Thermochemistry: Theory and Exercise Booklet

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THERMOCHEMISTRY
THEORY AND EXERCISE BOOKLET
CONTENTS
S.NO. TOPIC PAGE NO.
1 THEORY WITH SOLVED EXAMPLES ..................................... 3 – 15
2 CLASS ROOM PROBLEMS .................................................. 16 - 20
3 EXERCISE - I (SINGLE CHOICE) ......................................... 21 – 26
4 EXERCISE - II (MULTIPLE CHOICE) .................................... 27 – 28
5 EXERCISE - III (SUBJECTIVE LEVEL - I) .............................. 29 – 35
6 EXERCISE - IV (SUBJECTIVE LEVEL - II) ............................. 36 – 37
7 EXERCISE - V (JEE PROBLEMS) ......................................... 38 – 39
8 ANSWER KEY ................................................................... 40
394 - Rajeev Gandhi Nagar Kota, Ph. No. 0744-2209671, 93141-87482, 93527-21564
IVRS No. 0744-2439051, 0744-2439052, 0744-2439053 www.motioniitjee.com, email-info@motioniitjee.com
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JEE SYLLABUS :
THERMOCHEMISTRY
Internal energy, Enthalpy, Hess’s law; Heat of reaction, fusion and
vapourization.
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THERMOCHEMISTRY Page # 3
THERMOCHEMISTRY
Thermochemistry is the branch of physical chemistry which deals with the thermal or heat changes
caused by chemical reactions.
SPECIFIC HEAT (S)
Amount of energy required to raise the temp by 1º C of 1 gm of a substance.
Unit  Energy/gmºC
HEAT CAPACITY
The amount of heat required to raise the temperature by 1ºC or 1K of a given amount of a substance.
C=m×s
Unit  Energy/ºC
Total heat given to increase the temperature by t.
q = mst
MOLAR HEAT CAPACITY
The amount of heat required to raise the temp by 1º of 1 mole of a substance.
CLASSIFICATION OF MOLAR HEAT CAPACITY

(A) Molar heat capacity at constant pressure (Cp)
(B) Molar heat capacity at constant volume (Cv)
Relation between Cp and Cv
Cp – Cv = R (Mayor's formula)
Cp
= (Poison' Ratio)
Cv
RULES FOR THERMOCHEMICAL EQUATION
(1) It is necessary to mention physical state of all reactants and products.
(2) A  B
H = HB – HA
if H > 0 (Endothermic reaction)
H < 0  (Exothermic reaction)
If A  B + x kJ/mole
 H = –x kJ/mole
If A + x kJ/mole  B
or A B – x kJ/mole
 H = x kJ/mole
(3) After reversing a thermochemical eqn then sign of enthalpy also get changed.
e.g. A(g) + B(g)  C(g) + D(g)
H = x kJ
C(g) + D(g)  A(g) + B(g)
H = – x kJ
(4) When two reactions are added their enthalpies are also get added with their sigh.
e.g.
A(g) + B(g)  C(g) + D(g) H = x1 kJ
C(g) + E(g)  F(g) H = – x2 kJ
________________________________________
A(g) + B(g) + E(g)  D(g) + F(g)
H = x1– x2
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Page # 4 THERMOCHEMISTRY
(5) If a thermochemical equation is multiplied by a number then enthalpy is multiplied by the same
number.
e.g.
A(g) + B(g)  C(g) + D(g) H = x1 kJ
2A(g) + 2B(g)  2C(g) + 2D(g) H = 2x1 kJ
INTENSIVE PROPERTY
The property which does not depend upon the mass of substance is called intensive property.
e.g. density, refractive index, specific heat, etc.
EXTENSIVE PROPERTY
Mass dependent properties are called extensive properties

e.g.
H, S, G
* Two extensive property can be added or additive.

