Short Answer Type Questions – I

Q. 1. In a process, 701 J of heat is absorbed by a system and 394 J work is done by the
system. What is the change in internal energy for the process? [DDE, 2017-18]
Ans. Given, q = 701 J
W = − 394 J
(As work is done by the system)
∆U = ?
According to first law of thermodynamics,
∆U = 𝑞 + W
= 701 + (−394)
= 701 − 394 = 307 J
Q. 2. Classify the following as extensive or intensive properties:
Heat capacity, Density, Temperature, Molar heat capacity. [DDE, 2017-18]
Ans. Extensive Properties: Heat capacity and molar heat capacity (because these properties
depend upon the quantity of matter)
Intensive Properties: Density and temperature (Because these properties do not depend upon
quantity of matter)
Q. 3. Derive the relationship between ∆𝐇 and ∆𝐔. [DDE, 2017-18]
Ans. ∴ Heat absorbed at constant volume
𝑞𝑣 = ∆U …(i)
Where ∆U Change in internal energy but most of chemical reactions are carried out not at
constant volume, but in flask under constant atmospheric pressure. So, at constant pressure, e.g.,
(i) becomes
∆U = 𝑞𝑝 − 𝑝∆V …(ii)

Where qp = heat absorbed by the system

−p∆V = Expansion work done by the system

Or U2 − U1 = qp − p (V2 − V1 )

On rearranging, we get
qp = (U2 + pV2 ) − (U1 − pV1 ) …(iii)
Now, we know that enthalpy
H = U + pV …(iv)
So, equation (iii) becomes,
𝑞𝑝 = H2 − H1 = ∆H

For finite changes at constant Pressure, equation

(iv) Can be written as:
∆H = ∆U + p∆V …(v)
Since P is constant, so equation (v) becomes
∆H = ∆U + p∆V …(vi)
The equation (vi) shows the relationship between ∆H and ∆U.
Q. 4. Derive the relationship 𝐂𝐩 − 𝐂𝐯 = 𝐑 .
[KVS, Silchar Region-2016-17; DDE-2017-18]
Ans. If q is the amount of heat involved in a system
Then, at constant volume,
q = q v = Cv ∆T = ∆U …(i)
And at constant pressure.
q = q p = Cp∆T = ∆H …(ii)

For one mole of an ideal gas (n = 1).

Change in enthalpy
∆H = ∆U + ∆(pV)
= ∆U + ∆(pT)
∆H = ∆U + R∆T) …(iii)
On substituting the values of ∆H and ∆U in equation (iii) from equation (i) and (ii),

Cp∆T = Cv ∆T + R∆T

Or Cp = Cv + R
𝐶𝑝 − 𝐶𝑣 = R …(iv)
Q. 5. 1 g of graphite is burnt in a bomb calorimeter in excess of oxygen at 298 K and 1
atmospheric pressure according to the equation:

𝐂 (𝐠𝐫𝐚𝐩𝐡𝐢𝐭𝐞) + 𝐎𝟐 (𝐠) → 𝐂𝐎𝟐 (𝐠)

During the reaction, temperature rises from 298K to 299K. If the heat capacity of the bomb
calorimeter is 20.7 kJ/K. What is the enthalpy change for the above reaction at 298K and 1
atm?
Ans. Let quantity of heat from the reaction mixture = 𝑞

Heat capacity of calorimeter = Cv

∴ Quantity of heat absorbed by the calorimeter

𝑞 = Cv . ∆T
𝑞 has opposite sign because the heat is lost by the system which is equal to the heat gained by the
calorimeter.
∴ q = −Cv × ∆T = −20.7kJ/K × (299 − 298)K
= -20.7 kJ
Here,−ve sign indicates the exothermic nature of the reaction
∴ ∆U for the combustion of the 1 g of graphite

= −20.7 kJ K −1
For combustion of 1 mole (12 g) of graphite
12g mol−1 × (−20.7kJ)
=
1g
= −2.48 × 102 kJ mol −1 (∴ ∆ng = 0)

∴ ∆H = ∆U = −2.48 × 102 kJ mol−1

Q. 6. In an experiment, 1.35 mol of oxygen (𝐎𝟐 ) are heated at constant pressure starting at
11°C. How much heat must be added to the gas to double its volume?
Ans. Since oxygen (O2 ) is a diatomic gas,
5
∴ Cv = R
2
∴ Cp = Cv + R
5 7
= R+R= R
2 2
At constant pressure, if volume is doubled then temperature will also be doubled.
∴ TI = 11 + 273 = 284 K
∴ Tf = 2 × 284 = 568 K
Now, Q = n Cp(Tf − Ti )

