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Thermochemistry is the branch of physical chemistry which deals with the

thermal or heat changes caused by chemical reactions. It is based on first
law of thermodynamics.

ENTHALPY (H)
Chemical reactions are generally carried out at constant pressure (atmospheric
pressure) so it has been found useful to define a new state function Enthalpy
(H) as :
H = U + PV

r
and hence, H = U + (PV)

i
At constant pressure

S
H = U + P V
Combining with first law,

e
DH = qp

ir n c
“Therfore, heat exchange at constant pressure is equal to the change in
enthalpy of the reaction.”

P
Enthalpy change of a reaction rH)-Reaction enthalpy-Heat of reaction
The enthalpy change of a reaction may be defined as the amount of heat

y
lost or gained in the chemical reaction, when all the reactants and products

B
are maintained at the same temperature and pressure. The enthalpy change
of a chemical reaction may be given as

DrH = (sum of enthalpies of products) - (sum of enthalpy of reactants)

= S(· H)products – S( · H)reactants

where  is the stoichiometric coefficients of reactants and products,
respectively.
(i) Exothermic Reactions : The reactions which accomplish with evolution of
heat are called exothermic reactions. For such reactions D rH is negative,
which implies that

 P H (products) <  R H (reactants)

(ii) Endothermic Reactions : The reactions which accomplish with absorption of

heat are called endothermic reactions. For such reactions D rH is positive,
which implies that

 P H (products) >  R H (reactants)

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Factors affecting the H of the reactions are :

(i) Physical states of reactants & products
(ii) Allotropic forms of elements
(iii) Reaction condition
H = U + ng· RT
where H = Heat change of reaction at constant pressure or enthalpy
change.
U = Heat change of reaction at constant volume or internal energy
change.
ng = Total moles of gaseous products – total moles of gaseous reactants.
(iv) Temperature

Standard enthalpy of Reaction, rH°

r
The standard enthalpy of reaction is the enthalpy change for a reaction,

i
when all the participating substance (reactants and products) are in their

S
standard condition.

e
The standard condition are :

c
* Solid / liquid / gas should be at 1 bar

ir n
* for substance dissolved in solution concentration should be 1M.

Enthalpy changes in different types of chemical reactions

P
(1) Enthalpy of Formation, fH
It is the enthalpy change when one mole of a substance is formed from its

y
elements in their most standard state (also called reference states). For

B
example, the reference state of oxygen, carbon and sulphur are O 2 gas,
Cgraphite and Srhombic , respectively. Some reactions with standard molar
enthalpies of formation are :
1
H2(g) + O (g)  H2O(l) ; fH° = – 285.8 kJ mol–1
2 2
 By convention, enthalpy of formation(fH°) of an element in reference
state is taken as zero.

e.g. Δ f HO2 ( g ) = 0, Δ f H(C , graphite) = 0, Δ f H( S ,Rhombic) = 0, Δ f H( P,White) = 0

The enthalpy of formation can be used to determine the enthalpy change
of any reaction as

 rH =  a i  f H(Products) –  bi  f H(reactants)
i i

where ai and bi represent the coefficients of the products and reactants in

the balanced chemical equation.
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 Compounds with negative enthalpy of formation are called exothermic

compounds and compounds with positive enthalpy of formation are called
endothermic compounds.
Alert No. 1
Always keep in mind enthalpy of formation is defined for the formation of one mole of
substance.If in the reaction moles are different than we have to convert it for one mole
of substance.
for e.g. N2(g) + 3H2(g) 2NH3(g) , H = -200 kJ

r
Than enthalpy of formation of NH3 will be 200/2 i.e. -100 kJmol-1

i
(2) Enthalpy of Combustion, CH :

S
It is the enthalpy change (always negative) when one mole of the substance undergo complete

e
combustion.

c
For example

ir n
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) ; cH = – 890.8 kJ mol–1 at 298 K.
Since combustion is an exothermic process so cH will always be negative.
Application of Enthalpy of combustion :

P
1. Calorific value of fuels
2. Calculation of Enthalpy of formation

y
3. Maximum flame temperature

B
CALORIFIC VALUE
It is defined as the amount of energy released by the complete combustion of one gram of
a fuel .Calorific value is a measure of the quality of a fuel . In terms of Enthalpy of combustion
it can be represented as :
Enthalpy Of Combustion Δ c H
C.V . = =
Molar Mass of Fuel M .M
unit : Jg-1
Higher is the calorific value of a fuel better will be the quality of that fuel.

