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1. Choose the correct answer. A thermodynamic state function is a quantity
(i) used to determine heat changes
(ii) whose value is independent of path
(iii) used to determine pressure volume work
(iv) whose value depends on temperature only
Solution :
A thermodynamic state function is a quantity Whose value is independent of a path. Functions like p, V, T etc. depend only on the state of a system and not on the path.
Hence, alternative (ii) is correct.
2. For the process to occur under adiabatic conditions, the correct condition is:
(i) ∆T = 0
(ii) ∆p = 0
(iii) q = 0
(iv) w = 0
Solution : A system is said to be under adiabatic conditions if there is no exchange Of heat between the system and its surroundings. Hence, under adiabatic conditions, q = 0.
Therefore, alternative (iii) is correct,
3. The enthalpies of all elements in their standard states are:
(i) unity
(ii) zero
(iii) < 0
(iv) different for each element
Solution : The enthalpy of all elements in their standard state is zero. Therefore, alternative (ii) is correct
4. ΔU ⊖ of combustion of methane is −X kJ mol −1 . The value of ΔH⊖ is
(i)=ΔU ⊖
(ii) >ΔU ⊖
(iii) <=ΔU ⊖
(iv) = 0
Solution :
SinceΔH θ =ΔU θ +Δn g RT and ΔU θ =−Xkmol −1
ΔH θ =(−X)+Δn g RT
⇒△H θ <ΔU θ
Therefore, alternative (iii) is correct.
5. The enthalpy of combustion of methane, graphite and dihydrogen at 298 K are, –890.3kJmol −1 −393.5kJmol −1 , and −285.8kJmol −1
respectively. Enthalpy of formation of CH 4 will be
(i)−74.8kJmol −1
(ii)−52.27kJmol −1
(iii)+74.8kJmol −1
(iv)+52.26kJmol −1
Solution :
According to the question,
(i)CH 4 (g)+2O 2 (g)⟶CO 2 (z)+2H 2 O(g)ΔH=−890.3kJmol −1
(ii)C(x)+O 2 (y)⟶CO 2 (g)ΔH=−393.5kJmol −1
(iii)2H 2 (g)+O 2 (z)⟶2H 2 O(g)
ΔH=−285.8kJmol −1
Thus, the desired equation is the one that represents the formation of CH 4 (g) i.e..,
= [-395.5 + 2(-285.8) - (-890.3)] kJ Mol -1
= -74.8 kJ Mol -1
∴ Enthalpy of formation of CH 4 (g)=−74.8kJmol −1 Hence, alternative (i) is correct.
6. A reaction, A + B → C + D + q is found to have a positive entropy change. The reaction will be
(i) possible at high temperature
(ii) possible only at low temperature
(iii) not possible at any temperature
(iv) possible at any temperature
Solution :
For a reaction to be spontaneous, ΔG should be negative.
ΔG = ΔH – TΔS
According to the question, for the given reaction,
ΔS = positive
ΔH = negative (since heat is evolved)
⇒ ΔG = negative
Therefore, the reaction is spontaneous at any temperature.
Hence, alternative (iv) is correct.
7. In a process, 701 J of heat is absorbed by a system and 394 J of work is done by the system. What is the change in internal energy for the process?
Solution :
According to the first law of thermodynamics,
ΔU = q + W (i)
Where,
ΔU = change in internal energy for a process
q = heat
W = work
Given,
q = + 701 J (Since heat is absorbed)
W = –394 J (Since work is done by the system)
Substituting the values in expression (i), we get
ΔU = 701 J + (–394 J)
ΔU = 307 J
Hence, the change in internal energy for the given process is 307 J.
8. The reaction of cyanamide,NH 2 CN(s) with dioxygen was carried out in a bomb calorimeter, and ∆U was found to be –742.7kJmol −1 at 298 K. Calculate enthalpy change for the reaction at 298 K.
