Thermochemistry: Physical Chemistry

PHYSICAL CHEMISTRY
MEGA-XII
THERMOCHEMISTRY
" A SPECIALLY DESIGNED KIT FOR LEARNING."

THE KEY  Basic principles of subjects. An outline of the topics to be
discussed in class lectures.
EXERCISE I  Introductory problems based on JEE to get first hand
experience of problem solving.
EXERCISE II  A collection of good problems.
QUESTION BANK  Test your objective skill.
EXERCISE III  A collection of previous years JEE problems.
PHYSICAL CHEMISTRY NA (SODIUM SIR)
Thermochemistry
Heat of Reaction :
Heat of reaction is defined as the change in heat or the amount of heat evolved or absorbed when the number
of moles of reactants react completey to give the products as given by the balanced chemical equation.
Heat of formation :
Heat of formation is the change in heat enthalpy when one mole of a substance is formed directly from its
constituent elements at standard states.
Heat of combustion :
Heat of combustion is the change in heat enthalpy when one mole of a substance is completely burnt in oxygen.
Hess's law of constant heat summation :

This law states that the total heat change in a particular reaction is the same whether the reaction takes
place in one step or in a number of steps.
e.g., H
(i) A 
 B
H1
(ii) A   H2
 C  B
According to Hess's Law H = H1 + H2.
Applications of Hess's law :

(i) To determine heat of formation
(ii) To determine heat of reaction
Enthalpy of Transition :
Enthalpy of transition is the enthalpy change when one mole of one allotropic form changes to another.
For example : C(graphite)  C(diamond) Htrsº = 1.90 kJ mol–1.
Heat of fusion :
Heat of fusion is the change in heat enthalpy when one mole of a solid is compltely converted into liquid state
at its melting point.
Heat of vaporisation :
Heat of vaporisation is the change in heat enthalpy when one mole of a liquid is completely converted into its
vapours at its boiling point.
Heat of sublimation :
Heat of sublimation is the change in heat enthalpy when one mole of a solid is directly converted into vapours
at sublimation temperature.
Heat of solution :
Heat of solution is the change in heat enthalpy when one mole of a substance is dissolved in excess of water
so that further dilution does not involve any heat change.
Enthalpy of Dilution :
THERMOCHEMISTRY_MEGA-XII
The enthalpy of dilution is the change in enthalpy when a solution containing 1 mole of solute is diluted from
one concentration to another.
Enthalpy of Hydration :
Enthalpy of hydration of a given anhydrous salt is the enthalpy change when it combines with the requisite
amount of water to form a new hydrated stable salt. For exmaple, the hydration of anhydrous cupric sulphate
is represented by
CuSO4(s) + 5H2O()  CuSO4 · 5H2O(s)
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Enthalpy of neutralisation :
Enthalpy of neutralisation is the change in enthalpy when one gram equivalent of an acid is completely
neutralised by one gram equivalent of a base in dilute solutions.
Strong Acid + Strong Base  Salt + Water, Hºneut – 56 kJ/mol–1
Enthalpy of Ionization :
Whenever a weak acid (or base) reacts with a strong base (or acid), the release of heat is less than
57.1 kJ mol–1. It is because of the fact that these acids or bases are not completely ionized in solution.
Some of the heat is consumed in ionizing the acids and bases this heat is known as enthalpy of ionization.
Examples are :
HCN + Na+ OH–  Na+ + CN– + H2O
rHº = –12.13 kJ mol–1.
Enthalpy of Precipitation :
Enthalpy of precipitation is the enthalpy change when one mole of a precipitate is formed from constituents
ions (aq. form). For example :
BaCl2(aq.) + Na2SO4(aq)  BaSO4(s) + 2NaCl(aq) rHº = –24.27 kJ mol–1.
Enthalpy of formation of ions :

The enthalpy change when one mole of aqueous ions is obtained from element in its standard state as.
1
Cl (g) + aq  Cl–(aq) Hrº = Hrº (Cl–, aq)
2 2
By convention, the standard enthlpy of formation of H+(aq) is taken to be zero.
Bond enthalpies :
The bond enthalpy is the average of enthalpies required to dissociate the said bond present in different
gasesous compounds into free atoms or radicals in the gaseous state.
The bond enthalpy given for any particular pair of atoms is the average value of the dissociation enthaplies of
the bond for a number of molecules in which the pair of atoms appears.
Estimation of Enthalpy of a reaction from bond Enthalpies :

Let the enthalpy change for the gaseous reaction
C2H4(g) + HCl(g)  C2H5Cl(g)
be required from the bond enthalpy data. This may be calculated as follows :
 Energy required to   Energy released to 

   
H   break reac tants int o    from products from the 
 gasesous atoms   gaseous atms 
   
Resonance energy :
Hºresonance = Hºf, experimental – Hºf, calculated
= Hºc, calculated –Hºc, experimental
Enthalpy of atomisation :
Enthalpy of atomisation is define as the change in enthalpy when one mole of substance converts into
gaseous atoms.
EXERCISE-I
HEAT OF REACTION & IT'S TYPE
25
1. o
For urea NH2CONH2(S);  f H300 = – 333.75 kJ/mol. Find  f U300
o
of urea. (Use : R  J / mol  K )
3
2. Calculate rH° for Fe2O3(s) + 3CO(g)  2Fe(s) + 3CO2(g)

