Date : 20/03/2025 Chemistry GSEB Chapter : 4, 5 & 6

Time : 3 hours Std 11 : Chemistry Total Marks : 80

GSEB Chemistry

Section A
Write the answer of the following questions : (Each carries 1 Mark) [11]

1. What type of hybridization does SF6 molecule have?

2. What is the magnetic nature of O2 ?
3. What type of hydrogen bond is formed in o-nitrophenol?
4. Calculate the number of kJ of heat necessary to raise the temperature of 60.0 g aluminum from 35 °C to 55 °C. Molar heat capacity of Al is 24
J mol–1 K–1
5. Calculate the enthalpy change on freezing of 1.0 mol of water at 10.0°C to ice -10.0°C. ΔH = 6.03 kJ mol-1, Cp[H2O(l)] = 75.3 J mol-1 K Cp
[H₂O(s)] = 36.8 J mol-1 K
6. Write the third law of thermodynamics.
7. Give any two examples of extensive properties.
8. Give any two examples of intensive properties.
9. What is equilibrium?
I
State the characteristics of dynamic equilibrium.
DS

10.

11. Describe the dielectric constant of water.

Section B
Write the answer of the following questions : (Each carries 2 Marks) [24]

12. Explain the reason for formation of hydrogen bond with example.
13. Explain the formation of the CO3–2 ion in terms of (with reference to) resonance.
14. The reaction of cyanamide, NH2CN(s), with dioxygen was carried out in a bomb calorimeter, and ∆U was found to be –742.7 kJ mol–1 at 298
K. Calculate enthalpy change for the reaction at 298 K.
NH2CN(g) + O2(g) → N2(g) + CO2(g) + H2O(l)
15. Enthalpies of formation of CO(g), CO2(g), N2O(g) and N2O4(g) are –110, – 393, 81 and 9.7 kJ mol–1 respectively. Find the value of ∆rH for the
reaction : N2O4(g) + 3CO(g) → N2O(g) + 3CO2(g)
16. Calculate the enthalpy change for the process CCl4(g) → C(g) + 4 Cl(g) and calculate bond enthalpy of C – Cl in CCl4(g).
∆vapHK (CCl4) = 30.5 kJ mol–1.
∆fHK (CCl4) = –135.5 kJ mol–1.
∆aHK (C) = 715.0 kJ mol–1, where ∆aHK is enthalpy of atomisation
∆aHK (Cl2) = 242 kJ mol–1
17. For the reaction at 298 K,
2A + B → C
∆H = 400 kJ mol–1 and ∆S = 0.2 kJ K–1 mol–1
At what temperature will the reaction become spontaneous considering ∆H and ∆S to be constant over the temperature range.

Page No.: 1
18. Calculate the entropy change in surroundings when 1.00 mol of H2O(l) is formed under standard conditions. ∆fHK = –286 kJ mol–1.
19. Explain the relationship between Cp and Cv for an ideal gas.
20. Explain Hess’s Law of Constant Heat Summation
21. What is the minimum volume of water required to dissolve 1g of calcium sulphate at 298 K? (K for calcium sulfate is 9.1 × 10–6).
22. Calculate the pH of the following solutions:
(a) Dissolve 2 g of TIOH in water to form a 2L solution.
(b) Dissolve 0.3 g of Са(ОН)2 in water to make a 500 ml solution.
(c) Dissolve 0.3 g of NaOH in water to make a 200 ml solution.
(d) Dilute 1 ml of 13.6 M HCl with water to make 1 liter of solution.
23. Nitric oxide reacts with bromine to give nitrosyl bromide according to the procedure given below. 2NO(g) + Br2(g)  2NOBr(g) When 0.087
mol NO and 0.0437 mol Br₂ are mixed in a closed vessel at constant temperature, 0.0518 mol NOBr is obtained at equilibrium. Determine the
equilibrium amount of NO and Br2.
Section C
Write the answer of the following questions : (Each carries 3 Marks) [24]

