Chapter 12 Organic Chemistry Some Basic Principles and Techniques

(i) C-1 is sp² hybridised.

    C-2 is sp hybridised.

 

(ii) C-1 is sp³ hybridised.

     C-2 is sp² hybridised.

     C-3 is sp² hybridised.

 

(iii) C -1 and C-3 are sp³ hybridised.

      C-2 is sp² hybridised.

 

(iv) C-1 is sp² hybridised.

      C-2 is sp² hybridised.

      C-3 is sp hybridised.

 

(v) C₆H₆  All the 6 carbon atoms in benzene are sp² hybridised.

(i) C₆H₆

There are six C-C sigma (σ_C-C) bonds, six C-H sigma (σ_C-H) bonds and three C=C pi (π_C-C) resonating bonds in this compound.

 

(ii) C₆H₁₂

There are six C-C sigma (σ_C-C) bonds and twelve C-H sigma (σ_C-H) bonds in this compound.

 

(iii) CH₂Cl₂

There two C-H sigma (σ_C-H) bonds and two C-Cl sigma (σ_C-Cl) bonds in this compound.

 

(iv) CH₂=C=CH₂

There are two C-C sigma (σ_C-C) bonds, four C-H sigma (σ_C-H) bonds, and two C=C pi (π_C-C) bonds in this compound.

 

(v) CH₃NO₂

There are three C-H sigma (σ_C-H) bonds, one C-N sigma (σ_C-N) bond, one N-O sigma (σ_N-O) bond and one N=O pi (π_N-O) bond in this compound.

 

(vi) HCONHCH₃

There are two C-N sigma (σ_C-N) bonds, four C-H sigma (σ_C-H) bonds, one N-H sigma bond, and one C=O pi (π_C-O) bond in this compound.

The bond line formulae of the given compounds are:

(a) The prefix di in the IUPAC name indicates that two identical substituent groups are present in the parent chain. Since two methyl groups are present in the C–2 of the parent chain of this compound, the correct IPUAC name of the compound is 2, 2–dimethylpentane.It is an alkane molecule.

(b) Locant number 2, 4, 7 is lower than 2, 5, 7. Hence, the IUPAC name of this compound is 2, 4, 7–trimethyloctane. In lowest set of locants the sum of locants should be minimum, the locant with lowest total value is given the preference, i.e 2+4+7=13 is lower in value than 2+5+7=14.

(c) If the substituents are present in the equivalent position of the parent chain, then the lower number is given to the one that comes first in the name according to the alphabetical order. Hence, the correct IUPAC name of the given compound is 2–chloro–4–methylpentane

(d) Two functional groups – alcoholic and alkyne – are present in the given compound. The principal functional group is the alcoholic group. Hence, the parent chain will be suffixed with ol. The alkyne group is present in the C–3 of the parent chain & will be considered as substitutent. Hence, the correct IUPAC name of the given compound is But–3–yn–1–ol.

The first five members of each homologous series beginning with the given compounds are shown as follows:

(a)

H-COOH : Methanoic acid

CH₃-COOH : Ethanoic acid

CH₃-CH₂-COOH : Propanoic acid

CH₃-CH₂-CH₂-COOH : Butanoic acid

CH₃-CH₂-CH₂-CH₂-COOH : Pentanoic acid

 

(b)

CH₃COCH₃ : Propanone

CH₃COCH₂CH₃ : Butanone

CH₃COCH₂CH₂CH₃ : Pentan-2-one

CH₃COCH₂CH₂CH₂CH₃ : Hexan-2-one

CH₃COCH₂CH₂CH₂CH₂CH₃ : Heptan-2-one

 

(c)

H-CH=CH₂ : Ethene

CH₃-CH=CH₂ : Propene

CH₃-CH₂-CH=CH₂ : 1-Butene

CH₃-CH₂-CH₂-CH=CH₂ : 1-Pentene

CH₃-CH₂-CH₂-CH₂-CH=CH₂ : 1-Hexene

(a) 2, 2, 4-trimethylpentane

Condensed formula: (CH₃)₂CHCH₂C (CH₃)₃

Bond line formula:

 

(b) 2-hydroxy-1, 2, 3-propanetricarboxylic acid

Condensed Formula:  (COOH)CH₂C(OH) (COOH)CH₂(COOH)

Bond line formula:

The functional groups present in the given compound are carboxylic acid (-COOH) and alcoholic (-OH) groups.

