PART – A (Short Answer – 50 words)

1. (i) Name two alloys of transition metals.

Answer:
o Stainless steel (Iron + Chromium + Nickel)
o Brass (Copper + Zinc)
2. (ii) What is chrome plating?
Answer:
Chrome plating is a technique of electroplating a thin layer of chromium onto a metal
object to provide corrosion resistance, ease of cleaning, and an attractive appearance.
3. (iii) What is Optical Isomerism?
Answer:
Optical isomerism is a type of stereoisomerism in which compounds have the same
molecular formula but differ in the way they rotate plane-polarized light due to the
arrangement of atoms.
4. (iv) What do you mean by Coordination Compound?
Answer:
A coordination compound consists of a central metal atom or ion surrounded by
ligands (molecules or ions) bonded to it via coordinate bonds.
5. (v) Give two uses of Lanthanides.
Answer:
o Used in manufacturing strong permanent magnets
o Used in making phosphors for color television screens
6. (vi) What do you mean by Artificial Actinides?
Answer:
Artificial actinides are synthetic elements beyond uranium (like neptunium and
plutonium) that do not occur naturally and are produced in nuclear reactors or particle
accelerators.
7. (vii) Define Nucleation.
Answer:
Nucleation is the initial process in the formation of a crystal or a new phase, where
small clusters of atoms or molecules form a stable nucleus.
8. (viii) What is Lake Reagent?
Answer:
Lake reagent is used to form insoluble colored compounds (lakes) by combining
organic dyes with metal salts, commonly used in analytical chemistry.
9. (ix) What is retarding factor?
Answer:
In chromatography, the retarding factor (Rf value) is the ratio of the distance traveled
by the substance to the distance traveled by the solvent front.
10. (x) Define Accuracy.
Answer:
Accuracy refers to how close a measured value is to the true or accepted value.

Q.2 (a) [CoCl₄]²⁻ is dark blue while [Co(H₂O)₆]²⁺ is light pink in color. Why?

The color of a coordination compound arises due to d-d electronic transitions within the
metal ion when it is exposed to visible light. The specific color observed depends on the
nature of ligands and the crystal field they generate.
 [CoCl₄]²⁻ is a tetrahedral complex where chloride ions (Cl⁻) are weak field ligands.
They create a smaller crystal field splitting energy (Δtet), allowing electrons to absorb
lower energy (longer wavelength) light, resulting in the appearance of a dark blue
color.
 [Co(H₂O)₆]²⁺ is an octahedral complex where water molecules (H₂O) are stronger
field ligands than chloride ions. They cause greater splitting of d-orbitals (Δoct), and
the complex absorbs higher energy (shorter wavelength) light. As a result, it appears
light pink.

Thus, the different colors result from different ligand fields and geometries affecting
electronic transitions.

Q.2 (b) Why do transition elements act as good catalysts?

Transition metals and their compounds are often used as catalysts due to the following
reasons:

1. Variable Oxidation States:

Transition metals can easily change oxidation states, allowing them to donate or
accept electrons during redox reactions.
2. Formation of Complexes:
They form intermediate complexes with reactants, lowering the activation energy
and providing an alternate reaction pathway.
3. Large Surface Area:
In heterogeneous catalysis, transition metals like platinum or nickel provide high
surface area, facilitating effective contact with reactants.
4. Adsorption Properties:
They can adsorb molecules onto their surface, weakening bonds and promoting
chemical reactions (e.g., iron in the Haber process).
5. Multiple Coordination Numbers:
Their ability to form complexes with various geometries allows flexibility in
facilitating reactions.

Q.4 Explain Pourbaix diagram and its applications.

A Pourbaix diagram, also known as a potential–pH diagram, is a graphical representation

of the thermodynamic stability of various oxidation states of an element as a function of
electrode potential (E) and pH.

Features:

 The y-axis represents electrode potential (E) in volts.

 The x-axis represents pH.
 Different regions show which species (e.g., metal ion, oxide, or solid metal) is
thermodynamically stable.
Applications:

1. Corrosion Prediction:
Helps in identifying whether a metal is likely to corrode, remain passive, or stay
stable under specific environmental conditions.
2. Water Treatment:
Used to determine suitable conditions for precipitating heavy metals during water
purification.
3. Electrochemical Processes:
Crucial in designing electroplating, electrorefining, and electrowinning systems.
4. Battery Design:
Aids in choosing stable electrode materials over a range of pH values.

Pourbaix diagrams are useful for visualizing redox behavior and material stability under
aqueous conditions.

Q.5 Write IUPAC rule for nomenclature of complexes and names of ligands in complex.