FLAME TEMPERATURE
When a fuel burns definite quantities of products are formed and a definite amount of heat is
liberated. This quantity of heat may raise the temperature of the products sufficiently so as to
produce a flame. This temperature is termed as maximum flame temperature or calorific
intensity.
HESS'S LAW OF CONSTANT HEAT SUMMATION
According to Hess’s law (a consequence of first law), Whether a reaction is carried out in a
single step or in a series of several steps the enthalpy change would be the same for both the
paths.
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H
A B

H1 H3

H2
C D

So, acc. to Hess’s law H = H1 + H2 + H3

As such, the chemical equations can be treated ordinary algebraic expressions and can be added
or subtracted to yield the required equation. The corresponding enthalpy changes are also

i r
manipulated in the same way to obtain the enthalpy change for the desired equation.

S
(3) Enthalpy changes during phase transformations
(i) Enthalpy of Fusion, fus.H : It is the enthalpy change that accompanies melting of one mole

e
of a solid substance at constant temperature (melting point of solid) and pressure.

c
for example,

ir n
H2O(s)  H2O(l) ; fusH = + 6.00 kJ mol–1

(ii) Enthalpy of Vaporisation, vapH :

P
It is the amount of heat required to vapourise one mole of a liquid substance at constant temperature

y
(boiling point of liquid) and pressure for example :
H2O(l)  H2O(g) ; vapH = + 40.79 kJ mol–1

B
(iii) Enthalpy of Sublimation, subH :
It is the amount of heat required to sublime one mole of a solid substance at constant temperature
(sublimation temperature of solid) and pressure. For example
CO2(s)  CO2(g) ; subH = +25.2 kJ mol–1

(4) Ionisation Enthalpy (iH)

It is the enthalpy change (always positive) when an electron is remove from an isolated gaseous
atom in its ground state under conditions of constant temperature and pressure.
X(g)  X+(g) + e¯

(6) Electron Gain Enthalpy (egH)

It is the enthalpy change when an electron is added to a neutral gaseous atom to convert it into
a negative ion under conditions of constant temperature and pressure.
X(g) + e¯  X¯ (g)
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(7) Lattice Enthalpy (latticeH)

The lattice enthalpy of an ionic compound is the enthalpy change which occurs when one mole
of an ionic compound dissociates into its ions in gaseous state under conditions of constant
temperature and pressure.
Na+Cl¯ (s)  Na+(g) + Cl¯ (g) ;
lattice H = + 788 kJ mol–1

(8) Enthalpy of Atomisation, aH :

r
It is the enthalpy change (always positive) when one mole of a substance is completely dissociated

i
into atoms in the gaseous state, under constant pressure and temperature condition.
For example

S
C(s)  C(g), aH = 410.0 kJ mol–1
H2(g)  2H(g) ; aH = 435.0 kJ mol–1

c e
CH4(g)  C(g) + 4H(g) ; aH = 1665 kJ mol–1

ir n
(9) Enthalpy of Transition
It is the enthalpy change when one mole of one allotropic form changes to another under conditions

P
of constant temperature and pressure. For example
C(graphite)  C(diamond) trsH = 1.90 kJ mol–1

y
Enthalpy of Hydration, hydH :

B
(10)
It is the enthalpy change (always negative) when one mole of an anhydrous (or partly hydrated)
compound combines with the required number of moles of water to form a specific hydrate at
the specified temperature and pressure. For example :
CuSO4(s) + 5H2O(l)  CuSO4 · 5H2O(s) ; (hyd)H = – 78.20 kJ mol–1
(11) Enthalpy of Solution, solH :
It is the enthalpy change when one mole of a substance is dissolved in a specified amount of
solvent under conditions of constant temperature and pressure. When large volume of solvent is
taken, the enthalpy change is called enthalpy of solution at infinite dilution. For example

HCl(g)  HCl.10H2O ; solH =  69.5 kJ mol–1

this equation means on adding 1 mole of HCl to 10 moles of water 69.5 kJ of heat is evolved.