 

(c) Hexanedial Condensed Formula: (CHO) (CH₂)₄ (CHO)

Bond line Formula:

The functional group present in the given compound is aldehyde (-CHO).

The functional groups present in the given compounds are:

(a) Aldehyde (-CHO),  

Hydroxyl (-OH),  

Methoxy (-OMe),

C=C double bond 

 

(b) Amino (-NH2); primary amine,

Ester (-O-CO-),

Triethylamine (N(C₂H₅)₂); tertiary amine

 

(c) Nitro (-NO2),

C=C double bond

NO₂ group is an electron-withdrawing group. Hence, it shows -I effect. NO₂ group decreases the negative charge on the compound by withdrawing electrons towards it and stabilising it. On the other hand, ethyl group is an electron-releasing group. Hence, the ethyl group shows +I effect. This increases the negative charge on the compound, thereby destabilising it. Hence, O₂NCH₂CH₂O^- is expected to be more stable than CH₃CH₂O^-.

When an alkyl group is attached to a π system, it acts as an electron-donor group by the process of hyperconjugation. To understand this concept better, let us take the example of propene.

In hyperconjugation, the sigma electrons of the C-H bond of an alkyl group are delocalised. This group is directly attached to an atom of an unsaturated system. The delocalisation occurs because of a partial overlap of a sp³-ssigma bond orbital with an empty p orbital of the π bond of an adjacent carbon atom.

The process of hyperconjugation in propene is shown as follows:

This type of overlap leads to a delocalisation (also known as no-bond resonance) of the π electrons, making the molecule more stable.

 

An electrophile is a reagent that takes away an electron pair. In other words, an electron-seeking reagent is called an electrophile (E⁺). Electrophiles are electron-deficient and receiver of an electron pair.

Carbocations and (CH₃CH⁺₂) neutral molecules having functional groups such as carbonyl group   are examples of electrophiles.

A nulceophile is a reagent that brings an electron pair. In other words, a nucleus-seeking reagent is called a nulceophile (Nu:).

For example: OH-, NC-, carbanions (R₃C-), etc.

Neutral molecules such as H₂ö and ammonia also act as nulceophiles because of the presence of a lone pair.

Electrophiles are electron-deficient species and can receive an electron pair. On the other hand, nucleophiles are electron-rich species and can donate their electrons.

(a) CH₃COOH  +  HO^-  →   CH₃COO^- + H₂O

Here, HO^- acts as a nucleophile as it is an electron-rich species, i.e., it is a nucleus-seeking species.

(b) CH₃COCH₃  +  C-N  →  (CH₃)₂ C (CN) (OH)

Here, C-N acts as a nucleophile as it is an electron-rich species, i.e., it is a nucleus-seeking species.

(c) C₆H₅  +  CH₃C⁺O  →  C₆H₅COCH₃

Here, CH₃C⁺O acts as an electrophile as it is an electron-deficient species.

(a) It is an example of substitution reaction as in this reaction the bromine group in bromoethane is replaced by the -SH group.

(b) It is an example of addition reaction as in this reaction two reactant molecules combine to form a single product.

(c) It is an example of elimination reaction as in this reaction hydrogen and bromine are removed from bromoethane to give ethene.

(d) In this reaction, substitution takes place, followed by a rearrangement of atoms and groups of atoms.

(a) Compounds having the same molecular formula but with different structures are called structural isomers. The given compounds have the same molecular formula but they differ in the position of the functional group (ketone group).

In structure I, ketone group is at the C-3 of the parent chain (hexane chain) and in structure II, ketone group is at the C-2 of the parent chain (hexane chain). Hence, the given pair represents structural isomers.

 

(b) Compounds having the same molecular formula, the same constitution, and the sequence of covalent bonds, but with different relative position of their atoms in space are called geometrical isomers.

