Chemistry (55) Board Question Paper Solutions
- The question paper is divided into four sections.
- Section A: Q. No. 1 contains Ten multiple choice type of questions carrying One mark each. Q. No. 2 contains Eight very short answer type of questions carrying One mark each.
- Section B: Q. No. 3 to Q. No. 14 are Twelve short answer type of questions carrying Two marks each. (Attempt any Eight)
- Section C: Q. No. 15 to Q. No. 26 are Twelve short answer type of questions carrying Three marks each. (Attempt any Eight)
- Section D: Q. No. 27 to Q. No. 31 are Five long answer type of questions carrying Four marks each. (Attempt any Three)
- Use of log table is allowed. Use of calculator is not allowed.
- Figures to the right indicate full marks.
- For each multiple choice type of question, it is mandatory to write the correct answer along with its alphabet e.g. (a)......../ (b)......../ (c)......../ (d)........etc. No mark (s) shall be given, if ONLY the correct answer or the alphabet of the correct answer is written.
- Only the first attempt will be considered for evaluation.
$$ \text{CH}_3-\text{CH}=\text{CH}-\text{CH}_2-\text{CHO} \xrightarrow{\text{H}_2/\text{Ni}} ? \text{ is,} $$
Reason: $H_2/Ni$ is a strong reducing agent. It reduces both the carbon-carbon double bond ($C=C$) and the aldehyde group ($-CHO$) to a primary alcohol. The 5-carbon chain remains intact.
$$ \text{CH}_3\text{CH}_2\text{CH}_2\text{CH}_2\text{CH}_2\text{OH} \text{ (Pentan-1-ol)} $$
Reason: While most salts (like KNO3, NaBr, KCl) show increased solubility with temperature (endothermic dissolution), sodium sulphate (Na2SO4) shows anomalous behavior. Its solubility increases up to 32.4°C and then decreases as the temperature rises further.
Reason: The cation is Sodium. The anion is a complex ion $[AlF_6]^{3-}$. Since the complex is anionic, the metal ends with suffix '-ate' (Aluminate). The oxidation state of Al is: $x + 6(-1) = -3 \Rightarrow x = +3$.
Reason: Higher pKa means weaker acid. Electron withdrawing groups (like Cl) increase acidity (lower pKa). Acetic acid has no electron withdrawing Chlorine atoms, making it the weakest acid among the options, hence it has the highest pKa.
Reason: Isoprene is 2-methyl-1,3-butadiene ($C_5H_8$). It contains 5 carbon atoms.
Reason: A transition metal ion is colourless if it has a completely filled ($d^{10}$) or completely empty ($d^0$) d-orbital.
$Cu^+$ ($Z=29$) config: $[Ar] 3d^{10}$. Since d-orbital is full, d-d transition is not possible.
[Image Description: Chlorocyclohexane + Mg (dry ether) → A (H2O) → B]
The product 'B' in the above reaction sequence is
Reason:
Step 1: Chlorocyclohexane reacts with Mg in dry ether to form Cyclohexylmagnesium chloride (Grignard reagent 'A').
Step 2: Grignard reagent ('A') reacts with H2O to undergo hydrolysis, replacing -MgCl with -H.
Product B is Cyclohexane.
Reason: Carbylamine test is given only by primary amines (aliphatic or aromatic). Aniline is a primary aromatic amine. Dimethylamine is secondary, and Trimethylamine is tertiary.
Calculation:
Degree of dissociation, $\alpha = 0.05\% = 0.0005 = 5 \times 10^{-4}$.
Concentration, $C = 0.02 = 2 \times 10^{-2}$ M.
$$ K_a = C\alpha^2 = (2 \times 10^{-2}) \times (5 \times 10^{-4})^2 $$
$$ K_a = (2 \times 10^{-2}) \times (25 \times 10^{-8}) $$
$$ K_a = 50 \times 10^{-10} = 5 \times 10^{-9} $$
$$ 2N_2O_{5(g)} \rightarrow 2N_2O_{4(g)} + O_{2(g)} \text{ is } 4.98 \times 10^{-4} s^{-1}. $$ The order of reaction is _______
Reason: The unit of the rate constant ($k$) is $s^{-1}$ (time-1). This is the characteristic unit for a First Order reaction.