24. Discuss the shape of the following molecules using the VSEPR model : BeCl2, BCl3, SiCl4, ASF5, H2S, PH3
25. Write the rules of Fajan.
26. Write the postulates of VSEPR theory.
27. What is Formal charge? Explain it by giving example.
28. Calculate the standard enthalpy of formation of CH3OH(l) from the following data :
CH3OH(l) + O2(g) → CO2(g) + 2H2O(l); DrH0 = –726 kJ mol–1
I
C(graphite) + O2(g) → CO2(g); DcH0 = –393 kJ mol–1
DS

H2(g) + O2(g) → H2O(l); DfH0 = –286 kJ mol–1

29. Explain DH = qp
30. The solubility coefficients of Ag2CrO4 and AgBr are 1.1 x 10–12 and 5.0 × 10–13 respectively. Calculate the ratio of molarity of their saturated
solutions.
31. State the characteristic of a catalyst Explain the effect of a catalyst on equilibrium.

Section D
Write the answer of the following questions : (Each carries 4 Marks) [16]

32. What is Kc and Kp? Derive the relationship between Kc and Kp.
33. Explain the effect of a change in concentration on equilibrium.
34. The ionization constant of propanoic acid is 1.32 x 10–5. Then find its ionisation degree and pH of 0.05 M aqueous solution. If the solution
also contains 0.01 M HCI, find the ionization fraction of the solution.
35. The first ionization constant of H2S is 9.1 × 10–8. Calculate the concentration of HS– ion in its 0.1 M solution. If this solution contains 0.1 M
HCI, what will be the effect on the calculated concentration? If the secondary ionization constant of H2S is 1.2 × 10–13, calculate the
concentration of S–2 ion under both conditions.
Section E
Write the answer of the following questions : (Each carries 5 Marks) [5]

36. Describe the hybridization in case of PCl5. Why are the axial bonds longer as compared to equatorial bonds?

Page No.: 2
 Date : 20/03/2025 Chemistry GSEB Chapter : 4, 5 & 6
Time : 3 hours Std 11 : Chemistry Total Marks : 80

Answer Key

Section A
Write the answer of the following questions : (Each carries 1 Mark) [11]

1. What type of hybridization does SF6 molecule have?

 sp3d2
2. What is the magnetic nature of O2 ?
 Paramagnetic
3. What type of hydrogen bond is formed in o-nitrophenol?
 Intramolecular hydrogen bonding.
4. Calculate the number of kJ of heat necessary to raise the temperature of 60.0 g aluminum from 35 °C to 55 °C. Molar heat capacity of Al is 24
J mol–1 K–1
 q = n × C × DT
= × 24 × (55 – 35)
= 1066.77 J
= 1.07 J
5. Calculate the enthalpy change on freezing of 1.0 mol of water at 10.0°C to ice -10.0°C. ΔH = 6.03 kJ mol-1, Cp[H2O(l)] = 75.3 J mol-1 K Cp
[H₂O(s)] = 36.8 J mol-1 K
 The total enthalpy change will be equal to the sum of the enthalpy changes of the following three phases.
(1) The enthalpy changes ΔH1, when 1 mol of water is converted from 10 °C to 0 °C, is
DH1 = nCp⋅ DT
= 1 × 75.3 × (0 – 10)
= –753 J / mol
DH1 = –0.753 kJ / mol
(2) When 1 mol of water is converted to 1 mol of ice at 0 °C, the enthalpy change is ΔH2 then
DH2 = –DfusH = –6.03 kJ / mol
(3) The enthalpy change ΔH3 when 1 mol of ice is converted from 0 °C to –10 °C, is
DH3 = nCp ⋅ DT
= 1 × 36.8 × (–10 – 0)
= –368 J / mol
= –0.368 kJ / mol
Total enthalpy change
DH = DH 1 + DH 2 + DH 3
= –0.753 – 6.03 – 0.368
DH = –7.151 kJ/mol

6. Write the third law of thermodynamics.

 The entropy of any pure crystalline substance tends to be zero as the temperature approaches absolute zero.
7. Give any two examples of extensive properties.