IUPAC Rules for Naming Coordination Compounds:

1. Name the ligands first, followed by the central metal atom/ion.

2. Ligands are named in alphabetical order (not based on quantity).
3. Prefixes:
o Mono, di, tri, tetra, penta, hexa are used to indicate the number of identical
ligands.
o If the ligand name already contains a number prefix (e.g., ethylenediamine),
use bis, tris, tetrakis.
4. Anionic Ligands:
End with -o (e.g., chloro, cyano, hydroxo).
Neutral ligands keep their names (e.g., NH₃ = ammine, H₂O = aqua).
5. Metal Name:
o If the complex is an anion, the metal name ends with -ate (sometimes Latin
roots are used, e.g., ferrate for Fe).
o If it’s neutral or cationic, use the metal name as-is.
6. Oxidation State of the central metal is written in Roman numerals in parentheses.

Example:

 [Co(NH₃)₄Cl₂]Cl = Tetraamminechloridocobalt(III) chloride

 K₄[Fe(CN)₆] = Potassium hexacyanoferrate(II)

Q.6 (a) What is Lanthanide Contraction? Explain.

Lanthanide contraction refers to the gradual decrease in the size of lanthanide ions
(Ln³⁺) as the atomic number increases from lanthanum (La) to lutetium (Lu).
Causes:

 As electrons are added to the 4f orbitals, the nuclear charge increases.

 However, 4f electrons do not shield the nuclear attraction effectively.
 This increased nuclear pull contracts the electron cloud, resulting in smaller ionic
radii.

Consequences:

1. Similarity in atomic radii between 2nd and 3rd transition series elements (e.g., Zr
and Hf).
2. Increasing density and hardness of elements down the group.
3. Complexation behavior and basicity trends of lanthanide hydroxides are affected.

Lanthanide contraction plays a crucial role in periodic trends and chemical behavior of
elements.

Q.6 (b) Why the chemical properties of Lanthanides are almost same?

Lanthanides have similar chemical properties primarily because:

1. Same oxidation state:

All lanthanides predominantly exhibit the +3 oxidation state in compounds.
2. Similar ionic radii:
Due to lanthanide contraction, their ionic sizes are close, leading to comparable bond
lengths and coordination numbers.
3. Shielded 4f orbitals:
The 4f electrons are well shielded and do not participate in bonding, so chemical
reactions involve mainly the outer 5s and 5p orbitals.
4. Similar reactivity with water and acids, forming lanthanide hydroxides and salts.

As a result, lanthanides are difficult to separate chemically and show almost uniform
reactivity.

Q.7 (a) Actinides have greater tendency to form complex than Lanthanides. Explain.

Actinides form complexes more readily than lanthanides due to:

1. Larger ionic size variability:

Actinides exhibit multiple oxidation states (+3 to +6), unlike lanthanides (mostly
+3), offering more options for complexation.
2. More extended orbitals:
The 5f orbitals in actinides are less shielded and more available for bonding
compared to the deeply buried 4f orbitals in lanthanides.
3. Stronger covalent character:
Bonding in actinide complexes shows greater covalent character, facilitating
coordination with a variety of ligands.

Therefore, actinides tend to form more stable and diverse coordination compounds than
lanthanides.

Q.7 (b) What are the similarities between the later actinides and the later lanthanides?

Similarities include:

1. Predominant +3 oxidation state:

Both series favor the +3 state in their later members.
2. Contraction effect:
Like lanthanide contraction, actinides show actinide contraction leading to similar
ionic radii.
3. Poor shielding:
In both series, 4f (lanthanides) and 5f (actinides) electrons poorly shield, causing
similar bonding patterns.
4. Low solubility of hydroxides and oxalates:
Both form insoluble salts that resemble each other.

These similarities make the separation and identification of later actinides and lanthanides
quite challenging.

Q.8 Discuss briefly: (a) Post-precipitation (b) Occlusion

(a) Post-precipitation:

This occurs when foreign impurities are deposited onto a precipitate after its initial
formation.

 It can alter the purity and composition of the precipitate.

 Usually happens during standing or aging of the precipitate in solution.
 Example: Formation of BaSO₄ followed by post-precipitation of SrSO₄.

(b) Occlusion:

This is the trapping of impurities within the crystal lattice or between crystals of a
precipitate during its growth.

 Unlike adsorption (surface-level), occlusion is internal.

 Can lead to errors in gravimetric analysis.
 To avoid it, slow precipitation and digestion of precipitate are recommended.
Q.9 Explain Selectivity and Specificity.