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Heat released ($q$) = $-2 \text{ kJ}$ (negative because heat is lost).
Work done on the system ($w$) = $+6 \text{ kJ}$ (positive because work is done on system).
According to the first law of thermodynamics: $\Delta U = q + w$
$\Delta U = -2 \text{ kJ} + 6 \text{ kJ}$
$\Delta U = +4 \text{ kJ}$
Definition: The ligands which bind to the central metal atom or ion through two donor atoms are called bidentate ligands.
Example: Ethylenediamine (en) ($H_2N-CH_2-CH_2-NH_2$) or Oxalate ion ($C_2O_4^{2-}$).
Structure of Sulphurous Acid ($H_2SO_3$):
It contains one S=O double bond, two S-OH groups, and one lone pair on Sulfur.
Uses of Helium:
- It is used in filling observation balloons and weather balloons due to its lightness and non-inflammability.
- A mixture of He and O2 is used for respiration by deep-sea divers (to prevent 'bends').
Given:
Concentration $C = 0.01 \text{ M}$
$\Lambda_m = 18 \Omega^{-1} cm^2 mol^{-1}$
$\Lambda_0 = 400 \Omega^{-1} cm^2 mol^{-1}$
1. Degree of dissociation ($\alpha$):
$$ \alpha = \frac{\Lambda_m}{\Lambda_0} = \frac{18}{400} = 0.045 $$
2. Dissociation constant ($K_a$):
$$ K_a = \frac{C\alpha^2}{1-\alpha} $$
Since $\alpha$ is small ($0.045$), $1-\alpha \approx 1$.
$$ K_a \approx C\alpha^2 = 0.01 \times (0.045)^2 $$
$$ K_a = 0.01 \times 0.002025 $$
$$ K_a = 2.025 \times 10^{-5} $$
Proteins are classified into two types based on molecular shape:
- Fibrous Proteins: The polypeptide chains run parallel and are held together by hydrogen and disulphide bonds. They are fibre-like, insoluble in water.
Example: Keratin (hair, wool), Myosin (muscles). - Globular Proteins: The chains of polypeptides coil around to give a spherical shape. They are usually soluble in water.
Example: Insulin, Albumin.
Definition: A reaction which has higher order true rate law but experimentally follows first order kinetics because one of the reactants is present in large excess is called a pseudo-first order reaction.
Example: Hydrolysis of methyl acetate in acidic medium.
$$ CH_3COOCH_3 + H_2O \xrightarrow{H^+} CH_3COOH + CH_3OH $$
Here, water is present in excess, so its concentration remains practically constant. Rate depends only on [Methyl acetate].
Given:
Mass of solute ($W_2$) = 0.822 g
Volume ($V$) = 0.3 dm³ = 0.3 L
Osmotic Pressure ($\pi$) = 0.196 atm
Temperature ($T$) = 298 K
Gas Constant ($R$) = 0.0821 L atm K⁻¹ mol⁻¹
Formula: $M_2 = \frac{W_2 R T}{\pi V}$
Calculation:
$$ M_2 = \frac{0.822 \times 0.0821 \times 298}{0.196 \times 0.3} $$
$$ M_2 = \frac{20.108}{0.0588} $$
$$ M_2 \approx 342 \text{ g/mol} $$
(This corresponds to Sucrose).
Kolbe Reaction: It is the reaction used to prepare Salicylic acid from phenol.
When sodium phenoxide is treated with carbon dioxide ($CO_2$) at 398 K under a pressure of 6 atm followed by acid hydrolysis, salicylic acid (2-hydroxybenzoic acid) is formed.