Page No.: 1
 Mass and size
8. Give any two examples of intensive properties.
 Temperature and pressure
9. What is equilibrium?
 Equilibrium refers to a condition of a system where the forward and backward processes of a reversible reaction occur at the same rate.
10. State the characteristics of dynamic equilibrium.
 During dynamic equilibrium the rate of the forward and backward reaction are the same.
11. Describe the dielectric constant of water.
 The dielectric constant of water is 80.
Section B
Write the answer of the following questions : (Each carries 2 Marks) [24]

12. Explain the reason for formation of hydrogen bond with example.
 When hydrogen bonds is with a strongly electronegative element ‘X’, the electron shared between the two atoms moves away from the
hydrogen atom, so that the hydrogen atom becomes more electropositive compared to the other ‘X’.
 As the electron-pair is displaced towards ‘X’ it acquires a partial positive charge (δ+) when X acquires partial negative charge (δ-). As a result,
a polar molecule with a stable electrostatic attraction force is formed.

 The amount of H-bonding depends on the physical state of the compound. H-bonding is maximum in solid state and minimum in gaseous
state.
13. Explain the formation of the CO3–2 ion in terms of (with reference to) resonance.
 Sol. :
 The Lewis structure based on the presence of both single and double bonds between carbon and oxygen is incomplete because it represents
unequal bonds.
 According to experimental data, in the CO3–2 ion, all carbon-oxygen bonds are found to be equivalent. Therefore, carbonate ion can be better
described in resonance forms I, II, and III, which are depicted below:

14. The reaction of cyanamide, NH2CN(s), with dioxygen was carried out in a bomb calorimeter, and ∆U was found to be –742.7 kJ mol–1 at 298
K. Calculate enthalpy change for the reaction at 298 K.
NH2CN(g) + O2(g) → N2(g) + CO2(g) + H2O(l)
 Dng = np – nr
=2–
=2–
=–
DH = DU + DngRT
= –742.7 + (8.314 × 10–3) (298)
= –742.7 – 1.2
Page No.: 2
 = –743.9 kJ/mol
15. Enthalpies of formation of CO(g), CO2(g), N2O(g) and N2O4(g) are –110, – 393, 81 and 9.7 kJ mol–1 respectively. Find the value of ∆rH for the
reaction : N2O4(g) + 3CO(g) → N2O(g) + 3CO2(g)
 DrH = ∑DfH(product) – ∑DfH(reactant)
= [DfH(N2O) + 3DfH(CO2)] – [DfH(N2O4) + 3DfH(CO)
= [81 + 3(–393)] – [9.7 + 3(–110)]
= –777.7 kJ / mol
16. Calculate the enthalpy change for the process CCl4(g) → C(g) + 4 Cl(g) and calculate bond enthalpy of C – Cl in CCl4(g).
∆vapHK (CCl4) = 30.5 kJ mol–1.
∆fHK (CCl4) = –135.5 kJ mol–1.
∆aHK (C) = 715.0 kJ mol–1, where ∆aHK is enthalpy of atomisation
∆aHK (Cl2) = 242 kJ mol–1
 (i) CCl4(l) → CCl4(g) DvapH0 = 30.5 kJ/mol
 (ii) C(s) + 2Cl2(g) → CCl4(l) DfH0 = –135.5 kJ/mol
 (iii) C(s) → C(g) DaH0 = 715 kJ/mol
 (iv) Cl2(g) → 2Cl(g) DaH0 = 242 kJ/mol
 Now, CCl4(g) → C(g) + 4Cl(g) for this find out the enthalpy change.
DH = [715 + 2(242)] – [30.5 + (–135.5)]
= 1304 kJ / mol
Bond enthalpy of C – Cl = = 326 kJ / mol
17. For the reaction at 298 K,
2A + B → C
∆H = 400 kJ mol–1 and ∆S = 0.2 kJ K–1 mol–1
At what temperature will the reaction become spontaneous considering ∆H and ∆S to be constant over the temperature range.
 ΔG = 0 for a balanced process
\ DG = DH – TDS
\ 0 = DH – TDS
\ T DS = DH
\T= = = 2000 K
 The reaction is in equilibrium at a temperature of 2000 K. Hence at temperatures higher than 2000 K the reaction takes place spontaneous.
18. Calculate the entropy change in surroundings when 1.00 mol of H2O(l) is formed under standard conditions. ∆fHK = –286 kJ mol–1.
 H2(g) + O2(g) → H2O(l) Df H = –286 kJ / mol
 When 1 mole of H2O(l) is formed –286 kJ of heat is released. This heat is absorbed by the surrounding.
qsurr = +286 kJ / mol
DS = = = 0.9597 kJ / mol
19. Explain the relationship between Cp and Cv for an ideal gas.
 At constant volume, the heat capacity, C is denoted by Cv and at constant pressure, this is denoted by Cp.
 At constant qv = CvDT = DU
 At constant qp = CpDT = DH
 The difference between Cp and Cv can be derived for an ideal gas as:
 For a mole of an ideal gas, DH = DU + D(pV)
= DU + D(RT)
= D U + RD T