NH 2 CN(g) + 3/2O 2 (g)→N 2 (g)+CO 2 (g)+H 2 O(l)
Solution :
Enthalpy change for a reaction (ΔH) is given by the expression,
ΔH = ΔU + Δn
g
RT
Where,
ΔU = change in internal energy
Δn
g
= change in number of moles
For the given reaction,
Δng = ∑n
g
(products) – ∑n
g
(reactants)
= (2 – 1.5) moles
Δn
g
= 0.5 moles
And,
ΔU = –742.7 kJ mol
–1
T = 298 K
R = 8.314 × 10
–3
kJ mol
–1
K
–1
Substituting the values in the expression of ΔH:
ΔH = (–742.7 kJ mol
–1
) + (0.5 mol) (298 K) (8.314 × 10
–3
kJ mol
–1
K
–1
)
= –742.7 + 1.2
ΔH = –741.5 kJ mol
–1
9. Calculate the number of kJ of heat necessary to raise the temperature of 60.0 g of aluminium from 35°C to 55°C. Molar heat capacity of Al is 24 Jmol −1 K −1 .
Solution :
From the expression of heat (q) q=m⋅ c. ΔT
Where,
c= molar heat capacity
m= mass of substance
ΔT= change in temperature
Substituting the values in the expression of q:
q=(60/27mol)(24Jmol −1 K −1 )(20K)
q=1066.7J
q=1.07k
10. Calculate the enthalpy change on freezing of 1.0 mol of water at10.0°C to ice at
–10.0°C.ΔfusH=6.03kJmol−1 at 0 ∘ C
C p [H 2 O(I)]=75.3Jmol −1 K−1
C ρ [H 2 O(s)]=36.8Jmol −1 K −1
Solution :
Total enthalpy change involved in the transformation is the of the following changes:
(a) Energy change involved in the transformation of 1 mol of water at 10 ∘ C to 1 mol of water at 0 C.
(b) Energy change involved in the transformation of 1 mol of water at 0∘ to 1 mol of ice at 0 ∘ C
(c) Energy change involved in the transformation of 1 mol of ice at0∘C to 1 mol of ice at−10 ∘ C.
ΔH= C p [ H 2 OCl]ΔT+ ΔH fivering + C ρ [H 2 O (s) ]ΔT
=(75.3] mol −1 K −1 )(0−10)K + (−6.03 × 10 3 Jmol −1 )+(36.8] mol −1 K −1 )(−10 −0)K
=−7533 mol −1 − 6030Jmol −1 − 368Jmol −1
=−7151J mol −1
=−7.151kJmol −1
Hence, the enthalpy change involved in the transformation is−7.151kJmol −1 .
11. Enthalpy of combustion of carbon to CO 2 is –393.5−7.151kJmol −1 . Calculate the heat released upon formation of 35.2 g ofCO 2 from carbon and dioxygen gas.
Solution :
Formation of CO 2 from carbon and dioxygen gas can be represented as:
C(s) + O 2 (g)⟶CO 2 (g)
Δ f H=−393.5kJmol −1
(1 mole =44g) Heat released on formation of 44gCO 2 =−393.5kJmol−1
∴ Heat released on formation of 35.2gCO 2
=−314.8kJmol −1
12. Enthalpies of formation of CO(g), CO 2 (g), N 2 O(g) and N 2 O 4 (g) are −110,−393,81 and 9.7kJmol −1 respectively.
Find the value of ∆H for the reaction:
N 2 O 4 (g)+3CO(g)→N 2 O(g+3CO 2 (g]
Solution :
Δ r H for a reaction is defined as the difference between ΔH value of products and ΔH value of reactants.
