Unit 12 Organic Chemistry Some Basic Principal And Technique (Part-A)

Purification and Characterisation of organic compounds

Organic compounds, obtained from natural sources or synthesized in laboratory, are seldom pure. They are generally contaminated with impurities and therefore need purification. The principle and method of purification depend upon the nature of the substance (solid or liquid) and the type of impurity present in it.

Methods of Purification:

1.Sublimation

It involves direct conversion of a solid into the gaseous state on heating without passing through the intervening liquid state and vice versa on cooling. The process is useful to purify the compounds which sublime on heating and are associated with non volatile (solids) impurities.

Example : Camphor, naphthalene, anthracene, benzoic acid, iodine.

2.Crystallisation

This is the most commonly used technique for purification of solid compounds in laboratory. Crystals have definite geometrical shapes and are the purest form of a substance. The process by which an impure compound is converted into crystals is known as crystallisation. This method is based upon the principle that an organic compound is soluble in a suitable solvent / mixture of solvents at elevated temperature and insoluble at room temperature. For proper crytallisation choice of solvent is crucial. A suitable solvent :-

Should not react chemically with the impurities.

Should dissolve more of the substance on heating than at room temperature.

Either should not dissolve impurities or if it dissolves, it should be such an extent that impurities remain in solution (mother liquor) upon crystallisation.

Water, alcohol, chloroform, ether, benzene, acetone, ethyl acetate are commenly used solvents for crystallisation.

2.1 Fractional Crystallisation

This is the process of separation of different components of a mixture by repeated crystallisation. This method is employed to separate and purify two or more compounds having different solubilities in the some solvent.

3.Simple Distillation

It involves conversion of a liquid into vapours by heating followed by condensation of these vapours by cooling. This method is based upon the difference in boiling points of impurities and the compound to be purified. It is commonly used for the liquids, sufficiently stable at their boiling points and contain non volatile impurities.

Example: Benzene, ethanol, acetone, toluene, xylenes, CHCl3,CCl4 etc.

Simple distillation can also be employed for separation and purification of a mixture of two or more miscible organic liquids having sufficient difference in their boiling points. Upon distillation of such mixture, the more volatile liquid distils over first while the less volatile liquid distils over afterwards.

Example: Mixture of ether (b.p. 308 K ) and toluene (b.p. 384 K )

Mixture of hexane (b.p. 342 K ) and toluene.

Mixture of benzene (b.p. 353 K ) and aniline (b.p. 457 K )

3.1 Fractional Distillation

This method is employed when the boiling points of liquids of a mixture are very close to each other and separation can’t be done by simple distillation. Fractional distillation is carried out in fractionating column, specially designed for the purpose to increase the cooling surface area and to provide obstructions to the ascending vapours and descending liquid. This allows repeated and successive evaporations and condensations.

Example : This method is used to separate (1) petroleum into its useful fractions such as gasoline, kerosene oil, diesel oil etc. (2) acetone (b. p. 329 K ) and methyl alcohol (b.p. 338 K) from pyroligneous acid obtained by destructive distillation of wood.

3.2 Distillation under reduced pressure / Vacuum Distillation

This method is used for purification of high boiling liquids and the liquids which decompose at or below their boiling points. We know that a liquid boils when its vapour pressure becomes equal to the external pressure. Therefore, by reducing the external pressure acting on it, boiling point can be reduced and distillation can easily be achieved without decomposition. Water pumps / vacuum pumps are commonly used in laboratory to reduce the pressure above the liquid mixtures to be separated.

Example : Glycerol generally decomposes at its boiling point ( 563 K ). It can be distilled without decomposition at 453 K under 12 mmHg pressure.

3.3 Steam Distillation

This is very convenient method for separation and purification of organic compounds (solid / liquid) from nonvolatile organic / inorganic impurities. Method is applicable to the compounds that are volatile in steam, insoluble in water, boil above 373 K at 760 mm, decompose at / below its boiling point and contain nonvolatile impurities. Unlike Vacuum distillation, steam distillation makes the high boiling compound to distil at low temperature and avoids its decomposition, without reducing the total pressure acting on the solution.

The impure organic compound, mixed with water is taken in a round bottom flask and steam is passed through it. When the combined vapour pressure of mixture becomes equal to the atmospheric pressure, the mixture starts boiling. At this temperature, steam mixed with the vapours of compound passes over to the condenser, gets condensed and then collected in the receiver. The distillate contains the mixture of desired compound and water which are then separated with the help of a separating funnel.