Page No.: 3
 \ D H = D U + RD T
 On putting the values of ΔH and ΔU, we have
CpDT = CvDT + RDT
Cp = C v + R
Cp – Cv = R
20. Explain Hess’s Law of Constant Heat Summation
 “If a reaction takes place in several steps then its standard reaction enthalpy is the sum of the standard enthalpies of the intermediate
reactions into which the overall reaction may be divided at the same temperature.”
 Let us understand the importance of this law with the help of an example.
 Consider the enthalpy change for the reaction
C(graphite, s) + O2(g) → CO(g); DH6 = ?
 Although CO(g) is the major product, some CO2 gas is always produced in this reaction. Therefore, we cannot measure enthalpy change for the
above reaction directly. However, if we can find some other reactions involving related species, it is possible to calculate the enthalpy change
for the above reaction.
 Let us take the following reactions :
C(graphite, s) + O2(g) → CO2(g);
DrH6 = –393.5 kJ mol–1 .... (i)
CO(g) + O2(g) → CO2(g);
DrH6 = –283.0 kJ mol–1 ... (ii)
 We combine both the above reactions in such a way that we get the desired reactions. Let’s write equation (ii) reverse to get one mole CO(g) on
the right-hand side. Here the heat will be absorbed instead of generated. Hence, we will change the value of DrH6.
 CO2(g) → CO(g) + O2(g);
DrH6 = +283.0 kJ mol–1 ... (iii)
 Summing equation (i) and (iii) we get the desired equation.
C(graphite, s) + O2(g) → CO(g);
For that, DrH6 = (–393.5 + 283.0)
= –110.5 kJ mol–1
 In general if the enthalpy of the overall process A → B is DrH in a single phase and DrH1, DrH2, DrH3, ... are the enthalpies of different
intermediate processes finally giving the product B then calculating the other way round,
DrH = DrH1 + DrH2 + DrH3, ...
It represented as below:

21. What is the minimum volume of water required to dissolve 1g of calcium sulphate at 298 K? (K for calcium sulfate is 9.1 × 10–6).
 +
SSS
Ksp = [Ca+2] [SO4–2]
= (S) (S)
= S2
S=
=
= 3.017 × 10–3 M

Page No.: 4
 M=
VL =
VL = 2.437 L
22. Calculate the pH of the following solutions:
(a) Dissolve 2 g of TIOH in water to form a 2L solution.
(b) Dissolve 0.3 g of Са(ОН)2 in water to make a 500 ml solution.
(c) Dissolve 0.3 g of NaOH in water to make a 200 ml solution.
(d) Dilute 1 ml of 13.6 M HCl with water to make 1 liter of solution.
 (a) Atomic weight of TIOH = 221 u
M=
=
= 4.52 × 10–3 M
∴ [OH–] = 4.52 × 10–3 M
∴ pOH = –log [OH–]
= –log [4.52 × 10–3]
= 3 log 10 – log 4.52
= 3.0000 – 0.6551
∴ pOH = 2.3449
∴ pH = 14 – 2.3449
= 11.6551
(b) Molecular mass of Ca(OH)2 = 74 u
M=
=
= 0.0081 M
Now, → Ca+2(aq) + 2OH–(aq)

∴ [OH–] = 2 × 0.0081
= 0.0162
= 1.62 × 10–2 M
∴ pOH = –log [OH–]

= –log (1.62 × 10–2)

= 2 log 10 – log 1.62
= 2.0000 – 0.2095
∴ pOH = 1.7905
∴ pH = 14 – 1.7905
= 12.21
(c) Molecular mass of NaOH = 40 u
M=
=
M = 0.0375 M
(OH–) = 3.75 × 10­–2
∴ pOH = –log [OH–]

