 (d) C3H5O3
12. A chemical compound is heated and dried. To get accurate weight of this compound
(a) weigh in warm condition (b) weigh after cooling
(c) cool in desiccator (d) blow air through it
t
13. The ammonia evolved from the treatment of 0.03 g of an organic compound for the
in
estimation of nitrogen was passed in 100 mL of 0.1M sulphuric acid. The excess of the
organic compound is
(a) acetamide
Po
acid required 20 mL of 0.5M sodium hydroxide solution for complete neutralization. The
(b) benzamide
(c) urea (d) thiourea
y
ud
14. 116 mg of a compound on vapourization in a Victor Mayers apparatus displaces 44.8 mL

of air measured at STP. The molecular mass of the compound is
(a) 58 (b) 116
St
(c) 232 (d) 44.8

e
15. An organic compound having molecular mass 60 is found to contain C = 20%, H = 6.67%
and N = 46.67% while rest is oxygen. On heating it gives NH3 along with a solid residue.
m
The solid residue gives violet colour with alkaline copper sulphate solution. The
compound is
Ac
(a) CH3NCO (b) CH3CONH2

(c) (NH2)2CO (d) CH3CH2CONH2
Acme Study Point
LINKED COMPRE
Paragraph 1
Given are the isomers of C8H8O2.
O O
COEt CHO CO2H OH C CH3 CO2CHO
OCH3 CH3 OCH = CH2 OH OH

(a) (b) (c) (d) (e) (f)
Questions:
1. Which isomer gives positive iodoform test?
(a) a (b) b
t
(c) d (d) e
in
2. Which isomer gives positive Tollens test, also reacts with FeCl3?
(a) b
(c) c
Po
(b) f
(d) d
y
3. Which isomer reacts with NaHCO3?
ud
(a) c (b) d
(c) e (d) f
St
4. Which isomer on hydrolysis gives 1, 4-dihydroxybenzene?

(a) a (b) d
(c) e (d) f
e
m
Paragraph2
An organic acid (A) is widely used as a food additive. Its elemental composition is 41.4%
Ac
carbon, 3.5 % hydrogen and rest being oxygen. A solution made by dissolving 0.150 g of
(A) in water and diluting to a volume of 100 ml gave rise to an osmotic pressure of
240.3 mm of Hg at 298 K. For complete titration of 0.573 g sample of (A), 94.1 ml of
0.105 M NaOH was required to reach end point. Each mole of (A) reacts with 1 mole of
HCl to give an addition product and with 1 mole of H2 to give a reduction product
Questions:
1. The molecular weight of the food additive is
(a) 58 (b) 116
(c) 174 (d) 232
2. The basicity of organic acid (A) is

(a) 1 (b) 2
(c) 3 (d) 4
3. The molecular formula of the acid (A) would be

(a) C5H8O3 (b) C2H2O2
Acme Study Point

(c)
C7H12O2 (d) C4H4O4
4. Which cant be possible structures of the acid (A)?
HOOC COOH HOOC H
(a) C = C (b) C = C
H H H COOH
O
(c) H2C = C C O H (d) CH2 CH2
C=O COOH COOH
OH
5. If the compound (A) does not show geometrical isomerism, its structure would be
HOOC COOH HOOC H
(a) C = C (b) C = C
H H H COOH
t
in
O
(c) H2C = C C O H (d) CH2 CH2
C=O
OH
Po COOH COOH
y
ud
Paragraph 3
To arrive at the molecular formula and at the structural formula the different steps
involved are
St
(1) Qualitative analysis (2) Quantitative analysis

In the quantitative analysis the different steps involved are
(a) Extra element detection (b) Functional group analysis
e
In the quantitative analysis the percentage of every element is determined and then the
m
empirical and molecular formulae are determined. Both these are followed by structural
elucidation.
Ac
Questions:
1. Which of the following reagent is used to distinguish products of hydrolysis of
CH3COOCH=CH2
(a) NaHCO3 (aq) (b) Lucas reagent
(c) Baeyers reagent (d) Cerric ammonium nitrate (aq)
2. Which of the following reagents can be used to identify benzene in one go?
(a) Bromine water test (b) CHCl3 + AlCl3 (anhydrous) test
(c) I2 + NaOH (d) No test is available
3. The number of hydroxyl groups in a compound not containing any other functional group
can be determined by
(a) CH3COCl (b) CH3MgBr
(c) CH3OCH3 (d) Both (a) and (b)
Acme Study Point

