Chemistry questions

1.Integrated rate law for a first order reaction:

A reaction whose rate depends on the reactant concentration raised to the first power .Let us consider the
following first order reaction,

A→ product

Rate law can be expressed as

𝑅𝑎𝑡𝑒 = 𝑘[𝐴]1
where, K is the first order rate constant
𝑑[𝐴]
− = 𝑘[𝐴]1
𝑑𝑡

𝑑[𝐴]
− [𝐴]
= 𝑘𝑑𝑡

Integrate the above equations between the limits of time t=0 and time equal to t , While the concentration varies
from the initial concentration [𝐴0 ] to [A] at the later time.
[𝐴] 𝑑[𝐴] 𝑡
∫[𝐴 ] − [𝐴]
= 𝑘 ∫0 𝑑𝑡
0

(−𝑙𝑛[𝐴])[𝐴] 𝑡
[𝐴0 ] = 𝑘(𝑡)0

-𝑙𝑛[𝐴] − (−𝑙𝑛[𝐴0 ]) = 𝑘(𝑡 − 0)

−𝑙𝑛[𝐴] + 𝑙𝑛[𝐴0 ] = 𝑘𝑡
[𝐴 ]
ln ( [𝐴]0 ) = 𝑘𝑡

This equation is in natural logarithm .To convert it into usual logarithm with base 10, we have to multiply the
term by 2.303.
[𝐴0 ]
2.303 log [𝐴]
= 𝑘𝑡

2.303 [𝐴 ]
𝑘= log [𝐴]0
𝑡

2.Integrated rate law for zero order reaction:

A reaction in which the rate is independent of the concentration of the reactant over a wide range of
concentrations is called as zero order reaction. Such reactions are rare. Let us consider the following hypothetical
zero order reaction,

A→ product

Rate law can be written as

𝑅𝑎𝑡𝑒 = 𝑘[𝐴]0
𝑑[𝐴]
− = 𝑘(1)
𝑑𝑡

-d[A] = kdt

Integrate the above equation between the limits of [𝐴0 ] at zero time and [A] at some later time ‘t’,
[𝐴] 𝑡
− ∫[𝐴 ] 𝑑[𝐴] = 𝑘 ∫0 𝑑𝑡
0

Chemistry questions -1-

 [𝐴]
−([𝐴])[𝐴0 ] = 𝑘(𝑡)𝑡0

[𝐴0 ] – [𝐴] = 𝑘𝑡
[𝐴0 ]−[𝐴]
𝑘 = 𝑡

3.Half life period of a reaction

The half life of reaction is defined as a time recruit for the reactant concentration to reach one half of its
initial value. For a first order reaction, the half life is a constant i.e., it does not depend on the initial concentration.

The rate constant for a first order reaction is given by

2.303 [𝐴0 ]
𝑘= log [𝐴]
𝑡

[𝐴0 ]
At 𝑡 = 𝑡½ ; [𝐴] = 2

2.303 [𝐴 ]
𝑘= log [𝐴0 ] × 2
𝑡½ 0

2.303
𝑘= log 2
𝑡½

2.303×0.3010 0.6932
𝐾 = 𝑡½
= 𝑡½

0.6932
𝑡½ = 𝑘

4.Ostwald’s dilution law

Ostwald's dilution law relates the dissociation constant of the weak acid(𝐾𝑎 ) with its degree of dissociation
(𝛼) and the concentration (C).Degree of dissociation(𝛼) is the fraction of the total number of moles of a substance
that dissociates at equilibrium.
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑒𝑑
𝛼= 𝑡𝑜𝑡𝑎𝑙 𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒𝑠

We shall derive an expression for ostwald’s law by considering a weak acid i.e. acetic acid (𝐶𝐻3 𝐶𝑂𝑂𝐻). The
dissociation of acetic acid can be represented as

𝐶𝐻3 𝐶𝑂𝑂𝐻 ⇄ 𝐻+ + 𝐶𝐻3 𝐶𝑂𝑂−

The dissociation constant of acetic acid is,

[𝐻 + ][𝐶𝐻3 𝐶𝑂𝑂 −]
𝐾𝑎 = [𝐶𝐻3 𝐶𝑂𝑂𝐻]

𝐶𝐻3 𝐶𝑂𝑂𝐻 𝐻+ 𝐶𝐻3 𝐶𝑂𝑂−

Initial number of moles 1 — —
Degree of dissociation of 𝐶𝐻3 𝐶𝑂𝑂𝐻 𝛼 — —
Number of moles at equilibrium 1−𝛼 𝛼 𝛼
Equilibrium concentration (1 − 𝛼)𝐶 𝛼𝐶 𝛼𝐶

