Chemical Equilibrium –

1.Why Chemical equilibrium is Dynamic equilibrium ?

Ans: Dynamic equilibrium is when two opposite processes happen at the same rate,
keeping the system balanced. Chemical equilibrium happens in a reaction when reactants
and products stay constant over time. Chemical equilibrium is dynamic because reactions
keep happening. The forward and reverse reactions occur at the same rate. This keeps
the concentrations of reactants and products constant. Molecules continuously convert
into each other without a net change. An example is the Haber process, where nitrogen
and hydrogen form ammonia while ammonia breaks down at the same rate along with
produce nitrogen and hydrogen.

N2+3H2⇌2NH3

2.Homogenous and heterogenous- If in a reaction product and reactant are in same

state then it is called homogenous reaction. Example- The reaction between nitrogen and
hydrogen to form ammonia in the gas phase. 𝑁2(𝑔) +3𝐻2(𝑔)⇌2𝐻3(𝑔)

If in a reaction product and reactant are in different states then it is called homogenous
reaction. Example - The reaction of solid calcium carbonate decomposing into solid
calcium oxide and carbon dioxide gas. CaCO3(s)→CaO(s)+CO2(g).

3. Shorts note on “Le Chatelier principle”- Chemist Henry Le Chatelier proposed a

general principle which applies to all systems in equilibrium, and this principle is called
"Le Chatelier principle." It is stated as: When a stress is applied on a system at
equilibrium, the system tends to adjust itself so as to reduce the stress.There are three
ways in which stress can be caused in chemical equilibrium. They are:

I. Changing the concentration

II. Changing the pressure
III. Changing the temperature

4.Kp=Kc What do you infer from this?

Δn
The equation Kp=Kc(RT) shows the relation between equilibrium constants. If
Δn
Kp=Kc, then (RT) =1, which means Δn=0. This implies that the moles of gaseous
reactants and products are equal. As a result, the equilibrium constant remains the same
whether expressed in pressure or concentration.
5. What is standard free energy change? Derive a relationship between standard free
energy change and equilibrium constant of a reaction at a given temperature (Prove
that ∆G° = - RTIn K1) / Derive van't Hoff reaction isotherm for the reaction:
Ans:
6.Kp and Kc Relation-
Atomic Structure

1.Write Rutherford’s experiment of scattering of α-particles and give the drawbacks of

atomic model.
Ans-In 1909, Rutherford and Marsden conducted the Alpha Particle-Scattering Experiment
to study atomic structure. They aimed high-energy α-particles at a thin gold foil with a
fluorescent screen around it. Most particles passed through, showing that atoms are mostly
empty space. Some deflected, and a few bounced back, proving the presence of a dense,
positively charged nucleus. This led to Rutherford’s Nuclear Atom model. According to it –

• An atom has a tiny, dense nucleus that contains almost its entire mass, leaving the rest
of the atom mostly empty. The nucleus is about 10-13 cm in diameter, compared to the
atom's 10−8cm, making most of the atom empty space.
• The atom's positive charge is in the nucleus, while electrons occupy the empty space
around it. The nucleus repelled α-particles He2+causing them to scatter in different
directions.
• The electrons were moving in orbits or closed circular paths around the nucleus like
planets around the sun.

2. What is the significance of quantum numbers?

Ans- Quantum numbers define the position and behavior of electrons in an atom.
They determine the energy level, shape, orientation, and spin of orbitals. These numbers
help explain atomic structure, chemical bonding, and spectral lines. They are essential for
understanding electron configurations and periodic trends.

3. What are quantum numbers? Which orbitals are possible among 2s, 2d, 3f and 4f?
Ans-Quantum numbers describe an electron's energy level, orbital shape, orientation, and
spin.
The possible orbitals are 2s and 4f. The 2s orbital is possible because s-orbitals exist for all
n ≥1 . The 4f orbital is possible because f-orbitals exist for n ≥ 4 .The 2d and 3f orbitals are
not allowed. The 2d orbital is not possible because d-orbitals require n ≥ 3 The 3f orbital is
not possible because f-orbitals require n≥ 4 .
4. State postulates of Bohr’s theory of an atom and derive an expression for radius of
Bohr orbit of hydrogen atom.

Ans-Bohr proposed a model of the atom to explain the stability of electrons in orbits. The
key postulates are:

• Electrons move around the nucleus in specific circular orbits without occupying any
other paths. Each orbit has a fixed energy and is numbered as n = 1, 2, 3 (or K, L, M).
• While in these orbits, electrons do not lose or gain energy. These fixed orbits are
called stationary energy levels.
• Electrons can move between energy levels by absorbing or releasing a photon. The
lowest energy level is the ground state, and when an electron absorbs energy, it moves
to a higher excited state. The quantum or photon of energy absorbed or emitted is the
difference between t he lower and higher energy levels of the atom E = Ehigh - Elow =
hv. Here his Planck's constant and v the frequency of a photon emitted or absorbed
energy.
• The angular momentum of an electron is always a whole-number multiple of h/2π:
mvr = nh/2π
where n = 1, 2, 3, etc. Since n is always a whole number, angular momentum is
quantized. The value of n is called the Principal Quantum Number, representing the
electron's orbit and energy level.