= –log (3.75 × 10–2)

= 2 log 10 – log 3.75
= 2.0000 – 0.5740
pOH = 1.426
Page No.: 5
 pH = 14 – 1.426
= 12.574
(d) Dilution M1V1 = M2V2
∴ 13.6 × 1 = M2 × 1000

∴ M2 = 1.36 × 10–2 M

∴ [H3O+] = 1.36 × 10–2 M

Now, pH = –log [H3O+]

= –log (1.36 × 10–2)
= 2 log 10 – log 1.36
= 2.0000 – 0.1335
= 1.8665
23. Nitric oxide reacts with bromine to give nitrosyl bromide according to the procedure given below. 2NO(g) + Br2(g)  2NOBr(g) When 0.087
mol NO and 0.0437 mol Br₂ are mixed in a closed vessel at constant temperature, 0.0518 mol NOBr is obtained at equilibrium. Determine the
equilibrium amount of NO and Br2.


 Here, at equilibrium 2x= 0.0518

∴ x = 0.0259 mol
∴ [NO]eq = 0.087 – 2x
= 0.087 – 0.0518
= 0.0352 mol
∴ [Br2]eq = 0.0437 – x
= 0.0437 – 0.0259
= 0.0178 mol
Section C
Write the answer of the following questions : (Each carries 3 Marks) [24]

24. Discuss the shape of the following molecules using the VSEPR model : BeCl2, BCl3, SiCl4, ASF5, H2S, PH3
 (i) According to VSEPR, BeCI2, is an AB2 type compound, which is linear in shape.

 (ii) According to VSEPR, BCl3 is a compound of type AB3 having trigonal planar shape.

 (iii) According to VSEPR, SiCl4 is a AB4 type of compound, having tetrahedral shape.

 (iv) According to VSEPR, AsF5 is a AB5 type of compound, having trigonal bipyramid shape.

Page No.: 6
 (v) According to VSEPR, H2S is a AB2E2 type of compound, having bent or V shape.

 (vi) According to VSEPR, PH3 is a AB3E type of compound, having trigonal bipyramid shape.

25. Write the rules of Fajan.

 When the size of the cation is smaller and that of the anion is larger, the ionic bond exhibits more covalent characteristics.
 If the cation has a greater charge, then the covalent character of the ionic bond increases.
 When the sizes and charges are the same, the transition metal cation has an electronic configuration of (n–1)dns0, similar to that of noble gases
like ns2np6. Therefore, it undergoes more covalent bonding.
 The cation pulls the electronic charge towards itself, polarizing the anion more, resulting in an increase in the electron charge between them.
 The covalent bond forms in such a way that the charge density is concentrated between the two centers.
 The polarizability of the cation, the electronegativity of the anion, and distortion (polarization) metrics (polarizability) are crucial for
determining the covalent characteristics of the ionic bond.
26. Write the postulates of VSEPR theory.
 This theory provides a simple procedure to predict the shapes of covalent molecules. Sidgwick and Powell in 1940, proposed a simple theory
based on the repulsive interactions of the electron pairs in the valence shell of the molecules.
 It was further developed and redefined by Nyholm and Gillespie (1957), which is known as VSEPR principle.
 Postulates:
 The shape of a molecule depends upon the number of valence shell electron pairs (bonded or nonbonded) around the central atom.
 Pairs of electrons in the valence shell repel one another since their electron clouds are negatively charged.
 These pairs of electrons tend to occupy such positions in space that minimise repulsion and thus maximise distance between them.
 The valence shell is taken as a sphere with the electron pairs localising on the spherical surface at maximum distance from one another.
 A multiple bond is treated as if it is a single electron pair and the two or three electron pairs of a multiple bond are treated as a single super
pair.
 Where two or more resonance structures can represent a molecule, the VSEPR model is applicable to any such structure.
 The repulsive interaction of electron pairs decreases in the order:

27. What is Formal charge? Explain it by giving example.

 The shape of an atom or ion cannot be represented by a (polyatomic) Lewis dot-structure or Lewis diagram. Because the charge on an
atom/ion is not the charge of each molecule, but the total charge. Hence, it is imperative to know the charge on each atom, which is called the
formal charge.”
 “If a part of an atom has more electrons than its valence, it is negative and if it has fewer electrons, it is called positive charge.