Substituting the equilibrium concentration in the above equation

(𝛼𝐶)(𝛼𝐶) 𝛼2 𝐶 2
𝐾𝑎 = (1−𝛼)𝐶
= (1−𝛼)𝐶

𝛼2 𝐶
𝐾𝑎 = 1−𝛼

Chemistry questions -2-

 We know that weak acid dissociates only to a Very small extent. Compare to 1, 𝛼 is so small and hence in
the denominator (1 − 𝛼) ≈ 1 . The above expression now becomes,

𝐾𝑎 = 𝛼 2 𝐶
𝐾𝑎
𝛼2 = 𝐶

𝑘
𝛼 = √ 𝐶𝑎

The concentration of 𝐻+ (𝐻3 𝑂+ ) calculated using the 𝐾𝑎 value as below.

[𝐻+ ] = 𝛼𝐶

𝑘
[𝐻+ ] = (√ 𝑎 ) 𝐶
𝐶

𝑘𝑎 𝐶 2
=√ 𝐶

[𝐻+ ] = √𝐾𝑎 𝐶

Similarly for weak base

[𝑂𝐻− ] = √𝐾𝑏 𝐶

5. Henderson-Hasselbalch equation

The concentration of hydronium ion in an acidic buffer solution Depends on the concentration of the weak
acid to the concentration of its conjugate base percent in the solution i.e.,
[𝑎𝑐𝑖𝑑]
𝑒𝑞
[𝐻3 𝑂+ ] = 𝐾𝑎
[𝑏𝑎𝑠𝑒] 𝑒𝑞

The weak acid is dissociated only to a small extent. Moreover, due to the common ion effect, the
dissociation is further suppressed and hence the equilibrium concentration of the acid is nearly equal to the initial
concentration of the unionised acid. Similarly the concentration of the conjugate base is nearly equal to the initial
concentration of the added salt.
[𝑎𝑐𝑖𝑑]
[𝐻3 𝑂+ ] = 𝐾𝑎
[𝑠𝑎𝑙𝑡]

Here [acid] and [salt] represent the initial concentration of acid and salt, respectively used to prepare the
buffer solution

Taking logarithm on both sides of the equation

[𝑎𝑐𝑖𝑑]
log[𝐻3 𝑂 + ] = logK a + log [𝑠𝑎𝑙𝑡]

reverse the sign on both sides

[𝑎𝑐𝑖𝑑]
− log[𝐻3 𝑂+ ] = −log𝐾𝑎 − log [𝑠𝑎𝑙𝑡]

We know that

𝑝𝐻 = − log[𝐻3 𝑂+ ] and 𝑝𝐾𝑎 = −𝑙𝑜𝑔𝐾𝑎

[𝑎𝑐𝑖𝑑]
𝑝𝐻 = 𝑝𝐾𝑎 − log [𝑠𝑎𝑙𝑡]

[𝑠𝑎𝑙𝑡]
𝑝𝐻 = 𝑝𝐾𝑎 + log [𝑎𝑐𝑖𝑑]

Chemistry questions -3-

 [𝑠𝑎𝑙𝑡]
Similarly for a base buffer, 𝑝𝑂𝐻 = 𝑝𝐾𝑏 + log [𝑏𝑎𝑠𝑒]

6. Thermodynamics of cell reactions.

In the galvanic cell, the chemical energy is converted into electrical energy. The electrical energy produced
by the cell is equal to the product of the total charge of electrons and the emf of the cell which drives these
electrons between the electrodes.

If 'n' is the number of moles of electrons exchanged between the oxidising and reducing agent in the
overall cell reaction, then the electrical energy produced by the cell is given as below.

Electrical energy = charge of ‘n’ mole of electrons ×𝐸𝑐𝑒𝑙𝑙

Charge of 1 mole of electrons = one Faraday(1F)

∴Charge of ‘n’ moles of electrons = nF

Electrical energy = 𝑛𝐹𝐸𝑐𝑒𝑙𝑙

Charge of one electron = 1.602 × 10−19 𝐶

∴Charge of one mole of electrons = 6.023 × 1023 × 1.602 × 10−19 𝐶

= 96488 C

i.e., 1F ≈ 96500 C

This energy is used to do the electric work. Therefore the maximum work that can be obtained from a
galvanic cell is

(𝑤max )𝑐𝑒𝑙𝑙 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙

Here the (-) sign is introduced to indicate that the work is done by the system on the surroundings.

we know from the second law of thermodynamics that the maximum work done by the system is equal to
the change in the Gibbs free energy of the system.

i.e., 𝑊𝑚𝑎𝑥 = ∆ G

∆𝐺 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙

For a spontaneous cell reaction, the ∆G should be negative. The above expression indicates that 𝐸𝑐𝑒𝑙𝑙
should be positive to get negative ∆G value.