* Ratio of two extensive properties is Intensive.
* Intensive properties can not be added directly.
e.g. We can not add the density of two liquids to get the density of the final mixture of the two.
m
d
v
 m  dv
 dmix x(h1 + h2)A = d1h1A + d2h2A
d1h1A  d2h 2 A d1h1  d2h 2

 dmix = h1  h2 A  dmix = h1  h2
ENTHALPY
H = U + PV

Internal energy
H = U + PV + VP
(i) t constant Pressure
VP = 0 (as P = 0)
H = U + PV
(ii) At Constant Volume:
PV = 0 as V = 0
H = U + VP
(iii) If both are changing:-
H = U + (P2V2 – P1V1)
* Enthalpy is function of temperature i.e. changes with change in temperature.
H = U + PV
= U + nRT
* Enthalpy is always defined at constant temperature and it varies with variation in temperature.
H = U + PV
= nCVT + nRT = nT(CV + R)
H = n CpT
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 Enthalpy at cons tan t pressure.
H = E + nRT
Enthalpy at  Enthalpy at

a constant a constant
pressure Volume
n = no. of moles of gaseous product - no. of moles of gaseous reactant.
Note:-
In chemistry, At constant temp U  0
1 mole O2 (initially)
U = nCV T
As
After reaction  n changes

 n  0
 U  0
Also as after the reaction the nature of substance formed changes which may have different value of
internal energy at the same temp.
KIRCHOFF'S EQUATION
This gives the relation between enthalpy and temperature.

* Physical state is changed at constant temperature.
Molar heat capacity at

constant pressure of A (T2)
A
–T 1)
Cp(T 2 H2
A B (T2)
(T1)
1 )
H1 Cp (T 2–T 1
B Molar heat capacity of B
(T1)
According to Hess'Law
H2 + Cp(T2–T1) = H1 +Cp1 (T2– T1)
H2 – H1 = (Cp1 – Cp) (T2– T1)
= Cp (T2– T1)
H2  H1
Cp = T T
2 1
Where
Cp = Molar heat capacity of product –– Molar heat capacity of reactant
e.g.
N2(g) + 3H2(g)  2NH3(g)
Cp = 2Cp(NH3) – Cp(N2) – 3Cp(H2)
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* If the above formula (Kirchoff's eqn) is to be written for molar heat capacity at constant volume then
U2  U1
C V 
T2  T1
* If Cp is function of temperature
Cp = T2 + T
T2
Then T Cp dT  H2  H1
1
HEAT OF FORMATION
Enthalpy change during the formation of 1 mole of a compound form its most stable common occurring
form (also called reference states) of elements is called heat of formation.
C(s) + O2(g)  CO2(g)
H = Hf(CO2)
CO(g) + 1/2O2(g)  CO2(g)
H  HfCO2(g)
(because CO2 has not been formed form its element in their most stable form)
Similarly
CH2–CHO + H2  C2H5OH
H  Hf(C2H5OH)
Heat of reaction
Element Most stable form
H H2(gas)
O O2(gas)
N N2(gas)
F F2(gas)
Cl Cl2(gas)
Br Br2(gas)
I I2(solid)
C C(grapnite)
P P(white)
S S(rhombic)
* All metal exist in solid form (reference states)
ENTHALPY AT STANDARD STATE :-(Hº)

T = 25ºC = 298 K
P = 1 atm
Conc = 1M
Hº = Heat of formation at standard state
If A(g) + B(g)  C(g) + D(g) is any reaction, Heat of reaction for any thermochemical equation can be
written as
Hº = Hfº(product) – Hfº(Reactant)
If we use the above concept for the above given reaction then
Hº = Hfº(c) + Hfº(D) –Hfº(A) + Hfº(B)
Assumption :–
The heat of formation of most stable form of an element is taken as zero.
C(graphite) + O2(g) CO2(g)
Hº = Hfº(CO2) – HfºC(s) –Hfº(O2)(g)
 Hº = Hfº(CO2) (As HfºC(s) = 0 and HfºO2(g) = 0)
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Another example can be taken as

H2(g) + 1/2O2(g)  H2O(l)
Hº = Hfº(H2O) – Hfº(H2) – 1/2Hfº(O2)
O O
Hº = Hfº(H2O)
* Heat of formation is always –ve as the process is exothermic.
Ex.1 From the following data,