 Example :
 Ozone (O3)
 Lewis’s structure of O3 :

Page No.: 7
 The order 1, 2, 3 is given to identify oxygen and each neutral oxygen atom has 6 valence electrons. Formal charge of middel O atom (order 1)
= 6 – 2 – (6)
=6–2–3
=+1
 Formal charge of O atom at end (order 2)
= 6 – 4 – (4)
=6–4–2
=0
 Formal charge of O atom at end (order 3)
= 6 – 6 – (2)
=6–6–1
=–1
 So, the structure of O3 with formal charge :

28. Calculate the standard enthalpy of formation of CH3OH(l) from the following data :
CH3OH(l) + O2(g) → CO2(g) + 2H2O(l); DrH0 = –726 kJ mol–1
C(graphite) + O2(g) → CO2(g); DcH0 = –393 kJ mol–1
H2(g) + O2(g) → H2O(l); DfH0 = –286 kJ mol–1
 C + 2H2 + O2 → CH3OH(l) DfH0 = ?
C(graphite) + O2(g) → CO2(g);
DcH0 = –393 kJmol–1 .... (1)
2H2(g) + O2(g) → 2H2O(l);
DH0 = –572 klJ mol–1 ... (2)
Addition of eqn (1) and (2),

29. Explain DH = qp
 The heat absorbed at constant volume is equal to change in the internal energy.
DU = qV
 But most of the chemical reactions are carried out not at constant volume, but in flasks or test tubes under
constant atmospheric pressure.
ΔU = q + w write at constant pressure,
DU = qp – pDV
Where, qp = Heat absorbed by the system
p ⋅ DV = represent expansion work done by the system.
 Let us represent the initial state by subscript 1 and final state by 2.

Page No.: 8
 We can rewrite the above equation as :
U2 – U1 = qp – p(V2 – V1)
On rearranging, we get
qp = (U2 + pV2) – (U1 + pV1) ... ... (1)
 Now we can define another thermodynamic function, the enthalpy H [Greek word Enthalpien, to warm or heat content] as :
H = U + pV
 So, equation (1) becomes
qp = H2 – H1
\ qV = DH
 Although q is a path dependent function, H is a state function because it depends on U, p and V all of which are state functions. Therefore, ΔH
is independent of path. Hence, qp is also independent of path.
 ΔH = qp is the absorbed heat at constant pressure.
 ΔH is negative for exothermic reactions which evolve heat during the reaction and ΔH is positive for endothermic reactions.
30. The solubility coefficients of Ag2CrO4 and AgBr are 1.1 x 10–12 and 5.0 × 10–13 respectively. Calculate the ratio of molarity of their saturated
solutions.
 +
S 2S S
Ksp = [Ag+]2 [CrO4–2]
= (2S)2 (S)
Ksp = 4S3
S= =
S = 6.503 × 10–5 M
 AgBr(s) +
SSS
Ksp = [Ag+] [Br–]
= (S)2
S=
=
= 7.07 × 10–7 M
 Ratio of concentration of molarity = = 91.93
So, Ag2CrO4 is 92 time soluble than AgBr.
31. State the characteristic of a catalyst Explain the effect of a catalyst on equilibrium.
 A catalyst increases the rate of the chemical reaction by making available a new low energy pathway for the conversion of reactants to
products. It increases the rate of forward and reverse reactions that pass through the same transition state and does not affect equilibrium.
 Catalyst lowers the activation energy for the forward and reverse reactions by exactly the same amount. Catalyst does not affect the
equilibrium composition of a reaction mixture. It does not appear in the balanced chemical equation or in the equilibrium constant expression.
 Effect of catalyst on Equilibrium :
(1) + ∆H = –92.38 kJ/ mol
 The formation of NH3 from dinitrogen and dihydrogen which is highly exothermic reaction and proceeds with decrease in total number of
moles formed as compared to the reactants. Equilibrium constant decreases with increase in temperature. At low temperature rate decreases
and it takes long time to reach at equilibrium, whereas high temperatures give satisfactory rates but poor yields.
 German chemist, Fritz Haber discovered that a catalyst consisting of iron catalyse the reaction to occur at a satisfactory rate at temperatures,
where the equilibrium concentration of NH3 is reasonably favourable. Since the number of moles formed in the reaction is less than those of
reactants, the yield of NH3 can be improved by increasing the pressure.
 Optimum conditions of temperature and pressure for the synthesis of NH3 using catalyst are around 500°C and 200 atm.
(2) Similarly, in manufacture of sulphuric acid by contact process,