When all the cell components are in their standard state, the equation becomes

∆𝐺° = −𝑛𝐹𝐸°𝑐𝑒𝑙𝑙
We know that the standard free energy change is related to the equilibrium constant as per the following
expression.

∆𝐺° = 𝑅𝑇𝑙𝑛𝐾𝑒𝑞

𝑛𝐹𝐸°𝑐𝑒𝑙𝑙 = 𝑅𝑡𝑙𝑛𝐾𝑒𝑞
2.303𝑅𝑇
𝐸°𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔 𝐾𝑒𝑞
𝑛𝐹

7.Nernst Equation.

Nernst equation is the one which relates the cell potential and the concentration of the species involved in
an electrochemical reaction. Let us considered an electrochemical cell for which the overall redox reaction is,
Chemistry questions -4-
 𝑥A + 𝑦 B ⇄ 𝑙C + 𝑚D

The reactant quotient Q for the above reaction is given below

[C]𝑙 [D]m
𝑄= [𝐴]𝑥 [𝐵]𝑦

We have already learnt that,

∆G = ∆G° + RTlnQ

The Gibbs free energy can be related to the cell emf as follows

∆𝐺 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙 ; ∆𝐺° = −𝑛𝐹𝐸°𝑐𝑒𝑙𝑙

Substitute the above values
[C]𝑙 [D]𝑚
−𝑛𝐹𝐸𝑐𝑒𝑙𝑙 = −𝑛𝐹𝐸°𝑐𝑒𝑙𝑙 + 𝑅𝑇𝑙𝑛 [𝐴]𝑥[𝐵]𝑦

Divide the whole equation by (-nF)

𝑅𝑇 [ 𝐶]𝑙 [𝐷]𝑚
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − 𝑙𝑛 [𝐴]𝑥 [𝐵]𝑦
𝑛𝐹

2.303𝑅𝑇 [𝐶]𝑙 [𝐷]𝑚

𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − 𝑙𝑜𝑔 [𝐴]𝑥 [𝐵]𝑦
𝑛𝐹

The above equation is called Nernst equation.

At 25°C (298K) and substituting the known values of (𝑅 = 8.314𝐽𝐾 −1 𝑚𝑜𝑙−1 ) , ( 𝑇 = 298𝐾), (1𝐹 =
96500𝐶𝑚𝑜𝑙 −1 ) , the above equation becomes,
2.303×8.314×298 [𝐶]𝑙 [𝐷]𝑚
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − 𝑙𝑜𝑔 [𝐴]𝑥 [𝐵]𝑦
𝑛(96500)

0.0591 [𝐶] 𝑙 [𝐷]𝑚

𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − 𝑙𝑜𝑔 [𝐴]𝑥 [𝐵]𝑦 .
𝑛

8.packing efficiency of simple cubic system.

𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑 𝑏𝑦 𝑠𝑝ℎ𝑒𝑟𝑒 𝑖𝑛 𝑢𝑛𝑖𝑡 𝑜𝑛𝑒 𝑐𝑒𝑙𝑙
Packing efficiency = × 100
volume of unit cell

Consider cube with edge length ‘a’

Volume of cube with edge length a is, a×a×a = a³

Let ‘r’ be the radius of the sphere, 𝑎 = 2𝑟

𝑎
𝑟=2

Chemistry questions -5-

 4𝜋𝑟 3
Volume of sphere with radius 𝑟 = 3

4 𝑎 3 4 𝑎3
= 3 𝜋 ( 2 ) =⟩ 3 𝜋 8

𝜋𝑎 3
= 6

𝜋𝑎 3
Total volume occupied by sphere in a SC unit cell = 1 × 6

𝜋𝑎 3
= 6

𝜋𝑎3
6
Packing fraction of SC = × 100
𝑎3
𝜋
= 6 × 100
100𝜋 100×3.14
= 6
= 6
31.4
= = 52.33%
6

9. Packing efficiency of a Body Centred Cubic system.

Here, the spheres are touching along the leading diagonal of the cube.

In ∆ABC,

𝐴𝐶² = 𝐴𝐵² + 𝐵𝐶²

𝐴𝐶 = √𝐴𝐵2 + 𝐵𝐶 2

𝐴𝐶 = √𝑎 2 +𝑎2 = √2𝑎 2

𝐴𝐶 = √2𝑎

In ∆ACG,

𝐴𝐺 2 = 𝐴𝐶 2 + 𝐶𝐺 2

2
𝐴𝐺 = √𝐴𝐶 2 + 𝐶𝐺 2 = √(√2𝑎) + 𝑎 2

𝐴𝐺 = √3𝑎 2 = 𝑎√3

√3
𝑎√3 = 4𝑟 =⟩ 𝑟 = 𝑎
4
4
Volumes of sphere of radius r is 𝑉 = 3 𝜋𝑟 3

Chemistry questions -6-

 3
4 √3
𝑉 = 𝜋 (𝑎 )
3 4

√3 3
𝑉= 𝜋𝑎
16
No of spheres belongs to a unit cell in BCC arrangement is Two and hence the total volume of all spheres.