Paragraph4
Figure I illustrates a solubility based characterization procedure, often used by organic
chemists, for the qualitative analysis of monofunctional organic compounds. Table 1 lists
the organic compounds comprising the various solubility classes of Fig. I.
t
in
Figure I
Group
I
Po
Compounds
Salts of organic acids, amino acids, amine chlorides
Sugars (carbohydrates) and other polyfunctional compounds with hydrophilic
y
groups
ud
II Arenesulfonic acids
Monofunctional carboxylic acids, alcohols, ketones, aldehydes, esters, amides and
St
nitriles with 5 or less carbon atoms

Monofunctional amines with 6 or less carbon atoms
e
III Phenols with ortho-and/or para-lectron withdrawing groups, -diketones

m
Carboxylic acids with 6 or more carbon atoms

IV Sulfonamides, nitro-compounds, with -hydrogens
Ac
Phenols, oximes, enols imides and thiophenols with 6 or more carbon atoms
V Some oxy-ethers, anilines, aliphatic amines, with 8 or more carbon atoms
VI Neutral compounds containing sulfur or nitrogen with 6 or more carbon atoms
VII Ethers with 7 or less carbon atoms
Monofunctional esters, aldehydes, ketones, cyclic ketones, methyl ketones with
between 6 and 8 carbon atoms; epoxides
VIII Ethers, most other ketones
Unsaturated hydrocarbons, aromatic compounds, particularly those which possess
activating groups
Acme Study Point

Questions:
1. A certain water insoluble compound is insoluble in 5% sodium hydroxide, insoluble in 5%
HCI, and insoluble in concentrated H2SO4 and soluble in 5% sodium bicarbonate. In
which class should this compound be classified?
(a) III (b) IV
(c) VIII (d) IX
2. Benzoic acid should be soluble in which of the following solvent pairs?
(a) Water and 5% HCI (b) 5% NaOH and 5% NaHCO3
(c) 5% HCI and 5% NaOH (d) 85% H3PO4 and 5% NaOH
3. Low molecular weight amino acids fall into group I in Table 1. This is most likely due to
the fact that low molecular weight amino acids are:
(a) hydrophilic and basic (b) hydrophobic and amphoteric
(c) hydrophobic and lipophilic (d) hydrophilic and amphoteric
4. A critical step in acid catalyzed ester hydrolysis is the attack of water molecules on the
protonated ester. If the water molecules are replaced with an alcohol, then the reaction will
involve:
t
(a) transesterification of one ester to another
in
(b) reduction to the corresponding aldehyde
(c) base protonated ester hydrolysis to the corresponding acid
5.
Po
(d) decarboxylation to the corresponding C-H unit
A water soluble unknown is unreactive in the presence of sodium bicarbonate, gives a
positive 2,4-DNP test and negative Fehling's and Iodoform tests. In which of the following
y
classes should this compound be classified?
ud
(a) Aldehyde (b) Ketone

(c) Carboxylic acid (d) Alcohol
St
e
m
Ac
Acme Study Point
MATRIX MATCH
1.
ColumnI ColumnII
(A) Cerric ammonium nitrate solution (p) Carboxylic acid
(B) Neutral FeCl3 (q) 1o, 2o, 3o Nitro compounds
(C) NaHCO3 (aq) (r) Phenols
(D) Victor Meyers test (s) Alcohols
2.
ColumnI ColumnII
(A) Ammonical AgNO3 (p) The position of double bonds
(B) I2/NaOH (q) Presence of strongly acidic group
(C) NaHCO3 (r) Presence of acetylinic group
(D) Ozonolysis (s) Methyl Ketones
3.
Column I Column II
t
(A) 1-Butyne, 2-Butyne (p) neutral FeCl3
in
(B) Benzoic acid, Phenyl formate (q) I2/OH
(C) 1-Butanol, 2-Butanol (r) NaHCO3
(D) Pent-1-ene-2-ol, Pent-tene-3-ol Po (s) Tollens
4.
y
ColumnI (Mixture) ColumnII (Method for separation)
ud
(A) o and pnitrophenols (p) Steam distillation

(B) Naphthalene and urea (q) Simple distillation
St
(C) Heptane and octane (r) Sublimation

(D) Benzene and nitrobenzene (s) Gas chromatography
e
5.
ColumnI ColumnII
m
(A) O (p) Different colouration with Neutral

FeCl3
Ac
CH3C OH
(B) NO2 (q) Decolourization of Br2 water
O2N OH
NO2
(C) (r) Brisk effervescence with NaHCO3
SO3H
OH
(D) CH2=CHCH2CCH3 (s) Yellow ppt with I2/NaOH
6.
Acme Study Point

