Chemistry Test

General Instruction
 Full Marks : 20
 Max Time: 60 min
 Neatness is the priority. Do not waste the paper

A. Answer the Following Question (Any 4) [2 x 4 = 8]

1. Write the formulae of the following coordination compounds
a) potassium tetracyanidonickel (0) [At. No of nickel = 28]
b) triamminetrinitrocobalt (III) [At. No of cobalt = 27]
3-
2. [CoF6] is a coordination complex ion
i. What is the oxidation number of cobalt in the complex?
ii. How many unpaired electrons are there in the complex.
iii. State the magnetic behaviour of the complex
iv. Give the IUPAC name of the complex.
3. State Faraday’s Law of Electrolysis.
4. Derive the integrated rate equation for the first order reaction.
5. Define the the following terms
i. Specific conductance
ii. Kohlrauch’s Law

B. Answer the Following Question (Any 4) [3 x 4 = 12]

1. An aqueous solution containing 12.48 g of barium chloride (BaCl2) in 1000 g of water, boils at 100.0832˚C.
Calculate the degree of dissociation of barium Chloride. [kb = 0.512°C·kg/mol; At mass of Ba = 137; At mass of Cl
= 35.5]
2. For the cell
Zn | Zn2+ (a = 1) || Cu2+ (a = 1) | Cu
Given that EZn/Zn2+ = 0.761 V; ECu2+/Cu = + 0.339 V
(a) Write the cell reaction
(b) Calculate the emf and free energy change at 298 K involved in the cell. (1 F = 96,500 C)
3. For a first order reaction, it takes 5 minute for the initial concentration of 0.6 mol L-1 to become 0.4 mol L-1. How
long will it take for initial concentration to become 0.3 mol L-1.
4. Calculate the mass of silver deposited at cathode when a current of 2 amperes is passed through a solution of
AgNO3 for 15 minutes. (At wt of Ag = 108, 1 F = 96,500 C)
5. If 1.71 g of sugar (molar mass =342) are dissolved in 500 ml of an aqueous solution at 300 k, what will be its
osmotic pressure? [R = 0.0821]