Page No.: 9
 + Kc = 1.7 × 1026 K though the value of K is suggestive of reaction going to completion, but practically
the oxidation of SO2 to SO3 is very slow. Thus, platinum or divanadium penta-oxide (V2O5) is used as catalyst to increase the rate of the
reaction.
 If the value of the equilibrium constant Kc of a chemical process is very small, the use of a catalyst is not particularly useful.
Section D
Write the answer of the following questions : (Each carries 4 Marks) [16]

32. What is Kc and Kp? Derive the relationship between Kc and Kp.
 If the components of a chemical reaction in equilibrium are in solid, liquid or gas form, its Kc can be found. But if even one of its components
is in gaseous form, its equilibrium constants Kc and Kp can be found. Kc and Kp need not be equal for the reaction.
 A general reaction in which a and b moles of reactants A and B, respectively, produce c and d moles of C and D, respectively. Since this
reaction is reversible, equilibrium is established in a closed vessel at fixed temperature as follows.
aA(g) + bB(g)  cC(g) + dD(g)
 Now the concentrations in moles/liter of A, B, C and D at equilibrium are CA, CB, CC and CD respectively.
- (i)
 Here, since all the reactants and products are gaseous, their concentrations at equilibrium at partial pressures are PA, PB, PC and PD
respectively, as
∴ - (ii)
 Here each reactant and product is gaseous and therefore behaves like an ideal gas, integrating with the general gas equation,
PV = nRT
∴

∴ P = CRT
Where P = Pressure in unit Pa
n = Numbers of moles (Gas)
V = Volume of gas (litre)
T = Temperature (K)
= Concentration
E = 0.0831
 Now if the concentration of A, B C and D are CA, CB, CC and CD respectively then,
PA = CART, PC = CCRT
PB = CBRT, PD = CDRT
 Put this value of partial pressure in to eq(2)
b......(3)

Now,

Now, put
 But, putting (c + d) – (a + b) = (moles of gaseous products) – (moles of gaseous reactants) = ∆n(g)
Kp = Kc (RT)∆n(g)
 Now if Δn(g) = 0 that means the moles of product and reactant of gas is equal than Kp = Kc
If Δn(g) ≠ 0 then Kp ≠ Kc
If Δn(g) > 0 then Kp > Kc
If Δn(g) < 0 then Kp < Kc
 Always express the pressure in bar when calculating the value of Kp.
Page No.: 10
 1 Pa = 1N /m2 and 1bar = 105 Pa.
33. Explain the effect of a change in concentration on equilibrium.
 In general, when equilibrium is disturbed by the addition/removal of any reactant/ products, Le Chatelier’s principle predicts that:
 The concentration stress of an added reactant/product is relieved by net reaction in the direction that consumes the added substance.
 The concentration stress of a removed reactant/product is relieved by net reaction in the direction that replenishes the removed substance. or in
other words, “When the concentration of any of the reactants or products in a reaction at equilibrium is changed, the composition of the
equilibrium mixture changes so as to minimize the effect of concentration changes”.
 Concentration Effect in Homogeneous Equilibrium:
 In reaction, + 2HI(g), If H2 is added to the reaction mixture at equilibrium, then the equilibrium of the reaction is disturbed.
In order to restore it, the reaction proceeds in a direction where in H2 is consumed, i.e., more of H2 and I2 react to form HI and finally the
equilibrium shifts in right (forward) direction.
 This is in accordance with the Le Chatelier’s principle which implies that in case of addition of a reactant/product, a new equilibrium will be
set up in which the concentration of the reactant/product should be less than what it was after the addition but more than what it was in the
original mixture.