NaCl(s) + ∞ H2O(l)  Na+ (aq) + Cl¯ (aq) ; solH = 75.17 kJ mol–1

The value of H corresponding to this equation is called enthalpy pf solution at infinite dilution
and it is the maximum heat that can be released on dissolving one mole of HCl (g) in excess of
water.
(12) Enthalpy of Neutralisation neutH :
It is the enthalpy change (always negative) when one g-equivalent of an acid and one g-equivalent
of a base undergo complete neutralisation in aqueous solution and all the reactants & products
are at the same specified temperature and pressure.
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HCl(aq) + NaOH(aq)  NaCl(aq) + H2O(l) ; neutH = – 57.32 kJ eq–1

The enthalpy of neutralisation of strong acid and strong base is always constant (– 57.32 kJ eq –
1), independent from the acid and base taken.

Alert No. 2
But if a weak base or weak acid is present than Enthalpy of neutrilisation is less than 57.32 kJ
eq-1 as some part of the heat released will be utilised in the ionisation of the weak specie.
For e.g. Neutrilisation of CH3COOH(weak Acid) with NaOH(Strong base).
The process of neutrilisation can be as follows
(i) Ionisation of CH3COOH:
CH3COOH(aq)  CH3COO-(aq.) + H+(aq.) Hionisation
(ii) Neutrilisation
H+(aq.) + OH-(aq.) l) , neutH = – 57.32 kJ eq–1
So the enthalpy of reaction according to Hess’s law

i r
rH = -57.32 + Hionisation

(13) Resonance energy :

c e S
ir n
It is the difference in energy of most stable resonating structure and actual resonance hybrid.

Resonance Energy = fH(experimental) - fH(Theoretical)

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Measurement of U and H : calorimetry

y
The process of measurement of energy changes in the physical or chemical processes is carried

B
out in a vessel called Calorimeter, which is immersed in a known volume of a liquid, knowing the
heat capacity of the Calorimeter and the liquid in which Calorimeter is immersed, it is possible to
determine the heat absorbed or evolved in the process by measuring temperature changes.
Measurements are made under two different conditions :
(i) At constant volume, qv or U or E
(ii) At constant pressure, qp or H

(i) U measurement : For chemical reactions, heat absorbed at constant volume, is measured in a
bomb Calorimeter. In this Calorimeter, a steel vessel (the bomb) is immersed in a water bath. A
combustible substance is burnt in pure oxygen supplied in the bomb. Heat evolved during the
reaction is transferred to the water around the bomb and its temperature is monitored. Since the
bomb Calorimeter is sealed, its volume does not change, i.e., the energy changes associated with
reactions are measured at constant volume which will give the value of U .
Once U is known H can be calculated from the relation
H = U + (PV)
H = U + ngRT
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S i r
ir n c e
P
(ii) H measurement : Measurement of heat change at constant pressure (generally at atmospheric
pressure) can be done in a Calorimeter shown in the figure. In this case, the Calorimeter is left

y
open to atmosphere. As the reaction occurs in the Calorimeter, the temperature change is noticed

B
and then heat of reaction is measured with the knowledge of heat capacity of Calorimeter system.

TEMPERATURE DEPENDENCE OF ENTHALPY OF REACTION

(KIRCHOFF’S EQUATION)
Consider a general reaction A  B
The enthalpy change H = HB - HA
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On differentiating this equation w.r.t. temperature at constant pressure

∂ (Δ H ) ∂(H B ) ∂(H A )
=  = (CP)B  (CP)A = CP
∂T ∂T ∂T
So,on integrating both sides

ΔH T2

ΔH
∫ d (Δ H ) = ∫ ΔC P dT
T1

Case-1 : If CP is independent of temperature than

ΔH T2  ΔH T2 =CP (T2  T1)
Where, CP = CP(products)  CP (reactants)

i r
Case-2 : If CP is independent of temperature than

S
T 2

ΔH T2  ΔH T2 = ∫ Δ C P dT

e
T1

c
Bond Enthalpies (Bond energies), bondH :

ir n
Bond Enthalpy or Bond Energy :
“ It can be defined as the average energy required to dissociate a bond of a type in a
gaseous compound into its free atoms.”