C(s, graphite) + O2(g)  CO2(g) Hº = –393.5 kJ/mole
H2(g) + 1/2O2(g) H2O(l) Hº = –286 kJ/mole
2C2H6(g) + 7O2(g) 4CO2(g) + 6H2O(l) Hº = –3120 kJ/mole
Calculate the standard enthalpy of formation of
C2H6(g) (in kJ/mole)
Sol. From eqn(1) Hfº(CO2) = –393.5 kJ/mole
From eqn(2) Hfº(H2O) = –286 kJ/mole
From eqn (3) rHº 4 Hfº(CO2) + 6Hfº(H2O) –2 ×Hfº(C2H6) – 7×HfºO2(g)
– 3120 = 4 ×(–393.5) + 6×(–286) – 2×Hfº(C2H6) (As Hfº O2(g) = 0 )
 –3120 = –1574 –1716 – 2 ×Hfº(C2H6)
 –3120 + 3290 = – 2 ×Hfº(C2H6)
 170 = – 2 ×Hfº(C2H6)
 Hfº = – 85 kJ/mole
HEAT OF COMBUSTION
It is the enthalpy change (always –ve) when One mole of the substance undergo complete combustion.
C(s) + O2  CO2(g)
Hº = HCºC(s) = Hfº(CO2) – HfºC(s) – Hfº(O2)
Hº = = HCºC(s) = Hfº(CO2)
Other example
O O
H2 + 1/2 O2  H2O(g)
Hº = HCº (H2) = Hfº (H2O) – Hfº(H2) – 1/2Hfº (O2)

Hº = Hfº (H2) = Hfº (H2O)
Note :–
Heat of combustion is always exothermic except N2 and F2.
* N2 + O2  2NO
(It is an endothermic reaction)
* O2 + F2  OF2
(Since O has normally tendency to accept electron and opposite is happening above hence reaction
is is considered endothermic)
* Heat of reaction for any thermochemical equation can be written as (in form of heat of combustion)
Hrº = Heat of combustion of reactant – Heat of combustion of reactant .
Hrº = HCº (Reactant) – HCº (Product)
Ex.2 The enthalpy change for the reaction
C3H8(g) + H2(g)  C2H6(g) + CH4(g) at 25ºC is – 55.7 kJ/mole calculate the enthalpy of
combustion of C2H6(g). The enthalpy of combustion of H2, and CH4 are – 285.8 and – 890.0 kJ/
mole respectively. Enthalpy of combustion of propane is –2220 KJmol–1.
Sol. As we know any thermochemical eqn can be written in terms of heat of combustion as follows
Hrº = Hcº (Reactant) – HCº (Product)
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Hrº = Hcº (C3H8) + HCº (H2) – {Hcº(C2H6) + HCº(CH4) }

– 55.7 = (–2220 – 285.8) – {–890 +Hcº(C2H6) }
 Hcº(C2H6) (g) = – 1560.1 kJmol–1
Problems Based on Both HOC and HOF :

Ex.3 At 300K, the standard enthalpies of formation of C6H5COOH(s), CO2(g) and H2O(l) are –408, –
393 and –286 kJmol–1 respectively. Calculate the enthalpy of combustion of benzoic acid at
(i) constant pressure
(ii) constant volume.
Sol. 7C(s) + 3H2(g) + O2(g)  C6H5COOH(s) Hº = –408 kJ
 Hfº(C6H5COOH) = – 408 kJ
C(s) + O2(g)  CO2(g) Hº = –393 kJ
 Hfº(CO2) = –393 kJ
H2(g) + 1/2O2(g)  H2O(l) Hº = –286 kJ
 Hfº(H2O) = –286 kJ
C6H5COOH(s) + 15/2O2(g)  7CO2(g) + 3H2O(l)
HCº(C6H5COOH) = 7 HfºCO2 + 3Hfº(H2O) – 4Hfº(C6H5COOH)
= 7 ×(–393) + 3× (–286) + 408
HCº(C6H5COOH) = – 3609 + 408
= –3201 kJ/mol
enthalpy of combustion at constant pressure = – 3201 kJ mol–1
Also
H = U + ngRT
–3201 = U + (–0.5) × 8.31 × 10–3 × 300
(As n = 0.5, R = 8.314 × 10–3 kJ)
 U = – 3201 + 1.2471
U = –3199.7529
 enthalpy of combustion at constant volume = – 3199.7529
BOND ENERGY
It is defined for gaseous molecules. "The enthalpy change during the breaking of one mole of bond into
isolated gaseous atoms is called bond energy of the compound"
e.g. H2(g)  2H(g)
Hº = H  H
* ge fdlh Hkh reaction dks Heat of formation of product – Heat of formation of Reactant ds form esa fy[k ldrs gsa
vkSj vxj mij okys eqn dks Hkh oSls gh fy[kk tk;s rks
Hº =  H  H = 2H ºH(g) – H º(H )
f f 2
  H  H = 2H ºH(g)
f
 Hfº H(g) =
H  H
2
Similarly
HfºO(g) =
O  O
2
 NN
HfºN(g) =
2
* Let us consider the similar bond breaking In CH4
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CH4(g)  C(g) + 4 H(g)
H = 4  C  H =H ºC(g) + 4H ºH(g) – H º(CH )