Given : fH° (Fe2O3) = – 822 kJ/mol,
fH° (CO,g) = –110 kJ/mol,
fH° (CO2,g) = – 393 kJ/mol
3. On the basis of following data,
Evaluate the standard enthalpy of formation of tungsten carbide (WC)
3
(i) W(s) + O (g)  WO3 (s) rH° = – 837 kJ/mol
2 2
5
(ii) WC(s) + O (g)  WO3 (s) + CO2 (g) rH° = – 1196 kJ/mol
2 2
(iii) C(graphite) + O2 (g)  CO2 (g) rH° = – 393.5 kJ/mol
4. The standard heats of formation of CH4(g), CO2(g) and H2O(l) are 76.0, 400, 242 kJ mol 1. Calculate
amount of heat evolved by burning 2.24 m3 of methane measured at 1 atm & 273 K.
5. A cylinder of gas supplied by a company contains 11.2 kg of butane . The heat of combustion of butane is
3000 kJ/mol . A normal family requires 20 MJ of energy per day of cooking. If the cylinder lasts for
27 days, what percentage of gas is wasted due to inefficient combustion.
6. A cylinder of gas is assumed to contains 11.2 kg of butane. If a normal family needs 15,000 kJ of energy per
day for cooking, how long will the cylinder last if the enthalpy of combustion, H = –3000 kJ/mole for butane.
7. Calculate the enthalpy change (in kJ) when 8.5 g of NH3 is passed over heated CuO. The standard heat
enthalpies of formation of NH3(g), CuO(s) and H2O(  ) are –46.0, –155.0 and –285.0 kJ mol–1 respectively
and the reaction is
3 1 3 3
NH3 (g)   N2 (g)  H2O()  Cu(s)
CuO(s) 
2 2 2 2
8. The molar enthalpy of vaporization of benzene at its boiling point (353 K) is 30.84 kJmol–1 What is the molar
internal energy change? For how long would a 12 volt source need to supply a 0.5 A current in order to
vaporise 7.8 g of the sample at its boiling point ?
9. When 12.0 g of carbon reacted with oxygen to form CO & CO2 at 25ºC & constant pressure, 78.0 kcal of heat
was liberated and no carbon remained . Calculate the mass of oxygen which reacted.
Hfº (CO2) =  96 kcal mol1, Hfº (CO) =  24kcal mol1.
1 1
10. The heat of reaction H (g) + Cl2(g)  HCl(g) at 27°C is  22.1 kcal. Calculate the heat of reaction
2 2 2
at 77° C. The molar heat capacities at constant pressure at 27°C for hydrogen, chlorine & HCl are 6.80, 7.60
& 6.80 cal mol1 respectively.
11. Calculate the enthalpy change when infinitely dilute solution of CaCl2 and Na2CO3 mixed Hf° for Ca2+(aq),
CO32–(aq) and CaCO3 (s) are –130, –162, –289 kcal mol–1 repectively.
12. The enthalpies of neutralization of NaOH & NH4OH by HCl are 13680 calories and 12270 cal respectively.
What would be the enthalpy change if one gram equivalent of NaOH is added to one gram equivalent of NH4Cl
in solution ? Assume that NH4OH and NaCl are quantitatively obtained.
13. The heat of solution of anhydrous CuSO4 is –15.9 kcal and that of CuSO4.5H2O is 2.8 kcal. Calculate the
heat of hydration of CuSO4.
14. The standard enthalpy of neutralization of KOH with (a) HCN (b) HCl in dilute solution is 2480 cal/gmeq
and  3.68 kcal/gmeq respectively. Find the enthalpy of dissociation of HCN at the same temperature.
15. If the enthalpy of formation of HCl(g) and Cl–(aq) are –92.0 kJ/mole and – 167.0 kJ/mol, find the enthalpy of
solution of hydrogen chloride gas.
CALORIMETER
16. 0.16 g of methane was subjected to combustion at 27ºC in a bomb calorimeter. The temperature of calorimeter
system (including water) was found to rise by 0.5ºC.
Calculate the heat of combustion of methane at (i) constant volume and (ii) constant pressure.
 25 
The thermal capacity of calorimeter system is 17.7 kJ K1.  Use : R  J / mol  K 
 3 
17. A quantity of 1.92 g of methanol was burnt in a constant pressure calorimeter. The temperature of water
increased by 4.2°C. If the quantity of water surrounding the inner vessel was 2000 ml and the heat capacity
of the inner vessel was 2.0 kJ/°C. Calculate the heat of combustion of methanol.
[Specific heat of capacity of H2O = 4.2 J/g°C]
18. 1.0 liter sample of a mixture of CH4(g) & O2(g) measured at 25ºC & 740 torr was allowed to react at constant
pressure in a calorimeter which together with its contents had a heat capacity of 1260 cal/K. The complete
combustion of the methane to CO2 & H2O caused a temperature rise in the calorimeter of 0.667 K. What was
the mole percent of CH4 in the original mixture?
Hºcomb (CH4) =  215 kcal mol1 .
19. Two solutions initially at 25°C were mixed in a adiabatic constant pressure calorimeter. One contains 400 ml
of 0.2 M weak monoprotic acid solution. The other contain 100 ml of 0.80 M NaOH. After mixing temperature
increased to 26.2°C. How much heat is evolved in the neutralization of 1 mole of acid? Assume density of
solution is 1.0 g/cm3, and specific heat of solution is 4.2 J/g-K. Neglect heat capacity of the calorimeter.
20. When 1.0 g of fructose C6H12O6(s) is burnt in oxygen in a bomb calorimeter, the temperature of the calorimeter
water increases by 1.56°C. If the heat capacity of the calorimeter and its contents is 10.0 kJ/°C. Calculate
the enthalpy of combustion of fructose at 298 K.
BOND ENERGY
21. The enthalpy of dissociation of PH3 is 954 kJ/mol and that of P2H4 is 1.485 MJ/mol. What is the bond
enthalpy of the P–P bond?
22. Calculate the N–H bond enthalpy in NH3(g)

Given : B.E. (H – H) = 436 kJ/mol; fH (N, g) = 470 kJ/mol; fH (NH3, g) = –46 kJ/mol
23. Using the bond enthalpy data given below, calculate the enthalpy change for the reaction.
C2H4(g) + H2(g)  C2H6 (g)
Data:
Bond C–C C=C C–H H–H
Bond Enthalpy 337 kJ/mol 607 kJ/mol 411 kJ/mol 432 kJ/mol
24. Using the given data calculate enthalpy of formation of acetone (g) . [All values in kJ mol1]
Bond energy of : C  H = 413 ; C  C = 347 ; C = O = 728 ;
O = O = 496 ; H  H = 436 ; Hsubof C = 718
25. The polymerisation of ethylene to linear polyethylene is represented by the reaction

nCH2 = CH2  (–CH2 CH2)n where n has a large integral value .
Given that the average enthalpies of bond dissociation for C=C & CC at 298 K are  590 & + 331 kJ mol1
respectively. Calculate the enthalpy of polymerisation per mole of ethylene at 298 K .
26. From the following data :

Enthalpy of formation of CH3CN = 88 kJ/mol ,Enthalpy of formation of C2H6 = –84 kJ/mol
Enthalpy of sublimation of graphite = 720 kJ/mol
Enthalpy of dissociation of nitrogen = 946 kJ/mol ; Enthalpy of dissociation of H2 = 436 kJ/mol
C–H bond enthalpy = 415 kJ/mol
Calculate the (i) B.EC – C ; (ii) B.EC  N
27. The heat of combustion of acetylene is 312 kcal. If heat of formation of CO2 & H2O are 94 & 68 kcal
respectively, calculate C  C bond energy.
Given that heat of atomisation of C is 150 kcal and H – H bond energy and C – H bond energy are 103 kcal
and 93.64 kcal respectively.
28. The enthalpy change for the following process at 25°C and under constant pressure at 1 atm are as follows:
CH4(g)  C(g) + 4H(g) rH = 396 kcal/mole
C2H6(g)  2C(g) + 6H(g) rH = 676 kcal/mole

Calculate C–C bond energy in C2H6 & enthalpy of formation of C2H6(g)
Given: sub C(s) = 172 kcal/mole
B.E. (H–H) = 104 kcal/mole
29. Find the enthalpy of S–S bond from the following data.
(i) C2H5 – S – C2H5 (g) Hfo = – 147 kJ/mol
(ii) C2H5 – S – S – C2H5 (g) Hfo = – 202 kJ/mol
(iii) S (g) Hfo = 223 kJ/mol
30. Find the Bond enthalpy (in kJ/mol) of one "three centre two electron bond" in
B2H6 {B – H – B 2B(g) + H(g)} from the given data.
Hf0 [BH3(g)] = 100 kJ/mol ; Hf0 [B2H6(g)] = 36 kJ/mol
Ha0 [B(s)] = 565 kJ/mol ; Hf0 [H(g)] = 218 kJ/mol
RESONANCE ENERGY
31. The enthalpy of formation of ethane, ethylene and benzene from the gaseous atoms are –2841,
–2274 and –5506 kJ mol–1 respectively. Calculate the resonance energy of benzene. The bond enthalpy of
C–H bond is given as equal to 411 kJ/mol.
32. Calculate the heat of combustion of methyl alcohol at 298 K from the following data
Bond CH CO OH O=O C=O
Energy kJ mol1 414 351 464 494 711
Resonance energy of CO2 =  143 kJ mol1
Latent heat of vaporisation of methyl alcohol = 36 kJ mol1.
Latent heat of vaporisation of water = 40.6 kJ mol1.
BORN HABER CYCLE