In structures I and II, the relative position of Deuterium (D) and hydrogen (H) in space are different. Hence, the given pairs represent geometrical isomers.

 

(c) The given structures are canonical structures or contributing structures. They are hypothetical and individually do not represent any real molecule. Hence, the given pair represents resonance structures, called resonance isomers.

(a) The bond cleavage using curved-arrows to show the electron flow of the given reaction can be represented as

It is an example of homolytic cleavage as one of the shared pair in a covalent bond goes with the bonded atom. The reaction intermediate formed is a free radical.

 

(b) The bond cleavage using curved-arrows to show the electron flow of the given reaction can be represented as

It is an example of heterolytic cleavage as the bond breaks in such a manner that the shared pair of electrons remains with the carbon of propanone. The reaction intermediate formed is carbanion.

 

(c) The bond cleavage using curved-arrows to show the electron flow of the given reaction can be represented as

It is an example of heterolytic cleavage as the bond breaks in such a manner that the shared pair of electrons remains with the bromine ion. The reaction intermediate formed is a carbocation.

 

(d) The bond cleavage using curved-arrows to show the electron flow of the given reaction can be represented as

It is a heterolytic cleavage as the bond breaks in such a manner that the shared pair of electrons remains with one of the fragments. The intermediate formed is a carbocation.

Inductive effect

The permanent displacement of sigma electrons along a saturated chain, whenever an electron withdrawing or electron donating group is present, is called inductive effect.

Inductive effect could be + I effect or - I effect. When an atom or group attracts electrons towards itself more strongly than hydrogen, it is said to possess - I effect. For example,

F —← CH₂ —← CH₂ —← CH₂ —←CH₃

When an atom or group of atoms attracts electrons towards itself less strongly than hydrogen, it is said to possess + I effect. For example,

CH3  —→  CH2 →→ -Cl

Electrometric effect

It involves the complete transfer of the shared pair of  π-electrons to either of the two atoms linked by multiple bonds in the presence of an attacking agent. For example,

Electrometric effect could be + E effect or - E effect.

+ E effect: When the electrons are transferred towards the attacking reagent

- E effect: When the electrons are transferred away from the attacking reagent

 

(a) Cl₃CCOOH > Cl₂CHCOOH > ClCH₂COOH

The order of acidity can be explained on the basis of Inductive effect (- I effect). As the number of chlorine atoms increases, the - I effect increases. With the increase in - I effect, the acid strength also increases accordingly.

 

(b) CH3CH2COOH > (CH3)2 CHCOOH > (CH3)3 C.COOH

The order of acidity can be explained on the basis of inductive effect (+ I effect). As the number of alkyl groups increases, the + I effect also increases. With the increase in + I effect, the acid strength also increases accordingly.

(a) Crystallisation

Crystallisation is one of the most commonly used techniques for the purification of solid organic compounds.

Principle: It is based on the difference in the solubilites of the compound and the impurities in a solvent. The impure compound gets dissolved in the solvent in which it is sparingly soluble at room temperature, but soluble at higher temperature. The solution is concentrated to obtain a nearly saturated solution. On cooling the solution, the pure compound crystallises out and is removed by filtration.

For example, pure aspirin is obtained by recrystallising crude aspirin. Approximately 2 - 4 g of crude aspirin is dissolved in about 20 mL of ethyl alcohol. The solution is heated (if necessary) to ensure complete dissolution. The solution is then left undisturbed until some crystals start to separate out. The crystals are then filtered and dried.

 

(b) Distillation

This method is used to separate volatile liquids from non-volatile impurities or a mixture of those liquids that have a sufficient difference in their boiling points.

Principle: It is based on the fact that liquids having different boiling points vapourise at different temperatures. The vapours are then cooled and the liquids so formed are collected separately.

For example, a mixture of chloroform (b.p = 334 K) and aniline (b.p = 457 K) can be separated by the method of distillation. The mixture is taken in a round bottom flask fitted with a condenser. It is then heated. Chloroform, being more volatile, vaporizes first and passes into the condenser. In the condenser, the vapours condense and chloroform trickles down. In the round bottom flask, aniline is left.