y P
The bond enthalpy of diatomic molecules like H2, Cl2, O2 etc. may be defined as the enthalpy
change (always positive) when one mole of covalent bonds of a gaseous covalent substance is

B
broken to form products in the gas phase, under conditions of constant pressure and temperature.
For example
Cl2(g)  2Cl(g) ; Cl–ClH = +242 kJ mol–1
O2(g)  2O(g) ; O=OH = +428 kJ mol–1
Bond Dissociation Enthalpy :
“it is defined as the amount of energy required to break a given bond in a specific
compound.”
For example
CH4(g)  CH3(g) + H(g) ; H0 = 427 kJ
CH3(g)  CH2(g) + H(g) ; H0 = 418 kJ
CH2(g)  CH(g) + H(g) ; H0 = 460 kJ
CH(g)  C(g) + H(g) ; H0 = 343 kJ

Here Bond Energy = ΔH1 + ΔH 2 + ΔH 3 + ΔH 4

4
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But H1, H2 , H3 , H4 are respective C-H bond energies in each step.

In gas phase reactions, the standard enthalpy of reaction, rH°, is related with the bond enthalpies
of reactants and products as
rH° =  bond enthalpies (reactants) –  bond enthalpies (products)

COMPUTATION OF ENTROPY OF REACTION

nS nS

r
rS o  o
 o

i
i products i reactants

Where So is the standard molar entropy of substance.

S
Effect of temperature on Entropy of reaction
T2
rCp

e
 r S o T2   r S o T1   dT

c
T1
T

ir n
T2
If Cp is independent of temperature  r S o T2   r S o T1   r C p ln
T1

P
If Cp depends on temperature integration has to be carried out.
Effect of pressure on Entropy of reaction

y
p2
r S o p2  r S o p1  ng R ln

B
p1
GIBBS FREE ENERGY CHANGE FOR A CHEMICAL REACTION
G 0   G f (products)   G f (reactants)
0 0

 reactions having negative G are called exergonic while reactions having positive G are
called endergonic.

Alternatively G can also be calculated from Gibbs Helmholtz equation

i.e. Go = Ho + TSo
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S i r
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B
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Q.1. For the reaction of 1 mole of SO2(g) into SO3(g) into SO3(g) the enthalpy of reaction at constant
volume, E, at 298K is –97.027 kJ. Calculate the enthalpy of reaction, H, at constant pressure.

Q.2. H° for the reaction,

4S(s) + 6O2(g)  4SO3(g)
is – 1583.2 kJ. Calculate H°f of sulphur trioxide.

Q.3. Calculate the heat change in the reaction,

4NH3(g) + 3O2(g)  2N2(g) + 6H2O(l)

r
at 298 K given that heats of formation at 298 K for NH3(g) and H2O(l) are –46.0 and –286.0 kJ

i
mol–1 respectively.

S
Q.4. Calculate the heat of combustion of 1 mole of C2H4(g) to form CO2(g) and H2O(g) at 398 K and 1
atmosphere, given that the heats of formation of CO2(g), H2O(g) and C2H4(g) are –94.1, –57.8

c e
and + 12.5 kcal mol–1 respectively.

ir n
Q.5. The heats of combustion of CH4(g) and C2H2(g) are –890.3 and –1560 kJ mol–1 respectively.
Which has higher calorific value ?

P
Q.6. The heat of combustion of butane is 2800 kJ mol–1. What is the heat liberated by burning 1 kg of
butane in excess of oxygen supply ?

y
Q.7. The heat of formation of CH4(g), C2H6(g) and C4H10(g) are –74.8, –84.7 and –126.1 kJ mol–1

B
respectively. Arrange them is order of their efficiency as fuel per gram. Heats of formation of
CO2(g) and H2O(l) are –393.5 and –285.8 kJ mol–1 respectively.

Q.8. Calculate the amount of heat released when :

(i) 100 mL of 0.2 M HCl solution is mixed with 50 mL of 0.2 M KOH.
(ii) 200 mL of 0.1 M H2SO4 is mixed with 200 mL of 0.2 M KOH solution.