5. Discuss the following: Hund’s Rule of Maximum multiplicity, Pauli’s Exclusion

Principle, Aufbau principle.
Ans-
Hund’s Rule of Maximum Multiplicity: Electrons fill degenerate orbitals singly first, with
parallel spins, to maximize total spin. This minimizes electron repulsion and stabilizes the
atom.

Pauli’s Exclusion Principle: No two electrons in an atom can have the same set of four
quantum numbers. This ensures each orbital holds a maximum of two electrons with
opposite spins.

Aufbau Principle: Electrons occupy the lowest energy orbitals first before filling higher
ones. This follows the order given by the n + l rule.
6.Calculation of radius of orbits.

Ans-Consider an electron of charge 𝑒 revolving around a nucleus of charge 𝑍 is the atomic

number and 𝑒 is the charge on a proton. Let 𝑚 be the mass of the electron, 𝑟 the radius of the
orbit and 𝑣 the tangential velocity of the revolving electron.

The electrostatic force of attraction between the nucleus and the electron (Coulomb’s law):
Ze² / r²
The centrifugal force acting on the electron: m v² / r
Bohr assumed that these two opposing forces must be balancing each other exactly to keep
the electron in orbit. Thus, Ze² / r² = m v² / r
For hydrogen (Z = 1), therefore, e² / r² = m v² / r ...(1)
Multiplying both sides by r, e² / r = m v² ...(2)
According to one of the postulates of Bohr’s theory, the angular momentum of the revolving
electron is given by the expression: m v r = n h / 2π or v = n h / (2π m r)
Substituting the value of v in equation (2), e² / r = m (n h / (2π m r))²
Solving for r, r = n² h² / (4 π² m e²) ...(4)
Since the values of h, m, and e have been determined experimentally, substituting these
values in (4), we have: r = n² × 0.529 × 10⁻⁸ cm ...(5)
where n is the principal quantum number and hence the number of the orbit.

7. Using Bohr’s atomic model, derive an equation for total energy of orbit of an
electron.

Ans-For a hydrogen atom, the energy of the revolving electron, E, is the sum of its kinetic
energy- mv2/2 and potential energy - (-e2/r). Thus, the total energy is given by: E= (mv2/2) -
(e2/r).

According to Bohr, the electron in hydrogen orbits when two opposing forces balance, mv2
=(e2/r) . Then we write E=(e2/2r)-(e2/r)= -(e2/2r)…(1)

Solving Bohr’s eqution we get, electron’s radius r=(nh)2/4m(πe)2

Substituting the value of r from into equation (1) we get ,E= (-2π2me4)/(nh)2

Substituting the value of m,h,e in this equation, we get E=(-2.179×10-11)/n2 erg/atm

−2.179×10−11
Total energy of orbit of an electron, 𝐸 = J/atom
𝑛2
8. Define quantum numbers. Calculate the value of l, m and number of electrons of the
orbitals when n= 1, 2, 3, 4

Ans-Quantum number: The numbers that are used to describe atomic orbitals and to label
electrons that reside in them are called quantum numbers.

n l m Orbitals e
1 0 0 1s 2
2 0 0 2s 2
1 -1, 0, 1 2p 6
3 0 0 3s 2
1 -1 ,0, 1 3p 6
2 -2, -1, 0, 1, 2 3d 10
4 0 0 4s 2
1 -1, 0, 1 4p 6
2 -2 ,-1, 0, 1, 2 4d 10
3 -3 ,-2 ,-1 ,0, 1, 2, 3 4f 14

9. What is the wavelength of a photon emitted during a transition from the n i = 5 state
to the n f = 2 state in the hydrogen atom? R h = 2.18×10 -18 J.
E = R_H * (1/n_f^2 - 1/n_i^2) - E is the energy of the emitted photon
E = 2.18 × 10⁻¹⁸ J × (1/2² - 1/5²) = 4.578 × 10⁻¹⁹ J - R_H is the Rydberg constant (2.18 ×
10⁻¹⁸ J)
Using the equation: E = hc/λ - n_i is the initial energy level (5 in
this case)
Rearrange for λ: λ = hc/E - n_f is the final energy level (2 in
this case)
Substituting values: λ = (6.626 × 10⁻³⁴ J·s × 3.00 × 10⁸ m/s) / 4.578 × 10⁻¹⁹ J = 4.344 × 10⁻⁷
m = 434.4 nm
The wavelength of the photon emitted during the transition from n_i = 5 to n_f = 2 is
approximately 434.4 nm.
Solution
1. Define colligative properties. State Raoult’s law and derive the Raoult’s law from
Lowering of vapour pressure.
Ans- Colligative properties are physical properties of a solution .They depend on the
number of moles of solute in a solvent. Raoult’s law states that the relative lowering of
vapor pressure of a dilute solution equals the mole fraction of the solute.
(P - P_s) / P = n / (n + N)
Where P = vapor pressure of solvent,P_s = vapor pressure of solution,n = moles of solute,
N = moles of solvent. The vapor pressure of the solvent is P.The vapor pressure of the
solution is P_s.
When a solute dissolves, solute molecules block part of the surface, reducing vapor
pressure. The vapor pressure depends on the number of solvent moles, which is
proportional to the mole fraction of the solvent.
P_s ∝ N / (n + N)
P_s = k (N / (n + N)) ... (1)
For pure solvent, where n = 0:
P = k (N / N)
P = k ... (2)
Comparing (1) and (2), we get:
P_s = P (N / (n + N))
(P_s / P) = (N / (n + N))
1 - (P_s / P) = 1 - (N / (n + N))
(P - P_s) / P = (n + N - N) / (n + N)
(P - P_s) / P = n / (n + N)
Since P > P_s, this proves Raoult’s Law.
2. Describe a method for determining the molar mass of a non-volatile solute by the
relative lowering of vapour pressure of solvent.
Ans-- The molar mass of a non-volatile solute can be found by measuring how much it
lowers the vapor pressure of a solvent. Dissolve w grams of solute in W grams of solvent.Let
m and M be the molar masses of the solute and solvent, respectively.
Moles: Solute: n = w/m and Solvent: N = W/M
Using Raoult’s Law:
(P - P_s) / P = n / (n + N)=> (P - P_s) / P = (w/m) / ((w/m) + (W/M))
For dilute solutions, w/m is small, so we simplify:
(P - P_s) / P = (w/m) / (W/M) => m = (P / (P - P_s)) * (wM / W)