√3 3 √3 3
𝑉 = 2× 𝜋𝑎 = 𝜋𝑎
16 8
√3
𝜋𝑎 3
8
Packing efficiency = × 100
𝑎3

√3𝜋
= × 100
8

1.732
= × 3.141 × 100
8
= 68%

68% of the available volume is occupied. The available space is used more effectively than SC packing.

10.Homogeneous catalysis and heterogeneous catalysis.

Homogeneous catalysis:

In a homogeneous catalysed reaction the reactants products and catalyst are present in the same phase.

E.g. : 2𝑆𝑂2 (𝑔) + 𝑂2(𝑔) + [𝑁𝑂](𝑔) → 2𝑆𝑂3(𝑔) + [𝑁𝑂](𝑔)

In this reaction the catalyst NO, reactants, 𝑆𝑂2 and 02 , and products, 𝑆𝑂3 are present in the gaseous form.

Heterogeneous catalysis:

In a reaction, the catalyst is present in a different phase i.e. it is not present in the same phase as that of
reactants or products. This is generally referred as contact catalysis and the catalyst present is in the form of finely
divided metal or as gauze.

E.g. : In the Haber process for the manufacture of ammonia, iron is used as catalyst for the reaction
between hydrogen and nitrogen.
𝐹𝑒(𝑠)
𝑁2 (𝑔) + 3𝐻2 (𝑔) → 2𝑁𝐻3 (𝑔)

In this reaction reactants nitrogen𝑁2 , hydrogen 𝐻2 and products ammonia are in gaseous state but catalyst
iron [Fe] in solid state.

11.lyophilic colloidal sol and lyophobic colloidal sol

S.no Lyophilic colloidal sol Lyophobic colloidal sol

1. Definite attractive force or affinity exists between No attractive force exists between the dispersed
the disposed phase and dispersion medium. phase and dispersion medium.
2. Hence they are more stable. Hence they are less stable.
3. Will not get precipitated easily. Get precipitated easily.
4. Can be brought back to the colloidal solution even Cannot be brought back to the colloidal solution
after the precipitation by addition of the dispersion after the precipitation by addition of the dispersion
medium. medium.
5. Reversible sols. Irreversible sols.

Chemistry questions -7-

Y12. What are the differences between a sol and a gel?

Sol Gel
The liquid state of colloidal solution. The solid or semisolid stage of a colloidal solution.
Very low viscosity. Very high viscosity.
It does not have definite structure. It possesses definite structure.

13.Write the difference among graphite, diamond and fullerenes.

Graphite Diamond Fullerenes

Nature Soft. Very hard. Discrete molecules of
𝐶50 , 𝐶60
Conductivity Conducts electricity and Does not conduct 𝐶60 Bucky ball like
heat. electricity. structure.
Hybridization SP². SP³. SP².
Bond length C-C bond length is 1.41Å. C-C bond length is 1.54Å. C-C bond length is 1.44Å
Uses Lubricant oil. Rock drilling, cutting Catalyst medicine.
glasses.

14.Distinguish between primary, secondary and tertiary aliphatic amines

S.no. Reaction with Primary amine 1° Secondary amine 2° Tertiary amine 3°

1. 𝐻𝑁𝑂2 Forms alcohol Forms n-nitroso amine Forms salt
2. 𝐶𝐻𝐶𝑙3 \𝐾𝑂𝐻 Forms carbylamines No reaction No reaction
3. 𝐶𝐻3 𝐶𝑂𝐶𝑙 Forms N-alkyl acetamide Forms N, N dialkyl No reaction
acetamide
4. 𝐶𝑆2 𝑎𝑛𝑑 𝐻𝑔𝐶𝑙2 Forms alkyl isothio No reaction No reaction
cyanide.
5. Diethyl oxalate at Forms a solid dialkyl Forms N,N dialkyl oxamic No reaction
room temperature oxamide ester a liquid
With 3 molecules of Alkyl With 2 molecules of Alkyl With 3 molecules of
6. Alkyl halide halide: quaternary halide: quaternary Alkyl halide: quaternary
ammonium salt is formed ammonium salt is formed ammonium salt is
formed

Chemistry questions -8-