Column-I Column-II
(A) (p) I2/NaOH
NHCH3, H3C NH2
(B) CH3COCH2CHO, CH3COCH2COOH (r) Anhydrous ZnCl2/HCl
(C) HCOOH, HCHO (r) C6H5SO2Cl
(D) (s) NaHCO3
CH2OH, COCH3
t
in
Po
y
ud
St
e
m
Ac
Acme Study Point

SUBJECTIVE TYPE
1. A sample, containing 0.45 g of an organic compound, gave on combustion 0.792 g of CO2

and 0.324 g of H2O. Another 0.24 g of this substance was Kjeldahlized and the ammonia
evolved was observed in 50 ml of N/4 H2SO4. The excess acid required 77 ml of 0.10 N
NaOH for complete neutralization. Calculate the empirical formula of the compound.
2. 0.1325 g of an organic substance gave 0.225 g of barium sulphate in Carius method of

estimation of sulphur. Calculate the percentage of sulphur.
3. 0.369 g of an organic compound having carbon, hydrogen and oxygen was subjected to
combustion by Liebigs method. It gave 0.369 g of CO2 and 0.189 g of H2O. Calculate the
% of elements in the compound.
4. 0.423 g of an organic compound gave on combustion of 43.2 ml of nitrogen measured at

19.5C and 733.5 mm of pressure. Find the % of N in the compound aqueous tension at
19.5C is 17.8 mm.
t
in
5. A Dumas nitrogen analysis of a 5.72 mg sample of pphenylene diamine gave 1.31 ml of
Po
nitrogen at 20 and 746 mm. The gas was collected over saturated aqueous KOH solution
(the vapour pressure of water is 6 mm). Calculate the percentage of nitrogen in the
compound.
y
6. A dibasic organic acid containing 26.66% of carbon and 2.22% of hydrogen, gave a silver
ud
salt containing 71.05% of silver. What is the molecular formula of the acid? Give its
structural formula also.
St
7. A dibasic organic acid gave the following results on analysis, 0.2496 g of acid gave
0.3168 g of CO2 and 0.0864 g of H2O. 0.1092 g of acid is exactly neutralized by 21 ml
e
N/10NaOH. Calculate the molecular formula of the acid.

m
8. 0.177 g of a dibasic acid gave on combustion 0.2642 g CO2 and 0.081 g H2O. 0.2988 g of
its silver salt left 0.1944 g of silver on ignition. Write structural formula of its possible
Ac
isomers. What experiment would you perform to assign it a definite formula?
9. An organic compound contains 69.4% C, 5.8% H. A sample of 0.303 g of this compound

was analyzed for nitrogen by Kjeldahl method. The ammonia evolved was absorbed in
50 ml of 0.05 M H2SO4. The excess acid required 25 ml of 0.1 M NaOH for neutralization.
Determine molecular formula of the compound, if its molecular mass is 121. Draw
possible structures of this compound.
10. 0.0663 g of an organic compound gave 0.0621 g of carbon dioxide and 0.0381 g of water.
0.0980 g of the same compound gave 0.4860 g of barium sulphate. In a vapour density
determination, 0.205 g of the substance displaced 52.6 ml of air over water at 293 K and
773 mm of Hg pressure. The vapour pressure of water is 17 mm of Hg at 293 K. What is
the molecular formula of the compound?
11. A sample of 0.22 g of a volatile compound containing carbon, hydrogen and chlorine
yielded 0.195 g CO2 and 0.0804 g water on combustion in oxygen. 0.120 g of the
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compound
occupied a volume of 37.24 ml at 105C and 768 mm of Hg pressure. Calculate the
molecular formula of the compound.
12. 10.57 mg of an organic compound gave on combustion 1.08 ml of nitrogen, measured at

19.5C and 733.5 mm of pressure. Find the percentage of the nitrogen in the compound.
Given: Vapour pressure of water at 19.5C is 17.8 mm.
13. 6 mg of an organic compound containing phosphorus gave 11 mg of Mg2P2O7 by the usual

analysis. Calculate the percentage of phosphorus in the compound.
14. The quantative analysis of a well known broad spectrum antibiotic says that it contains
C = 57.49%, H = 5.39%, N = 8.39%, S = 9.58%. If each molecule of the antibiotic
contains one atom of sulphur, deduce the molecular formula of the antibiotic.
15. A monoacid base contains 53.3% carbon, 15.5% hydrogen and 31.2% nitrogen. 1.0 g of
the chloroplatinate of the base gave 0.39 g of platinum. What is the molecular formula of
the base?
t
in
Po
y
ud
St
e
m
Ac
Acme Study Point