 

(c) Chromatography

It is one of the most useful methods for the separation and purification of organic compounds.

Principle: It is based on the difference in movement of individual components of a mixture through the stationary phase under the influence of mobile phase.

For example, a mixture of red and blue ink can be separated by chromatography. A drop of the mixture is placed on the chromatogram. The component of the ink, which is less adsorbed on the chromatogram, moves with the mobile phase while the less adsorbed component remains stationary.

Fractional crystallisation is method used for separating two compounds with different solubilities in a solvent S. The process of fractional crystallisation is carried out in four steps.

(a) Preparation of the solution: The powdered mixture is taken in a flask and solvent is added to it slowly and stirred simultaneously. The solvent is added till solute is just dissolved in the solvent. This saturated solution is then heated.

(b) Filtration of the solution: The hot saturated solution is then filtered through a filter paper in a China dish.

(c) Fractional crystallisation: The solution in a China dish is now allowed to cool. Firstly, the less soluble compound crystallises , while the more soluble compound remains in the solution. After separating these crystals from the liquor, the latter is concentrated once again. The hot solution is allowed to cool and consequently, the crystals of the more soluble compound are obtained.

(d) Isolation and drying: These crystals are separated from the mother liquor by filtration. Finally, the crystals are dried.

The differences among distillation, distillation under reduced pressure, and steam distillation are given in the following table.

S.No	Distillation	Distillation under reduced pressure	Steam distillation
1	It is used for the purification of compounds that are associated with non-volatile impurities or those liquids, which do not decompose on boiling. In other words, distillation is used to separate volatile liquids from non-volatile impurities or a mixture of those liquids that have sufficient difference in boiling points.	This method is used to purify a liquid that tends to decompose on boiling. Under the conditions of reduced pressure, the liquid will boil at a low temperature than its boiling point and will, therefore, not decompose.	It is used to purify an organic compound, which is steam volatile and immiscible in water. On passing steam, the compound gets heated up and the steam gets condensed to water. After some time, the mixture of water and liquid starts to boil and passes through the condenser. This condensed mixture of water and liquid is then separated by using a separating funnel.
2	Mixture of petrol and kerosene is separated by this method.	Glycerol is purified by this method. It boils with decomposition at a temperature of 593 K. At a reduced pressure, it boils at 453 K without decomposition.	A mixture of water and aniline is separated by steam distillation

 

Lassaigne's test: This test is used to detect the presence of nitrogen, sulphur, halogens, and phosphorous in an organic compound. These elements are present in covalent form in an organic compound. These are converted into the ionic form by fusing the compound with sodium metal.

The cyanide, sulphide, and halide of sodium formed are extracted from the fused mass by boiling it in distilled water. The extract so obtained is called Lassaigne's extract. This Lassaigne's extract is then tested for the presence of nitrogen, sulphur, halogens, and phosphorous.

 

(a) Test for nitrogen

Lassaignes's extract     +     Ferrous Sulphate

                                           ⬇     Conc. sulphuric acid

                                   Prussian blue colour

                                   (Ferriferro cyanide)

 

Chemistry of the test

In the Lassaigne's test for nitrogen in an organic compound, the sodium fusion extract is boiled with iron (II) sulphate and then acidified with sulphuric acid. In this process, sodium cyanide first reacts with iron (II) sulphate and forms sodium hexacyanoferrate (II). Then, on heating with sulphuric acid, some iron (II) gets oxidised to form iron (III) hexacyanoferrate (II), which is Prussian blue in colour. The chemical equations involved in the reaction can be represented as

6CN^-   +   Fe²⁺    →      [Fe(CN)₆]^4-

3[Fe(CN)₆]^4-   +    4Fe³⁺        →    Fe₄[Fe(CN)₆]₃ 

                                                     Prussian blue colour

 

(b) Test for sulphur

(i) Lassaignes's extract  +   Lead acetate    →    Black precipitate

Chemistry of the test

In the Lassaigne's test for sulphur in an organic compound, the sodium fusion extract is acidified with acetic acid and then lead acetate is added to it. The precipitation of lead sulphide, which is black in colour, indicates the presence of sulphur in the compound.