33. Calculate the electron gain enthalpy of fluorine atom using the following data . Draw the Born  Haber's cycle.
All the values are in kJ mol1 at 25ºC . Hdiss (F2) = 160, Hfº (NaF(s)) = 571, I.E. [Na(g)] = 494,
Hsub [Na(s)] = 101 . Lattice energy of NaF(s) = 894.
34. Cesium chloride is formed according to the following equation
Cs(s) + 0.5Cl2(g)  CsCl(s) .
The enthalpy of sublimation of Cs, enthalpy of dissociation of chlorine, ionization energy of Cs & electron
gain enthalpy of chlorine are 81.2, 243.0, 375.7 and –348.3 kJ mol1. The energy change involved in the
formation of CsCl is 388.6 kJ mol1 . Calculate the lattice energy of CsCl.
35. The BornHaber cycle for rubidium chloride (RbCl) is given below (the energies are in kcal mol1)
1 –105
Rb(s) + Cl (g) RbCl(s)
2 2
28.75 –159.5
+20.5
Cl(g) Cl¯(g)Rb+ (g)
X
Rb(g) 96.0
Find the value of X.
EXERCISE-II
1. From the following data,
C(s, graphite) + O2(g)  CO2(g) H oreaction = – 393.5 kJ/mole

1
H2(g) + O (g)  H2O (l) H oreaction = – 286 kJ/mole
2 2
2C2H6(g) + 7O2(g)  4CO2 (g) + 6H2O(l) H oreaction = – 3120 kJ/mole
Calculate the standard enthalpy of formation of C2H6 (g) (in kJ/mole).
2. Calculate the mass of mercury which can be liberated from HgO at 27ºC by the treatment of excess HgO
with 36 kJ of heat at
(a) constant pressure (b) constant volume conditions.
Given : Hfº (HgO, s) =  90 kJ mol1 & Atomic mass (Hg) = 200 g mol1 .
3. From the following data of H of the following reactions

C(s) + 1/2O2(g) — CO(g) ; H = –110 KJ
and C(s) + H2O(g) — CO(g) + H2(g) ; H = 132 KJ
Calculate the mole composition of the mixture of steam and oxygen on being passed over coke at
1273 K, keeping the reaction temperature constant.
4. An intimate mixture of ferric oxide & Al is used as solid rocket fuel. Calculate the fuel value per gm &
fuel value per CC of the mix. Heats of formation & densities are :
Hfº (Al2O3) =  399 k cal/mole ; Hfº (Fe2O3) =  199 kcal / mole,
density of Fe2O3 = 5.2 g/cc ; density of Al = 2.7 g/cc.
5. A person takes 15 breaths per minute . The volume of air inhaled in each breath is 492.6 ml and contains
21% of oxygen by volume . The exhaled air contains 16% of oxygen by volume . If all the oxygen is used
in the combustion of sucrose, how much of the latter is burnt in the body per day & how much heat is
evolved. Hcomb of sucrose is =  6000 kJ mol1 . Take temperature to be 300 K throughout.
6. The enthalpies of neutralization of a weak acid HA & a weak acid HB by NaOH are –6900 cal/equivalent &
–2900 cal/equivalent respectively . When one equivalent of NaOH is added to a solution containing one
equivalent of HA & one equivalent of HB, the enthalpy change was –3900 calories. In what ratio is the base
distributed between HA & HB ?
7. Calculate the heat produced when 3.420 litre of octane (C8H18) reacts with oxygen to form CO & water vapour
at 25º C. The density of octane is 0.80 gm/ml. Heat of combustion of C8H18 is –1303 kcal/mol .
Hfº CO2(g) =  94 kcal mol1 ; Hfº CO(g) =  26 kcal mol1 ;
Hfº H2O(l) =  68 kcal mol1 ; Hfº H2O(g) =  58 kcal mol1
8. When 1.36 g of sodium acetate trihydrate (M = 136) was mixed into 100 mL of 0.2 M HCl (aq) at 25ºC in a
solution calorimetry, its temperature fell by 0.4ºC. The cooling occurred due to reacton :
H3O+ (aq) + CH3COONa · 3H2O(s)  Na+(aq) + CH3COOH(aq) + 4H2O (l)
The heat capacity of calorimeter was 90 J/K and heat capacity density of the acid solution is
4.0 (J/Kml). Calculate Hfo (Na+, aq) in kJ/mol.
Hfo [CH3COOH (aq)] = – 485 kJ/mol
Hfo [H2O (l)] = – 285 kJ/mol
Hfo [CH3 COONa · 3H2O(s)] = – 1600 kJ/mol
9. Compute the heat of formation of liquid methyl alcohol in kJ mol1, using the following data. Heat of vaporisation
of liquid CH3OH = 38 kJ/mol . Heat of formation of gaseous atoms from the elements in their standard
states: H = 218 kJ/mol ; C = 715 kJ/mol ; O = 249 kJ/mol.
Average Bond energies C – H = 415 kJ/mol ; C – O = 356 kJ/mol; O – H , 463 kJ/mol
10. Calculate the enthalpy change for the reaction XeF4 (g) Xe+(g) + F(g) + F2(g) + F(g).
The average XeF bond energy is 34 kcal/mol, first I.E. of Xe is 279 kcal/mol, electron affinity of F is
85 kcal/mol & bond dissociation energy of F2 is 38 kcal/mol.
11. By using the following data draw an appropriate energy cycle & calculate the enthalpy change of hydration of
(i) the chloride ion ; (ii) the iodide ion.
Comment on the difference in their values.
* enthalpy change of solution of NaCl(s) =  2 kJ/mol.
* enthalpy change of solution of NaI(s) = + 2 kJ/mol.
* enthalpy change of hydration of Na+(g) =  390 kJ/mol.
* lattice energy of NaCl =  772 kJ/mol.
* lattice energy of NaI =  699 kJ/mol.
12. Calculate the proton gain enthalpy of NH3(g) from the following data (in kJ/mole)
H dissociation : H2(g) = 218 ; H dissociation : Cl2(g) = 124
H formation : NH3(g) = – 46 ; Hf : NH4Cl(s) = –314

Lattice energy of NH4Cl (s) = – 683
Ionization energy of H = 1310
Electron affinity of Cl = 348
13. Heat of combustion of gaseous isoprene (C5H8)
CH2 = CH  C  CH2 to CO2 (g) & H2O (l) is –3185 kJ/mole.

|
CH3
Calculate the heat of formation and compare with bond energies. Calculate the resonance energy of isoprene.
Given : fH (CO2, g) = –393 kJ/mol ; fH (H2O, l)= –285 kJ/mol
Bond energies of C–H, C–C & C=C are 413, 348 and 615 kJ.
Heat of atomization of carbon and H2 are 718 and 436.
14. The enthalpy of formation of C2H5OH(l) is 66 kcal/mol. The enthalpy of combustion of CH3OCH3 is 348
kcal/mol.Given that the enthalpies of formation of CO2(g) and H2O(l) are 94 kcal/mol & 68 kcal/mol
respectively, calculate H for the isomerisation of ethanol to methoxymethane. All data are at 25ºC.
15. From the following data calculate rH for the reaction (in kJ/mol),
XOH (aq)  X+ (aq.) + OH–(aq)
Hionization (HA, aq.) = 15 kJ/mol ;
Hsolution (HA, g) = –30 kJ/mol ;
Hsolution (XOH, g) = –20 kJ/mol
H2O()  H+(aq) + OH–(aq) ; H = 57 kJ/mol
XA(aq) + H2O ()  HA(g) + XOH(g) ; H = 86 kJ/mol
QUESTION BANK
1. Which of the following is not an endothermic reaction?
(A) Combustion of methane (B) Decomposition of water
(C) Dehydrogenation of ethene to ethylene (D) Conversion of graphite to diamond
2. For which of the following change H E?