Selectivity refers to a reagent’s or method's ability to differentiate between various

components in a mixture.

 High selectivity = effective separation or identification of one component from others.

 Example: In complexometric titration, EDTA is selective for metal ions under specific
pH.

Specificity means the method or reagent reacts only with one specific substance and
nothing else.

 Example: Enzymes in biochemistry have high specificity for their substrates.

In analytical chemistry, selectivity is desirable for separation, while specificity is crucial for
identification.

Q.10 Discuss basic principles of Chromatography.

Chromatography is a separation technique based on the distribution of components

between two phases:

 Stationary phase: fixed in place (solid or liquid on a solid support)

 Mobile phase: moves through the stationary phase (liquid or gas)

Basic Principles:

1. Differential Partitioning:
Compounds distribute differently between the two phases due to solubility and
polarity differences.
2. Retention factor (Rf):
It reflects how far a compound travels relative to the solvent front.
3. Types of interactions:
o Adsorption (solid-liquid)
o Partition (liquid-liquid)
o Ion exchange
o Size exclusion
4. Resolution:
Depends on the interaction strength, flow rate, and the length of the column or paper.

Chromatography is widely used in chemical analysis, drug purity testing, and biochemical
separations.

Q.11 (a) What do you mean by precision of single measurement?

Precision refers to the closeness of repeated measurements of the same quantity.

 In the case of a single measurement, precision is evaluated by the instrument’s
ability to reduce error and provide consistent readings under controlled conditions.
 A highly precise instrument gives nearly the same result every time, even if the result
is not accurate.

Example:

A scale that reads 1.00 g repeatedly for the same object (though actual mass is 1.05 g) is
precise but not accurate.

Q.11 (b) What is Quotient Test? Explain.

The Quotient Test is a mathematical method used in analytical chemistry and physics to
evaluate the convergence or divergence of a numerical series.

 In chemistry, it can also refer to the Q test (quotient test for outliers) used in
statistical analysis of data sets to identify outlier values.

Q Test Formula:

Q=GapRange=xsuspect−xnearestxmax−xminQ = \frac{\text{Gap}}{\text{Range}} = \frac{x_{suspect} -

x_{nearest}}{x_{max} - x_{min}}Q=RangeGap=xmax−xminxsuspect−xnearest

 If Q > Q critical (from a table), the value can be rejected as an outlier.

It is commonly used in experimental chemistry to ensure data integrity and reliability.

Q.12 Write a note on the characteristic properties of d-block elements.

The d-block elements, also called transition elements, are found in groups 3 to 12 of the
periodic table and have their valence electrons filling the d-orbitals. They exhibit several
unique physical and chemical properties due to their partially filled d subshells.

1. Variable Oxidation States

 d-block elements can show a range of oxidation states due to similar energies of the
(n-1)d and ns orbitals.
 Example: Iron can exist in +2 and +3 oxidation states (Fe²⁺ and Fe³⁺), while
manganese can show up to +7.
 This allows them to act as redox catalysts.

2. Formation of Colored Compounds

 Transition metal compounds often exhibit bright colors due to d–d transitions.
 Electrons absorb visible light to move between split d-orbitals caused by ligand fields
in coordination compounds.
 Example: [Cu(H₂O)₆]²⁺ is blue; [Fe(SCN)]²⁺ is blood-red.

3. Paramagnetism

 Most d-block elements are paramagnetic due to the presence of unpaired d electrons.
 The number of unpaired electrons determines the magnetic moment.
 Cr³⁺ (3d³) and Mn²⁺ (3d⁵) are examples.

4. Catalytic Properties

 d-block metals and their oxides often act as catalysts because:

o They form intermediate compounds,
o Can change oxidation states easily,
o Have large surface areas.

5. Complex Formation

 They have a strong tendency to form coordinate complexes with ligands like NH₃,
H₂O, CN⁻, etc.
 This is due to their small ionic radii, high nuclear charge, and availability of vacant d
orbitals.

6. Metallic Character

 They are all metals — hard, dense, with high melting and boiling points.
 They exhibit metallic bonding and conduct electricity.

7. High Enthalpy of Atomization

 A large amount of energy is required to break bonds between atoms, leading to high
melting/boiling points and strength.

These characteristics make d-block elements important in industries, catalysis, material

science, and bioinorganic chemistry.

Q.13 Write short notes on any three of the following:

(a) Effective Atomic Number (EAN) Concept

EAN is the total number of electrons around a central metal atom in a complex, including
those from ligands.