f f f 4
** Enthalpy of reaction in terms of bond energy for a thermochemical eqn can be written as
Hfº = B.E.(Reactant) – B.E. (products)
Ex.4 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 336.81 606.68 410.87 431.79
(kJ/mol) (kJ/mol) (kJ/mol)
Sol. rHº =  reac tant   product

H º =  C  C  4 C  H   H  H   C  C  6 C  H
r
Hrº = 606.68 + 4×410.87 + 431.79 –336.81 –6×410.87

= 2681.95 –2802.03
Hrº = –120.08 kJ/mol
HEAT OF HYDROGENATION
"Enthalpy change during the addition of 1 mole of H2 to an unsaturated compound. is called heat of
hydrogentation."
Hydrogenation is an exothermic process. of therefore heat of hytdrogentaiton is always –ve.
e.g.
CH2 = CH2 + H2  CH3 –CH3
Hrº = Hº (Hydrogenation) (CH2 = CH2)
+ H2
 Hrº = Hº (Hydrogenation)

of cyclohexene
Ex.5 Compare the heat of hydrogenation of the following alkene

(1) C – C – C = C (2) C – C = C – C (cis) (3) C – C = C – C (trans)
(4) C – C = C (5) C = C – C = C
C
1
Sol. Stability of alkene 
Heat of hydrogenation
The above concept is true as long as no. of double bonds are equal as heat of hydrogenation is
defined for per mole of double bond. It will be certainly larger for higher number of double bonds
irrespective of their stability.
(1) C – C – C = C (2 × H)
(2) C – C = C – C ( 6 × H)
(cis)
(3) C – C = C – C (6 × H)
(trans)
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C
(4) C=C (6 × H)
C
(5) C = C – C = C (2 double bonds)
As we know trans > cis (stability)
 Heat of hydrogen (trans) < Heat of hydrogenation (cis)
H
CH3 – CH = CH – CH3 CH3– CH –CH = CH2
(less stable) ( + I of CH3 reduce the stability)
CH3 H CH2 H
C=C C–C
CH3 H CH3 H
(more stable) (more stable as nothing is

trying to reduce its stability)
of therefore decreasing order of heat of hydrogenation of alkene

5>1>2>3>4>
Ex.6 Find Hf of HCl(g) if bond energies of H2, Cl2 and HCl are 104, 58, 103 kcal/mole respectively.
Sol. H – Cl  H(g) + Cl(g)
 H  Cl = H ºH(g) + H ºCl(g) – H ºHCl(g)

f f f
1 1
103 =
2  H  H + 2  Cl  Cl – H ºHCl(g)
f
1 1
103 = ×104 + ×58 – Hfº HCl(g)
2 2
HfºHCl(g) = – 22 kcal/mol.
HEAT OF ATOMISATION
" When one mole of any substance is converted into gaseous atoms enthalpy change during the
process is called heat of atomisation." It is always + ve due to endothermic nature of the process.
HEAT OF SUBLIMATION
Enthalpy change during the conversion of one mole of solid to 1 mole of gaseous phase directly
without undergoing into liquid phase is called enthalpy of sublimation or heat of sublimation,
It is always + ve due to endothermic nature of the process.
e.g.
C(s)  C(g)
Hº = HsubºC(s) = Hfº C(g) – Hfº C(s)
O
HsubºC(s) = Hfº C(g)
HsubºC(s) = Hfº C(g) =HºatmosationC(g)
Ex.7 Using the given data, calculate enthalpy of formation of acetone(g) [All values in kJmol–1]
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bond enthalpy of C–H = 413.4, C – C = 347.0 (C = O) = 728.0