Sodium Phenoxide + CO2 → Sodium Salicylate →(H+) Salicylic Acid
Iron (Fe), Z = 26. Configuration: $[Ar] 3d^6 4s^2$.
Electronic Configurations:
$Fe^{2+}$: $[Ar] 3d^6$
$Fe^{3+}$: $[Ar] 3d^5$
Stability:
$Fe^{3+}$ is more stable than $Fe^{2+}$.
Reason: $Fe^{3+}$ has a half-filled d-orbital ($3d^5$), which confers extra stability according to Hund's rule compared to the partially filled $3d^6$ of $Fe^{2+}$.
Benzophenone is prepared by treating Benzonitrile with Phenylmagnesium bromide (Grignard reagent) followed by acid hydrolysis.
$C_6H_5-CN + C_6H_5MgBr \xrightarrow{\text{dry ether}} C_6H_5-C(NMgBr)-C_6H_5$ (Complex)
Complex $+ H_3O^+ \rightarrow C_6H_5-CO-C_6H_5$ (Benzophenone) $+ NH_3 + Mg(OH)Br$
The monomers are:
- Adipic Acid (Hexanedioic acid):
$HOOC-(CH_2)_4-COOH$ - Hexamethylenediamine (Hexane-1,6-diamine):
$H_2N-(CH_2)_6-NH_2$
The ionic product of water ($K_w$) is given by:
$$ K_w = [H^+][OH^-] $$
Taking negative logarithm to the base 10 on both sides:
$$ -\log_{10} K_w = -\log_{10} ([H^+][OH^-]) $$
$$ -\log_{10} K_w = (-\log_{10} [H^+]) + (-\log_{10} [OH^-]) $$
By definition, $-\log_{10} K_w = pK_w$, $-\log_{10} [H^+] = pH$, and $-\log_{10} [OH^-] = pOH$.
$$ pK_w = pH + pOH $$
At 298 K, $K_w = 1 \times 10^{-14}$, so $pK_w = 14$.
Therefore, $pH + pOH = 14$.
- (i) Methyl chloride in presence of anhydrous AlCl3
- (ii) Fuming H2SO4
(i) Friedel-Crafts Alkylation:
Chlorobenzene reacts with methyl chloride in the presence of anhydrous $AlCl_3$ to give a mixture of 2-chlorotoluene (minor) and 4-chlorotoluene (major).
(ii) Sulphonation:
Chlorobenzene reacts with fuming sulphuric acid to give 2-chlorobenzenesulphonic acid (minor) and 4-chlorobenzenesulphonic acid (major).
\(\Delta H^\circ(H-H) = 435 \text{ kJ mol}^{-1}\)
\(\Delta H^\circ(N-N) = 159 \text{ kJ mol}^{-1}\)
Reaction structure:
$H_2N-NH_2 (g) + H-H (g) \rightarrow 2(NH_3)$
Bonds Broken (Reactants):
1 N-N bond
4 N-H bonds (in hydrazine)
1 H-H bond
Bonds Formed (Products):
2 moles of $NH_3$ (each has 3 N-H bonds) = 6 N-H bonds.
$\Delta_r H^\circ = \Sigma \text{Bond Enthalpy (Reactants)} - \Sigma \text{Bond Enthalpy (Products)}$
$= [1(N-N) + 4(N-H) + 1(H-H)] - [6(N-H)]$
Simplifying (canceling 4 N-H):
$= [1(N-N) + 1(H-H)] - [2(N-H)]$
Substituting values:
$= [159 + 435] - [2 \times 389]$
$= 594 - 778$
$= \mathbf{-184 \text{ kJ}}$
- (i) acetonitrile
- (ii) nitroethane
- (iii) propionamide
(i) From Acetonitrile ($CH_3CN$): Mendius Reduction
$CH_3-C\equiv N + 4[H] \xrightarrow{Na/C_2H_5OH} CH_3-CH_2-NH_2$ (Ethanamine)
(ii) From Nitroethane ($C_2H_5NO_2$):
$C_2H_5-NO_2 + 6[H] \xrightarrow{Sn/conc. HCl} C_2H_5-NH_2 + 2H_2O$
(iii) From Propionamide ($C_2H_5CONH_2$): Hoffmann Bromamide Degradation
$C_2H_5-CO-NH_2 + Br_2 + 4KOH \rightarrow C_2H_5-NH_2 + K_2CO_3 + 2KBr + 2H_2O$
(This reaction reduces the carbon chain by one carbon).
