So, [H+]=10−4 M[\text{H}^+] = 10^{-4} \, \text{M} and [OH−]=10−10 M[\text{OH}^-] =
10^{-10} \, \text{M}.
03. Conjugate acids and bases:
Definition: o A conjugate acid is formed when a base gains a proton (H+H^+). o A conjugate base is formed when an acid loses a proton. Conjugate bases: 1. HOClHOCl → Conjugate base: OCl−OCl^- 2. H2CO3H_2CO_3 → Conjugate base: HCO3−HCO_3^-
04. Define internal energy and its consequences:
Internal energy (UU):
o It is the total energy contained within a chemical system, including kinetic and potential energy of particles. Consequences of increasing internal energy: o Increases temperature. o Facilitates chemical reactions by overcoming activation energy barriers. 2 Numan Composing Rajjar Whats App:03425747395
o Can lead to phase changes (e.g., melting, evaporation).
05. Oxidation number of nitrogen in the following compounds:
1. N2ON_2O: Total oxidation number = 0. Let oxidation number of NN be xx: 2x+(−2)=0
⟹ x=+12x + (-2) = 0 \implies x = +1 2. NO2NO_2: Total oxidation number = 0. Let xx be the oxidation number of NN: x+2(−2)=0 ⟹ x=+4x + 2(-2) = 0 \implies x = +4 3. N2O2N_2O_2 (dinitrogen dioxide): Total oxidation number = 0. Let xx be the oxidation number of each NN: 2x+2(−2)=0 ⟹ x=+22x + 2(-2) = 0 \implies x = +2 4. NH2−NH_2^-: Total charge = -1. Let xx be the oxidation number of NN: x+2(−1)=−1 ⟹ x=−1x + 2(-1) = -1 \implies x = -1
06. Faraday's First Law of Electrolysis:
Statement: The mass (mm) of a substance deposited or liberated at an electrode is
directly proportional to the electric charge (QQ) passed through the electrolyte.
m=ZQm = ZQ
Where:
o ZZ = Electrochemical equivalent of the substance.
07. Steps for identifying the limiting reagent:
1. Write a balanced chemical equation.
2. Calculate the moles of each reactant. 3. Compare the mole ratio of reactants with the ratio in the balanced equation. 4. The reactant that produces the least amount of product is the limiting reagent.
Explanation: This equation relates energy (E\mathcal{E}) of a photon to the speed of
light (cc), Planck's constant (hh), and wavenumber (αˉ\bar{\alpha}, reciprocal of 3 Numan Composing Rajjar Whats App:03425747395
wavelength): E=hν=hcαˉ\mathcal{E} = h\nu = hc\bar{\alpha} Derived from ν=c/λ\nu =
c/\lambda and αˉ=1/λ\bar{\alpha} = 1/\lambda.
09. Applications of dipole moment:
1. Determining molecular polarity.
2. Estimating bond character (ionic vs covalent). 3. Predicting molecular shape and geometry. 4. Understanding physical properties like boiling and melting points. 5. Applications in spectroscopy and material sciences.
10. Prove that σ\sigma-bond is stronger than π\pi-bond:
A σ\sigma-bond involves head-on overlap of atomic orbitals, resulting in greater overlap
and stronger bonding. A π\pi-bond results from the sideways overlap of orbitals, with less effective overlap.
Experimentally, bond dissociation energy supports that σ\sigma-bonds are stronger.
11. Shortcomings of Bohr's atomic model:
1. Only applicable to hydrogen-like atoms (single electron).
2. Fails to explain fine spectral lines and Zeeman effect. 3. Does not account for electron-electron interactions in multi-electron atoms. 4. Incompatible with the uncertainty principle.
Sec C 14 (a) Derivation and Explanation of Van der Waals' Equation for a Real Gas
The Van der Waals equation modifies the ideal gas law PV=nRTPV = nRT to account for real gas behavior. It considers two factors: finite molecular size and intermolecular forces.
1. Correction for Molecular Volume:
In an ideal gas, molecules are assumed to have negligible volume. However, real gas molecules occupy space, reducing the effective volume available for movement. 4 Numan Composing Rajjar Whats App:03425747395
Effective volume: Veffective=V−bV_{\text{effective}} = V - b Where:
o bb is a constant proportional to the volume of one mole of gas molecules.
2. Correction for Intermolecular Forces:
In real gases, attractive forces between molecules reduce the pressure exerted on the container walls compared to ideal behavior.
Corrected pressure: Pcorrected=P+aV2P_{\text{corrected}} = P + \frac{a}{V^2} Where:
o aa is a constant representing the strength of intermolecular attractions. o aV2\frac{a}{V^2} is the pressure correction term, inversely proportional to the square of the molar volume.
3. Van der Waals Equation:
Substituting the corrections into the ideal gas law gives:
(P+aV2)(V−b)=nRT\left(P + \frac{a}{V^2}\right)(V - b) = nRT
For 1 mole of gas (n=1n = 1):
(P+aV2)(V−b)=RT\left(P + \frac{a}{V^2}\right)(V - b) = RT
Expanding and rearranging yields:
P=RTV−b−aV2P = \frac{RT}{V - b} - \frac{a}{V^2}
Physical Significance:
aa: Accounts for attractive forces between molecules. Larger aa means stronger intermolecular forces. bb: Accounts for finite molecular volume. Larger bb means larger molecular size.
Van der Waals’ equation describes gas behavior more accurately at high pressures and low temperatures, where deviations from ideal gas laws are significant.