(A) H2 (g) + I2 (g) 2HI (g) (B) HCl (aq)+ NaOH(aq)  NaCl(aq) + H2O(l)
(C) C(s) + O2(g)  CO2(g) (D) N2 (g)+ 3H2(g)  2NH3(g)
3. rH of which of the following reactions is zero?

(A) H2(g)  2H+ (g) + 2e– (B) 2H(g) + aq  2H+(aq) + 2e–
(C) 2H(g)  2H+(g) + 2e– (D) H2(g) + aq  2H+(aq) + 2e–
4. Which of the reaction defines molar Hfo ?
1 1
(A) CaO(s) + CO2(g)  CaCO3 (s) (B) Br2(g) + H2(g)  HBr (g)
2 2
3
(C) N2(g) + 2H2(g) + O (g)  NH4NO3(s) (D) I2(s) + H2(g)  2HI(g)
2 2
5. Given, H2(g) + Br2(g)  2HBr(g), H1° and standard enthalpy of condensation of bromine is H2°,
standard enthalpy of formation of HBr at 25ºC is
(A) H1°/2 (B) H1°/2 + H2° (C) H1°/2 – H2° (D) (H1° – H2°)/2
6. W hat amount of heat (in kJ) is released in forming 31.2 g AsH 3 by the following reaction?
(At. wt. As = 75, H = 1)
Given: 2As(s) + 3H2(g)  2AsH3 (g) H°= – 773.4 kJ
(A) 309.36 (B) 154.68 (C) 77.39 (D) 38.67
7. How much heat will be required at constant pressure to form 1.28 kg of CaC2 from CaO(s) & C(s) ?
Given : fH° (CaO, s) = –152 kcal/mol.
fH° (CaC2, s) = –14 kcal/mol
fH° (CO, g) = –26 kcal/mol
(A) + 112 kcal (B) 224 kcal (C) 3840 kcal (D) 2240 kcal
8. Assuming that water vapour is an ideal gas, the internal energy change (U) when 1 mol of water is vapourised at
1 bar pressure and 100ºC, (Given : Molar enthalpy of vapourization of water at 1 bar and 373 K = 41 kJ mol–1 and
R = 8.3 J mol–1 K–1) will be
(A) 37.904 kJ mol–1 (B) 41.00 kJ mol–1 (C) 4.100 kJ mol–1 (D) 3.7904 kJ mol–1
9. (H – U) for the formation of carbon monoxide (CO) from its elements at 298 K is (R = 8.314 J K–1 mol–1)
(A) 1238.78 J mol–1 (B) –2477.57 J mol–1 (C) 2477.57 J mol–1 (D) – 1238.78 J mol–1
10. Consider the reaction, N2(g) + 3H2(g)  2NH3(g) ; is carried out at constant temperature and pressure. If H
and U are enthalpy change and internal energy change respectively, which of the following expressions is true?
(A) H = 0 (B) H = U (C) H < U (D) H > U
11. The difference between H and E on a molar basis for the combustion of n-octane at 25ºC would be :
(A) –13.6 kJ (B) – 1.14 kJ (C) –11.15 kJ (D) + 11.15 kJ
12. A(g)  2B(g) ; rH = 20 kJ/mole at 300K
If CP,m(A) = 20 J/K-mol and CP,m(B) = 5 J/K-mol. Which of the following statement is correct?
(A) H will be increase on increasing temperature
(B) H will decrease on increasing temperature.
(C) H will be unaffected by temperature change.
(D) H will decrease on decreasing temperature.
13. The molar heat capacities at constant pressure (assume constant with respect to temperature) of A, B and
C are in ratio of 1.5 : 3.0 : 2.0. If enthalpy change for the exothermic reaction A + 2B  3C at 300 K is
–10 kJ/mol & Cp,m (B) is 300 J/mol then enthalpy change at 310 K is
(A) –8.5 kJ/mol (B) 8.5 kJ/mol (C) – 11.5 kJ/mol (D) None of these
14. What is the standard enthalpy changes at 298 K for the following reaction?
CO2 (g) + C(diamond)  2CO(g)
Given : H of (CO, g) = –110.5 kJ/mol ; H of (CO2,g) = –393.5 kJ/mol
H otransition [C(graphite)  C(diamond)] = 2.0 kJ/mol

(A) –172.5 kJ/mol (B) –170.5 kJ/mol (C) –174.5 kJ/mol (D) None of these
15. For the allotropic change represented by the equation C (graphite)  C (diamond), H = 1.9 kJ. If 6 g of
diamond and 6 g of graphite are separately burnt to yield CO2, the heat liberated in first case is
(A) less than in the second case by 1.9 kJ (B) more than in the second case by 11.4 kJ
(C) more than in the second case by 0.95 kJ (D) less than in the second case by 11.4 kJ
16. The enthalpy of neutralisation of a weak acid in 1 M solution with a strong base is – 56.1 kJ mol–1. If the
enthalpy of ionization of the acid is 1.5 kJ mol–1 and enthalpy of neutralization of the strong acid with a strong
base is – 57.3 kJ mol–1, what is the % ionization of the weak acid in molar solution (assume the acid to be
monobasic)?
(A) 10 (B) 15 (C) 20 (D) 25
17. The enthalpy of neutralisation of HCl and NaOH is –57 kJ mol–1. The heat evolved at constant pressure
(in kJ) when 0.5 mole of H2SO4 react with 0.75 mole of NaOH is equal to
(A) 57 × 3/4 (B) 57 × 0.5 (C) 57 (D) 57 × 0.25
18. What is the value of fH° (C2H6,g) ?