Example : Aniline, nitrobenzene, essential oils, o-nitrophenol and bromobenzene can be purified by this process.

4.Differential Extraction

This method is also known as solvent extraction. The technique is used to separate organic compounds (solid / liquid) from their aqueous solutions. In a separating funnel, the aqueous solution of organic compound is mixed with a small quantity of the suitable organic solvent. Solvent should be immiscible with water and highly miscible with the organic compound. The separating funnel is stoppered and the contents are shaken thoroughly. The organic compound, being more soluble is solvent, gets dissolved in it. The funnel is allowed to stand for some time so that the water layer separates out from the organic layer. Both the layers are separated and the process is repeated several time with the water layer in order to extract the entire / maximum amount of the organic compound. Organic compound is then recovered from the solvent through distillation / evaporation. Larger the number of extractions, greater the amount of the compound extracted. Benzene, ether, chloroform and carbon tetrachloride are some generally used solvents for extraction.

Example : Benzoic acid can be separated from its aqueous solution using benzene as a solvent.

5.Chromatography

This is the modern analytical technique, discovered by Tswett (1906) to separate the components of a mixture. The technique is based upon the principle of selective adsorption of various components of a mixture between the two phases; stationary phase and mobile phase. It is widely used, not only for separation but for purification, identification and characterization of the components present in a mixture.

Depending upon the nature of the stationary and the mobile phases, the different types of chromatographic techniques, commonly used are given in the table.

Some common types of chromatographic techniques

S. No. Technique Stationary Phase Mobile Phase Uses
1. Adsorption or column chromatography Solid Liquid Large scale separations, qualitative and quantitative analysis
2. Thin layer chromatography (TLC) Solid Liquid Qualitative analysis
3. High performance liquid chromatography (HPLC) Solid Liquid Qualitative and quantitative analysis
4. Gas-liquid chromatography (GLC) Liquid (Supported on inert solid) Gas Qualitative & quantitative analysis
5. Partition chromatography / Paper chromatography Liquid (supported on cellulose of paper) Liquid Qualitative & quantitative analysis of polar organic compounds (sugars, amino acids etc.)

Some common terms used in chromatography

(i) Mobile phase

Phase that moves through the stationary phase. It may be liquid or a gas.

(ii) Stationary phase

It is the substance fixed in place for the chromatography. It may be solid or liquid supported on solid. For example silica layer in TLC.

(iii) Eluent

The solvent used in column chromatography is know as eluent. During elution (running) of eluent (solvent) from the column, the most weakly adsorbed component is eluted first by least polar solvent while more strongly adsorbed component is eluted later by highly polar solvents.

(iv) Rf Value

It is the ratio of the distance travelled by a component to the distance travelled by the solvent front. It is a constant for a given component under a given set of conditions. Therefore, it is possible to identify the various components by determining their Rf values.

Qualitative analysis of organic compounds

It is detection of various elements present in the compound.

1.Detection of carbon and hydrogen

Organic compound is heated with dry cupric oxide and produced vapours are passed through lime water or anhydrous CuSO4. If lime water turns milky, it shows presence of CO2 or carbon. If anhydrous CuSO4, turns blue it shows presence of H2O or hydrogen

Compound +CuOΔCO2+H2O+Cu

CO2+Ca(OH)2CaCO3+H2O

lime water milkiness

H2O+CuSO4CuSO45H2O

colourless blue

2.Detection of other elements

Nitrogen, sulphur & halogen are detected by Lassaigne’s test. Compound is heated with sodium metal and poured in cold & distilled water. This, after heating for sometime, gives Lassaigne’s solution or sodium extract. In Lassaigne solution, elements present in compound, get converted from their covalent to easily identifiable ionic forms

e.g. Na+C+NNaCN

Na+SNa2 S

Na+XNaX = halogen

(i) Test for nitrogen

Lassaigne extract is boiled with FeSO4 and acidified with dil. H2SO4. Formation of prussian blue colour confirms the presence of N.

6NaCN+FeSO4Na4[Fe(CN)6]+Na2SO4

sodium hexacyanoferrate(II)

3Na4[Fe(CN)6]+4Fe+3Fe4[Fe(CN)6]3+12Na+

ferri ferrocyanide (prussian blue)

Note : On heating with FeSO4, sodium ferrocyanide is formed and at the same time some ferrous (Fe+2 ) ions are oxidized to ferric ( Fe+3 ) ion which react with sodium ferrocyanide to give ferri ferrocyanide.