14 (b) Difference Between a Continuous and Line Spectrum
5 Numan Composing Rajjar Whats App:03425747395
Feature Continuous Spectrum Line Spectrum
A spectrum that contains all wavelengths A spectrum consisting of discrete lines of
Definition within a given range. specific wavelengths.
Emitted by incandescent solids, liquids, or Emitted by excited atoms or molecules in
Source dense gases. gaseous state.
Smooth, unbroken distribution of colors (like
Appearance Series of distinct lines on a dark background. a rainbow).
Hydrogen emission spectrum, sodium vapor
Example Sunlight, blackbody radiation. lamps.
Caused by transitions of many electrons Caused by specific electronic transitions in
Origin across energy levels. isolated atoms.
Explanation:
Continuous spectrum arises when a large number of closely spaced energy levels are occupied, such as in solids. Line spectrum results from quantized electronic transitions in atoms or molecules, emitting photons of precise energies.
15 (a) Planck's Quantum Theory
Planck's Quantum Theory revolutionized physics by introducing the concept that energy is quantized, not continuous. It was proposed by Max Planck in 1900 to explain blackbody radiation.
Key Postulates of Planck's Quantum Theory:
1. Quantization of Energy: o Energy is emitted or absorbed by matter in discrete packets called quanta (or photons for light). o The energy (EE) of a quantum is proportional to its frequency (ν\nu), given by: E=hνE = h\nu where hh is Planck’s constant (6.626×10−34 J\cdotps6.626 \times 10^{-34} \, \text{J·s}). 2. Energy Levels: o Atoms and molecules exist in specific energy levels. Transitions between these levels involve the absorption or emission of quanta. 3. Blackbody Radiation: o The energy emitted by a blackbody (a perfect emitter) is not continuous but occurs in discrete packets, explaining why classical theories failed. 6 Numan Composing Rajjar Whats App:03425747395
15 (b) Corrosion
Definition: Corrosion is the natural process by which metals react with their environment, leading to the deterioration of the metal. It is commonly a redox reaction, such as the rusting of iron.
Example: Rusting of iron (FeFe) in the presence of moisture and oxygen forms Fe2O3⋅xH2OFe_2O_3·xH_2O (hydrated iron oxide).
Mechanism of Corrosion (Rusting of Iron):
1. Anodic Reaction (Oxidation):
o Iron loses electrons to form ferrous ions: Fe→Fe2++2e−\text{Fe} \rightarrow \text{Fe}^{2+} + 2e^- 2. Cathodic Reaction (Reduction): o Oxygen reacts with water and the electrons released at the anode: O2+4H++4e−→2H2OO_2 + 4H^+ + 4e^- \rightarrow 2H_2O 3. Overall Reaction: o The ferrous ions combine with oxygen and water to form rust: 4Fe2++3O2+6H2O→4Fe(OH)34\text{Fe}^{2+} + 3O_2 + 6H_2O \rightarrow 4Fe(OH)_3 o This dehydrates to form Fe2O3⋅xH2OFe_2O_3·xH_2O (rust).
Methods for Prevention of Corrosion:
1. Barrier Protection: o Coating the metal surface to prevent contact with air and moisture. o Examples: Painting, applying oil/grease, or using polymer coatings. 2. Galvanization: o Coating the metal (e.g., iron) with a layer of zinc. o Zinc is more reactive and acts as a sacrificial anode, protecting the underlying metal from corrosion.
Other methods include cathodic protection, alloying, and using corrosion inhibitors. 7 Numan Composing Rajjar Whats App:03425747395
16 (a) Raoult's Law and Lowering of Vapor Pressure
Statement of Raoult's Law:
For a solution, the partial vapor pressure of a volatile component is directly proportional to its mole fraction in the solution. Mathematically:
PA=XAPA0P_A = X_A P_A^0
Where:
PAP_A = Partial vapor pressure of the solvent in the solution.
PA0P_A^0 = Vapor pressure of the pure solvent. XAX_A = Mole fraction of the solvent in the solution.
Lowering of Vapor Pressure:
When a non-volatile solute is added to a solvent:
1. The mole fraction of the solvent (XAX_A) decreases.
2. According to Raoult’s law, the partial vapor pressure of the solvent (PAP_A) also decreases since it is proportional to XAX_A.
Explanation:
The presence of solute particles reduces the number of solvent molecules available at the surface to escape into the vapor phase. This leads to a decrease in the vapor pressure of the solution compared to the pure solvent.
Relative Lowering of Vapor Pressure:
PA0−PAPA0=XB\frac{P_A^0 - P_A}{P_A^0} = X_B
Where:
XBX_B = Mole fraction of the solute.
8 Numan Composing Rajjar Whats App:03425747395
16 (b) Differences Between Molecularity and Order of a Reaction
Feature Molecularity Order of Reaction
The number of reacting species (molecules,
The sum of the powers of the Definition atoms, or ions) involved in a single step of a concentration terms in the rate law. reaction.
Determined from the reaction mechanism Determined experimentally from the
Determination (elementary step). rate law.
Can be a fraction, whole number, or
Nature Always a whole number (1, 2, or 3). zero.
Only applies to individual steps (elementary
Dependence Refers to the overall reaction. reactions).
For 2NO+O2→2NO22NO + O_2 \rightarrow For the reaction A→BA \rightarrow
Example 2NO_2, the molecularity of the elementary step is B, if rate = k[A]2k[A]^2, the order is 3. 2.
Key Notes:
Molecularity cannot be zero, but order can be zero.
Molecularity is theoretical, while order is experimentally determined.