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 Answer
A1. a) K₄[Ni(CN)₄]
b) [Co(NH₃)₃(NO₂)₃]
A2. For the complex [CoF₆ ]³⁻ :
i. Oxidation number of cobalt
Let the oxidation number of cobalt be x.
Each fluoride ion (F) has a charge of -1, and there are six fluoride ions.
So, x + 6(-1) = -3.
x - 6 = -3
x = +3.
Oxidation number of cobalt = +3
ii. Number of unpaired electrons
Cobalt in the +3 oxidation state has an electron configuration of [Ar] 3d⁶.
Fluoride (F⁻ ) is a weak field ligand, so it does not cause pairing of electrons.
In 3d⁶, there are 4 unpaired electrons.
iii. Magnetic behavior
With 4 unpaired electrons, the complex is paramagnetic.
iv. IUPAC name of the complex
The IUPAC name is hexafluorocobaltate(III) ion.
A3. Faraday's law of electrolysis states that the amount of chemical change produced at an electrode is
directly proportional to the amount of electricity passed through the cell
A4.
A5. Definition:
 Molecularity: Number of reactant molecules involved in an elementary step.
 Order: Sum of the exponents of concentration terms in the rate law.
Values:
 Molecularity: Always a whole number (1, 2, 3, etc.).
 Order: Can be zero, a fraction, or a whole number.
Determination:
 Molecularity: Theoretical; determined from reaction mechanism.
 Order: Experimental; determined from rate law.
Applicability:
Molecularity: Only for elementary reactions.
Order: Applies to both elementary and complex reactions.
B1. To calculate the degree of dissociation of barium chloride (BaCl2), we can use the formula for boiling
point elevation:
ΔT_b = i * K_b * m
Where:
ΔT_b = Boiling point elevation = 100.0832°C - 100°C = 0.0832°C
i = van 't Hoff factor (degree of dissociation)
 K_b = ebullioscopic constant of water = 0.512°C·kg/mol
m = molality of the solution (mol of solute per kg of solvent)
Step 1: Calculate the molality (m) of the solution
Molar mass of BaCl2 = (137 + 2 * 35.5) = 208 g/mol
Molality, m = moles of BaCl2 / mass of solvent in kg
Mass of BaCl2 = 12.48 g
Moles of BaCl2 = 12.48 g / 208 g/mol = 0.06 mol
Mass of water = 1000 g = 1 kg
So, molality, m = 0.06 mol / 1 kg = 0.06 mol/kg
Step 2: Apply the formula for boiling point elevation
ΔT_b = i * K_b * m
0.0832°C = i * 0.512°C·kg/mol * 0.06 mol/kg
Solving for i:
i = 0.0832°C / (0.512 * 0.06) = 2.7
Step 3: Calculate the degree of dissociation (α)
For BaCl2, it dissociates as:
BaCl2 → Ba²⁺ + 2Cl⁻
The theoretical value of i for BaCl2 (if it dissociates completely) would be 3 (1 for Ba²⁺ and 2 for
Cl⁻ ).
Degree of dissociation, α = i / 3
α = 2.7 / 3 = 0.9
Answer: The degree of dissociation of barium chloride (BaCl2) is 0.9.
B2. (a) Cell Reaction:
The overall cell reaction is:
Zn(s) + Cu²⁺ (aq) → Zn²⁺ (aq) + Cu(s)
(b) Calculation of EMF and Free Energy Change:
EMF of the Cell (E°cell):
The standard EMF of the cell is calculated using the formula:
E°cell = E°cathode - E°anode
Given: E°cathode = ECu²⁺ /Cu = +0.339 V E°anode = EZn/Zn²⁺ = -0.761 V
E°cell = 0.339 V - (-0.761 V)
E°cell = 1.100 V
Free Energy Change (ΔG°):
The relationship between free energy change and cell potential is:
ΔG° = -nFE°
Where: n = number of electrons transferred (2 for this reaction) F = Faraday constant (96,485 C/mol)
ΔG° = - (2) × (96,485) × (1.100)
ΔG° = -212,267 J/mol
ΔG° = -212.27 kJ/mol
B3. For a first-order reaction, the integrated rate law is:
 ln([A]₀ / [A]) = kt
Step 1: Calculate the rate constant (k).
Initial concentration ([A]0) = 0.6 mol L⁻ ¹
Final concentration ([A]) = 0.4 mol L⁻ ¹
Time (t) = 5 minutes
ln(0.6 / 0.4) = k × 5
ln(1.5) = k × 5
k = ln(1.5) / 5
k = 0.405 / 5
k = 0.081 min⁻ ¹
Step 2: Calculate the time for [A]₀ = 0.6 mol L⁻ ¹ to become [A] = 0.3 mol L⁻ ¹.
ln(0.6 / 0.3) = k × t
ln(2) = 0.081 × t
t = ln(2) / 0.081
t = 0.693 / 0.081
t ≈ 8.56 minutes
Final Answer: It will take approximately 8.56 minutes for the initial concentration to become 0.3 mol
L⁻ ¹.
B4. To calculate the mass of silver deposited, we use Faraday's First Law of Electrolysis:
Mass deposited (m) = (Z × I × t)
Where Z is the electrochemical equivalent, I is the current, and t is the time.
Electrochemical equivalent (Z):
Z = Molar mass of Ag / (n × F)
Molar mass of Ag = 108 g/mol
n = 1 (number of electrons for Ag ⁺ → Ag)
F = 96,500 C/mol
Z = 108 / 96,500 = 0.001118 g/C
Current (I) and Time (t):
I=2A
t = 15 minutes = 15 × 60 = 900 seconds
Calculate mass (m):
m=Z×I×t
m = 0.001118 × 2 × 900
m = 2.0124 g
Final Answer:
The mass of silver deposited at the cathode is 2.012 grams.
B5. To calculate the osmotic pressure, use the formula:
Osmotic pressure (π) = (n / V) × R × T
Step 1: Calculate the number of moles of sugar (n).
Mass of sugar = 1.71 g
Molar mass of sugar = 342 g/mol
n = mass / molar mass = 1.71 / 342 = 0.005 moles
Step 2: Convert the volume to liters.
Volume = 500 mL = 0.5 L
Step 3: Use the values to calculate the osmotic pressure.
Gas constant (R) = 0.0821 L atm mol⁻ ¹ K⁻ ¹
Temperature (T) = 300 K
π = (n / V) × R × T
π = (0.005 / 0.5) × 0.0821 × 300
π = 0.01 × 0.0821 × 300
π = 0.2463 atm
Final Answer: The osmotic pressure of the solution is 0.246 atm.

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