(ii) Test for sulphur

(a) Sodium extract is acidified with acetic acid and lead acetate is added to it which gives black ppt of PbS and shows the presence of ’ S ‘.

Na2 S+(CH3COO)2 PbPbS+2CH3COONa black (b) Lassaigne extract reacts with sodium nitroprusside and gives violet colour.

Na2 S+Na2(Fe(CN)5NO) violet Na4[Fe(CN)5NOS]

Note: If ’ N ’ and ’ S ’ both are present in compound they form sodium thiocyanate in Lassaigne extract, due to insufficient sodium.

Na+C+N+SΔNaSCN

Therefore, during test of ’ N ‘, instead of prussian blue, blood red colouration appears.

3NaSCN+Fe+3 ferric thiocyanate (blood red)  Fe(SCN)3+3Na+

Note: In excess of sodium metal, sodium thiocyanate decomposes to sodium sulphide & sodium cyanide. Therefore, L E is prepared in excess of sodium.

NaSCN+Na (excess) Na2 S+NaCN

(iii) Detection of halogens

If ’ N ’ or ’ S ’ present in the compound they may interfere in the AgNO3 test for halogen. Therefore, before the test for halogens, sodium extract is boiled with conc. HNO3 to decompose Na2 S and NaCN in the form of H2 S and HCN.

Na2 S+Conc.HNO3H2 S

NaCN+Conc.HNO3HCN

Now, sodium extract is treated with AgNO3, which gives precipitate of silver halide

NaX+AgNO3AgX+NaNO3

Sod. extract ppt. X=Cl,Br,I

(iv) Detection of phosphorus

Organic compound is fused with sodium peroxide to convert phosphorus into sodium phosphate, which on further reaction with ammonium molybdate & conc. HNO3 gives yellow ppt/colouration of ammonium phosphomolybdate. 2P (From organic compound) +Na2O2ΔNa3PO4+2Na2O

Na3PO4+3HNO3ΔH3PO4+3NaNO321HNO3+H3PO4+12(NH4)2MoO4(NH4)3PO412MoO3+21NH4NO3+12H2O Amm. molybdate  \qquad Amm. phospho molybdate (yellow) 

Quantitative analysis of organic compounds

This is done to calculate the percentage of each element in the compound.

1.Estimation of ’ C ’ and ’ H ’ [Liebig’s Method]

A known mass of organic compound in burnt in presence of excess of CuO. ’ C ’ and ’ H ’ of the compound oxidize to CO2 and H2O, respectively. These vapours are passed through weighed ’ U ’ tubes having anhydrous CaCl2 followed by KOH solution. CaCl2 absorbs H2O while KOH absorbs CO2. Increase in the mass of CaCl2 and KOH gives the amount of H2O and CO2 produced in combustion which inturn gives the of H and C present in the compound.

Calculation of % of ’ C ’ and ’ H ’ : Suppose mass of compound =Wg

 mass of CO2/H2O produced =wg

For CO2C

44 g12 g

44 gCO2 Contains 12 gC '

w g CO 22 contains 1244×wgC '

of ’ C ’ in Wg organic compound

For HH2O2H

18g2g

18 g of H2O contains 2 g of ’ H '

w g of H2O contains 218×wgH '

of ’ H ’ in Wg organic compound

2.Estimation of ’ N '

There are two most commenly used methods (i) Duma’s method (ii) Kjeldahl’s method.

(i) Duma’s Method: This method is applicable to all organic compounds containing nitrogen. organic compound is heated with excess of CuO to give free nitrogen, CO2 and H2O

CxHy N2+CuOΔXCO2+Y2H2O+Z2 N2+Cu

Now, the above mixture is collected over conc. KOH solution which absorbs all the gases except N2. The volume of N2 collected is calculated at STP.