S^2-  +  Pb²⁺    →   PbS

                            (Black)

(ii) Lassaignes's extract  +   Sodium nitroprusside   →    Violet colour

 

Chemistry of the test

The sodium fusion extract is treated with sodium nitroprusside. Appearance of violet colour also indicates the presence of sulphur in the compound.

S^2-  +  [Fe(CN)₅ NO]^2-    →    [Fe(CN)₅NOS]^-4

                                                   (Violet)

If in an organic compound, both nitrogen and sulphur are present, then instead of NaCN, formation of NaSCN takes place.

Na + C + N + S → NaSCN

This NaSCN (sodium thiocyanate) gives a blood red colour. Prussian colour is not formed due to the absence of free cyanide ions.

Fe³⁺  + SCN   →    [Fe(SCN)]²⁺

                              (Blood Red)

 

(c) Test for halogens

Chemistry of the test

In the Lassaigne's test for halogens in an organic compound, the sodium fusion extract is acidified with nitric acid and then treated with silver nitrate.

X^-   + Ag⁺    →    AgX

                         (X = Cl,Br,I)

If nitrogen and sulphur both are present in the organic compound, then the Lassaigne's extract is boiled to expel nitrogen and sulphur, which would otherwise interfere in the test for halogens.

In Dumas method, a known quantity of nitrogen containing organic compound is heated strongly with excess of copper oxide in an atmosphere of carbon dioxide to produce free nitrogen in addition to carbon dioxide and water. The chemical equation involved in the process can be represented as

The traces of nitrogen oxides can also be produced in the reaction, which can be reduced to dinitrogen by passing the gaseous mixture over a heated copper gauge. The dinitrogen produced is collected over an aqueous solution of potassium hydroxide. The volume of nitrogen produced is then measured at room temperature and atmospheric pressure.

On the other hand, in Kjeldahl's method, a known quantity of nitrogen containing organic compound is heated with concentrated sulphuric acid. The nitrogen present in the compound is quantitatively converted into ammonium sulphate. It is then distilled with excess of sodium hydroxide. The ammonia evolved during this process is passed into a known volume of H₂SO₄. The chemical equations involved in the process are

The acid that is left unused is estimated by volumetric analysis (titrating it against a standard alkali) and the amount of ammonia produced can be determined. Thus, the percentage of nitrogen in the compound can be estimated. This method cannot be applied to the compounds, in which nitrogen is present in a ring structure, and also not applicable to compounds containing nitro and azo groups.

Estimation of halogens

Halogens are estimated by the Carius method. In this method, a known quantity of organic compound is heated with fuming nitric acid in the presence of silver nitrate, contained in a hard glass tube called the Carius tube, taken in a furnace. Carbon and hydrogen that are present in the compound are oxidized to form CO₂ and H₂O respectively and the halogen present in the compound is converted to the form of AgX. This AgX is then filtered, washed, dried, and weighed.

Let the mass of organic compound be m g.

Mass of AgX formed = m₁ g

1 mol of Agx contains 1 mol of X.

Therefore, Mass of halogen in m1 g of AgX = (Atomic mass of X x m₁ g) / (Molecular mass of AgX)

Thus, % of halogen will be  =   (Atomic mass of X x m₁ x 100) / (Molecular mass of AgX x m)

 

Estimation of Sulphur

In this method, a known quantity of organic compound is heated with either fuming nitric acid or sodium peroxide in a hard glass tube called the Carius tube. Sulphur, present in the compound, is oxidized to form sulphuric acid. On addition of excess of barium chloride to it, the precipitation of barium sulphate takes place. This precipitate is then filtered, washed, dried, and weighed.

Let the mass of organic compound be m g.

Mass of BaSO₄ formed = m₁ g

1 mol of BaSO₄ = 233 g BaSO₄ = 32 g of Sulphur

Therefore, m1 g of BaSO₄ contains 32 x m₁ / 233  g of sulphur

Thus, percentage of sulphur = 32 x m₁ x100 / 233 x m

 

Estimation of phosphorus

In this method, a known quantity of organic compound is heated with fuming nitric acid. Phosphorus, present in the compound, is oxidized to form phosphoric acid. By adding ammonia and ammonium molybdate to the solution, phosphorus can be precipitated as ammonium phosphomolybdate.