EAN=Z−x+2n\text{EAN} = Z - x + 2nEAN=Z−x+2n

 Z = atomic number of the metal

 x = oxidation state
 n = number of ligand donor pairs
If the EAN equals the atomic number of the nearest noble gas, the complex is considered
stable.
Example: [Fe(CN)₆]⁴⁻ → EAN = 26 - 2 + 12 = 36 (krypton)

(b) Chelate Effect

Chelation involves ligands that form multiple bonds with a metal ion, creating a ring
structure.

 Chelates are more stable than complexes with monodentate ligands.

 Reasons for Stability:
o Entropy increase: more disorder when one chelating ligand replaces multiple
monodentates.
o Steric protection: ring structures resist displacement.
 Example: Ethylenediamine (en) forms stable chelates with Ni²⁺.

(c) Analysis of Redox Cycle

Redox cycles involve the repeated reduction and oxidation of chemical species, often in
catalytic or environmental systems.

 Applications:
o Industrial catalysis (e.g., Vanadium in sulfuric acid production).
o Biological systems (e.g., NAD⁺/NADH in respiration).
 Analytical redox cycles help understand reaction mechanisms and electron transfer
processes.

Q.14 Give name, symbol and electronic configuration of Lanthanides.

Lanthanides consist of 15 elements from lanthanum (La, Z=57) to lutetium (Lu, Z=71).

Here’s a representative list:

Name Symbol Atomic Number Electronic Configuration*

Lanthanum La 57 [Xe] 5d¹ 6s²

Cerium Ce 58 [Xe] 4f¹ 5d¹ 6s²

Praseodymium Pr 59 [Xe] 4f³ 6s²

Neodymium Nd 60 [Xe] 4f⁴ 6s²

Name Symbol Atomic Number Electronic Configuration*

Samarium Sm 62 [Xe] 4f⁶ 6s²

Europium Eu 63 [Xe] 4f⁷ 6s²

Gadolinium Gd 64 [Xe] 4f⁷ 5d¹ 6s²

Terbium Tb 65 [Xe] 4f⁹ 6s²

Dysprosium Dy 66 [Xe] 4f¹⁰ 6s²

Holmium Ho 67 [Xe] 4f¹¹ 6s²

Erbium Er 68 [Xe] 4f¹² 6s²

Thulium Tm 69 [Xe] 4f¹³ 6s²

Ytterbium Yb 70 [Xe] 4f¹⁴ 6s²

Lutetium Lu 71 [Xe] 4f¹⁴ 5d¹ 6s²

*Configurations vary slightly due to orbital energy considerations.

Q.15 Write short notes on the following:

(a) Contamination of Precipitates

Occurs when foreign substances are adsorbed, occluded, or incorporated into a precipitate.

 Causes:
o Rapid precipitation
o Co-precipitation
o Post-precipitation
 Remedies:
o Slow addition of reagents
o Digestion of precipitate
o Re-precipitation

Contamination affects the accuracy of gravimetric analysis.

(b) Use of Organic Solvents

Organic solvents (e.g., ethanol, acetone) are used in:

 Precipitation reactions to reduce solubility
 Chromatography as mobile phases
 Spectroscopy to dissolve samples

Key properties: volatility, polarity, and ability to dissolve non-polar compounds.

(c) Co-precipitation

It is the simultaneous precipitation of substances that are not normally insoluble under
reaction conditions.

 Occurs due to:

o Adsorption
o Occlusion
o Isomorphic inclusion
 Problematic in analysis as it introduces impurities in the target compound.

Q.16 Write short notes on any three of the following:

(a) Significant Figures

Significant figures indicate the precision of a measurement.

 Rules:
o All non-zero digits are significant.
o Zeros between digits are significant.
o Leading zeros are not.
o Trailing zeros after a decimal are significant.

Used in reporting scientific data to reflect measurement accuracy.

(b) Types of Errors

1. Systematic Errors – reproducible and affect accuracy (e.g., calibration error).

2. Random Errors – unpredictable variations affecting precision.
3. Gross Errors – due to human mistakes like incorrect readings.

Understanding errors helps in improving the reliability of results.

(c) Stationary and Mobile Phases in Chromatography

 Stationary phase: Fixed surface (e.g., silica, paper).

 Mobile phase: Liquid or gas that carries analytes through the stationary phase.

Separation occurs based on differential partitioning of components between the two phases.

(d) Adsorption Chromatography

A method where separation occurs due to differences in adsorption of components on a

solid surface.

 Stationary phase: solid (e.g., alumina, silica gel)

 Mobile phase: solvent or gas

Used for separating organic mixtures, pigments, or drugs.