P1V1T1=P2V2T2V1= Volume of N2 gas P1= Pressure of N2-Aqueous tension T1= Room temperature V2=P1V1T1×273760 Letit be ‘V’ ml

Calculation of % of ’ N '

22400 mL of N2 at STP weighs =28 g

VmL of N2 at STP weighs =2822400×Vg

% of N in W g organic compound =2822400×VW×100

(ii) Kjeldahl’s Method

Compound is heated with conc.H2SO4. ’ N ’ in the compound gets converted into (NH4)2SO4. Resulting acidic mixture is heated with excess of NaOH to liberate NH3 gas. NH3 is absorbed in excess of standard H2SO4 solution. The amount of H2SO4 consumed tells about the amount of NH3 produced. The volume of acid left, after absorption of NH3, is found by titration against standard alkali solution.

Organic compound +H2SO4(NH4)2SO4

(NH4)2SO4+NaOHNa2SO4+2NH3+H2O

NH3+H2SO4(NH4)2SO4

Let the mass of organic compound taken =Wg

Volume of H2SO4 of normality N1=V1 mL

Volume of NaOH of normality N2, used =V2 mL

Now V2 mL of N1NaOH=V2 mL of N1H2SO4 left unused

Volume of H2SO4 used up by NH3=(V1V2)mL of N1 normality = Volume of NH3 evolved

1000 mL of 1 NNH3 contains 14 gN '

(V1V2)mL of 1 NNH3 will contain 141000×(V1V2)×N1 gN '

This is mass of ’ N ’ in Wg of compound.

% of N=141000×(V1V2)×N1×100 W or % of N=1.4× normality of acid × volume of acid used  mass of compound 

3.Estimation of Halogens : (Carius Method)

A known mass of organic compound is heated with fuming HNO3 in presence of AgNO3. The halogen of compound gets precipitated in the form of AgX which can be filtered, washed, dried & weighed.

Let the mass of organic compound =Wg

& mass of AgX formed = wg

AgXAg

(108+ atomic mass of halogen )=( atomic mass of halogen )

Now 1 mole of AgX contains 1 g atom of X(X=Cl,Br,I)

wg of AgX contains = Atomic mass of X(108+ at. mass of X)×wg

This is mass of halogen (X) present in Wg of compound

of halogen =( at. mass of X)(108+ at. mass of X)×WW×100

4.Estimation of Sulphur: (Carius method)

A known mass of compound is heated with fuming HNO3. Sulphur present in the compound gets converted into H2SO4 which is then precipitated as BaSO4.

S+H2O+30( from HNO3)ΔH2SO4

H2SO4+BaCl2BaSO4

BaSO4S

233 g32 g

mass of ’ S ’ in w g of BaSO4=32233×wg

% of ‘S’ in Wg compound

% of S=32233×WW×100

5.Estimation of Phosphorus (Carius method)

When known mass of compound is heated with fuming HNO3, phosphorus of compound is oxidised to H3PO4 which is precipitated as magnesium ammonium phosphate and then ignited to give magnesium pyrophosphate.

Mg2P2O7P2

222 g31×2 g

mass of phosphorus in wg of Mg2P2O7=62222×wg

of ‘P’ in W g organic compound

of P=62222×WW×100

6.Estimation of Oxygen

Oxygen, in an organic compound, can be calculated by the difference method.

Percentage of oxygen =(100 Sum of of all other elements )

Calculations of Empirical and Molecular Formula

Empirical Formula

It is the simplest whole number ratio between the atoms of various elements present in one molecule of the substance. eg. ratio of H & O in H2O2 is 1 : 1, therefore, Empirical formula is HO.

Molecular Formula

It gives the actual number of atoms of various elements present in one molecule of the compound eg. actual no. of atoms of H and O in H2O2 is 2 & 2, Therefore, molecular formula is H2O2.

Relationship between Empirical and Molecular formula

Molecular formula =n× (Empirical formula)

Where n is a simple integer 1,2,3, etc. given by the equation

n= Molecular mass  Empirical formula mass 

For example empirical formula of glucose is CH2O

Its empirical formula mass =12+(2×1)+16=30

Molecular Mass of glucose =180

n= Molecular mass  Empirical formula mass =18030=6

Molecular formula of glucose =n× (Empirical formula)

=6×(CH2O)=C6H12O6

Steps to calculate Empirical formula

1. Devide the percentage of each element by its atomic mass to get the relative number of atoms in the molecule.

2. Devide the result obtained in the above step by the smallest value among them to get the simplest ratio of atoms of various elements present in the molecule.

3. If the ratio obtained in step 2 is not a whole no., then multiply the figures with a suitable integer to make it simplest whole number ratio.