- Prevention of Waste or By-products: It is better to prevent waste than to treat or clean up waste after it is formed.
- Atom Economy: Synthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product.
- Less Hazardous Chemical Synthesis: Wherever practicable, synthetic methods should be designed to use and generate substances that possess little or no toxicity to human health and the environment.
Manufacture of $H_2SO_4$ (Contact Process):
- Burning of Sulphur to form $SO_2$:
$S + O_2 \rightarrow SO_2$ - Catalytic oxidation of $SO_2$ to $SO_3$ ($V_2O_5$ catalyst):
$2SO_2 + O_2 \rightleftharpoons 2SO_3$ - Absorption of $SO_3$ in conc. $H_2SO_4$ to form Oleum:
$SO_3 + H_2SO_4 \rightarrow H_2S_2O_7$ (Oleum) - Dilution of Oleum with water:
$H_2S_2O_7 + H_2O \rightarrow 2H_2SO_4$
Uses of $SO_2$:
- It is used in refining petroleum and sugar.
- It is used as a bleaching agent for wool and silk.
Reaction: $CH_3Br + OH^- \rightarrow CH_3OH + Br^-$
Mechanism (SN² - Substitution Nucleophilic Bimolecular):
- It is a single-step concerted mechanism.
- Backside Attack: The nucleophile ($OH^-$) attacks the carbon atom from the side opposite to the leaving group ($Br$).
- Transition State: A transition state is formed where the C-OH bond is partially formed and the C-Br bond is partially broken. Carbon is pentacoordinate here.
- Inversion of Configuration: As the leaving group departs, the configuration of the carbon atom inverts (Walden Inversion), like an umbrella turning inside out.
Basicity of Lanthanoids:
Due to Lanthanoid Contraction, the atomic/ionic size decreases from $La^{3+}$ to $Lu^{3+}$. As the size decreases, the covalent character of the M-OH bond increases (and ionic character decreases). Since $La^{3+}$ is the largest, the La-O bond is most ionic and breaks easily to release $OH^-$ ions, making $La(OH)_3$ the strongest base. $Lu(OH)_3$ has the most covalent character, making it the weakest base.
Catalytic Applications:
- Finely divided Iron (Fe) is used in the Haber process for Ammonia synthesis.
- Nickel (Ni) is used in the hydrogenation of oils to fats.
- (i) chlorobenzene to phenol
- (ii) ethanal to ethanol
- (iii) iodomethane to methoxy methane
(i) Dow Process:
Chlorobenzene heated with NaOH at 623K and 300 atm followed by acid hydrolysis yields Phenol.
$C_6H_5Cl + NaOH \rightarrow C_6H_5ONa \xrightarrow{H^+} C_6H_5OH$
(ii) Reduction:
Ethanal is reduced using $H_2/Ni$ or $LiAlH_4$.
$CH_3CHO + H_2 \xrightarrow{Ni} CH_3CH_2OH$
(iii) Williamson Synthesis:
Iodomethane reacts with sodium methoxide.
$CH_3I + NaOCH_3 \rightarrow CH_3-O-CH_3 + NaI$
Cryoscopic Constant ($K_f$): It is defined as the depression in freezing point produced when 1 mole of a non-volatile solute is dissolved in 1 kg of solvent.