( O = O ) = 495.0 , H – H = 435.8 subH of C = 718.4
O
Sol. CH3 – C – CH3 3C(g) + 6H(g) + O(g)
O
6  C  H +  C  O + 2  C  C = 3H ºC(g) + 6H ºH(g) + H ºO(g) –
f f f
Hfº( CH3 – C – CH3 )
O
6 1
6 × 413.4 + 728 + 2 × 347 = 3 × 718.4 + × 435.8 + ×495.0 – Hfº( CH3 – C – CH3 )
2 2
O
Hfº( CH3 – C – CH3 ) = – 192.3 kJmol-1
Ex.8 The enthalpy of combustion of acetylene is 312 kcal. If enthalpy of formation of CO2 and H2O
are –94.38 and –68.38 kcal respectively
Calculate C  C bond enthalpy.
Given that enthalpy of atomisation of 150 kcal and H – H bond enthalpy and C – H bond
enthalpy are 103 kcal and 93.64 kcal respectively.
5
Sol. HC  CH + O  2CO2 + H2O
2 2
HCº(CH  CH) = 2Hfº(CO2) + Hfº(H2O) – Hfº(C2H2)
– 312 = 2 × (–94.38) + (–68.38) – Hfº(C2H2)
Hfº(C2H2) = 54.86
CH  CH  2C(g) + 2H(g)
 C  C + 2  C  H = 2H ºC(g) + 2H ºH(g) – H º(CH  CH)

f f f
1
C  C +2 × 93.64 = 2 × 150 + 2 ×
2
× 103 –54.86   C  C = 160.86 kJmol –1
RESONANCE ENERGY
"The energy difference between resonance hybrid and most stable canonical structure is called
resonance energy".
Resonance energy is always –ve as nature of the process is exothermic.
Ex.9 The enthalpy of formation of ethane, ethylene and benzene from the gaseous atoms are –
2839.2,
–2275.2 and –5506 kJmol–1 respectively. Calculate the resonance energy of benzene. The
bond enthalpy of C – H bond is given as equal to + 410.87 kJ/mol.
Sol. 2C(g) + 6H(g)  C2H6 Hº = –2839.2
C2H6  2C(g) + 6H(g) Hº = 2839.2
C – C + 6C – H = 2839.2 Hº = 2839.2
C – C + 6 × 410.87 = 2839.2
C – C = 373.98 ... (1)
2C(g) + 4H(g)  C2H4(g) Hº = –2275.2
C2H4  2C(g) + 4H(g) Hº = 2275.2
C = C + 4C – H = 2275.2
C = C) = 631.72 ...(2)
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6C(g) + 6H(g)  C6H6 Hº = –5506

C6H6  6C(g) + 6H(g) Hº = 5506
 3C = C + 3C – C + 6C – H + x = 5506
Putting all the values from eqn , 1, & ( 2) we get x = 23.68
 Resonance energy of benzene = – 23.68 kJ/mole
BOMB CALORIMETER
O2 gas
w
mole w m gm of
M water
Heat evolved = mst + Ct


Heat capacity of container
ms t  Ct 
Heat of combustion = – w
 
M
M
=– ms t  Ct  = – M  tms  C = – M  t [C' + C]
w w w
Heat capacity Heat capacity

of water of container
M
 H = –  t  C  Heat capacity of system
w
Ex.10 When 1.0 gm of fructose C6H12O6 (s) is burnt in oxygen in a bomb calorimeter, the
temperature of the calorimeter water increases by 1.56ºC. If the heat capacity of the
calorimeter and its contents is
10.0 kJ/ºC. Calculate the enthalpy of combustion of fructose at 298 K.
Sol. Heat capacity of the system

M
HC = C  t 
w
180
= 10  1.56 = –2808 kJ/mole
1
HEAT OF SOLUTION
Enthalpy change during the dissolution of 1 mole of salt in excess of solvent.
KCl(s) + aq  KCl (aq)
Hº = Heat of soln of KCl (s)
Note :-
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(1) Heat of solution is always exothermic for the anhydrous form of salts which can form their hydrates.
e.g. CuSO4, Na2SO4, FeSO4, ZnSO4, CaCl2, LiCl etc.
CuSO4(s) + aq  CuSO4(aq) H < 0
(2) Heat of solution is endothermic for the hdyrated form of the salt.
CuSO4 . 5H2O + aq  CuSO4(aq) H > 0
(3) Heat of soln is endothermic for the salts which do not form their hydrates.
e.g. NaCl, NaNO3, KCl etc.
INTEGRAL HEAT OF SOLUTION