4. Now write the symbols of the various elements present along with the whole numbers obtained in step 3. This gives the empirical or simplest formula.

Steps to determine Molecular formula

1. Determine empirical formula from percentage composition of atoms of various elements present.

2. Calculate empirical formula mass.

3. Calculate molecular mass by suitable method.

4. Determine value of n;n= Molecular mass  Empirical formula mass 

5. Multiply empirical formula by ’ n ’ to get the molecular formula

Molecular formula =nx (Empirical formula)

Empirical and Molecular formulae of some compounds

Compound Empirical Formula Molecular Formula
Benzene CH C6H6
Glucose CH2O C6H12O6
Sucrose C12H22O11 C12H22O11
Hydrogen peroxide HO H2O2
Carbon di oxide CO2 CO2
Methane CH4 CH4
Sodium Carbonate Na2CO3 Na2CO3

Solved problems

Question 1. Calculate empirical and molecular formula of an organic compound containing 58.53 carbon, 4.06 hydrogen, 11.38% nitrogen and rest is oxygen. Molecular mass of compound is 123 .

Show Answer

Answer

Element % Atomic Mass Moles of atoms Simplest atomic ratio Simplest whole no. atomic ratio
Carbon 58.53 12 58.5312=4.88 4.880.813 6
Hydrogen 4.06 1 4.061=4.06 4.060.813 5
Nitrogen 11.38 14 11.3814=0.813 0.8130.813 1
Oxygen 26.03 16 26.0316=1.63 1.630.813 2

Therefore, the empirical formula is C6H5NO2

Empirical formula mass =(12×6)+(5×1)+14+(16×2)=123

n= Molecular mass  Empirical formula mass =123123=1

Empirical formula = Molecular formula =C6H5NO2

Question 2. Calculate molecular formula of compound (Molecular mass =88 ), having 54.2 carbon, 9.2 hydrogen and 36.6 oxygen.

Show Answer

Answer (i) Calculation of empirical formula from composition

Element % Atomic mass Moles of atoms Simplest atomic ratio Simplest whole no. atomic ratio
C 54.2 12 54.212=4.51 4.512.29 2
H 9.2 1 9.21=9.2 9.22.29 4
O 36.6 16 36.616=2.29 2.292.29 1

Empirical formula =C2H4O

(ii) Calculation of molecular formula

 Empirical formula mass =(2×12)+(4×1)+16=44

n= Molecular mass  Empirical formula mass =8844=2

Molecular formula =2(C2H4O)=C4H8O2

Question 3. 0.246 g of an organic compound gave 0.198 g of CO2 and 0.1014 g of water on complete combustion. 0.37 g of compound gave 0.638 g of silver bromide. What is the molecular formula of the compound if its vapour density is 54.4 .

Show Answer

Answer (a) Calculation of composition

(i) of ’ C=1244× Mass of CO2 produced  Mass of compound taken ×100

=1244×0.1980.246×100=21.95

(ii) of ’ H=218× Mass of H2O produced  Mass of compound taken ×100

=218×0.10140.246×100=4.58

(iii) of ‘Br’ =80188× Mass of AgBr formed  Mass of compound taken ×100

=80188×0.6380.37×100=73.37

(iv) The given compound does not contain oxygen since the sum of of C,H,Br is approx 100

i.e. 21.95+4.58+73.37=99.90100

(b) Calculation of empirical formula

Element Atomic
mass
Moles of atoms Simplest
atomic ratio
Simplest whole
no. atomic ratio
C 21.95 12 21.9512=1.83 1.830.917 2
H 4.58 1 4.581=4.58 4.580.917 5
Br 73.37 80 73.3780=0.917 0.9170.917 1

Thus, the empirical formula of the compound is C2H5Br

(c) Determination of molecular formula

Vapour density of the compound =54.4

Molecular mass of the compound =2× Vapour density

=2×54.4=108.8

n= Molecular mass  Empirical formula mass =108.8(2×12)+(5×1)+(1×80)=108.81091

Molecular formula =C2H5Br

Question 4. 0.25 g of an organic compound upon Kjeldahl’s analysis evolved ammonia which was absorbed in 25 mL of INH2SO4. The residual acid required 30 mL of N2NaOH solution. Find the of ’ N ’ in the compound.