Q.9. When 100 mL each of HCl and NaOH solutions are mixed, 5.71 kJ of heat was evolved. What is
the molarity of two solutions ? The heat of neutralisation of HCl is 57.1 kJ.

Q.10.Determine the enthalpy of the reaction,

C3H8(g) + H2(g)  C2H6(g) + CH4(g)
at 25°C, using the given heat of combustion values under standard conditions.
Compound H2(g) CH4(g) C2H6(g) C (graphite)
H°(kJ mol )–1
–285.8 –890.0 –1560.0 –393.5
The standard heat of formation of C3H8(g) is –103.8 kJ mol–1

Q.11. The standard enthalpy of combusition at 25° C of hydrogen cyclohexene (C6H10) and cyclohexane
(C6H12) are –241,–3800 and –3920 kJ mol–1 respectively. Calculate the heat of hydrogenation of
cyclohexene.
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Q.12. From the following data of heats of combustion, find the heat of formation of CH3OH(l) :
3
CH3OH(l) + O2(g)  CO2(g) + 2H2O(l); H = –726 kJ
2
C(s) + O2(g)  CO2(g); H = –394 kJ
1
H2(g) + O2(g)  H2O(l); H = –286 kJ
2
Q.13. Calculate the heat of formation of methane, given that
Heat of formation of water = –286 kJ mol–1
Heat of combustion of methane = –890 kJ mol–1
Heat of combustion of carbon = –393.5 kJ mol–1

Q.14. The heat of formation of C6H6(l), H2O(l) and CO2(g) are 11.70, –68.4 and –94.0 kcal
respectively. Calculate the heat of combustion of benzene (l).
Ans.

i r
Q.15. Calculate the enthalpy of transition of rhombic sulphur to monoclinic sulphur from the
following data :

S
S(rhombic) + O2(g)  SO2(g); H = –297.5 kJ
S(monoclinic) + O2(g)  SO2(g); H = –299.9 kJ

e
Ans.

ir n c
Q.16.Calculate H for the reaction,
1
H2(g) + O2(g)  H2O(g)
2

P
given that bond energies of H–H and O=O bond and O–H bond are 433 kJ mol –1, 492 kJ mol–1 and
464 kJ mol–1.

y
Ans.

B
Q.17. Use the following bond dissociation energies to compute the C–H bond energy in methane
(i) CH4(g)  CH3(g) + H(g); H = 475 kJ mol–1
(ii) CH3(g)  CH2(g) + H(g); H = 470 kJ mol–1
(iii) CH2(g)  CH(g) + H(g); H = 416 kJ mol–1
(iv) CH(g)  C(g) + H(g); H = 355 kJ mol–1
Ans.

Q.18. The standard free energy of formation in the gaseous state of methanol, dimethyl ether and
water are –38.7, –27.3 and –54.6 kcal respectively. Is the transformation of methanol to dimethyl
ether and water in gaseous state possible ?
2CH3OH  CH3OCH3 + H2O

Q.19.For the reaction,

1
Ag2O = 2Ag(s) + O (g)
2 2
Calculate the temperature at which free energy change is zero. At a temperature lower than this,
predict whether the forward of the reverse reaction will be favoured. Give reason.
(H = 30.56 kJ and S = + 0.066 kJ K–1 mol–1 at one atmosphere)
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Q.20. Calculate the boiling point of the liquid if its entropy of vaporization is 110 J K–1 mol–1 and
the enthalpy of vaporization is 40.85 kJ mol–1.

Q.21. Using S° values, calculates the entropy of the reaction,

1
SO2 (g) + O (g)  SO3(g)
2 2
The S° values for SO2, O2 and SO3 are 248.5, 205.0 and 256.2 J K–1 mol–1
Q.22. For the reaction,
Br2(l) + Cl2(g)  2BrCl(g)

i r
H = 29.37 kJ mol–1 and S = 104 J K–1 mol–1. Find the temperature above which the
reaction would become spontaneous.