ANSWERS
STRAIGHT OBJECTIVE TYPE
O - Level
1. c 2. d 3. c 4. a 5. b
6. b 7. c 8. b 9. b 10. b
11. b 12. b 13. a 14. c 15. d
16. b 17. c 18. a 19. d 20. d
I - Level
1. a 2. a 3. b 4. c 5. c
6. c 7. b 8. c 9. c 10. a
t
in
E - Level
1.
6.
d
a
2.
7.
d
b
3.
8.
d
b
Po 4.
9.
a
c
5.
10.
c
a
y
11. b 12. c 13. c 14. a 15. c
ud
LINKED COMPREHENSION TYPE

St
Paragraph-1
1. d 2. b 3. a 4. b
e
Paragraph-2
m
1. b 2. b 3. d 4. d 5. c
Ac
Paragraph-3
1. c 2. b 3. d
Paragraph-4
1. d 2. b 3. d 4. a 5. b
MATRIX MATCH TYPE

1. A-s, B-r, C-p, D-q
2. A-r, B-s, C-q, D-p
3. A-s, B-r, C-q, D-p
4. A-p, B-r, C-s, D-q
5. A-p, s, B-p, r, C-q, p, r, D-q, s
6. A-r, B-p, s, C-s, D-p, q
Acme Study Point

SUBJECTIVE TYPE
1. C4H8N2O
2. 23.32%
3. C = 27.27%, H = 5.69% and O = 67.04%
4. N = 11.22%
5. N = 26%
6. C2H2O4, H O C C O H 7. C3H4O4
O O
8. Molecular formula: C4H6O4
t
Possible structures:
in
COOH
CH2 COOH
CH2 COOH
Succinic acid
CH3 CH
COOH Po
Methyl malonic acid
y
Can be distinguished by decarboxylation.
ud
9. Molecular formula = nC7H7NO = C7H7NO

Structure
St
O
CHO C NH2
e
NH2
m
Ac
10. C2H6S2 11. C2H4Cl2
12. 11.22 % 13. 51.20
14. C16H18N2SO4 15. C2H7N

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FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 1

Detection of elements (N, S, Halogens); Detection and identification of the

generally useful for the identification of unknown organic compounds:

(e) Saturation test

(a) Lassaignes test (for nitrogen, sulphur and halogens)

FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 2

Fe(OH)2 + 2NaCN Fe(CN)2 + 2NaOH

An intense blue colouration is produced due to the formation of Prussian blue.

(ii) For sulphur

(iii) For halogens:

FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 3

NaI + AgNO3 AgI + NaNO3

Formula used in the determination of empirical, molecular and structural

FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 4

where Kf = Molal freezing point depression constant

100 K b weight of compound

where Kb = Molal boiling point elevation constant

DETECTION OF FUNCTIONAL GROUPS

(a) Tests for carboxylic group

FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 5

(b) Tests for aldehyde group

precipitate of Cu2O is obtained.

RCHO + 2CuO RCOOH + Cu2O

(iv)Benedicts test: Take 45 ml of Benedicts reagent in a testtube. Add a few ml of the

FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 6

(d) Tests for phenolic group Po

green. This is a characteristic reaction of compounds having enolic group. (=COH).

may take place by orthoortho, orthopara, parapara coupling reaction.

FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 7

testtube. Add excess of bromine water. A yellowish white precipitate is obtained.

FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 8

(e) Tests for alcoholic group

alcoholic group in the given compound.

Distinction between primary, secondary and tertiary alcohols

FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 9

(f) Tests for primary amines(NH2)

This test is applicable to aliphatic and aromatic primary amines.

naphthol (Orangered dye)

(g) Tests for secondary amines (NH)

Liebermanns nitroso test: Dissolve some organic compound in 3 ml of conc. HCl

(h) Tests for nitro group

FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 10

naphthol (Phenyl azo naphthol dye)

QUANTITATIVE ELEMENTAL ANALYSIS

determine their amounts by quantitative methods. The methods usually involve

inorganic compounds as can be estimated either by volumetric or gravimetric method.

ESTIMATION OF CARBON AND HYDROGEN

FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 11

FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 12

Azoxy (N = N) , nitroso (NO) compounds and nitrogen present in pyridine ring.

FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 13

Weight of crucible + lid + silver salt = W1 g

Weight of silver salt = (W1 W) g

Equivalent weight of silver salt =

FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 14

Equivalent weight of base B = 2 2

If the acidity of the base is n, then

Molecular weight of base = 1 195 410

FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 15

Given: Aqueous tension of water = 11.5 mm of Hg at 19C.

FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 16

233 g of BaSO4 gives 32 g of sulphur.

FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 17