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26. (d): Since the ideal gas expands spontaneously into vacuum, Pext =0, hence work done is also
zero.

27. (c): According to Gibbs equation,

ΔG=ΔH −TΔS
when ΔG=0 , ΔH =TΔS
Given, ΔH =40.63 kJmol −1=40.63 ×1 03 Jmo l−1
−1 −1
ΔS=108.8 J K mo l
3
ΔH 40.63 × 10
T= = =373.43 K
ΔS 108.8

28. (d): Gas phase reaction

PC l 5(g )−−PC l 3( g) +C l 2(g )
ΔH =ΔE + Δ ng RT
Δ ng =¿ Change in number of moles of product and reactant species.
Since Δ ng =+ ve , hence ΔH =+ ve
also, one mole of PC 15 is dissociated into two moles of PC l 3 and C l 2 in the same phase.
Therefore, ΔS=S product −S reactant
ΔS =+ve .

29. (b): Δ ng =2−4=−2, ΔH = ΔE−2 RT

30. (a) Solubility of mol mol ionizes completely in the

solution as :
+
s s

31. (b):

Percentage of pyridine that forms pyridinium ion

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32. (d):If the reaction is multiplied by , then new equilibrium constant,

33. (a)

34. (d): We know that, at

At

35. (c): is an electron deficient species and acts as Lewis base.

36. (c): The equilibrium constant for the reverse reaction will be

37. (d)

38. (a)For the reaction,

CaCO3(g) ⇌ CaO(s) + CO2(g)
PCO
Kp = 2 and KC = [CO2]
( [CaCO3] = 1 and [CaO] = 1 for solids]
According to Arrhenius equation we have
−ΔH °r / RT
K = Ae

Taking logarithm, we have

ΔH or
log K p =log A−
RT (2 .303 )
This is an equation of straight line. When log Kp is plotted against 1 / T. we get a straight line.

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The intercept of this line = log A, slope = –∆H°r / 2.303 R

Knowing the value of slope from the plot and universal gas constant R, ∆Hr° can be
calculated.
(Equation of straight line : Y = mx + C. Here,
ΔH or
log K p =−
1
2 .303 R T ( )
+ log A

Y m x C

K p =K c ( RT )Δn K <K
39. (b) ; When Δn=2−(2+1)=−1 , i.e. negative, p c .

[ SO 3 ] [ SO 2 ]2 [ O 2 ] 1
K 1= K 2= K 2=
[ SO 2 ] [ O 2 ] 1/ 2
[ SO3 ] 2 K 21
40. (c) and ; .

41. (c)

42. (a)

There are 21 bonds.

43. (d): Friedel‐Crafts reaction:

Chlorobenzene, bromobenzene and chloroethene are not suitable halide components as bond
acquires some double bond character due to resonance of lone pair of electrons with ‐bond.

44. (a) : Biphenyl is coplanar as all ‐atoms are hybridised.

45. (d): Pyrrole has maximum electron density on 2 and 5. It generally reacts with electrophiles at the
C‐2 or C‐5 due to the highest degree of stability of the protonated intermediate.
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Attack at position 3 or 4 yields a carbocation that is a hybrid of structures (I) and (II). Attack at position
2 or 5 yields a carbocation that is a hybrid not only of structures (III) and (IV) (analogous to I and II)
but also of structure (V). The extra stabilization conferred by (V) makes this ion the more stable one.
Also, attack at position 2 or 5 is faster because the developing positive charge is accommodated by
three atoms of the ring instead of only two.

46. Ans. 1
Sol. U = Q + W
 U = QV (W = 0 at constant volume)
= m × s × t (m = mass of gas
s = specific heat)
= 0.5 × 40 × (20.814 – 8.314) × 4 Joule
= 1 KJ

47. Ans. 6 kJ
Sol. U = Q + W
= Hv + PV
= 3 + nRT
= 3 + RT = (3 + 8.314 × 353 ×10–3/KJ)
= 5.935 KJ
~ 6 KJ

48. Ans. 1
T1 – T2 600 – 300 1
Sol.  = T 1 = 600 = 2
Δw 1
 = Δq or W =  × q = 2 × 2 × 103 = 103 J
= 1 KJ

49. (282)

Ans. = 282

50. (2.5 × 10–5 ; 4.6 )

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= 2.5 x 10–5
pKa= 5 – log 2.5 = 4.6

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