Given : fH° (CH4, g) = –66 kJ/mol ; subH° (C, S) = 718 kJ/mol
B.E. (C – C) = 345 kJ/mol , B.E. (H – H) = 436 kJ/mol
(A) –85 kJ/mol (B) 633 kJ/mol
(C) –185 kJ/mol (D) None of these
19. NH3(g) + 3Cl2(g)  NCl3(g) + 3HCl (g); –H1

N2(g) + 3H2(g)  2NH3(g); H2
H2(g) + Cl2(g)  2HCl (g) ; H3

The heat of formation of NCl3 (g) in the terms of H1, H2 and H3 is
H2 3 H2 3
(A) Hf = – H1 +  H3 (B) Hf = H1 +  H3
2 2 2 2
H2 3
(C) Hf = H1 –  H3 (D) None
2 2
20. If x1, x2 and x3 are enthalpies of H–H, O=O and O–H bonds respectively, and x4 is the enthalpy of vaporisation
of water, estimate the standard enthalpy of combustion of hydrogen
x2 x2 x2 x2
(A) x1+ –2x3+x4 (B) x1+ –2x3–x4 (C) x1+ –x3+x4 (D) 2x3–x1– –x4
2 2 2 2
21. C(s) + O2(g)  CO2, (g) ; H = – 94.3 kcal
1
CO(g) + O (g)  CO2(g) ; H = – 67.4 kcal
2 2
O2(g)  2O(g) ; H = 177.4 kcal
CO(g)  C (g) + O(g) ; H = 230.6 kcal
Calculate H for C(s) C(g) (in kcal)
(A) 171 (B) 154 (C) 117 (D) 115
22. The standard molar enthalpies for formation of cyclohexane() & benzene() at 25°C are 156 & +49 kJ/mol
respectively. The standard enthalpy of hydrogenation of cyclohexene(l) at 25º is  119 kJ mol1. Use these
data to estimate the magnitude of the resonance energy of benzene.
(A) 252 kJ mol–1 (B) 240 kJ mol–1 (C) 152 kJ mol1 (D) None of these
23. Find rUº for the reaction 4HCl (g) + O2(g) 2Cl2(g) + 2H2O (g) at 300 K. Assume all gases are ideal.
Given : H2(g) + Cl2(g) 2HCl (g) r Hº300 = – 184.5 kJ/mole
2H2(g) + O2(g) 2H2O (g) r Hº300 = – 483 kJ/mole (Use R = 8.3 J/mole)
(A) 111.5 kJ/mole (B) –109.01 kJ/mole (C) – 111.5 kJ/mole (D) None
24. The enthalpy change involved in the oxidation of glucose is –2880 kJ/mol. 25 % of this energy is available for
muscular work. If 10 kJ of muscular work is needed to walk 100 meter, what is the maximum distance (in
meter) that a person will be able to walk after eating 60.0 g of glucose?
(A) 2400 (B) 960 (C) 24 (D) None of these
25. Reactions involving gold have been of particular interest to a chemist . Consider the following reactions,
Au(OH)3 + 4 HCl  HAuCl4 + 3 H2O , H =  28 kcal
Au(OH)3 + 4 HBr HAuBr4 + 3 H2O , H =  36.8 kcal
In an experiment there was an absorption of 0.44 kcal when one mole of HAuBr4 was mixed with
4 moles of HCl . What is the percentage conversion of HAuBr4 into HAuCl4 ?
(A) 0.5 % (B) 0.6 % (C) 5 % (D) 50 %
26. 50.0 mL of 0.10 M HCl is mixed with 50.0 mL of 0.10 M NaOH. The solution temperature rises by 3.0°C.
Calculate the enthalpy of neutralization per mole of HCl. [take proper assumptions]
(A) –2.5 × 102 kJ (B) –1.3 × 102 kJ (C) –8.4 × 101 kJ (D) –6.3 × 101 kJ
27. If the enthalpies of formation of Al2O3 and Cr2O3 are – 1596 kJ and – 1134 kJ respectively, then the value of H
for the reaction; 2Al + Cr2 O3 2Cr + Al2 O3 is :
(A) –462 kJ (B) – 1365 kJ (C) – 2530 kJ (D) +2530 kJ
28. The heat of combustion of yellow phosphorus and red phosphorus are – 9.91 kJ and – 8.78 kJ respectively.
The heat of transition of yellow phosphorus to red phosphorus is :
(A) – 18.69 kJ (B) + 1.13 kJ (C) +18.69 kJ (D) – 1.13 kJ
29. Hfo of water is –285.8 kJ mol–1. If enthalpy of neutralisation of monoacid strong base is –57.3 kJ mol–1, Hfo
of OH– ion will be
(A) –228.5 kJ/mol–1 (B) 228.5 kJ/mol–1 (C) 114.25 kJ/mol–1 (D) –114.25 kJ/mol–1
30. Hydrazine, a component of rocket fuel, undegoes combustion to yield N2 and H2O.
N2H4(l) + O2(g)  N2(g) + 2H2O (l)
What is the enthalpy of combustion of N2H4 (kJ/mol) ?
Given Reaction H
2NH3 (g) + 3N2O(g)  4N2(g) + 3H2O () – 1011 kJ
N2O (g) + 3H2(g)  N2H4(l) + H2O() – 317 kJ
4NH3(g) + O2(g)  2N2H4(l) + 2H2O() – 286 kJ
1
H2(g) + O (g)  H2O () – 285 kJ
2 2
(A) – 620.5 (B) – 622.75 (C) 1167.5 (D) + 622.75
31. The enthalpy changes of the following reactions at 27°C are
1
Na(s) + Cl (g)  NaCl (s) rH = –411 kJ/mol
2 2
H2(g) + S (s) + 2O2 (g)  H2SO4 () rH = –811 kJ/mol
2Na(s) + S(s) + 2O2 (g)  Na2SO4 (s) rH = –1382 kJ/mol
1 1
H2(g) + Cl2(g)  HCl (g) rH = –92 kJ/mol; R = 8.3 J/K-mol
2 2
from these data, the heat change of reaction at constant volume ( in kJ/mol) at 27°C for the process
2NaCl (s) + H2SO4 (l)  Na2SO4 (s) + 2HCl (g) is :
(A) 67 (B) 62.02 (C) 71.98 (D) None
32. The reaction CH4(g) + Cl2(g)  CH3Cl(g) + HCl(g) has H = –25 kCal.
Bond Bond Energy
kcal
 C—Cl 84
 H—Cl 103
 C— H x
 Cl —Cl y
x:y=9:5
From the given data, what is the bond energy of Cl—Cl bond
(A) 70 kCal (B) 80 kCal (C) 67.75 kCal (D) 57.85 kCal
33. The standard enthalpy of formation of NH3 is –46.0 kJ mol–1. If the enthalpy of formation of H2 from its atoms
is –436 kJ mol–1 and that of N2 is –712 kJ mol–1, the average bond enthalpy of N – H bond in NH3 is
(A) + 1056 kJ mol–1 (B) – 1102 kJ mol–1 (C) – 964 kJ mol–1 (D) + 352 kJ mol–1
34. The enthalpy of combustion of methane gas in terms of given data is

Bond energy ( kJ / mol)
C H O  H C O O O Re sonance Energy of CO 2  Y (kJ / mol)
 X1  X 2  X 3  X 4 H vaporizati on (H 2 O, l )  Z (kJ / mol)
(A) 4X1 + 2X4 – 2X3– 4X2 + Y + Z (B) 4X1 + 2X4 – 2X3 – 4X2 + Y – 2Z
(C) 4X1 + 2X4 – 2X3– 4X2 – Y – Z (D) None of these
Comprehension (Q.35 to Q.38)
A mixture of hydrogen gas and the theoretical amount of air at 25°C and a total pressure of 1 atm, is exploded
in a closed rigid vessel. If the process occurs under adiabatic condition then using the given datas
answer the questions that follow :
Given (i) CP = 8.3 cal deg–1 mol–1; (ii) CP = 11.3 cal deg–1 mol–1 ; H f [H2O(g)] = –57.8 Kcal
[Assume composition of air is 80% N2, 20% O2 by volume]
35. The value of CP of N2 & H2O will be (in cal. deg.–1 mol–1)
(A) 8.3, 8.3 (B) 8.3, 11.3 (C) 11.3, 11.3 (D) 11.3, 8.3
36. What will be the maximum temperature attained if the process occurs in adiabatic container.
(A)  2940 K (B)  2665 K (C)  1900 K (D)  298 K
37. What will be the final pressure in atm.