Show Answer

Answer. Volume of acid taken =25 mL

Volume of alkali used for neutralization of excess acid =30ml of N2NaOH

30 mLN2NaOH30 mLN2H2SO415 mL1 NH2SO4

Volume of 1 NH2SO4 used by ammonia =2515=10 mL

Further 10 mL of 1 NH2SO4=10 mL of 1 NNH3 solution

But, 1000 mL of 1 NNH3 contain =14 g N

10 mL1 NNH3 will contain =14×101000=0.14 gN '

Therefore, 0.25 g compound contains 0.14 gN '

of ’ N=0.14×1000.25=28

Question 5. 0.5 g of an organic compound, when treated by Carius method, gave 0.65 gBaSO4. Calculate the of ’ S ’ in the compound.

Show Answer

Answer.

 By formula, % of ‘S’ =32233× Mass of 2BaSO4 Mass of compound ×100=32233×0.650.5×100=17.85% 

Question 6. 0.2 g of an organic compound containing phosphorus gave 0.32 g of Mg2P2O7 by the usual analysis. Calculate the % of ’ P ’ in the compound.

Show Answer

Answer. By formula, of P=62222× Mass of Mg2P2O7 Mass of compound ×100

=62222×0.320.2×100=44.68%

Question 7. 0.35 g of a substance gave 0.25 g of silver bromide in Carius method of halogen estimation. Find the of bromine in the compound.

Show Answer

Answer. By formula, \% of Br= Atomic mass of Br(108+ Atomic mass of Br)× wt. of AgBr Mass of substance ×100

=80188×0.250.35×100=30.39%

Question 8. 0.15 g of an organic compound gave 25 mL of nitrogen, collected at 300 K and 715 mm pressure in Duma’s method. Calculate the percentage of nitrogen in the compound (Aqueous tension of water at 300 K is 15 mm ).

Show Answer

Answer. By formula, of N=2822400× Volume of N2 Collected at STP  Mass of compound ×100

Atmospheric pressure =715 mmHg

Room temperature =300 K

Vapour pressure of water at 300 K=15 mm

Actual pressure of gas =71515=700 mmHg

Volume of nitrogen collected at STP =P1 V1 T1×273760=700×25300×273760

By putting the volume of nitrogen collected at STP, into the formula, we get

=17.46%

Question 9. 0.35 g of a substance on combustion gave 0.52 g of CO2 and 0.3 g of H2O. Calculate the percentage of ‘C’ & ’ H ’ in it.

Show Answer

Answer (i) % of C=1244× Mass of CO2 formed  Mass of substance ×100

=1244×0.520.35×100=40.51%

 (ii) % of H=218× Mass of H2O formed  Mass of substance ×100=218×0.30.35×100=9.52%

Question 10. 0.25 g of an organic compound at NTP gave 31 mL of N2 gas by Duma’s estimation method. Find out percentage of ’ N '

Show Answer

Answer. % of N=2822400× volume of N2 collected  weight of compound ×100

=2822400×310.25×100=15.5%

Question 11. Suggesta suitable method to separate :-

(a) Mixture of o-nitrophenol and p-nitrophenol

(b) Mixture of benzene (b.p.353K) and toluene (b.p.384K)

(c) Sugar containing impurity of common salt.

(d) Acetone (b.p. 329K) and methanol (b.p.338K)

(e) Mixture of benzoic acid and naphthalene

Show Answer

Answer (a) o-nitrophenol is steam volatile while p-nitrophenol is not, therefore, they can be separated by steam distillation.

(b) For benzene and toluene, boiling point difference 30 K is sufficient to separate them through simple distillation. moreover, both of them contain non volatile impurities.

(c) Sugar containing impurity of common salt can be purified by crystallization using hot ethanol which dissolves sugar but not the common salt.

(d) Acetone and methanol can be separated by fractional distillation as their boiling points are very close to each other (difference in b.p. 10C ).

(e) Crystallization with hot water; benzoic acid will dissolve while naphthalene remains insoluble.