= (1.35 mol) (7/2R) (568K − 284 K)

= (1.35 mol) (7/2 × 8.314 J mol −1 K −1 ) (568K − 284 K)
= 1.11 × 104 J
Q. 7. Calculate the internal energy of 1 mole of an ideal gas at 𝟐𝟓𝟎°𝐂.
Ans. Given n = 1 mol
T = 250 + 273 = 523 K
∴ Internal energy for an ideal gas
3
E= nRT
2
3
= × (1 mol) × (8.314 J mol−1 K −1 )(523 K)
2
= 6519.195 J
= 6520 J
Q.8. The mass of a helium atom is 𝟔. 𝟔𝟔 × 𝟏𝟎−𝟐𝟕 𝐤𝐠. Compute the specific heat at constant
volume for helium gas (in J/kg. K) from the molar heat capacity at constant volume.
Ans. Molar mass of helium = 4.00 g
∴ Molar heat capacity at constant volume of monoatomic gas for 1 mole
3
Cv = R
2
∴ Specific heat at constant volume for ‘He’ gas
3
(Cv )H = R/Molar mass of He
2
3
= × 8.314 J mol−1 K −1 /4g mol−1 × 10−3 kg/1g
2
= 3116 J/kg. K
Q. 9. Show that for an isothermal expansion of an ideal gas (𝐢)𝚫𝐔 = 𝟎 𝐚𝐧𝐝 (𝐢𝐢)𝚫𝚮 = 𝟎.
Ans. (i) For one mole of an ideal gas
∆𝑈
𝐶𝑣 = ( )
∆𝑇 v
Or ∆U = Cv ∆T
For isothermal process, T is constant
∴ ∆T = U
∴ ∆U = 0
(ii) ∴ ∆H = ∆U + ∆(pV)
For an ideal gas pV = RT
∴ ∆H = ∆U + ∆(RT) = ∆U + R∆T
Since T is constant for isothermal process
∴ ∆T = 0
Also ∆U = 0
∴ ∆H = 0
Q. 10. (a) What does the following diagram indicate?
(b) What for it is used?

Ans. (a) Bomb calorimeter

(b) Bomb calorimeter is used for the measurement of ∆U.
Q.11. State and explain Hess's Law of constant heat summation with a suitable example.
[KVS, Mumbai Region, 2015-16]
[KVS, Silchar Region, 2016-17 IDDE, 2017-18]
Ans. According to this law, "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."
∆r H = ∆r H1 + ∆r H2 + ∆r H3 + ⋯
It can be represented as:

Example:
1
C(graphite, s) + O2 (g) → CO(g); ∆rH Θ = ?
2

Steps:
(𝐢) C(graphite, s) + O2 (g) → CO2 (g); ∆r H Θ = −393.5 kJ mol−1
1
(𝐢𝐢) CO(g) + O2 (g) → CO2 (g); ∆r H Θ = −283.0 kJ mol−1
2
To get one mole of CO(g) on the right, we reverse equation (i). In this, heat is absorbed instead
of being released, so we change sign of ∆r H Θ value.
1
(𝐢𝐢𝐢) CO2 (g) → CO(g) + O2 (g) ; ∆r HxΘ = +283.0 kJ mol−1
2
Adding equation (i) and (iii) to get the desired equation
1
C(graphite, s) + O (g) → CO(g)
2 2
For which, ∆rH Θ = (−395.5 + 283.0)
= −110.5 kJ mol−1
Q. 12. Calculate the enthalpy change for the reaction.
𝐇𝟐 (𝐠) + 𝐁𝐫𝟐 (𝐠) → 𝟐𝐇𝐁𝐫(𝐠)
Given the bond enthalpies 𝐇𝟐 , 𝐁𝐫𝟐 and HBr are 435 kJ mol-1 and 𝟑𝟔𝟖 𝐤𝐉 𝐦𝐨𝐥−𝟏
respectively.
Ans. For the reaction,
H2 (g) + Br2 (g) → 2HBr(g)
For reactions,
Bond enthalpy of 1 mole of H-H bond = 435 kJ mol-1
Bond enthalpy of 1 mole of Br-Br bond = 192 KJ mol-1
For products,
Bond enthalpy of 2 moles of H-Br bond = −2 × 368
= −736 kJ mol−1
∴ Enthalpy changes for the reaction
∆rH Θ = 435 + 192 − 736
= −109 kJ mol−1
Q. 13. The bond dissociation energy of gaseous 𝐇𝟐 , 𝐂𝐥𝟐 Ch and HCI are 104, 58 and 103
kcal/ mol respectively. Calculate the enthalpy of formation of HCI gas.
Ans. For the reaction,
H2 (g) + Cl2 (g) → 2HCl(g)
For reactants,
Bond energy of mole of H-H bond = 104 kcal/mol
Bond energy of mole of Cl-Cl bond = 58 kcal/mol
For products
Bond energy of moles of H-Cl bond = −2 × 103
= −206 kcal/mole
∴ Enthalpy change for the reaction:
∆rH = 104 + 58 − 206 = −44 kcal/mole
∴ Enthalpy of formation of one mole of HCl gas
−44
= = −22 kcal/mole
2
Q. 14. The standard molar heat of formation of ethane, carbon dioxide and water vapour
are -21.1, -94.1 and -68.3 kcal respectively. Calculate the standard molar heat of
combustion of ethane.
Ans. Given that
(i) 2C(s) + 3H2 (g) → C2 H6 (g); ∆fH Θ
= −21.1 kcal