(A)  8.5 (B)  7.6 (C)  5.46 (D)  0.85
38. If E1 is initial internal energy at initial temperature T1 & E2 is the final internal energy at higher final
temperature T2 then which option is true
(A) E1 > E2 (B) E2 > E1
(C) E1 = E2 (D) can't be compared from the given data
Assertion - Reason :
39. Statement-1 :On increasing the temperature, enthalpy of reaction may increase or decrease or remain constant.
Statement-2 :Heat capacity of reactants may be greater than, less than or equal to heat capacity of products.
(A) Statement-1 is True, Statement-2 is True ; Statement-2 is a correct explanation for Statement-1
(B) Statement-1 is True, Statement-2 is True ; Statement-2 is NOT a correct explanation of Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
40. Statement-1 :Standard enthalpy of isomerisation of an enantiomer into another is zero.

Statement-2 : Two enantiomers have same standard enthalpy of formation.
41. In the following questions, two statements are given :

One labelled as Assertion A and the other as Reason R. Examine the two statements carefully and mark the
correct choice (A), (B), (C) and (D) according to the instructions given below
(A) if both A and R are correct and R is corret explanation of A
(B) if both A and R are correct but R is not the explanations of A
(C) if A is correct but R is wrong
(D) if A is wrong but R is correct
Assertion : f Hº400 is zero for O2(g)
Reason : fHº298 is zero for O(g)
42. Statement-1 :fHº of sulphur (rhombic) at 25ºC is zero.

Statement-2 :fHº of an element at standard states is zero.
43. Statement-1 : The enthalpy of neutralization of the reaction between HCl and NaOH is –13.7 kcal/mol. If
the enthalpy of neutralization of oxalic acid (H2C2O4) by a strong base in – 25.4 kcal/mol,
then the enthalpy change (| fH|) of the process H2C2O 4  2H+ + C2O 42– is
11.7 kcal/mol.
Statement-2 : H2C2O4 is a weak acid.
44. Statement-1 :Dissolution of salt in water may be exothermic or endothermic.

Statement-2 : Lattice dissociation enthalpy may be greater than or less than enthanlpy of hydration.
More than one may correct :

45. From the following data at 25°C
Reaction rH° kJ/mol
1 1
H2(g) + O2(g)  OH (g) 42
2 2
1
H2(g) + O2(g)  H2O(g) –242
2
H2(g)  2H(g) 436
O2(g)  2O(g) 495
Which of the following statement(s) is/are correct:
(A) Statement : rH° for the reaction H2O (g)  2H(g) + O(g) is 925.5 kJ/mol
(B) Statement : rH° for the reaction OH(g)  H(g) + O(g) is 502 kJ/mol
(C) Statement : Enthalpy of formation of H(g) is –218 kJ/mol
(D) Statement : Enthalpy of formation of OH(g) is 42 kJ/mol
46. Select correct statement(s)

(A) fHº (C(s, diamand))  0 (B) fHº (P(s, white))  0
(C) fHº (Cl2, g) = 0 (D) fHº (H+, aq) = 0
47. 100 ml 0.5 N H2SO4 (strong acid) is neutralised with 200 ml 0.2M NH4OH in a constant pressure calorimeter
which results in temperature rise of 1.4 °C. If heat capacity of calorimeter content is 1.5 kJ/°C.
Which statement is/are correct
Given : HCl + NaOH  NaCl + H2O + 57 kJ
CH3COOH + NH4OH  CH3COONH4 + H2O + 48.1 kJ
(A) Enthalpy of neutralisation of HCl v/s NH4OH is – 52.5 kJ/mol

(B) Enthalpy of dissociation (ionization) of NH4OH is 4.5 kJ/mol
(C) Enthalpy of dissociation of CH3COOH is 4.6 kJ/mol
(D) H for 2H2O(l)  2H+ (aq.) + 2OH¯(aq.) is 114 kJ
48. Which of the following do/does not represent H formation of the product.
1 2
(A) H (g) + (aq)  H+(aq) + e (B) O (g)  O2(g)
2 2 3 3
(C) NH4+(g) + Cl– (g)  NH4Cl(s) (D) P4(black) + 5O2(g)  P4O10(s)
Match The Column :

49. Column-I Column-II
Reaction Standard enthalpy (rHº)
(A) C(gr) + O2(g)  CO2(g) (P) fHº
(B) I2(s)  I2(g) (Q) cHº
(C) H2(g)  2H(g) (R) sub Hº
(D) Br2()  2Br(g) (S) Hbond Diss.
(T) Hatomisation
50. Carefully observe the given diagrams which indicates standard enthalpy of formation of different states of one
mole Mg and 2 mole Cl atom and match the entries in column A and B provided.
Energy (kJ) State of Mg and Cl2

2+
+2600 [Mg (g) + 2Cl(g)]
2+
+2360 [Mg (g) + Cl2(g)]
[Mg (g) + 2Cl–(g)]
2+
+1870
[Mg (g) + 2Cl–(aq)]

2+
+1110
+170 [Mg(g) + Cl2(g)]

0 [Mg(s) + Cl2(g)]
–640 [MgCl2(s)]
[Mg (aq) + 2Cl–(aq)]
2+
–790
Column-I Column-II
(A) Hf [Mg2+(aq)] (P) –1900 kJ/mol
(B) Hf [Cl–(aq)] (Q) +460 kJ/mol
(C) Hhydration [Mg2+(g)] (R) –625 kJmol
(D) | L.E.MgCl2 (s) | (S) +2510 kJ/mol

L.E. = Lattice enthalpy
Integer Type :
51. It is known that enthalpy of neutralisation of a strong acid and strong base is –13.68 kcal mol–1. If enthalpy
of neutralisation of N2H4 with strong acid is –11.68 kcal mol–1. Calculate enthalpy (in kcal) of following
reaction :
N2H4(aq) + H2O()  N2H5 (aq) + OH–(aq)

52. Calculate the value of Z
1
Z × Enthalpy of atomisation of C2H6(g) (in kcal)
170
Given :
Energy (kcal mol–1) 80 100
Bond C–C C–H
53. 1.0 gm of magnesium atoms in vapour state absorb 50 kJ of energy to convert all Mg into Mg ions.
Calculate the value of Z.
% of Mg1 – % of Mg2
Z
18.28
Given :
(IE1)Mg = 740 kJ mol–1
(IE2)Mg = 1450 kJ mol–1
54. An athlete eat 10 gm of glucose. He utilise 50% of this gained energy in an event. In order to avoid storage
of energy in body, calculate the mole of water he would need to perspire enthalpy of H2O for evaporation is
43.33 kJ mol–1. (Given : 1 mol of glucose produce 1560 kJ of energy)
55. Given :
H+(aq) + OH– (aq)  H2O() rH = –56 kJ mol–1.
If enthalpy of formation of H2O() is –286 kJ mol–1 calculate
|  f HOH– |
Z
57.5
EXERCISE-III
1. Diborane is a potential rocket fuel which undergoes combustion according to the reaction,
B2H6(g) + 3O2(g)  B2O3(s) + 3H2O(g)
From the following data, calculate the enthalpy change for the combustion of diborane :
3
2B(s) + O (g)  B2O3(s) ; H = –1273 kJ
2 2
1
H2(g) + O2(g)  H2O(l) ; H = –286 kJ
2
H2O(l)  H2O(g) ; H = 44 kJ
2B(s) + 3H2(g)  B2H6(g) ; H = 36 kJ [JEE 2000]
2. Hf for CO2(g), CO(g) and H2O(g) are –393.5, –110.5 and –241.8 kJ mol–1 respectively. The standard
enthalpy change (in kJ) for the reaction

CO2(g) + H2(g)  CO(g) + H2O (g) is
(A) 524.1 (B) 41.2 (C) –262.5 (D) – 41.2 [JEE 2000]
3. Which of the following reactions defines H f ?

