Thermochemistry

Solution-Ex-1
1. For standard state  H 0f  0

2. Hess’s law is used for all types of enthalpies or heats.

3. It is alway defined per moles.

1
H 2  O 2 
 H 2 O ; H  2x KJ/mol
2

4. H   OH – H 2 O ; Hº  –13.7 Kcal

Hº   f Hº (H 2 O) – (  f Hº H  f Hº OH – )

–13.7 = –68 – (0   f Hº OH – )

 f Hº OH –  –68  13.7

f Hº OH–  –54.3

5. eq n 1 2  eq n 2  H 0f co  2

6. Given : Heat of formation of A = – 84 kJ and heat of formation of B = –156 kJ.

We know that lower the negative value of heat of formation, lower will be its stability.
Since the compound A has lower negative value of heat of formation, therefore it is less stable
than B.

7. For this reaction ng = 0 than E = H.

8. H = –ve for exothermic reaction.

H + ve for endothermic reaction
Enthalpy of fusion is +ve.

9. The equation of formation of HCI is

1 1
H – H  Cl – Cl  H – Cl
2 2
H =  (B.E.) Reactants
–(B.E.) Products

1 1 
   434   242  –  431
2 2 
= – 93 kJ mol –1

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 Thermochemistry
10. H = (Hƒ)N2O + 2(Hƒ)H2O – (Hƒ)NH4NO3

 81.46  2( 285.78)  ( 367.54)

= –122.56 kJ
 H = U + ng RT
–122.56 = U + 1 × 8.314 × 10–3 × 298
U = –125.04 kJ

5756
11. H 0C    2878 kJ mol1
2
5.8 g means 0.1 mole will give 0.1 × 2878 = 287.8 kJ

12. Heat of neutralisation of a strong acid and strong base is equal to –13.7 kcal.

13. Heat released in the neutralisation of 0.25 mol HCI

= 0.25 × 57.1
= 14.3 kJ

14. C(graphite)  O 2 (g) 

 CO 2 (g)
Combustion of 2g C X KJ
Combustion of 12g C 6X KJ
 Combustion of 1 mol C 6X KJ
hence  f H CO2  –6X KJ

15. CH3–CH3  CH3– CH 2 + H ...(1)

CH3– CH 2  CH2= CH2 + H ...(2)

rev. of (1) + (2)
= –420 + 168 = –252 KJ

16. Reaction of C(graphite) with H2(g) is an example of heat of hydrogenation.

17. x + y R + S rH

 r H   f H (R )   f H (S) –  f H X –  f HS

18. G° = H° – TS° = 34 – 298 × 0.116

= – 0.568 KJ.

19. ( H1º  2)  ( H º2  2) – ( H 3º )

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 Thermochemistry
20. Given Heat of combustion of carbon
= – 390 kJ and heat of combustion of carbon monoxide = –278 kJ.
We know that combustion reaction C(s) is
C  O 2(g )  CO
(s)
(Carbon) (Oxygen )
2(g )
(Charbon dioxide)
..(i)
And combustion reaction of CO(s) is
1
CO(s)  O 2(g)  CO2(g)
(Carbon monoxide) 2 (Charbon dioxide)
..(ii)
(Oxygen )

Substracting equation (ii) from (i), we get the reaction

1
C(s)  O 2(g)  CO(g )
(Carbon ) 2 (Charbon monoxide)
(Oxygen )

Therefore heat of formation of carbon monoxide (CO) = Heat of combustion of C

– Heat of combustion of CO
= (–390) –(–278) = –112 kJ.

21. CH4 C + 4H, H = 320

EC–H = 80 cal
C2H6 2C + 6H, H = 360
360 = EC–C + 6EC–H
EC–C = 360 – 480 = –120 Kcal
i.e. C–C bond has energy equal to 120 Kcal

22. Na(s) Na(g)

H for above process can be both atomisation as well as sublimation.

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 Thermochemistry

Solutions-Ex-1A
1. Heat of reaction is same even if different paths have been followed.