S
Q.23. For the synthesis of ammonia,
N2(g) + 3H2(g)  2NH3(g)

e
Calculate H°, S° and G° at 300 K using the following data :

c
Species N2 H2 NH3

ir n
H°f/(kJ mol )–1
0 0 –46.2
S°/(JK–1 mol–1) 191.5 130.6 192.5

Q.24. The polymerisation of ethylene to linear polyethylene is represented by the reaction,

P
where, n has a large integral value. Given that the average enthalpies of bond dissociation

y
for C = C and C–C at 298K are +590 and +331 kJ mol–1 respectively, calculate the enthalpy

B
of polymerisation per mole of ethylene at 298 K.

Q.25. Calculate the entropy of ideal mixing when 2 moles of N2, 3 moles of H2 and 2 moles of NH3
are mixed at constant temperature, assuming no chemical reaction is occurring.

Q.26. Calculate free energy change for the reaction :

H2(g) + Cl2(g)  2H – Cl(g)
by using the bond energy and entropy data.
Bond energies of H–H, Cl–Cl and H–Cl bonds are 435 kJ mol –1, 240 kJ mol–1 and 430 kJ
mol–1 respectively. Standard entropies of H2, Cl2 and HCl are 130.59, 222.95 and 186.68 J
K–1 mol–1 respectively.
Q.27. 1 mole of an ideal gas is allowed to expand isothermally at 27° C until its volume is tripled.
Calculate Ssys and Suniv under the following conditions :
(a) the expansion is carried out reversibly.
(b) the expansion is a free expansion.
Q.28. One kilogram water at 0° C is brought into contact with a heat reservoir at 100°C. Find :
(a) change in entropy when temperature reaches to 100°C.
(b) what is the change in entropy of reservoir ?
(c) change in entropy of universe.
(d) the nature of process.

Q.29. A liquid freezes into solid (H = –500 J mol–1) at 100 K and 1 atm. Find the values of :
(i) Gibbs free energy change
(ii) Entropy change.
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Q.30 Calculate standard enthalpies of formation of carbondisulphide (l) . Given the standard enthalpy
of combustion of carbon (s) , sulphur (s) & carbondisulphide (l) are :  393.3,  293.72 and
 1108.76 kJ mol 1 respectively.

Q.31 From the following data at 25°C, Calculate the standard enthalpy of formation of FeO(s) and
of Fe2O3(s).
Reaction  r H o (kJ/mole)
(1) Fe2O3(s) + 3C(g)  2Fe (s) + 3CO(g) 492.6
(2) FeO (s) + C(g)  Fe(s) + CO(g) 155.8
(3) C(g) + O2(g)  CO2(g) –393.51
(4) CO(g) +1/2 O2(g)  CO2(g) –282.98

i r
Q.32 The enthalpy change for the reaction C3H8(g) + H2(g)  C2H6(g) + CH4(g) at 25º C is
 55.7 kJ/mol. Calculate the enthalpy of combustion of C2H6(g). The enthalpy of combustion of

S
H2, & CH4 are 285.8 & 890.0 kJ/mol respectively. Enthalpy of combustion of propane is

e
2220 kJ mol1.

ir n c
Q.33 At 300 K, the standard enthalpies of formation of C6H5COOH(s), CO2 (g) & H2O (l) are 
– 408, – 393 & –286 kJ mol –1 respectively .
Calculate the heat of combustion of benzoic acid at:

P
(i) constant pressure
(ii) constant volume.

Q.34

Q.35 B y
A cylinder of gas is assumed to contains 11.2 kg of butane. If a normal family needs 20,000 kJ of
energy per day for cooking, how long will the cylinder last if the enthalpy of combustion, H =
–2658 kJ/mole for butane.

Using bond enthalpy data, calculate enthalpy of formation of isoprene .

5 C(s) + 4 H2(g)  H2C = C — C = CH2(g)

| |
CH 3 H

Given : C  H = 98.8 k Cal ; H  H = 104 k Cal ;

C  C = 83 k Cal ; C = C = 147 k Cal &
C(s)  C(g) = 171 k Cal .