Phosphorus can also be estimated by precipitating it as MgNH₄PO₄ by adding magnesia mixture, which on ignition yields Mg₂P₂O₇.

Let the mass of organic compound be m g.

Mass of ammonium phosphomolybdate formed = m₁ g

Molar mass of ammonium phosphomolybdate = 1877 g

Thus, percentage of phosphorus = (31 x m₁ x 100 %) / (1877 x m) 

If P is estimated as Mg₂P₂O₇,

Then percentage of phosphorus =  (62xm1x100%) / (222xm)

In paper chromatography, chromatography paper is used. This paper contains water trapped inside it, which acts as the stationary phase. On the base of this paper, the solution of the mixture is spotted. The paper strip is then suspended in a suitable solvent, which acts as the mobile phase. This solvent rises the chromatography paper by capillary action and in the procedure, it flows over the spot. The components are selectively retained on the paper (according to their differing partition in these two phases). The spots of different components travel with mobile phase to different heights. The paper so obtained (shown in the given figure) is known as a chromatogram.

While testing the Lassaigne's extract for the presence of halogens, it is first boiled with dilute nitric acid. This is done to decompose NaCN to HCN and Na₂S to H₂S and expel these gases. If any nitrogen and sulphur are present in the form of NaCN and Na₂S, then they are removed. The chemical equations involved in the reaction are represented as

NaCN  +   HNO₃   →    NaNO₃   +   HCN

Na₂S  +  2HNO₃  →    2NaNO₃   + H₂S

 

Nitrogen, sulphur, and halogens are covalently bonded in organic compounds. For their detection, they have to be first converted to ionic form. This is done by fusing the organic compound with sodium metal. This is called “Lassaigne's test“. The chemical equations involved in the test are

Na + C + N  →  NaCN

Na + S + C + N   →  NaSCN

2Na + S  →  Na₂S

Na + X  →  NaX

                 (X = Cl , Br, I)

Carbon, nitrogen, sulphur, and halogen come from organic compounds.

Sublimation is used to separate a mixture of camphor and calcium sulphate. In this process, the sublimable compound changes from solid to vapour state without passing through the liquid state. Camphor is a sublimable compound and calcium sulphate is a non-sublimable solid. Hence, on heating, camphor will sublime while calcium sulphate will be left.

In steam distillation, the organic liquid starts to boil when the sum of vapour pressure due to the organic liquid (p₁) and the vapour pressure due to water (p₂) becomes equal to atmospheric pressure (p), i.e. p = p₁ + p2. Since p₁ < p₂, organic liquid will vapourise at a lower temperature than its boiling point.

CCl₄ will not give the white precipitate of AgCl on heating it with silver nitrate. This is because the chlorine atoms are covalently bonded to carbon in CCl₄. To obtain the precipitate, it should be present in ionic form and for this, it is necessary to prepare the Lassaigne's extract of CCl₄.

Carbon dioxide is acidic in nature and potassium hydroxide is a strong base. Hence, carbon dioxide reacts with potassium hydroxide to form potassium carbonate and water.

2KOH   +  CO₂   →     K₂CO₃  +  H₂O

Thus, the mass of the U-tube containing KOH increases. This increase gives the mass of CO2 produced. From its mass, the percentage of carbon in the organic compound can be estimated.

The addition of sulphuric acid will precipitate lead sulphate, the addition of acetic acid will ensure a complete precipitation of sulphur in form of lead sulphate due to common ion effect. Hence, it is necessary to use acetic acid for acidification of sodium extract for testing sulphur by lead acetate test.

Percentage of carbon in organic compound = 69 %

That is, 100 g of organic compound contains 69 g of carbon

. ∴0.2 g of organic compound will contain 69x.02 / 100 = 0.138g of C

Molecular mass of carbon dioxide, CO₂ = 44 g

That is, 12 g of carbon is contained in 44 g of CO₂.