(A) C(diamond) + O2(g)  CO2(g) (B) 1/2 H2(g) + 1/2 F2(g)  HF(g)
(C) N2(g) + 3H2(g)  2NH3 (D) CO(g) + 1/2O2(g)  CO2(g) [JEE 2003]
4. In a constant volume calorimeter, 3.5 g of a gas with molecular weight 28 was burnt in excess oxygen at
298.0 K. The temperature of the calorimeter was found to increase from 298.0 K to 298.45 K due to the
combustion process. Given that the heat capacity of the calorimeter is 2.5 kJ K–1, the numerical value for the
enthalpy of combustion of the gas in kJ mol–1 is [JEE 2009]
5. The bond energy (in kcal mol–1) of a C–C single bond is approximately
(A) 1 (B) 10 (C) 100 (D) 1000 [JEE 2010]
6. The species which by definition has ZERO standard molar enthalpy of formation at 298 K is :
(A) Br2(g) (B) Cl2(g) (C) H2O(g) (D) CH4(g) [JEE 2010]
7. Using the data provided, calculate the multiple bond energy (kJ mol–1) of a CC bond C2H2. That energy is
(take the bond energy of a C–H bond as 350 kJ mol–1)
2C(s) + H2(g)  C2H2(g) H = 225 kJ mol–1
2C(s)  2C (g) H = 1410 kJ mol–1
H2(g)  2H(g) H = 330 kJ mol–1
(A) 1165 (B) 837 (C) 865 (D) 815 [JEE 2012]
8. The standard enthalpies of formation of CO2(g), H2O() and glucose(s) at 25°C are – 400 kJ mol, – 300 kJ mol
and – 1300 kJ mol, respectively. The standard enthalpy of combustion per gram of glucose at 25°C is
(A) +2900 kJ (B) –2900 kJ [JEE Advanced 2013]
(C) –16.11 kJ (D) +16.11 kJ
9. For complete combustion of ethanol, C2H5OH() + 3O2(g)  2CO2(g) + 3H2O(), the amount of heat produced
as measured in bomb calorimeter, is 1364.47 kJ mol–1 at 25ºC. Assuming ideality the Enthalpy of combustion,
CH, for the reaction will be [JEE Main 2014]
(R = 8.314 kJ mol–1)
(A) –1361.95 kJ mol–1 (B) –1460.50 kJ mol–1
(C) –1350.50 kJ mol–1 (D) –1366.95 kJ mol–1
Paragraph for question no. 10 to 11

When 100 mL of 1.0 M HCl was mixed with 100 mL of 1.0 M NaOH in an insultaed beaker at constant
pressure, a temperature increase of 5.7°C was measured for the beaker and its constant (Expt. 1). Because
the enthalpy of neutralization of a strong acid with a strong base in a constant (– 57.0 kJ mol–1), this
experiment could be used to measure the calorimeter constant. In a second experiment (Expt. 2), 100 mL of
2.0 M acetic acid (Ka = 2.0 × 10–5) was mixed with 100 mL of 1.0 M NaOH (under identical conditions to
Expt. 1) where a temperature rise of 5.6°C was measured. [JEE Advance 2015]
(Consider heat capacity of all solutions as 4.2 J g K and density of all solutions as 1.0 g mL–1)
–1 –1
10. Enthalpy of dissociation (in kJ mol–1) of acetic acid obtained from the Expt. 2 is
(A) 1.0 (B) 10.0 (C) 24.5 (D) 51.4
11. The pH of the solution after Expt. 2 is

(A) 2.8 (B) 4.7 (C) 5.0 (D) 7.0
12. The heats of combustion of carbon and carbon monoxide are –393.5 and –283.5 kJ mol–1, respectively.
The heat of formation (in kJ) of carbon monoxide per mole is : [JEE Main 2016]
(A) 110.5 (B) 676.5 (C) –676.5 (D) –110.5
13. Given [JEE Main 2017]

C(graphite) + O2(g)  CO2(g) ; rHº = –393.5 kJ mol–1
1
H2(g) + O (g)  H2O() ; rHº = –285.8 kJ mol–1
2 2
CO2(g) + 2H2O()  CH4(g) + 2O2(g) ; rHº = +890.3 kJ mol–1
Based on the above thermochemical equations, the value of rHº at 298 K for the reaction
C(graphite) + 2H2(g)  CH4(g) will be
(A) –144.0 kJ mol–1 (B) +74.8 kJ mol–1 (C) +144.0 kJ mol–1 (D) –74.8 kJ mol–1
14. For which of the following reactions, H is equal to U ? [Online JEE Main 2018]
(A) N2(g) + 3H2(g) 2NH3(g) (B) 2HI(g)  H2(g) + I2(g)
(C) 2NO2(g)  N2O4(g) (D) 2SO2(g) + O2(g)  2SO3(g)
15. The combustion of benzene () gives CO2(g) and H2O(). Given that heat of combustion of benzene at
constant volume is –3263.9 kJ mol–1 at 25°C; heat of combustion (in kJ mol–1) of benzene at constant
pressure will be: (R = 8.314 JK–1 mol–1) [JEE Main 2018]