Δ,H=∑Δ,H( products )−∑Δ f H( reactants )
For the given reaction,
N 2 O 4(g) + 3CO (g) ⟶ N 2 O (g) + 3CO 2 (g)
Δ r H=[ {ΔfH(N 2 O)+3ΔJH(CO 2 )}−{ΔfH (N 2 O 4 ) + 3ΔjH(CO)} ]
Substituting the values ofΔH for N 2 O,CO 2 ,N 2 O 4 , and CO
From the question, we get:
Δ r H=[ { 81kJmol −1 + 3(−393)kJmol −1 } − {9.7kJmol −1 +3(−110) kJmol −1 }]
Δ r H=−7777kJmol −1
Hence, the value ofΔ r H
for the reaction is −777.7 kJmol −1 .
13. Given
N 2 (g) + 3H 2 (g) ⟶ 2NH 3 (y);
Δ r Hθ=−92.4kJmol −1
What is the standard enthalpy of formation ofNH 3 gas?
Solution : Standard of formation of a compound is the charge in enthalpy that takes place during the formation of 1 mole Of a substance in its standard form from its constituent elements in their standard state.
Re-writing the given equation for 1 mole of NH 3(g).
1/2N 2 (g)+3/2H 2 (g)⟶NH 3(g)
∴ Standard enthalpy of formation of NH 3(g)
=1/2 Δ r Hθ = 1/2(−92.4 kJmol −1 )= −46.2kJmol −1
14. Calculate the standard enthalpy of formation ofCH 3 OH(l) from the following data:
CH 3 OH(l)+3/2O 2 (g]→CO 2 (g)+2H 2 O(l): Δ,H∘=−726kJmol −1
C(graphite) +O 2 (g)→CO2(g]: ΔeH=−393kJmol −1
H 2 (g)+1/2O 2 (g)→H 2 O(1); Δ,H=−286kJmol −1
Solution :
The reaction that takes place during the formation ofCH 3 OH(l) can be written as:
C(s) + 2H 2 O(g) + 1/2O 2 (G), ⟶ CH 3 OH( η) (1)
The reaction (I) can be obtained from the given reactions by following the algebraic calculations as:
Equation (ii) + 2 × equation (iii) – equation (i)
Δ
f
Hθ [CH
3
OH(l)] = ΔcH
θ
+ 2Δ
f
H
θ
[H
2
O(l)] – Δ
r
H
θ
= (–393 kJ mol
–1
) + 2(–286 kJ mol
–1
) – (–726 kJ mol
–1
)
= (–393 – 572 + 726) kJ mol
–1
Δ
f
H
θ
[CH
3
OH(l)] = –239 kJ mol
–1
15. Calculate the enthalpy change for the process CCl 4 (g)→C(g)+4Cl(g) and calculated bond enthalpy of C−Cl in CCl 4 (g)
Δ va pH θ (CC|4) = 30.5kJmol −1 Δ f H θ (CCl4) =−135.5kJmol−1
Δ a H θ (C) = 715.0kJmol −1 , where Δ a H θ is enthalpy of atomisation
Δ 2 H θ (Cl 2 ) = 242kJmol −1
Solution :
The chemical equations implying to the given values of enthalpies” are:
(1) CCl
4(l)
à CCl
4(g)
; ΔvapH
Θ
= 30.5 kJmol
−1
(2) C
(s)
à C
(g)
ΔaH
Θ
= 715 kJmol
−1
(3) Cl2
(g)
à 2Cl
(g)
; Δ
a
H
Θ
= 242 kJmol
−1
(4) C
(g)
+ 4Cl
(g)
à CCl
4(g)
; ΔfH
Θ
= -135.5 kJmol
−1
ΔH for the process CCl
4(g)
à C
(g)
+ 4Cl
(g)
can be measured as:
ΔH=Δ
a
H
Θ
(C) + 2ΔaH
Θ
(Cl
2
) – Δ
vap
H
Θ
–ΔfH
= (715kJmol
−1
) + 2(kJmol
−1
) – (30.5kJmol
−1
) – (-135.5kJmol
−1
)
Therefore, H= 1304kJmol
−1
The value of bond enthalpy for C-Cl in CCl
4
(g)
= 1304/4kJmol
−1
= 326 kJmol
−1
16. For an isolated system, ∆U = 0, what will be ∆S ?
Solution :
ΔS will be positive i.e., greater than zero
Since ΔU = 0, ΔS will be positive and the reaction will be spontaneous.