Question 12. Give method for the purification of

(a) Camphor

(b) Nitrobenzene

(c) Kerosene having water impurity

Show Answer

Answer. (a) Camphor sublimes upon heating, thus can easily be purified by sublimation

(b) Nitrobenzene, having very high b.p. (483K), insoluble in water and containg nonvolatile impurities, can be purified using steam distillation

(c) Kerosene can be purified from impurities of water by solvent extraction using a separating funnel since both are immiscible

Practice Problems

Question 1. In the Lassaigne’s test for ’ N ’ the prussian blue colour is obtained due to the formation of

(a) Na4[Fe(CN)6]

(b) Fe4[Fe(CN)6]

(c) Fe2[Fe(CN)6]

(d) Fe3[Fe(CN)6]

Show Answer Answer: (b)

Question 2. A mixture of liquid A and B having boiling points 365 K and 356 K, respectively, can be separated by

(a) Simple distillation

(b) Steam distillation

(c) Fractional distillation

(d) Distillation under reduced pressure

Show Answer Answer: (c)

Question 3. The best and latest technique for isolation, purification and separation of organic compounds is

(a) Crystallization

(b) Distillation

(c) Sublimation

(d) Chromatography

Show Answer Answer: (d)

Question 4. In which out of the following compounds, ’ N ’ can not be analysed by Lassaigne’s test

(a) Nitrobenzene

(b) Aniline

(c) Urea

(d) Hydrazine

Show Answer Answer: (d)

Question 5. Which of the following compounds is / are formed when an organic compound containing both N & S is fused with sodium

(a) Thiocyanate

(b) Nitrate and sulphide

(c) Cyanide and sulphite

(d) Sulphide & cyanide

Show Answer Answer: (d)

Question 6. In Duma’s method, ’ N ’ is determined in the form of

(a) NaCN

(b) Gaseous nitrogen

(c) Ammonium sulphate

(d) Gaseous ammonia

Show Answer Answer: (b)

Question 7. The concentration of C=85.45 is not obeyed by the Empirical formula

(a) C2H4

(b) C4H8

(c) C2H6

(d) CH2

Show Answer Answer: (c)

Question 8. An organic compound decomposes below its boiling point, can be purified by

(a) Simple distillation

(b) Sublimation

(c) Distillation under reduced pressure

(d) Fractional distillation

Show Answer Answer: (c)

Question 9. Camphor can be purified by

(a) Crystallization

(b) Sublimation

(c) Distillation

(d) Extraction

Show Answer Answer: (b)

Question 10. The appearance of blood red colouration during Lassaigne’s test indicates

(a) Presence of S

(b) Presence of N

(c) Presence of N& S

(d) Presence of halogen

Show Answer Answer: (c)

Question 11. Identify the compound that con not be Kjeldahlised

(a) Urea

(b) Pyridine

(c) Aniline

(d) Benzamide

Show Answer Answer: (b)

Question 12. Which of the following fertilizers has the highest percentage of ’ N '

(a) Ammonium sulphate

(b) Urea

(c) Ammonium nitrate

(d) Calcium cyanamide

Show Answer Answer: (c)

Question 13. The Lassaigne’s extract is boiled with dil. HNO3 before testing for halogens because

(a) Silver halides are soluble in HNO3

(b) Ag2 S is soluble in HNO3

(c) AgCN is soluble in HNO3

(d) Na2 S and NaCN are decomposed by HNO3

Show Answer Answer: (d)

Question 14. In the Kjeldahl’s method of estimation of ’ N ’ present in a soil sample, ammonia evolved from 0.75 g of sample, neutralized 10 mL of 1MH2SO4. The % of ’ N ’ in the soil is

(a) 37.33

(b) 45.33

(c) 35.33

(d) 43.33

Show Answer Answer: (a)

Question 15. 31.7 mL of moist N2 was obtained from 0.2033 g of an organic compound in Duma’s method at 14C and 758 mm pressure. If aq. tension at 14C=14 mm, the of ’ N ’ in the sample is

(a) 19.25

(b) 18.15

(c) 19.01

(d) 20.2

Show Answer Answer: (b)

Question 16. 0.189 g of substance, during Carius determination gave 0.287 g of AgCl. What is the of chlorine in the sample

(a) 40.20

(b) 38.36

(c) 37.57

(d) 39.04

Show Answer Answer: (c)

Question 17. 0.40 g of an organic compound containing phosphorus gave 0.555 g of Mg2P2O7 in Carius analysis. % of phosphorus in the organic compound is

(a) 38.75

(b) 50.23

(c) 40.57

(d) 37.85

Show Answer Answer: (a)

Question 18. A compound has C,H,N in the following percentage : C=40. What is its Empirical formula

(a) CH2 N

(b) C2H5 N

(c) CH5 N

(d) CH4 N

Show Answer Answer: (d)