(A) –3267.6 (B) 4152.6 (C) –452.46 (D) 3260
16. Given : [JEE Main Online 2019]
(i) C(graphite) + O2(g) CO2(g) ; rH= x kJ mol–1
1
(ii) C(graphite) + O (g)  CO(g) ; rH= y kJ mol–1
2 2
1
(iii) CO(g) + O (g)  CO2(g) ; rH= z kJ mol–1
2 2
Based on the above thermochemical equations, find out which one of the following algebraic relationships is
correct?
(A) x = y – z (B) x = y + z (C) z = x + y (D) y = 2z – x
17. Enthalpy of sublimation of iodine is 24 cal g–1 at 200°C. If specific heat of I2(s) and I2(vap) are 0.055 and 0.031
cal g–1K–1 respectively, then enthalpy of sublimation of iodine at 250°C in cal g–1 is : [JEE Main Online 2019]
(A) 22.8 (B) 5.7 (C) 11.4 (D) 2.85
18. For silver, Cp(JK–1mol–1) = 23 + 0.01T. If the temperature (T) of 3 moles of silver is raised from 300K to 1000
K at 1 atm pressure, the value of H will be close to [JEE Main Online 2019]
(A) 62 kJ (B) 16 kJ (C) 13 kJ (D) 21 kJ
19. Choose the reaction(s) from the following options, for which the standard enthalpy of reaction is equal to the
standard enthalpy of formation. [JEE Advance 2019]
(A) 2H2(g) + O2(g)  2H2O() (B) 2C(g) + 3H2(g)  C2H6(g)
3 1
(C) O (g)  O3(g) (D) S (s) + O2(g)  SO2(g)
2 2 8 8
ANSWER KEY
EXERCISE-I
1. –325 kJ/mol 2. –27 kJ/mol 3. – 34.5 kJ/mol 4. 80.8 MJ
5. 10% 6. 40 days 7. – 74.5 kJ
8. E = 27.91 KJ mol1, t = 514 sec. 9. 28 g O2
10. 22.12 kcal 11. 3 kcal 12.  410 cal 13. –18.7 kcal
14. 11.2 kcal 15. –75 kJ/mole
16. (i) 885 kJ/mol (ii) 890 kJ/mol 17. –728 kJ/mole 18. 10%
19. –31.5 kJ/mole 20. –2808 kJ/mole 21. 213 kJ / mol 22. 390 kJ/mol
23. –120 kJ/mol 24. 190 kJ mol1 25. 72 kJ mol1
26. (i) 342 kJ/mol (ii) 890 kJ/mol 27. B.E.C  C = 161 kcal
28. B.E.C–C = 82 kcal/mole ; f H [C2H6(g)] = –20 kcal/mole 29. 278 kJ/mol
30. B.E.B–H–B = 455 kJ/mole 31. –25 kJ/mol 32. –668.2 kJ mol-1
33. –352 kJ mol–1 34. 618.7 kJ mol1 35. 90.75 kcal mol1
EXERCISE-II
1. –85 kJ/mole 2. (a) 80 g (b) 81.13 g
3. mole % O2(g) = 37.5, H2O(g) = 62.5 4. 0.9346 kcal g1, 3.94 kcal cm3
5. w = 615.6 g, qP = –10.8 MJ/day 6. 1:3
7.  669 kcal mol1, 16.056 Mcal 8. –240.40 kJ/mol
9.  266 kJ/mol 10. 292 kcal/mol
11. HHydration(Cl)= 384 kJ/mol, HHydration(I)=307 kJ/mol
12. – 718 kJ/mol 13. –30.06 kJ/mol
14. 22kcal mol1 15. 6

QUESTION BANK
1. A 2. D 3. D 4. C 5. D 6. B 7. D
8. A 9. A 10. C 11. C 12. B 13. C 14. D
15. C 16. C 17. A 18. A 19. A 20. B 21. D
22. C 23. C 24. A 25. C 26. A 27. A 28. D
29. A 30. A 31. B 32. D 33. D 34. D 35. B
36. A 37. A 38. C 39. A 40. A 41. C 42. A
43. D 44. A 45. AD 46. ACD 47. ABD 48. BCD
49. A – P, Q ; B – P, R ; C – S, T ; D – T 50. A–Q ; B–R ; C–P ; D–S
51. 2 52. 4 53. 2 54. 1 55. 4
EXERCISE-III
1. –2035kJ mol–1 2. B 3. B 4. 5. C 6. B
7. D 8. C 9. D 10. A 11. B 12. D

13. D 14. B 15. A 16. B 17. A 18. A
19. CD

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PHYSICAL CHEMISTRY

" A SPECIALLY DESIGNED KIT FOR LEARNING."

Hess's law of constant heat summation :

Applications of Hess's law :

Enthalpy of formation of ions :

Estimation of Enthalpy of a reaction from bond Enthalpies :

 Energy required to   Energy released to 

2. Calculate rH° for Fe2O3(s) + 3CO(g)  2Fe(s) + 3CO2(g)

(iii) C(graphite) + O2 (g)  CO2 (g) rH° = – 393.5 kJ/mol

22. Calculate the N–H bond enthalpy in NH3(g)

25. The polymerisation of ethylene to linear polyethylene is represented by the reaction

26. From the following data :

C2H6(g)  2C(g) + 6H(g) rH = 676 kcal/mole

BORN HABER CYCLE

Find the value of X.

C(s, graphite) + O2(g)  CO2(g) H oreaction = – 393.5 kJ/mole

3. From the following data of H of the following reactions

H dissociation : H2(g) = 218 ; H dissociation : Cl2(g) = 124

H formation : NH3(g) = – 46 ; Hf : NH4Cl(s) = –314

13. Heat of combustion of gaseous isoprene (C5H8)

CH2 = CH  C  CH2 to CO2 (g) & H2O (l) is –3185 kJ/mole.

2. For which of the following change H E?

3. rH of which of the following reactions is zero?

4. Which of the reaction defines molar Hfo ?

Given : H of (CO, g) = –110.5 kJ/mol ; H of (CO2,g) = –393.5 kJ/mol

H otransition [C(graphite)  C(diamond)] = 2.0 kJ/mol

18. What is the value of fH° (C2H6,g) ?

19. NH3(g) + 3Cl2(g)  NCl3(g) + 3HCl (g); –H1

H2(g) + Cl2(g)  2HCl (g) ; H3

21. C(s) + O2(g)  CO2, (g) ; H = – 94.3 kcal

(A) –462 kJ (B) – 1365 kJ (C) – 2530 kJ (D) +2530 kJ

31. The enthalpy changes of the following reactions at 27°C are

34. The enthalpy of combustion of methane gas in terms of given data is

37. What will be the final pressure in atm.

40. Statement-1 :Standard enthalpy of isomerisation of an enantiomer into another is zero.

41. In the following questions, two statements are given :

Reason : fHº298 is zero for O(g)

42. Statement-1 :fHº of sulphur (rhombic) at 25ºC is zero.

44. Statement-1 :Dissolution of salt in water may be exothermic or endothermic.

More than one may correct :

46. Select correct statement(s)

(A) Enthalpy of neutralisation of HCl v/s NH4OH is – 52.5 kJ/mol

Match The Column :

Energy (kJ) State of Mg and Cl2

[Mg (g) + 2Cl–(aq)]

+170 [Mg(g) + Cl2(g)]

(D) | L.E.MgCl2 (s) | (S) +2510 kJ/mol

N2H4(aq) + H2O()  N2H5 (aq) + OH–(aq)

52. Calculate the value of Z

enthalpy change (in kJ) for the reaction

3. Which of the following reactions defines H f ?

Paragraph for question no. 10 to 11

11. The pH of the solution after Expt. 2 is

13. Given [JEE Main 2017]

pressure will be: (R = 8.314 JK–1 mol–1) [JEE Main 2018]

1. –325 kJ/mol 2. –27 kJ/mol 3. – 34.5 kJ/mol 4. 80.8 MJ

5. 10% 6. 40 days 7. – 74.5 kJ

8. E = 27.91 KJ mol1, t = 514 sec. 9. 28 g O2

14. 11.2 kcal 15. –75 kJ/mole

23. –120 kJ/mol 24. 190 kJ mol1 25. 72 kJ mol1

28. B.E.C–C = 82 kcal/mole ; f H [C2H6(g)] = –20 kcal/mole 29. 278 kJ/mol

1. –85 kJ/mole 2. (a) 80 g (b) 81.13 g

5. w = 615.6 g, qP = –10.8 MJ/day 6. 1:3