Chemistry Homework Solution
1. Preparation of Benzoic Acid from Benzene via Di-
azonium Salt Formation
Concept Overview: This synthesis involves converting benzene into benzoic acid through
a sequence of reactions: nitration, reduction, diazotization, and finally, Sandmeyer reac-
tion followed by oxidation.
Steps:
1. Nitration of Benzene:
H SO
C6 H6 + HNO3 −−2−−→
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C6 H5 NO2 + H2 O
2. Reduction of Nitrobenzene to Aniline:
Sn/HCl
C6 H5 NO2 + 3 H2 −−−−→ C6 H5 NH2 + 2 H2 O
3. Diazotization of Aniline:
0-5 ◦C
C6 H5 NH2 + NaNO2 + 2 HCl −−−→ C6 H5 N2 + Cl− + 2 H2 O
4. Sandmeyer Reaction (Cyanation):
C6 H5 N2 + Cl− + CuCN −−→ C6 H5 CN + CuCl + N2 ↑
5. Hydrolysis of Benzonitrile to Benzoic Acid:
H+ /heat
C6 H5 CN + 2 H2 O −−−−−→ C6 H5 COOH + NH3
Reaction Scheme:
Benzene −→ Nitrobenzene −→ Aniline −→ Benzene diazonium chloride −→ Benzonitrile −→ Benzoic
Final Answer: Benzoic acid is obtained from benzene through diazotization and Sand-
meyer cyanation followed by hydrolysis.
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2. Preparation of Ethylamine Using Gabriel’s Phthal-
imide Synthesis
Concept Overview: Gabriel synthesis produces primary amines from alkyl halides
using phthalimide as a protected nitrogen source.
Steps:
1. Formation of Potassium Phthalimide:
C6 H4 (CO)2 NH + KOH −−→ C6 H4 (CO)2 NK + H2 O
2. Alkylation:
C6 H4 (CO)2 NK + C2 H5 Br −−→ C6 H4 (CO)2 N(C2 H5 ) + KBr
3. Hydrolysis:
C6 H4 (CO)2 N(C2 H5 ) + 2 H2 O + NaOH −−→ C2 H5 NH2 + C6 H4 (COONa)2
Reaction Scheme:
Phthalimide −→ Potassium phthalimide −→ N-ethylphthalimide −→ Ethylamine
Final Answer: Ethylamine is prepared by alkylating potassium phthalimide with ethyl
bromide followed by alkaline hydrolysis.
3. Short Note on Osazone Formation
Concept Overview: Osazones are crystalline derivatives formed when reducing sugars
react with phenylhydrazine.
Reaction Principle:
• The carbonyl group (C=O) at C-1 and C-2 of reducing sugars reacts with 3 moles
of phenylhydrazine.
• The first mole forms a hydrazone; the next two oxidize the adjacent carbon and
form an osazone.
• Example: Glucose and fructose form the same osazone (glucosazone) because they
differ only at C-1 and C-2.
Illustration:
Glucose + 3 C6 H5 NHNH2 −−→ Glucosazone + NH3 + Aniline + H2 O
Final Answer: Osazone formation helps identify sugars based on crystalline shape and
melting point.
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4. Haworth Projection of α-D- and β-D-Glucopyranose
Concept Overview: The Haworth projection shows cyclic structures of glucose.
• α-form: OH on anomeric carbon (C1) is down (opposite to CH2 OH).
• β-form: OH on anomeric carbon is up (same side as CH2 OH).
Structures:
α-D-Glucopyranose:
OH OH
CH2 OH
β-D-Glucopyranose:
OH OH
CH2 OH
Note: In α-D-glucopyranose, the anomeric OH is trans to the CH2 OH group (down). In
β-D-glucopyranose, the anomeric OH is cis to the CH2 OH group (up).
Final Answer: α-D-glucopyranose and β-D-glucopyranose differ in the orientation of
the OH group at C1 (anomeric carbon).
5. Isoelectric Point of Amino Acid
Concept Overview: The isoelectric point (pI) is the pH at which an amino acid has
no net electrical charge.