Question 19. 1.89g of an organic compound containg C,H&O gave 2.64 gCO2 and 1.08 g2O upon combustion. Its Empirical formula is

(a) C2H2O

(b) CH2O

(c) CH3O

(d) C2H2O2

Show Answer Answer: (b)

Question 20. When acetic acid and lead acetate are added to sodium extract during Lassaigne’s test, appearance of black precipitate shows the presence of

(a) Phosphorus

(b) Nitrogen

(c) Sulphur

(d) Halogen

Show Answer Answer: (c)

Question 21. An organic substance from its aqueous solution can be separated by

(a) Simple Distillation

(b) Steam distillation

(c) Solvent extraction

(d) Fractional distillation

Show Answer Answer: (c)

Question 22. In steam distillation, the vapour pressure of the volatile compound is

(a) Equal to atmospheric pressure

(b) Less than atmospheric pressure

(c) More than atmospheric pressure

(d) Exactly half of the atomospheric pressure

Show Answer Answer: (b)

Question 23. Refining of petroleum involves the process of

(a) Simple distillation

(b) Steam distillation

(c) Distillation under reduced pressure

(d) Fractional distillation

Show Answer Answer: (d)

Question 24. In Kjeldahl’s method, the nitrogen present in the compound is converted into

(a) Gaseous ammonia

(b) Gaseous nitrogen

(c) Ammonium sulphate

(d) Ammonium nitrate

Show Answer Answer: (a)

Question 25. The property which serves as a criterion of purity of an organic compound its

(a) Solubility in water

(b) Conductivity

(c) Density

(d) Crystalline nature

Show Answer Answer: (d)

Question 26. Separation of two substances by fractional crystallization depends upon their difference in

(a) Densities

(b) Solubilities

(c) Melting points

(d) Boiling points

Show Answer Answer: (b)

Question 27. The separation of the constituents of a mixture by column chromatography depends upon their

(a) Different solubilities

(b) Different boiling points

(c) Different refractive index

(d) Differential adsorption

Show Answer Answer: (d)

Question 28. Ammonia evolved from 0.4 g of an organic substance by Kjeldahl’s method was absorbed in 30 mL of semi-normal (N/2) H2SO4. The excess of the acid was neutralised by the addition of 30 mL of N5NaOH. % of ’ N ’ in the substance is

(a) 30.5

(b) 31.5

(c) 33.5

(d) 32.5

Show Answer Answer: (b)

Question 29. An organic compound contains carbon 34.6 and hydrogen 3.84, the rest being oxygen. Its vapour density is 52 . The molecular formula of the compound is

(a) C3H5O

(b) C3H4O2

(c) C3H3O

(d) C3H4O4

Show Answer Answer: (d)

Question 30. If two compounds have same Empirical formula but different Molecular formula, they must have

(a) Different percentage composition

(b) Same viscosity

(c) Different molecular weight

(d) Same vapour density

Show Answer Answer: (c)

Question 31. An oxide of nitrogen contains 30.43 of nitrogen. The molecular weight of the compound is equal to 92 a.m.u. What is the molecular formula of the compound

(a) N2O3

(b) N2O4

(c) N2O5

(d) N2O

Show Answer Answer: (b)

Question 32. An acid contains C,H&0. Its 4.24mg, upon burning gives 8.45mgCO2 and 3.46mgH2O. Molecular mass of acid is 88 amu. What is its molecular formula

(a) C3H8O2

(b) C4H8O2

(c) C2H4O2

(d) C3H6O2

Show Answer Answer: (b)

Question 33. A compound contains 4.07 and 71.65 chlorine. Its molecular mass is 98.96 . What is its molecular formula

(a) C2H4Cl2

(b) CH3Cl

(c) C2H6Cl

(d) C3H7Cl2

Show Answer Answer: (a)

Question 34. The most satisfactory method to separate sugars is

(a) Fractional crystallization

(b) Sublimation

(c) Chromatography

(d) Benedict’s reagent

Show Answer Answer: (c)

Question 35. 0.36 g of the compound during Duma’s estimation gave 48.88 cm3 of N2 at 300 K and 740 mm pressure. What is the percentage of nitrogen (Aqueous tension at 300 K is 15 mm )

(a) 14.73

(b) 15.34

(c) 16.43

(d) 13.37

Show Answer Answer: (a)