Maharashtra Board HSC Chemistry
July 2022 Question Paper - Full Detailed Solutions
(i) Cyclohexyl chloride + Mg \(\xrightarrow{\text{Dry ether}}\) A \(\xrightarrow{\text{H}_2\text{O}}\) B. The product 'B' is _______.
Step 1: Reaction of Cyclohexyl chloride with Mg in dry ether forms Cyclohexyl magnesium chloride (Grignard reagent 'A').
Step 2: Hydrolysis of Grignard reagent (A) yields the corresponding alkane.
Reaction: \(\text{C}_6\text{H}_{11}\text{Cl} + \text{Mg} \xrightarrow{\text{ether}} \text{C}_6\text{H}_{11}\text{MgCl} \xrightarrow{\text{H}_2\text{O}} \text{C}_6\text{H}_{12} (\text{Cyclohexane}) + \text{Mg(OH)Cl}\).
(ii) General electronic configuration of 3d series of ‘d’ block elements is _______.
(iii) Correct IUPAC name of tert-butyl alcohol is _______.
Structure: \(\text{(CH}_3)_3\text{C-OH}\). The longest chain is propane (3 carbons), with a methyl group and OH group at carbon 2.
(iv) The standard emf of the following cell at 298K is _______.
\(\text{Zn(s)}|\text{Zn}^{+2}(1\text{M})||\text{Cr}^{+3}(0.1\text{M})|\text{Cr(s)}\)
\(\text{E}^\circ_{\text{Zn}} = -0.76\text{V}, \text{E}^\circ_{\text{Cr}} = -0.74\text{V}\)
Calculation: \(E^\circ_{\text{cell}} = E^\circ_{\text{cathode}} - E^\circ_{\text{anode}}\)
\(E^\circ_{\text{cell}} = E^\circ_{\text{Cr}} - E^\circ_{\text{Zn}} = (-0.74\text{V}) - (-0.76\text{V}) = +0.02\text{V}\).
(v) In the following oxyacid, chlorine has +7 oxidation state:
Calculation: \(1(+1) + x + 4(-2) = 0 \Rightarrow 1 + x - 8 = 0 \Rightarrow x = +7\).
(vi) The work done during isothermal irreversible expansion of 2 moles of helium from 2dm³ to 4 dm³ at 1 bar pressure and at 298K is _______.
Calculation: Work \(W = -P_{\text{ext}} \Delta V\)
\(W = -1 \text{ bar} \times (4 - 2) \text{ dm}^3 = -2 \text{ bar dm}^3\)
\(1 \text{ bar dm}^3 = 100 \text{ J}\)
\(W = -200 \text{ J} = -0.2 \text{ kJ}\).
(vii) The correct relation between edge length and radius of an atom in simple cubic lattice is _______.
(viii) Lactose on hydrolysis gives _______.
(ix) ZWT in green chemistry stands for:
(x) The most basic amine amongst the following is _______.
Reason: In aqueous solution, secondary amines are more basic than tertiary and primary due to a combination of inductive effect, solvation effect, and steric hindrance. For methyl substituted amines: \(2^\circ > 1^\circ > 3^\circ > \text{NH}_3\).
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(i) Write relation between molar conductivity and conductivity of solution.
Where:
\(\Lambda_m\) is molar conductivity (S cm² mol⁻¹)
\(k\) is conductivity (S cm⁻¹)
\(C\) is concentration in mol L⁻¹ (Molarity)
(ii) Calculate effective atomic number of Co⁺³ in [Co(NH₃)₆]³⁺ complex.
\(Z\) (Atomic no. of Co) = 27
\(X\) (Oxidation state) = +3 (So, electrons lost = 3)
\(Y\) (Electrons donated by ligands) = \(6 \times 2 = 12\)
\(\text{EAN} = 27 - 3 + 12 = 36\).
(iii) Write the name of reaction during conversion of phenol to salicylic acid.
(iv) Write the IUPAC name of α-methylpropionic acid.
IUPAC Name: 2-Methylpropanoic acid.
(v) Write the formula of Hinsberg’s reagent.
(vi) Write the name of monomer used for preparation of Nylon 6.