H T2 – H T1
2.  r CP  & when H is positive then increase in temperature will increase H.
T2 – T1

3. (A, (B), (C) reaction combining with O2 and exothenic & (D) endothermic.

4. It is always exothenic

5. Rise in temperature will be highest if the extent of neutralisation is max because of which heat
evolved will be maximum.
For max. neutrolisation –
(gram equivalents)Acid = (gram equivalents)Base
V × 0.5 × 2 = (100 – V) × 1 × 1
V = 100 – V

V  50

 VH2SO4  50 mL

VNaOH  100 – 50  50 mL

6. By applying Hess law we can obtain H for HA  H   A 

7. Dissociation is an endothermic process. Formation is mostly exothermic process.

H  E (if ng  0)
H  E (if ng  0)

8. ACCn To born haber cycle 150 + 350 + 200  3q  1000 = 750

q = 150
2q
 3
100

9. 8C  s   9O 2  g   C8 H18   
H  E  ngRT
9  2  300
Z  55.6   61Kcal
1000
Z
 1
61

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 Thermochemistry

Solutions-Ex-2
1. Fuel value (calorific value) is amount of heat liberate when 1 gm of a substance is completely
burnt.

C H
C.V. 
Mw

2. Smaller the atom, bond attraction will be strong.

3. The given reaction is :

CO2(g) + H2 (g)  CO(g) + H2O(g)

 r H 0    f H 0 CO   f H 0 H2 O  –   f H 0 CO2   f H 0 H 2 

= [(–110.5)+(–241.8)]–[(–393.5)+0]
= + 41.2 kJ

4. Hess law includes initial reactants and final products.

1
5. H 2 (g)  O 2 (g) 
 H 2 O(g) ; H
2

1
H  x1  x 2 – 2x 3 ....(i)
2

H 2 O( ) 
 H 2 O(g)

H '  x 4

 H 2 O()
then H 2 O(g) 

H ''  –x 4
Apply Hess law

1
x1  x 2 – 2x 3 – x 4
2

3
6. 2B(s)  O 2 (g) 
 B2 O3
2
2mol combustion of B is equvalent to 1 mol formation of B2O3.

1
 1 mol combustion of B is equivalent to mol formation of B2O3.
2

1
 C H (B)   f H B2 O3
2

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 Thermochemistry

7. 3C 2 H2(g) 
 C 6 H 6(g) H  ??

 
H   H F
Pr oduct
 
–  H F
reac tan t

H    H   F – 3   H   C H
F 2 2
C6 H 6

H° = 85 – 3 × (230) = 85 – 690 = –605 KJ

8. Hf° : (Heat of formation)

Energy transfer for formation of one moles from its natural occuring element in their standard
state.
1 1
H2(g) + F2(g) HF(g)
2 2

9. 2Mg + SiO2 
 2MgO + Si

 r H o  2 f H(MgO,
o o
s)   f H(SiO2 , s)

= 2 × (–34.7) + 48.4
= – 21 kJ

10. Compounds with high heat of formation are less stable because energy rich state leads to
instability.

11. N2+1/2 O2 N2O (N=N=O) H°f

H°f = HNN + 1/2 HO=O – HN = N – HN=O
= 946 + 1/2 × 498 – 418 – 607 = 170 KJ
Resonance energy = H  exp  H  cal
 82  170
 88KJ

12. 250 ml of 4N NaOH = 500 ml of 2N NaOH

It will completely neutralize 500 ml of 2N HCl
 Heat evolved from 1000 ml of 1N HCl = x (Given)
 heat evolved from 500 ml of 2N HCl = x.

13. Heat of formation is the formation of one mole of the substance from its elements in their standard
state.

1 1
14. Aim: K(s) + O2(g) + H2(g) KOH(s)
2 2
eq. (ii) + eq. (i) - eq. (iii) gives
H = – 48 + (-68.39) – (–14) = – 68.39 – 48 + 14.