Relation (Elevation of Boiling Point $\Delta T_b$ and Molar Mass $M_2$):
1. $\Delta T_b \propto m$ (molality).
2. $\Delta T_b = K_b \times m$.
3. Molality $m = \frac{\text{moles of solute}}{\text{mass of solvent in kg}} = \frac{W_2/M_2}{W_1/1000} = \frac{W_2 \times 1000}{M_2 \times W_1}$.
4. Substituting $m$:
$$ \Delta T_b = K_b \times \frac{W_2 \times 1000}{M_2 \times W_1} $$
5. Rearranging for $M_2$:
$$ M_2 = \frac{1000 \times K_b \times W_2}{\Delta T_b \times W_1} $$
Solubility Product ($K_{sp}$): It is the product of the concentrations of the ions of a sparingly soluble salt in its saturated solution at a given temperature, raised to the power equal to the number of ions produced per formula unit.
Derivation for $PbI_2$:
Equilibrium: $PbI_2(s) \rightleftharpoons Pb^{2+}(aq) + 2I^-(aq)$
Let $s$ be the solubility in mol/L.
$[Pb^{2+}] = s$
$[I^-] = 2s$
$K_{sp} = [Pb^{2+}][I^-]^2$
$K_{sp} = (s)(2s)^2$
$K_{sp} = s \times 4s^2$
$K_{sp} = 4s^3$
- (i) octahedral voids
- (ii) tetrahedral voids
- (iii) total voids formed in 0.4 mol of it?
Let $N$ be the number of atoms in the packing.
Number of atoms in 0.4 mol = $0.4 \times 6.022 \times 10^{23} = 2.4088 \times 10^{23}$.
(i) Number of Octahedral voids = $N$ = $2.4088 \times 10^{23}$.
(ii) Number of Tetrahedral voids = $2N$ = $2 \times 2.4088 \times 10^{23} = 4.8176 \times 10^{23}$.
(iii) Total voids = $N + 2N = 3N$.
Total = $3 \times 2.4088 \times 10^{23} = \mathbf{7.2264 \times 10^{23}}$
Double Salt: A molecular compound that dissociates completely into simple ions when dissolved in water.
Example: Mohr's Salt $[FeSO_4 \cdot (NH_4)_2SO_4 \cdot 6H_2O]$ gives $Fe^{2+}$, $NH_4^+$, and $SO_4^{2-}$ ions.
Coordinate Compound: A compound containing a complex ion that retains its identity in solution and does not dissociate into simple ions.
Example: $K_4[Fe(CN)_6]$ gives $4K^+$ and $[Fe(CN)_6]^{4-}$. It does not give test for $Fe^{2+}$ or $CN^-$.
Applications:
1. Cisplatin $[Pt(NH_3)_2Cl_2]$ is used in cancer treatment.
2. EDTA is used in the treatment of lead poisoning.
Aldol Condensation of Ethanal:
When ethanal (containing $\alpha$-hydrogen) is treated with dilute alkali (NaOH), two molecules condense to form 3-hydroxybutanal (Aldol), which upon heating loses water to form But-2-enal (Crotonaldehyde).
$2CH_3CHO \xrightarrow{\text{dil. NaOH}} CH_3-CH(OH)-CH_2-CHO \xrightarrow{\Delta, -H_2O} CH_3-CH=CH-CHO$
Reaction of Benzaldehyde with Conc. KOH (Cannizzaro Reaction):
Benzaldehyde has no $\alpha$-hydrogen. It undergoes self-oxidation and reduction.
$2C_6H_5CHO + \text{conc. } KOH \rightarrow C_6H_5COOK \text{ (Pot. Benzoate)} + C_6H_5CH_2OH \text{ (Benzyl Alcohol)}$
Isomorphism: Two or more substances having the same crystal structure are said to be isomorphous (e.g., NaF and MgO).
Integrated Rate Law (1st Order):
Consider $A \rightarrow \text{Products}$.