(vii) Write cell representation of standard hydrogen electrode.
(viii) Write chemical composition of Zieglar-Natta catalyst.
(ii) Ebullioscopic constant (\(K_b\)): It is defined as the elevation in boiling point produced when 1 mole of non-volatile solute is dissolved in 1 kg (1000 g) of the solvent.
Formula: \(\text{pH} = -\log_{10}[\text{H}_3\text{O}^+]\)
\(\therefore [\text{H}_3\text{O}^+] = \text{antilog}(-\text{pH})\)
\([\text{H}_3\text{O}^+] = \text{antilog}(-3.12)\)
\([\text{H}_3\text{O}^+] = \text{antilog}(\bar{4}.88)\)
From antilog table for 0.88: Value is 7586.
Answer: \([\text{H}_3\text{O}^+] = 7.586 \times 10^{-4} \text{ M}\).
\(\Lambda_0 = \lambda_+^0 + \lambda_-^0\)
Application: It is used to calculate the molar conductivity of weak electrolytes at infinite dilution, which cannot be determined experimentally by extrapolation.
| Schottky Defect | Frenkel Defect |
|---|---|
| It is produced due to the absence of an equal number of cations and anions from lattice sites. | It is produced when an ion (usually cation) leaves its lattice site and occupies an interstitial site. |
| Density of the crystal decreases. | Density of the crystal remains constant. |
| Usually shown by ionic compounds with high coordination numbers (e.g., NaCl, KCl). | Usually shown by ionic compounds with low coordination numbers (e.g., AgCl, ZnS). |
1. Enthalpy is defined as \(H = U + PV\).
2. For a change in state at constant pressure:
\(\Delta H = \Delta U + P\Delta V\) ...(1)
3. For an ideal gas reaction, \(PV = nRT\).
Let \(n_1\) be moles of gaseous reactants and \(n_2\) be moles of gaseous products.
\(PV_1 = n_1RT\) and \(PV_2 = n_2RT\).
\(P\Delta V = P(V_2 - V_1) = PV_2 - PV_1\)
\(P\Delta V = n_2RT - n_1RT = (n_2 - n_1)RT = \Delta n_g RT\).
4. Substituting this value in equation (1):
\(\Delta H = \Delta U + \Delta n_g RT\)
When chlorine reacts with excess ammonia, ammonium chloride and nitrogen gas are formed.
\(8\text{NH}_3 \text{ (excess)} + 3\text{Cl}_2 \rightarrow 6\text{NH}_4\text{Cl} + \text{N}_2\)
(ii) Action on Phosphorous:
Chlorine reacts with phosphorus to form phosphorus trichloride (limited Cl₂) or phosphorus pentachloride (excess Cl₂).
\(\text{P}_4 + 6\text{Cl}_2 \rightarrow 4\text{PCl}_3\)
(or \(\text{P}_4 + 10\text{Cl}_2 \rightarrow 4\text{PCl}_5\)).
(ii) Calamine: \(\text{ZnCO}_3\)
Case 1: 99.9% completion
\([A]_0 = 100\), \([A]_t = 100 - 99.9 = 0.1\)
\(t_{99.9\%} = \frac{2.303}{k} \log \frac{100}{0.1} = \frac{2.303}{k} \log(1000)\)
\(t_{99.9\%} = \frac{2.303}{k} \times 3\) ...(1)
Case 2: 90% completion
\([A]_0 = 100\), \([A]_t = 100 - 90 = 10\)
\(t_{90\%} = \frac{2.303}{k} \log \frac{100}{10} = \frac{2.303}{k} \log(10)\)
\(t_{90\%} = \frac{2.303}{k} \times 1\) ...(2)
Taking ratio of (1) and (2):
\(\frac{t_{99.9\%}}{t_{90\%}} = \frac{3 \times (2.303/k)}{1 \times (2.303/k)} = 3\)
\(\therefore t_{99.9\%} = 3 \times t_{90\%}\). (Hence Proved)
\(\text{C}_2\text{H}_5\text{Br} + \text{NaI} \xrightarrow{\text{dry acetone}} \text{C}_2\text{H}_5\text{I} + \text{NaBr}\)
(ii) Ethyl fluoride (Swarts Reaction):
\(\text{C}_2\text{H}_5\text{Br} + \text{AgF} \rightarrow \text{C}_2\text{H}_5\text{F} + \text{AgBr}\)
(Note: Other metal fluorides like \(\text{Hg}_2\text{F}_2, \text{CoF}_2\) can also be used).