17. For the reaction at 298 K,
2A + B → C
∆H = 400kJmol −1
and ∆S = 0.2kJmol −1
At what temperature will the reaction become spontaneous considering ∆H and ∆S to be constant over the temperature range.
Solution :
From the expression
ΔG= ΔH−TΔS
Assuming the reaction at equilibrium,δ
T for the reaction would be:
T=(ΔH−ΔG)1/ΔS=ΔH/ΔS(ΔG=0 at equilibrium)
=400kJmol −1 0.2 kJK −1 mol −1 T=2000K
For the reaction to be spontaneous,ΔG must be negative. Hence, for the given reaction to be spontaneous, T should be greater than 2000 K.
18. For the reaction,2Cl(g)→Cl 2 (g) , what are the signs of ∆H and ∆S ?
Solution :
∆H and ∆S are negative
The given reaction represents the formation of chlorine molecule from chlorine atoms. Here, bond formation is taking place. Therefore, energy Is being released. Hence ∆H is negative.
Also, two moles of atoms have more randomness than one mole of a molecule. Since spontaneity is decreased, ∆S is negative for the given reaction.
19. For the reaction
2A(g)+B(g)→2D(g)ΔUe=−10.5kJ and ΔS∘=−44.1JK −1
Calculate ΔG ⊖ for the reaction, and predict whether the reaction may occur spontaneously
Solution :
For the given reaction,
2A(g)+B(g)→2D(g)Δηg=2−(3)=−1 mole
Substituting the value of ΔU θ
in the expression of ΔH:
ΔH θ =ΔU θ +Δn g RT
=(−10.5kJ)−(−1)(8.314×10 −3 kJK−1 mol −1 ) (298K) = −10.5kJ −2 .48kJΔH ⊖ =−12.98kJ
Substituting the values ofΔH ⊖ and ΔS ⊖ in the expression of ΔG ⊖
ΔG θ = △H θ −TΔS θ
=−12.98kJ − ( 298K) (−44.1JK −1 ) = −12.98kJ + 13.14 kJ ΔG ⊖ =+0.16kJ
SinceΔG θ for the reaction is positive, the reaction will not occur spontaneously.
20. The equilibrium constant for a reaction is 10. What will be the value of ∆G ⊖ ? R = 8.314JK −1 mol −1
T = 300 K.
Solution :
From the expression, ΔG θ = −2.303 RT logk eq
ΔG θ for the reaction,
=(2.303) (8.314JK −1 mol −1 ) (300K) log10=−5744.14Jmol −1
=−5.744kkmol −1
21. Comment on the thermodynamic stability of NO(g) , given
12N 2(g) +12O 2(g) →NO (g) ;
Δ r H ⊖ = 90kJmol −1 NO (g) + 12O 2(g) →NO 2 (g):
Δ r H e = −74kJmol −1
Solution :
The positive value of Δ r H indicates that heat is absorbed during the formation of NO(g), j. This means that NO(g) has higher than the reactants(N2 and O2) .
Hence, NO (g) is unstable. The negative value o f Δ r H
H indicates that heat is evolved during the formation ofNO 2(g) from NO (g) and O 2(g)
. The product,NO 2(g) is stabilized with minimum energy.
Hence, unstableNO (g) changes to unstableNO 2(g).
22. Calculate the entropy change in surroundings when 1.00 mol ofH 2 O(l) is formed under standard conditions.ΔH θ =−286kJ mol −1
Solution :
It is given that 286 kJmol −1 of heat is evolved the formation of 1 mol ofH 2 O(l).
Thus, an equal amount of heat will be absorbed by the surroundings.
q surr = +286 kJmol −1
Entropy change(ΔS surr ) for the surroundings = q surr / 7
=286kJmol −1 / 298k
∴ΔS surt =959.73 Jmol −1 K −1