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 Thermochemistry

Hº
15. 2C(S)  2H 2(g ) 
 C2 H 4
x1

2C(S) + 3H2(g) C2H6 x2

 C2H4 + H2 C2H6 H’
H1 = –x1 + x2 = x2 – x1

16. If n g   ve then H  E .

17. 2C(s)  2O 2 (g)  2CO 2 (g); H  787 kJ

1
H 2 (g)  O 2 (g)  H 2O(l) ; H  286 kJ
2

5
2CO 2 (g)  H 2 O(l)  O 2 (g)  C 2H 2 (g); H  1301kJ
2

Net reaction : 2C(s)  H 2 (g)  C2 H 2 (g); [(787)  (286)  (1301)]kJ  228 kJ

18. Given Heats of combustion (H) for C(s), H2(g) and CH4(g) are –394.8, –285.6

C (s)  2H 2(g)  CH 4(g)

and –894.6 kJ mol respectively and reaction: (Carbon) (Hydrogen ) (Methane)

C  S  O 2  CO 2  394 ..........(i)

1
H 2  O 2  H 2 O  285.6  2 .........(ii)
2

CH 4  2O 2  CO 2  2H 2 O  894.6 ........(iii)

eq (i) + 2  eq n (ii)  (iii) =

We know that heat of combustion for the reaction (H) = H(product) – H(reactant)
= [(–394.8) + 2 × (–285.6)] + 894.6
= –71.4 kJ.

19. n(CH2=CH2)  (H2C–CH2)n

H  590  662  72KJ

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 Thermochemistry

Solutions-Ex-2A
1. Hess’s law

2. (A) Enthalpy of reaction of conversion of one entantiomer to another enantiomer is zero.

(C) Enthalpy of precipitation reaction is not equal to zero.

3. (A) The energy released in neutralisation of HF and NaOH is greater than 57.3 kJmol–1
(B) HF (aq)  H+ (aq) + F– (aq)
is exothermic reaction.
(D) HCl (aq)  H+(aq) + Cl– (aq) r

4. Work out the energy in by breaking the bonds :-

1 C  C  2  C  H  1 H  H

 (198  2  98  103)kcal

 497 kcal

Then work out the energy released by forming bonds :-

4  C  H  1 C  C

 (4  98  145)kcal

 537 kcal

Enthalpy changed = Energy in – Energy out

= 497 – 537
= – 40 kcal

5. HA(g)  HA(aq.) H = –70.7 KJ/mol

BOH(g)  BOH(aq.) H = –20 KJ/mol
HA(aq.)  H+(aq.) + A– (aq.) H = 15 KJ/mol
BOH(aq.)  B+(aq.) + OH–(aq.) H = 0 KJ/mol
H+(aq.) + OH–(aq.)  H2O() H = –57.3 KJ/mol

(A) HA(aq.) + BOH–(aq.) BA(aq.) + H2O() ; rH = – 42.3 KJ/mol

(C) HA(g) H+(aq.) + A–(aq.) ; rH = – 55.7 KJ/mol

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 Thermochemistry

PV 1 1
6. (n) H2    0.04902 mol
RT 0.0821 298

Energy consumed in dissociating H2 molecules is

E1  (n) H2  436 kjmol 1

 (0.04902  436)kj

 17.84 kj

Amount of H-atoms, n 2  2  n H2

 2  0.04902 [ 1H 2  2H atoms]

 0.08184 mol
Energy required to excite one mol of H-atom from ground state to Ist excited state

1 1 
E  N A R H h c  2  2 
1 2 

3
 NAR Hhc
4

3
  (6.023  10 23 mol1 )(10967 cm 1 )(6.626 10 34 )(3 10 8 cms 1 )
4

 9848.5Jmol1

For exciting, n2 moles of H-atom

E 2  n 2  E

 .08184  9848.5Jmol 1

 0.806 kJ

 Total energy required = E1 + E2

= (17.84 +0.806) kJ
= 18.65 kJ

7. As e s are remove amount of energy required increases.

8. AR; BS; CP; DQ

9. AR; BS; CQ; DP

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