Example:
The nitrite ion (\(\text{NO}_2^-\)) can bind to the central metal via nitrogen or oxygen.
1. \([Co(NH_3)_5(NO_2)]^{2+}\) - Nitro complex (yellow), linked through N.
2. \([Co(NH_3)_5(ONO)]^{2+}\) - Nitrito complex (red), linked through O.
It forms acyl chloride (acid chloride).
\(\text{R-COOH} + \text{SOCl}_2 \rightarrow \text{R-COCl} + \text{SO}_2 \uparrow + \text{HCl} \uparrow\)
(ii) Action of Phosphorus Pentoxide (P₂O₅):
It acts as a dehydrating agent to form acid anhydride.
\(2\text{R-COOH} \xrightarrow{\text{P}_2\text{O}_5, \Delta} (\text{RCO})_2\text{O} + \text{H}_2\text{O}\)
(i) Action of Bromine water:
Phenol reacts with bromine water to give a white precipitate of 2,4,6-Tribromophenol.
\(\text{Phenol} + 3\text{Br}_2(\text{aq}) \rightarrow 2,4,6\text{-Tribromophenol} + 3\text{HBr}\)
(ii) Action of Conc. Nitric Acid:
Phenol reacts with concentrated nitric acid in the presence of conc. sulfuric acid to form 2,4,6-Trinitrophenol (Picric acid).
\(\text{Phenol} + 3\text{HNO}_3 (\text{conc}) \xrightarrow{\text{conc. H}_2\text{SO}_4} 2,4,6\text{-Trinitrophenol} + 3\text{H}_2\text{O}\)
Aldehydes or ketones containing at least one \(\alpha\)-hydrogen atom undergo a reaction in the presence of a dilute alkali (like NaOH, KOH, or \(\text{Na}_2\text{CO}_3\)) as catalyst to form \(\beta\)-hydroxy aldehydes (aldol) or \(\beta\)-hydroxy ketones (ketol). This reaction is called Aldol condensation.
General Reaction (for Acetaldehyde):
\(2\text{CH}_3\text{CHO} \xrightarrow{\text{dil. NaOH}} \text{CH}_3\text{-CH(OH)-CH}_2\text{-CHO}\) (3-Hydroxybutanal / Aldol)
Upon heating, the aldol loses water to form an \(\alpha,\beta\)-unsaturated aldehyde:
\(\text{CH}_3\text{-CH(OH)-CH}_2\text{-CHO} \xrightarrow{\Delta} \text{CH}_3\text{-CH=CH-CHO} + \text{H}_2\text{O}\) (But-2-enal)
The steady decrease in the atomic and ionic radii of lanthanoid elements with increasing atomic number is called lanthanoid contraction. This is due to the poor shielding effect of 4f electrons.
Similarities between Lanthanoids and Actinoids:
1. Both series involve the filling of f-orbitals (4f for lanthanoids, 5f for actinoids).
2. Both show a common oxidation state of +3.
3. Both are electropositive metals and act as strong reducing agents.
4. Both show contraction in atomic and ionic sizes (Lanthanoid contraction and Actinoid contraction).
Reaction: \(\text{C(s)} + 2\text{H}_2(\text{g}) + \frac{1}{2}\text{O}_2(\text{g}) \rightarrow \text{CH}_3\text{OH(l)}\)
Given Data:
1. \(\text{CH}_3\text{OH} + \frac{3}{2}\text{O}_2 \rightarrow \text{CO}_2 + 2\text{H}_2\text{O} \quad \Delta H_1 = -726 \text{ kJ}\)
2. \(\text{C} + \text{O}_2 \rightarrow \text{CO}_2 \quad \Delta H_2 = -393 \text{ kJ}\)
3. \(\text{H}_2 + \frac{1}{2}\text{O}_2 \rightarrow \text{H}_2\text{O} \quad \Delta H_3 = -286 \text{ kJ}\)
Calculation:
To get the target equation:
Keep eq(2) as is: \(\text{C} + \text{O}_2 \rightarrow \text{CO}_2 \quad (-393)\)
Multiply eq(3) by 2: \(2\text{H}_2 + \text{O}_2 \rightarrow 2\text{H}_2\text{O} \quad (2 \times -286 = -572)\)
Reverse eq(1): \(\text{CO}_2 + 2\text{H}_2\text{O} \rightarrow \text{CH}_3\text{OH} + \frac{3}{2}\text{O}_2 \quad (+726)\)
Summing these:
\(\Delta H = -393 - 572 + 726\)
\(\Delta H = -965 + 726 = -239 \text{ kJ mol}^{-1}\).
\(\text{CH}_2=\text{CH}_2 + \text{I-Cl} \rightarrow \text{CH}_2(\text{I})-\text{CH}_2(\text{Cl})\)
Product: 1-Chloro-2-iodoethane.
(ii) SO₂ oxidised with V₂O₅:
\(2\text{SO}_2 + \text{O}_2 \xrightarrow{\text{V}_2\text{O}_5} 2\text{SO}_3\)
Product: Sulphur trioxide. (This is a key step in Contact Process).
(iii) Cu + Conc. H₂SO₄:
\(\text{Cu} + 2\text{H}_2\text{SO}_4 (\text{conc}) \rightarrow \text{CuSO}_4 + \text{SO}_2 \uparrow + 2\text{H}_2\text{O}\)
Product: Copper sulfate, sulfur dioxide, and water.
Given: Mass \(x = 0.5 \text{ g}\), \(\rho = 8.55 \text{ g cm}^{-3}\), \(a = 330.6 \text{ pm} = 3.306 \times 10^{-8} \text{ cm}\).
1. Calculate Volume of sample:
\(V_{\text{total}} = \text{Mass} / \text{Density} = 0.5 / 8.55 = 0.05848 \text{ cm}^3\).
2. Calculate Volume of one unit cell:
\(V_{\text{cell}} = a^3 = (3.306 \times 10^{-8})^3 = 36.13 \times 10^{-24} \text{ cm}^3\).
3. Number of unit cells:
\(N_{\text{cells}} = V_{\text{total}} / V_{\text{cell}} = \frac{0.05848}{36.13 \times 10^{-24}} = 1.62 \times 10^{21}\) unit cells.
4. Number of atoms:
For BCC, \(Z = 2\) atoms/cell.
\(\text{Total atoms} = 2 \times 1.62 \times 10^{21} = 3.24 \times 10^{21}\) atoms.
Part B: Preparation of glucose from sucrose
Sucrose is hydrolyzed by boiling with dilute HCl or H₂SO₄ in alcoholic solution to give glucose and fructose.
\(\text{C}_{12}\text{H}_{22}\text{O}_{11} + \text{H}_2\text{O} \xrightarrow{\text{H}^+} \text{C}_6\text{H}_{12}\text{O}_6 (\text{Glucose}) + \text{C}_6\text{H}_{12}\text{O}_6 (\text{Fructose})\).
Action of Hot Cu (573 K):
1. 1° Alcohol: Undergoes dehydrogenation to form Aldehydes.
\(\text{R-CH}_2\text{OH} \xrightarrow{\text{Cu, 573K}} \text{R-CHO} + \text{H}_2\)
2. 2° Alcohol: Undergoes dehydrogenation to form Ketones.
\(\text{R}_2\text{CH-OH} \xrightarrow{\text{Cu, 573K}} \text{R}_2\text{C=O} + \text{H}_2\)
Assumed Freezing point of pure water (\(T_f^0\)) = 273.15 K (or approx 273 K).
Given: \(T_f\) (sugar) = 271 K.
\(\Delta T_f\) (sugar) = \(273.15 - 271 = 2.15 \text{ K}\) (Using 273.15 is standard).
Formula: \(\Delta T_f = K_f \times \frac{W_2 \times 1000}{M_2 \times W_1}\)
For both solutions, \(W_2\) (5g), \(W_1\) (95g), and \(K_f\) are same.