Therefore, 0.138 g of carbon will be contained in 44x0.138/12 = 0.506 g of CO₂

Thus, 0.506 g of CO₂ will be produced on complete combustion of 0.2 g of organic compound.

Percentage of hydrogen in organic compound is 4.8.

i.e., 100 g of organic compound contains 4.8 g of hydrogen.

Therefore, 0.2 g of organic compound will contain 4.8x0.2/100 = 0.0096 g of H

It is known that molecular mass of water (H₂O) is 18 g.

Thus, 2 g of hydrogen is contained in 18 g of water.

∴0.0096 g of hydrogen will be contained in 18x0.0096/2 = 0.0864g of water

Thus, 0.0864 g of water will be produced on complete combustion of 0.2 g of the organic compound.

Given that, total mass of organic compound = 0.50 g

60 mL of 0.5 M solution of NaOH was required by residual acid for neutralisation.

60 mL of 0.5 M NaOH solution = 60/2 mL of 0.5M  H₂SO₄ = 30 mL of 0.5 M H₂SO₄

∴Acid consumed in absorption of evolved ammonia is (50-30) mL = 20 mL

Again, 20 mL of 0.5 MH₂SO₄ = 40 mL of 0.5 MNH₃

Also, since 1000 mL of 1 MNH3 contains 14 g of nitrogen,

∴ 40 mL of 0.5 M NH3 will contain 14x40x0.5 / 1000 = 0.28 g of N

Therefore, percentage of nitrogen in 0.50 g of organic compound 0.28/0.50 x 100 = 56 %

Given that, Mass of organic compound is 0.3780 g.

Mass of AgCl formed = 0.5740 g

1 mol of AgCl contains 1 mol of Cl.

Thus, mass of chlorine in 0.5740 g of AgCl

=  35.5x0.5740 / 143.32

= 0.1421 g

∴ Percentage of chlorine = 0.1421/0.3780 x100 = 37.59%

Hence, the percentage of chlorine present in the given organic chloro compound is 37.59%.

Total mass of organic compound = 0.468 g [Given]

Mass of barium sulphate formed = 0.668 g [Given]

1 mol of BaSO₄ = 233 g of BaSO₄ = 32 g of sulphur

Thus, 0.668 g of BaSO₄ contains 32x0.668/233 g of sulphur = 0.0917 g of sulphur

Therefore, percentage of sulphur = 0.0197/0.468 x100 = 19.59 %

Hence, the percentage of sulphur in the given compound is 19.59 %.

 6          5         4           3        2      1

CH₂ = CH – CH₂ – CH₂ – C ≡ CH

In the given organic compound, the carbon atoms numbered as 1, 2, 3, 4, 5, and 6 are sp, sp, sp³, sp³, sp², and sp² hybridized respectively. Thus, the pair of hybridized orbitals involved in the formation of C₂-C₃ bond is sp - sp³.

In the Lassaigne's test for nitrogen in an organic compound, the sodium fusion extract is boiled with iron (II) sulphate and then acidified with sulphuric acid. In the process, sodium cyanide first reacts with iron (II) sulphate and forms sodium hexacyanoferrate (II). Then, on heating with sulphuric acid, some iron (II) gets oxidised to form iron (III) hexacyanoferrate (II), which is Prussian blue in colour. The chemical equations involved in the reaction can be represented as

Hence, the Prussian blue colour is due to the formation of Fe₄[Fe(CN)₆]₃.

The answer is b.

It is a tertiary carbocation. A tertiary carbocation is the most stable carbocation due to the electron releasing effect of three methyl groups. An increased + I effect by three methyl groups stabilizes the carbocation.

(d) Chromatography

Chromatography is the most useful technique of separation and purification of organic compounds. It was first used to separate a mixture of coloured substances.

CH₃CH₂I + KOH(aq) → CH₃CH₂OH + KI

It is an example of nucleophilic substitution reaction. The hydroxyl group of KOH (OH-) with a lone pair acts as a nucleophile and substitutes iodide ion in CH₃CH₂I  to form ethanol.