3. What is the molal elevation constant? Show the relationship between the elevation of
boiling point and lowering of vapor pressure.
Ans-The molal elevation constant measures boiling point rise. It occurs when 1 mole of
solute dissolves in 1 kg of solvent. Boiling happens when vapor pressure meets atmospheric
pressure. Solute lowers vapor pressure, needing more heat to boil. If T₀ is the boiling point of
the pure solvent and T₁ is the boiling point of the solution, the boiling point elevation is: ΔT
= T₁ - T₀
The elevation in boiling point is directly proportional to the lowering of vapor pressure:
ΔT ∝ P - Pₛ….(1)
Since P is constant for the same solvent at a fixed temperature, we get:
ΔT ∝ (P - Pₛ) / P ..(2)
From Raoult’s law:(P - Pₛ) / P = (wM) / (mW)
Comparing (1) and (2): ΔT ∝ (wM) / (mW)
Since M is the molar mass of the solvent and a constant: ΔT ∝ w / (mW)
Merging the constant: ΔT = k_b * (w / m) * (1 / W)
m = molar mass of solute, w = weight of solute ,k_b = molal elevation constant ,W = weight
of solvent
 4. What do you understand by depression of freezing point? Derive an expression
relating the freezing point depression of a solution with the mole fraction of the
dissolved solute.

Ans- A liquid freezes when its vapor pressure matches or drops below its solid
phase.Adding a solute increases molecules, making freezing harder. More heat must be
lost.If T_f^0 is the pure solvent’s freezing point and T_f is the solution’s, their difference
ΔT is freezing point depression. ΔT = T_f' - T_f

The depression of the freezing point is directly proportional to the lowering of vapor
pressure.

ΔT ∝ P - Ps ........(1)

Since P is a constant for the same solvent at fixed temperature, from (1) we can write,

ΔT ∝ (P - P_s) / P ........(2)

From Raoult’s law,(P - P_s) / P = nK / nW

Comparing (1) and (2),ΔT ∝ nK / nW

Since M is the molar mass of the solvent, it’s a constant, so,ΔT ∝ K / W

ΔT = k_f × (1 / W) = k_f / w

If w/m or the solute is 1 mol and 1/W or the solvent is 1 kg then ΔT = k_f.

If the mass of the solvent (W) is given in grams, it has to be converted to kilograms.
So, the final expression becomes:

ΔT = k_f × (1 / W) = (1000 k_f) / (wW)

Here: m = molar mass of solute ,w = weight of solute , k_f = molal depression constant
, W = weight of solvent , ΔT = freezing point depression.
5. Define osmosis? State van’t Hoff’s law of osmotic pressure and deduce osmotic
pressure equation p = CRT. The symbols have their usual significance.
Ans- Osmosis is the movement of a solvent from a lower concentration to a higher
concentration through a semipermeable membrane. This membrane allows only the
solvent to pass through, not the solutes.

The equation for this is:

PV = nRT

So, P = (n / V) RT

P=CRT , (n/V)=C

6. Define osmotic pressure. How molecular weight of a substance can be determined

by

osmotic pressure method?

Ans- Osmotic pressure (P)stops solvent flow through a membrane. It follows (P = CRT).
To find molecular weight (M), dissolve mass (w) in volume (V) and measure (P). Use

(M = wRT/PV) ,Substitute values to get (M). This works for large molecules like
proteins.

Using the Van’t Hoff equation:P= VnRT

Since the number of moles n is given by n= w/M, substituting this in: P=wRT /MV

Rearranging for M- M=wRT/PV

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Phase: A state of matter with uniform properties
(like solid, liquid, or gas).
Component: A basic substance that makes up a
system.
Degrees of Freedom: The number of independent
ways a system can change or move.