\(\Delta T_f \propto \frac{1}{M_2}\)
\(\frac{\Delta T_f(\text{glucose})}{\Delta T_f(\text{sugar})} = \frac{M(\text{sugar})}{M(\text{glucose})}\)
\(\frac{\Delta T_f(\text{glucose})}{2.15} = \frac{342}{180}\)
\(\Delta T_f(\text{glucose}) = 2.15 \times 1.9 = 4.085 \text{ K}\)
Freezing Point of Glucose = \(273.15 - 4.085 = 269.065 \text{ K}\).
Part B: Complete Reaction
\(\text{R}'\text{-NO}_2 + 6[\text{H}] \xrightarrow{\text{Sn/Conc. HCl}} \text{R}'\text{-NH}_2 + 2\text{H}_2\text{O}\)
Product is Primary Amine (\(\text{R}'\text{-NH}_2\)).
Derivation for Weak Acid (HA):
Consider a weak acid HA dissociated in water:
\(\text{HA} \rightleftharpoons \text{H}^+ + \text{A}^-\)
Let \(C\) be the initial concentration and \(\alpha\) be degree of dissociation.
At eq: \([\text{HA}] = C(1-\alpha)\), \([\text{H}^+] = C\alpha\), \([\text{A}^-] = C\alpha\).
Dissociation constant \(K_a = \frac{[\text{H}^+][\text{A}^-]}{[\text{HA}]}\)
\(K_a = \frac{(C\alpha)(C\alpha)}{C(1-\alpha)} = \frac{C\alpha^2}{1-\alpha}\)
For weak acids, \(\alpha \ll 1\), so \(1-\alpha \approx 1\).
\(K_a = C\alpha^2\) or \(\alpha = \sqrt{K_a/C}\).
Applications of Electrochemical Series:
1. To compare the relative strength of oxidizing and reducing agents.
2. To predict the spontaneity of a redox reaction (feasible if \(E^\circ_{\text{cell}}\) is positive).
\(2\text{NO}_2(\text{g}) + \text{F}_2(\text{g}) \rightarrow 2\text{NO}_2\text{F}(\text{g})\)
(b) Rate Law: Rate depends on the slow step.
\(\text{Rate} = k[\text{NO}_2][\text{F}_2]\)
(c) Reaction Intermediate: \(\text{F}(\text{g})\) (produced in step 1, consumed in step 2).
Preparation of Teflon:
Polymerization of tetrafluoroethylene under high pressure with peroxide catalyst.
\(n \text{CF}_2=\text{CF}_2 \xrightarrow{\text{Polymerisation}} -(\text{CF}_2-\text{CF}_2)_n- \text{ (Teflon/PTFE)}\)
Werner Theory Postulates:
1. Metals possess two types of valencies: Primary valency (ionizable, corresponds to oxidation state) and Secondary valency (non-ionizable, corresponds to coordination number).
2. Secondary valencies are directional in space (giving geometry), whereas primary valencies are non-directional.
1. It is a unimolecular reaction (First order kinetics), Rate \(\propto [\text{Substrate}]\).
2. It takes place in two steps. Step 1 is formation of carbocation (slow/RDS).
3. It proceeds via a planar carbocation intermediate.
4. It results in racemization (mixture of retention and inversion products).
Carbylamine Test Reaction:
Aliphatic or aromatic primary amines heat with chloroform and alcoholic KOH to form foul-smelling isocyanides.
\(\text{R-NH}_2 + \text{CHCl}_3 + 3\text{KOH(alc)} \xrightarrow{\Delta} \text{R-NC} \text{ (Isocyanide)} + 3\text{KCl} + 3\text{H}_2\text{O}\).