Rate $= -\frac{d[A]}{dt} = k[A]$.
$\frac{d[A]}{[A]} = -k dt$.
Integrating both sides from $t=0$ ($[A]_0$) to $t=t$ ($[A]_t$):
$$ \int_{[A]_0}^{[A]_t} \frac{d[A]}{[A]} = -k \int_0^t dt $$
$$ \ln[A]_t - \ln[A]_0 = -kt $$
$$ \ln \frac{[A]_0}{[A]_t} = kt $$
Converting $\ln$ to $\log_{10}$:
$$ k = \frac{2.303}{t} \log_{10} \frac{[A]_0}{[A]_t} $$
Or if $a$ is initial conc and $x$ is amount reacted: $k = \frac{2.303}{t} \log_{10} \frac{a}{a-x}$.
- (i) CaF₂
- (ii) Cane sugar
Action of Conc. H₂SO₄:
(i) CaF₂: Forms Hydrogen Fluoride.
$CaF_2 + H_2SO_4 \rightarrow CaSO_4 + 2HF$
(ii) Cane Sugar: Dehydrating action causes charring (formation of carbon).
$C_{12}H_{22}O_{11} \xrightarrow{H_2SO_4} 12C + 11H_2O$
Nucleotide: It is the repeating unit of nucleic acids (DNA/RNA), consisting of three components: a pentose sugar, a nitrogenous base, and a phosphate group.
Preparation of PAN: Addition polymerization of Acrylonitrile.
$n(CH_2=CH-CN) \xrightarrow{\text{Polymerization/Peroxide}} -[CH_2-CH(CN)]_n-$ (PAN)
Kohlrausch Law: At infinite dilution, each ion migrates independently of its co-ion and contributes to the total molar conductivity of an electrolyte a definite share, which depends only on its own nature.
$\Lambda_0 = \nu_+ \lambda_+^0 + \nu_- \lambda_-^0$.
Applications of Electrochemical Series:
1. To predict feasibility of reaction: A metal with lower electrode potential can displace a metal with higher electrode potential from its salt solution.
2. To calculate EMF: $E^\circ_{cell} = E^\circ_{cathode} - E^\circ_{anode}$.
Unit of Cell Constant ($b$):
$b = l/A$. Unit is $m^{-1}$ or $cm^{-1}$.
- (i) Intensive property
- (ii) Enthalpy of sublimation
(i) Intensive Property: A property whose value is independent of the amount of substance present in the system (e.g., Temperature, Pressure).
(ii) Enthalpy of Sublimation: The enthalpy change that accompanies the conversion of one mole of a solid directly into its vapor at constant temperature and pressure.
Work Calculation:
Formula: $W_{max} = -2.303 nRT \log_{10} \frac{V_2}{V_1}$
Given: $n=2$, $T=300K$, $R=8.314$, $V_1=20$, $V_2=30$.
$W = -2.303 \times 2 \times 8.314 \times 300 \times \log_{10} \frac{30}{20}$
$W = -11488.28 \times \log_{10} (1.5)$
$W = -11488.28 \times 0.1761$
$W = -2023 \text{ J}$ or $-2.023 \text{ kJ}$.
(Negative sign indicates work done by the system).
- (i) methyl iodide to methyl isocyanide.
- (ii) methyl cyanide to ethanoic acid.
Mineral: A naturally occurring substance found in the earth's crust containing a metal in free or combined state.
IUPAC Name of $[Fe(CO)_5]$: Pentacarbonyliron(0).
Conversions:
(i) Methyl iodide to Methyl isocyanide: React with Silver Cyanide ($AgCN$).
$CH_3I + AgCN \rightarrow CH_3NC + AgI$
(ii) Methyl cyanide to Ethanoic acid: Acid hydrolysis.
$CH_3CN + 2H_2O + HCl \rightarrow CH_3COOH + NH_4Cl$
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