Q.36 The enthalpy of atomization of PH3 is 954 kJ mol–1 and that of P2H4 is 1.485 M J mol–1. What is
the bond enthalpy of the P–P bond?
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Q.37 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 336.81 kJ/mol 606.68 kJ/mol 410.87 kJ/mol 431.79 kJ/mol

Q.38 Calculate the average bond enthalpy of the O–H bond in water at 298K using the data/information
given below :-
f H0[H(g)] = 218 kJ/mol

r
(1)

i
(2) f H0[O(g)] = 249.2 kJ/mol
(3) f H0[H2O(g)] = –241.8 kJ/mol

S
The average bond enthalpy of the O–H bond in water is defined as one-half of the enthalpy
change for the reaction H2O(g)  2H(g) + O(g).

c e
Also, determine the average Bond Energy, U of the O–H bond in water at 298K. Assume ideal

ir n
gas behaviour.
Q.39 From the following data :
Enthalpy of formation of CH3CN = 87.86 kJ/mol

P
Enthalpy of formation of C2H6 = – 83.68 kJ/mol
Enthalpy of sublimation of graphite = 719.65 kJ/mol

y
Enthalpy of dissociation of nitrogen = 945.58 kJ/mol

B
Enthalpy of dissociation of H2 = 435.14 kJ/mol
C–H bond enthalpy = 414.22 kJ/mol
Calculate the bond enthalpy of (i) C – C ; (ii) C  N

Q.40 The enthalpy of combustion of acetylene is 312 kCal per mole. If enthalpy of formation of
CO2 & H2O are 94.38 & 68.38 kCal per mole respectively, calculate C  C bond enthalpy.
Given that enthalpy of atomisation of C is 150 kCal per mole and H – H bond enthalpy and
C – H bond enthalpy are 103 kCal per mole and 93.64 kCal per mole respectively.
Q.41 The enthalpies of neutralization of NaOH & NH4OH by HCl are  13680 Cal 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.

Q.42 The enthalpy of solution of anhydrous CuSO4 is – 15.9 kCal and that of CuSO4.5H2O is 2.8
kCal. Calculate the enthalpy of hydration of CuSO4.

Q.43 Determine H for the following reaction at 500K and constant pressure :
CO(g) + H2O (g)  CO2 (g) + H2 (g)
use the following data :
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Substance Cp(J/mol K) fH(298K) (kJ/mol)

CO 29.12 –110.5
H2O 33.58 –241.8
CO2 37.11 –393.5
H2 29.89 0.0

Q.44 If the enthalpy of formation of HCl (g) and Cl– (aq) are –92.3 kJ/mole and – 167.44 kJ/mol, find
the enthalpy of solution of hydrogen chloride gas.

Q.45 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

r
at 1273 K, keeping the reaction temperature constant.

i
Q.46 Using the date given below , establish that the vapourisation of CCl 4 (l) at 298 K to produce

S
CCl4 (g) at 1 atm pressure does not occur spontaneously .
Given : CCl4 (l , 1 atm)  CCl4 (g , 1 atm) ; S º = 94.98 JK 1 mol 1;

e
f H º (CCl4, g) =  106.7 kJ mol1 & f H º (CCl4, l) =  139.3 kJ mol1

Q.47

ir n
CO(g)
c
From the given table answer the following questions:

CO2(g) H2O(g) H2(g)

P
H°f)298 (-kCal/mole) –26.42 –94.05 –57.8 0
G°f)298 (-kCal/mole) –32.79 –94.24 –54.64 0

y
S°298 (-Cal/Kmole) 47.3 51.1 ? 31.2

B
Reaction: H2O(g) + CO(g) H2(g) + CO2(g)
(i) Calculate r H 298 (ii) Calculate r G 298 (iii) Calculate r S 298

(iv) Calculate r E 298 (v) Calculate S 298 [H2O(g)]

Q.48 Calculate the enthalpy of formation of HCl (g) at 1450 K and 1 bar pressure, given that
H of [HCl,g] = – 92.3 kJ/mol at 298 K and
Cp,m(H2,g) = [29.06 – 0.8363 × 10–3 T + 20.11×10–7 T2 ] J/k mol