Given:
\(T_b^\circ = 77.06^\circ \text{C}\)
\(T_b = 84.27^\circ \text{C}\)
\(\Delta T_b = 84.27 - 77.06 = 7.21 \text{ K}\) (or \(^\circ \text{C}\), difference is same)
\(W_2 = 50 \text{ g}, W_1 = 150 \text{ g}, K_b = 2.77 \text{ K kg mol}^{-1}\)
Formula: \(M_2 = \frac{1000 \times K_b \times W_2}{\Delta T_b \times W_1}\)
\(M_2 = \frac{1000 \times 2.77 \times 50}{7.21 \times 150}\)
\(M_2 = \frac{138500}{1081.5} \approx 128.06 \text{ g mol}^{-1}\).
Pseudo First Order Reaction:
A chemical reaction which is not first order (usually higher order, like bimolecular) but behaves as a first order reaction because one of the reactants is present in large excess.
Example: Acid hydrolysis of ethyl acetate.
\(\text{CH}_3\text{COOC}_2\text{H}_5 + \text{H}_2\text{O (excess)} \xrightarrow{\text{H}^+} \text{CH}_3\text{COOH} + \text{C}_2\text{H}_5\text{OH}\).
Rate = \(k'[\text{Ester}][\text{H}_2\text{O}]\), since \([\text{H}_2\text{O}]\) is constant, Rate = \(k[\text{Ester}]\).
Copper sulfate is a salt of a strong acid (H₂SO₄) and a weak base (Cu(OH)₂). In aqueous solution, it undergoes hydrolysis to form an acidic solution due to the presence of free \(\text{H}^+\) ions.
\(\text{Cu}^{2+} + 2\text{H}_2\text{O} \rightleftharpoons \text{Cu(OH)}_2 + 2\text{H}^+\)
Colour of Transition Metal Ions:
1. Transition metal ions often have incomplete d-orbitals (\(d^{1-9}\)).
2. When ligands approach, the d-orbitals split into two energy levels (crystal field splitting).
3. Electrons absorb energy from the visible region of light to jump from lower d-orbitals to higher d-orbitals (d-d transition).
4. The transmitted light (complementary color) is observed as the color of the compound.
The enthalpy change for a chemical reaction is the same regardless of the path by which the reaction occurs (i.e., whether it takes place in one step or multiple steps). \(\Delta H = \Delta H_1 + \Delta H_2 + ...\)
Interhalogen Compounds:
Compounds formed by the reaction of two or more different halogens are called interhalogen compounds. General formula \(XY_n\) where X is a larger halogen and Y is a smaller halogen. (e.g., \(\text{ICl}, \text{BrF}_3\)).
Uses of Neon:
1. Used in neon discharge lamps and advertising signs (glows orange-red).
2. Used in beacon lights for safety of air navigation as the light penetrates fog.
Heteroleptic Complexes: Complexes in which the metal is bound to more than one kind of donor group. Ex: \([\text{Co(NH}_3)_4\text{Cl}_2]^{+}\).
Conversions:
(i) Carboxylic acid to Ester (Esterification):
\(\text{R-COOH} + \text{R'-OH} \xrightarrow{\text{conc. H}_2\text{SO}_4} \text{R-COOR'} + \text{H}_2\text{O}\)
(ii) Carboxylic acid to Acid Amide:
\(\text{R-COOH} + \text{NH}_3 \rightarrow \text{R-COONH}_4 \xrightarrow{\Delta} \text{R-CONH}_2 + \text{H}_2\text{O}\)
Identify A and B:
Reaction: Isopropyl alcohol \(\xrightarrow{\text{PBr}_3}\) A \(\xrightarrow{\text{NH}_3 \text{ excess}}\) B
1. \(\text{CH}_3\text{-CH(OH)-CH}_3 + \text{PBr}_3 \rightarrow \text{CH}_3\text{-CH(Br)-CH}_3\) (A = Isopropyl bromide / 2-Bromopropane).
2. \(\text{CH}_3\text{-CH(Br)-CH}_3 + \text{NH}_3 (\text{excess}) \rightarrow \text{CH}_3\text{-CH(NH}_2)\text{-CH}_3\) (B = Isopropyl amine / Propan-2-amine).
Action of hot HI on Glucose:
When glucose is heated with HI for a long time, it undergoes reduction to form n-hexane. This indicates all 6 carbons are in a straight chain.
\(\text{Glucose} \xrightarrow{\text{HI, }\Delta} \text{n-Hexane}\).
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