Formula:
pK1 + pK2
pI = (for amino acids without ionizable side chains)
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Explanation: At pI, the amino acid exists as a zwitterion (NH3 + ), and migration in an
electric field stops.
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Illustration:
−− +
H2 N ↽−⇀
− NH3 (zwitterion)
Final Answer: The isoelectric point is the pH where the amino acid is electrically
neutral (zwitterionic).
6. Preparation of L-Alanine by Strecker Synthesis
Concept Overview: Strecker synthesis forms α-amino acids from aldehydes using NH3
and HCN.
Steps:
1. Reaction of Acetaldehyde with Ammonia and HCN:
CH3 CHO + NH3 + HCN −−→ CH3 CH(NH2 )CN (Amino nitrile)
2. Hydrolysis of Amino Nitrile:
CH3 CH(NH2 )CN + 2 H2 O + HCl −−→ CH3 CH(NH2 )COOH + NH4 Cl
Reaction Scheme:
CH3 CHO −−→ CH3 CH(NH2 )CN −−→ CH3 CH(NH2 )COOH
Final Answer: L-Alanine is synthesized from acetaldehyde via amino nitrile intermedi-
ate in the Strecker synthesis.
7. Inner vs Outer Orbital Complexes: K3[Fe(CN)6]
and K3[FeF6]
Concept Overview: The nature of ligand field strength determines whether a complex
is inner orbital (low-spin) or outer orbital (high-spin).
Explanation:
• [Fe(CN)6 ]3 – : CN – is a strong field ligand → causes pairing of 3d electrons → uses
d2 sp3 hybridization (inner orbital).
• [FeF6 ]3 – : F – is a weak field ligand → no pairing → uses sp3 d2 hybridization (outer
orbital).
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Diagram:
[Fe(CN)6 ]3− → d2 sp3 (inner orbital, low-spin)
3− 3 2
[FeF6 ] → sp d (outer orbital, high-spin)
Final Answer: K3 [Fe(CN)6 ] is inner orbital (low-spin), while K3 [FeF6 ] is outer orbital
(high-spin).
8. Chelating Complex Stability
Concept Overview: Chelating ligands form multiple bonds to a metal ion, creating a
ring structure.
Explanation:
• Chelates are more stable due to the chelate effect, which is both enthalpic (stronger
bonding) and entropic (fewer free particles → higher entropy).
• Example: [Cu(en)2 ]2+ is more stable than [Cu(NH3 )4 ]2+ .
Illustration:
[Cu(en)2 ]2+ → two 5-membered chelate rings
Final Answer: Chelating complexes are more stable due to the chelate effect (enhanced
entropy and bond strength).
9. Magnetic Properties of [NiCl4]2 – and Ni(CO)4
Concept Overview: Magnetic behavior depends on whether d-electrons are paired or
unpaired.
Explanation:
• [NiCl4 ]2 – : Cl – is weak field → no pairing → d8 configuration → two unpaired
electrons → paramagnetic (tetrahedral).
• Ni(CO)4 : CO is strong field → pairing occurs → d10 configuration → no unpaired
electrons → diamagnetic (tetrahedral).
Diagram:
[NiCl4 ]2− → sp3 (tetrahedral, paramagnetic)
Ni(CO)4 → dsp2 (tetrahedral, diamagnetic)
Note: Ni(CO)4 is actually tetrahedral with sp3 hybridization (not dsp2 ), but with all
electrons paired due to strong field CO ligands.
Final Answer: Both are tetrahedral, but [NiCl4 ]2 – is paramagnetic (weak field), while
Ni(CO)4 is diamagnetic (strong field).
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10. Geometrical Isomers of [CoCl2(en)2]+
Concept Overview: The complex has coordination number 6 (octahedral geometry).
Explanation: Two bidentate ligands (en) and two monodentate Cl – ligands can be
arranged:
• Cis-isomer: Cl ligands adjacent.
• Trans-isomer: Cl ligands opposite.
Structures:
Cis-[CoCl2 (en)2 ]+
Cl
N
N Co Cl
N
N
Trans-[CoCl2 (en)2 ]+
Cl
N
N Co N
N
Cl
Final Answer: [CoCl2 (en)2 ]+ exhibits cis and trans geometrical isomerism.