 The same point can be explained in terms of the reaction quotient, Qc,
Qc =
 Addition of hydrogen at equilibrium results in value of Qc being less than Kc . Thus, in order to attain equilibrium again reaction moves in the
forward direction.
 Similarly, we can say that removal of a product also boosts the forward reaction and increases the concentration of the products and this has
great commercial application in cases of reactions, where the product is a gas or a volatile substance. In case of manufacture of ammonia,
ammonia is liquified and removed from the reaction mixture so that reaction keeps moving in forward direction.
 Concentration Effect in Heterogeneous Equilibrium:
2CaO(s) +
 The decomposition of solid CaCO3 in a closed vessel is as follows.
 If more CaO is to be obtained in this process, the CO2 gas formed must be removed because CO2(g) reacts with CaO(g) to reduce the yield.
 Hence, the removal of CO2(g) from the process vessel keeps the value of Qc lower than the value of Kc. Consequently, the reaction continues
in the forward direction. Therefore, more CaO(s) can be obtained, which is an important material for construction.
34. The ionization constant of propanoic acid is 1.32 x 10–5. Then find its ionisation degree and pH of 0.05 M aqueous solution. If the solution
also contains 0.01 M HCI, find the ionization fraction of the solution.


Now, ∝ =
= = 0.016248
∴ [H3O+] = C∝

Page No.: 11
 = 0.05 × 0.016248
= 8.124 × 10–4
∴ pH = –log [H3O+]

= –log (8.124 × 10–4)

= 4 log 10 – log 8.124
= 4.0000 – 0.9098 = 3.0902
If 0.01 M HCl already added in the solution
Ka =
∴ 1.32 × 10–5 =

∴ C∝ = ( 0.05 – C∝ ≅ 0.05)
∴ C∝ = 6.60 × 10–5

∴∝=

= 1.32 × 10–3
35. The first ionization constant of H2S is 9.1 × 10–8. Calculate the concentration of HS– ion in its 0.1 M solution. If this solution contains 0.1 M
HCI, what will be the effect on the calculated concentration? If the secondary ionization constant of H2S is 1.2 × 10–13, calculate the
concentration of S–2 ion under both conditions.
 H2S + H2O H3O+ + HS–
∴ ka1 =
∴ [H3O+] =
=
[H3O+] = 9.54 × 10–5 M
 In presence of 0.1 M HCl [H3O+] = 0.1 M
∴ ka1 =
∴ 9.1 × 10–8 =

∴ [HS–] = 9.1 × 10–8 M

So, for common ion effect the concentation of [HS–] is decreases.
 Secondary ionization constant (ka2)
HS– + H2O H3O+ + S–2 (in absence of HCl)
ka2 =
ka2 =
52 = 1.2 × 10–13
 In presence of 0.1 M HCl
ka2 =
∴ 1.2 × 10–12 =

∴ S–2 = 1.092 × 10–19 M

Section E
Write the answer of the following questions : (Each carries 5 Marks) [5]

36. Describe the hybridization in case of PCl5. Why are the axial bonds longer as compared to equatorial bonds?
Page No.: 12
 The electronic configuration of phosphorus (Z=15) in its ground and excited states is as follows.

 Hybridizing all five orbitals (one s, three p and one d) gives a set of five sp3d hybrid orbitals, which will be oriented towards all five corners of
the trigonal bi-pyramid.

 All the bond angle and not same in trigonal bipyramid geometry. In PCl5, phosphorus’s five sp3d hybrid orbitals mix with the p-orbitals of
chlorine, each carrying a lone electron, forming five P-Cl sigma bonds.
 Three P-Cl bonds lie in one plane, forming 120º angles with each other. These bonds are called equatorial bonds. The remaining two P-Cl
bonds are formed above and below the plane defined by the equatorial bonds, forming 90° angles with the plane. These bonds are called axial
bonds.
 Axial bonds experience slightly longer bond lengths compared to equatorial bonds due to increased repulsion between them in the presence of
axial bonds. Therefore, axial bonds are weaker, making the axial P-Cl bonds more reactive in the case of PCl5 molecule.

Page No.: 13