(ii) C(s) + O2 (g) → CO2 (g); ∆f H Θ

= −94.1 kcal
1
(iii) H2 (g) + O2 (g) → H2 O(g); ∆f H Θ
2

= −68.3 kcal

We have to calculate ∆cH Θ of the equation.

1
C2 H6 (g) + 3 O2 (g) → 2CO2 (g) + 3H2 O(g) ; ∆cH Θ =?
2
Applying inspection method:
[−eqn. (i) + 2 × eqn. (ii) + 3 × eqn. (iii)] we get
1
−2C(s) − 3H2 (g) + 2C(s) + 2O2 (g) + 3H2 + 1 O2 (g) → C2 H6 (g) + 2CO2 (g) + 3H2 O(g)
2
∆cH Θ = −(−21.1) + 2 × (−94.1) + 3 × (−68.33) = −372.0 kcal

Q. 15. The enthalpy of combustion of ethyl alcohol is −𝟏𝟑𝟖𝟎 𝒌𝑱 𝒎𝒐𝒍𝒆−𝟏 . If enthalpies of

formation of 𝑪𝑶𝟐 and 𝑯𝟐 𝑶 are −𝟑𝟗𝟒. 𝟓 𝒂𝒏𝒅 − 𝟐𝟖𝟔. 𝟓 𝒌𝑱 𝒎𝒐𝒍𝒆−𝟏 𝒓𝒆𝒔𝒑𝒆𝒄𝒕𝒊𝒗𝒆𝒍𝒚. Calculate
the enthalpy of formation of ethyl alcohol.
[KVS, Silchar Region, 2016-17]
1
Ans. 2C(s) + 3H2 (g) + O2 (g) → C2 H5 OH(𝑙)∆Hf0 =?
2

C(s) + 2H2 (g) + 2H2 (g) → CO2 (g) + 2H2 O (𝑙)

∆H = [2X(−286) + (−394.5)]
= −572 − 394.5
= −966.5 kJ/mol
1
2C(s) + 3H2 (g) + O2 (g) → C2 H2 OH(𝑙)
2
∆H = −966.5 − (−1380)
= −966.5 + 1380
= 413.5 kJ/mole
Q. 16. Define the term entropy. Write its unit. How does entropy of a system change on
increasing temperature? [DDE, 2017-18]
Ans. Entropy: It is a measure of degree of randomness or disorderness in an isolated system.
It is represented by the symbol 'S',
+q sys.rev.
∆Ssystem =
T
Its unit is J K −1 mol−1
The entropy of system increase with increase in temperature.
Q. 17. The equilibrium constant for a reaction is 2. What will be the value of ∆𝑮°? (𝑹 =
𝟖. 𝟑𝟏𝟒 𝑱 𝑲−𝟏 𝒎𝒐𝒍−𝟏 , 𝑻 = 𝟒𝟎𝟎𝑲)
Ans. Given, K=2
R = 8.314 JK −1 mol−1
T = 400 K
∆G° = ?
∵ ∆𝐺° = −2.303 𝑅𝑇 log 𝐾
= −2.303 × 8.314 × 400 × log 2
= −2.303 × 8.314 × 400 × 0.3010
= −2305.31 J mol−1
= −2.05 kJ mol−1
Q. 18. The enthalpy of vaporization of a liquid is 𝟑𝟎 𝐤𝐉 𝐦𝐨𝐥−𝟏 and entropy of vaporization
is 𝟕𝟓 𝐉 𝐊 −𝟏 𝐦𝐨𝐥−𝟏 . Calculate the boiling point of liquid at 1 atm.
[DDE, 2017-18]

Ans. Given, ∆vap H Θ = 30 𝑘𝐽 𝑚𝑜𝑙−1

= 30,000 J mol−1
∆S = 75 JK −1 mol−1
T=?