Cp,m(Cl2,g) = [39.69 + 10.14 × 10–3 T – 40.37 ×10–7 T2 ] J/k mol

Cp,m(HCl,g) = [28.16 + 1.81 × 10–3 T + 15.46 ×10–2 T2 ] J/k mol

Over the temperature range of 298 K to 1450 K

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Q.49 Find the Bond enthalpy (in kJ/mol) of one "three centre two electron bond" in B 2H6
{B–H–B  2B(g) + H(g)} from the given data.
H 0f [BH3(g)]= 100 kJ/mole H 0f [B2H6(g)] = 36 kJ/mole
Hatm [B(s)] = 565 kJ/mole Hatm [H2(g)] = 436 kJ/mole

Q.50 At temperatures above 85 K, decarboxylation of acetic acid becomes a spontaneous process

i r
under standard state conditions. What is the standard entropy change (in J/K-mol) of the reaction.
CH3COOH (aq)  CH4(g) + CO2(g)

S
Given : H 0f [CH3COOH (aq)] = – 484 kJ/mole

c e
H 0f [CO2(g)] = –392 kJ/mole

ir n
H 0f [CH4(g)] = –75 kJ/mole

P
Q.51 By using the following data draw an appropriate enthalpy cycle & Calculate the enthalpy change
of hydration of (i) the chloride ion ; (ii) the iodide ion.

y
Comment on the difference in their values.
enthalpy change of solution of NaCl(s) =  2 kJ/mol.

B
*
* enthalpy change of solution of NaI(s) = + 2 kJ/mol.
* enthalpy change of hydration of Na+(g) =  390 kJ/mol.
* lattice enthalpy of NaCl =  772 kJ/mol.
* lattice enthalpy of NaI =  699 kJ/mol.
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Answer Key
1. H = –98.267 kJ 2.395.8 kJ 3.H° = –1532 kJ 4. –316.3 kcal

5.CH4 6.49655 kJ 7.CH4 > C2H6 > C4H10 8.(i) 0.57 kJ (ii) 2.18 kJ

9.1 M 10. –55.7 kJ 11.–121 kJ mol–1 12.–240 kJ mol–1 13.–75.5 kJ mol–1

14.–780.9 kcal 15.+2.4 kJ 16.–249 kJ 17.424 kJ mol–1 18.Yes

19. 463 K 20.371.36 K 21.–94.2 J K–1 mol–1 22.Above 282.4 K

23.H° = –92.4 kJ mol–1, S° = –198.3 J K–1 mol–1 G° = –32.91 kJ mol–1

24. 25.62.80 J K–1 26.190.9 kJ

i r
27.(a) Ssys = 9.135 J K–1 mol–1 Ssys = –9.135 J K–1 mol–1 , Suniv = 0

S
(b) Suniv = Ssys = 9.135 J K–1 mol–1

e
28.(a) 312 cal K–1, (b) –268.1 cal K–1, (c) 43.9 cal K–1, (d) spontaneous

29. Liquid   Solid

 
(i) G = 0, at equilibrium
H 500

ir n c
P
(ii) S =  –1
= –5 J K mol –1
T 100

y
30.128.02 kJ Q.31 –266.3 kJ/mol and –824.2 kJ/mol Q.32 –1560.1 kJ mol–1

B
Q.33 (i)  3201 kJ/mol (ii)  3199.75 kJ/mol Q.34 25.66 days

Q.35 + 20.6 k Cal Q.36 213 kJ / mol

Q.37 – 120.08 kJ/mol Q.38 E(O–H) = 463.5 kJ/mol U = 461 kJ/mol

Q.39 (i) 343.08 kJ/mol–1 ; (ii) 891.2 kJ/mol–1

Q.40 EC  C = 160.86 kCal / mol

Q.41  1410 Cal Q.42 – 18.7 kCal / mole

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Q.43  H = – 40.3 kJ Q.44 – 75.14 kJ/mole

Q.45 mole % O2(g) = 37.5, H2O(g) = 62.5

Q.46 Gº = 4.29 kJ mol1

Q.47 (i) – 9.83 kCal/mole; (ii) – 6.81 kCal/mole, (iii) – 10.13 Cal / K mole, (iv) –9.83 kCal/mole,
(v) + 45.13 Cal/ K mole

r
Q.48 –95.1 kJ/mol Q.49 EB–H–B = 455 kJ/mole

i
Q.50 255 J/K mole Q.51 for Cl 384 kJ mol1, for I  307 kJ

c e S
P ir n
B y