∆vap H Θ
∵ ∆S =
T
∆vap H Θ
or T=
∆S
30000
=
75
= 400 K
Q. 19. Define entropy. What will be the sing of ∆𝑺 for reaction:
𝐂𝐚𝐂𝐎𝟑 (𝐬) → 𝐂𝐚𝐎(𝐬) + 𝐂𝐎𝟐 (𝐠) [KVS, Silchar Region, 2016-17]
Ans. Entropy is defined as a measure of degree of randomness or disorderness in an isolated
system.
It is related to heat absorbed at a constant temperature of the system in a reversible process as
q rev
S=
T
For reaction, CaCO3 (s) → CaO(s) + CO2 (g)
The sing of ∆𝑆 is negative so it is not spontaneous.
Q. 20. Calculate the entropy change ∆𝑺 per mole for following reaction:

Combustion of hydrogen in a fuel cell at 298 K.

𝟏
𝐇𝟐 (𝐠) + 𝐎 (𝐠) → 𝐇𝟐 𝐎(𝐠)
𝟐 𝟐
∆𝐇 = 𝟐𝟒𝟏. 𝟔𝟎 𝐤𝐉
∆𝐆 = 𝟐𝟖𝟖. 𝟒𝟎 𝐤𝐉.
Ans. ∆G = ∆H − T∆S
Putting in the values,
−288.40 = −241.6 − 298 × ∆S
−288.4 + 241.6
∴ ∆S =
−298
= 0.157 kJ K −1 mol−1
Q. 21. Calculate ∆𝐫 𝐆 for conversion of oxygen to ozone, 𝟑/𝟐 𝑶𝟐 (𝒈) → 𝑶𝟑 (𝒈)𝒂𝒕 298 K, if 𝐊p
for this conversion is 𝟐. 𝟒𝟕 × 𝟏𝟎−𝟐𝟗 .
Ans. Given, T = 298 K
K p = 2.47 × 10−29

∆rGΘ = ?

∵ ∆rGΘ = −2.303 𝑅𝑇 log K p

= −2.303 × (8.314 J K −1 mol−1 ) × (298 K) × log(2.47 × 10−29)

= 163000 J mol−1
= 163 kJ mol−1
Q. 22. Find out the value of equilibrium constant for the following reaction at 298 K.
𝟐𝐍𝐇𝟑 (𝐠) + 𝐂𝐎𝟐 (𝐠) ⇌ 𝐍𝐇𝟐 𝐂𝐎𝐍𝐇𝟐 (𝐚𝐪) + 𝐇𝟐 𝐎(𝐥)

Standard Gibbs energy change, ∆𝐫𝐆𝚯 at the given temperature id −𝟏𝟑. 𝟔 𝐤𝐉 𝐦𝐨𝐥−𝟏 .
Ans. Given, T = 298 K

∆rGΘ = −13.6 kJ mol−1

𝑅 = 8.314 𝐽 𝐾 −1 𝑚𝑜𝑙 −1
K= ?
∴ ∆rGΘ K = −2.303RT log K
−∆rGΘ
𝑜𝑟 log 𝐾 =
2.303 𝑅𝑇
−(−13.6 × 103 J 𝑚𝑜𝑙 −1 )
=
2.303 × 8.314 𝐽𝐾 −1 𝑚𝑜𝑙−1 × 298 𝐾
= 2.38
∴ K = antilog 2.38
= 2.4 × 102
Q. 23. Predict in which the following, entropy increase or decreases:
(i) 𝟐𝐍𝐚𝐇𝐂𝐎𝟑 (𝐬) → 𝐍𝐚𝟐𝐂𝐎𝟑 (𝐬) + 𝐂𝐎𝟐 (𝐠) + 𝐇𝟐 𝐎(𝐠)
(ii) 𝐇𝟐 (𝐠) → 𝟐𝐇(𝐠)
Ans. (i) Reactant, NaHCO3 is a solid and it has low entropy. Among products, there are one solid
and two gases. So, the products represent a condition of higher entropy.
(ii) H2 (g) → 2H(g)
Here, one molecule of hydrogen gives two hydrogen atoms i.e. number of particles increases
leading to more disordered state. Two moles of hydrogen atoms have higher entropy than one
mole of dihydrogen molecule.