Enthalpy change when 1 mole of salt is dissolved in given amount of solvent.
e.g. KCl(s) + 20 H2O  KCl (20H2O) _____________(1) H2 = x
KCl(s) + 100 H2O  KCl (100H2O) _____________(2) H2 = y
HEAT OF DILUTION
Reversing the eqn (1) and adding in (2)
KCl(20H2O) + 80H2O  KCl(100H2O)
H = y – x
enthalpy change when the conc. of salt changes from one to another on the basis of dilution
 H = y – x = Heat of dilution
HEAT OF HYDRATION
Ethalpy change during the formation of hdyrated form of salt from its anhydrous form. It is always
exothermic.
CuSO4(s) + 5H2O  CuSO4.5H2O
H = Heat of hydration of CuSO4(s)
Ex.11 Heat of soln of CuSO4(s) and CuSO4.5H2O is 15.9 and 19.3 kJ/mol respectively. Find the heat
of hydration of CuSO4(s)
Sol. CuSO4(s) + aq  CuSO4(aq) ___________(1)
H = –15.9
CuSO4.5H2O + aq  CuSO4(aq) ___________(2)
H = 19.3
Reversing eqn (1) and adding (2)
CuSO4(s) + aq  CuSO4(aq)
H = 15.9
CuSO4.5H2O + aq  CuSO4(aq)
H = 19.3
______________________________________________
CuSO4.5H2O  CuSO4(s)
H = 35.2
 CuSO4(s)  CuSO4.5H2O
H = –35.2
 Heat of hydration of CuSO4(s) = –35.2 kJ/mol
HEAT OF NEUTRALISATION
Enthalpy change during neutralisation of 1 gm equivelant of Acid with 1 gm equivelant of base in
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dilute soln is called heat of neutralisation.

HCl(aq) + NaoH(aq)  NaCl + H2O
H+ + Cl– + Na+ + OH–  Na+ + Cl– + H2O
H+(aq) + OH–(aq)  H2O(aq)
Hº = –13.7 Kcal
H2SO4(aq) + 2NaOH(aq) Na2SO4 + 2H2O
2H+ + SO42– + 2Na+ + 2OH–  2Na+ + SO42– + 2H2O
2H+ + 2OH–  2H2O
H = –13.7 × 2
Note :-
In case of weak Acid or weak bases the observed value is little lower because of a part of it is used
in dissociating weak Acid or weak base which is not at all completely ionised at dilute solution
unditions.
These are however, completely ionised at infinite dilution. e.g.
CH3COOH + NaOH  CH3COONa + H2O
H = –13.7 + x
As we know, H+ + OH–  H2O H = –13.7 kcal ____(1)
– +
CH3COOH  CH3COO + H Hº = x ____(2)
Add eqn (1) + (2)
__________________________________
CH3COOH  OH–  CH3COO– + H2O Hº = y
Ex.12 100 ml 0.5M H2SO4(strong Acid) is neutralised by 200 ml 0.2 M NH4OH. In a constant pressure
calorimeter which results in temperature rise of 1.4ºC. If heat capacity of calorimeter
constant is
1.5 kJ/ºC.
Which statement is/are correct.
Given: HCl + NaOH NaCl + H2O + 57 kJ
CH3COOH + NH4OH  CH3COONH4 + H2O + 48.1 kJ
(A) Ethalpy of neutralisation of HCl v/s NH4OH is –52.5 kJ/mol
(B) Ethalpy of dissociation (ionisation) of NH4OH is 4.5 kJ/mol
(C) Ethalpy of dissociation of CH3COOH is 4.6 kJ/mol
(D) H for 2H2O(l)  2H+(aq) + 2OH–(aq) is 114 kJ
Sol. (A) Total heat evolved due to the neutralization = C × t = 1.5 × 1.4 = 2.1
M. eq of H2SO4 = 100 ×0.5 = 50
M.eq of NH4OH = 20 × 0.2 = 40
Since NH4OH is limiting hence energy will evolved according to it.
 0.04 gm eq produces 2.1 kJ
2 .1 210
1 gm eq produces = 1 = = 52.5
0.04 4
 Heat of neutralisation = –52.5 kJ
(B) –57 + x = – 52.5
 x = – 52.5 + 57 = 4.5
 Enthalpy of dissociation of NH4OH = 4.5 kJ/mol
(C) 57–(x + y) = 48.1

 x + y = 8.9
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 4.5 + y = 8.9  y = 4.4

 enthalpy of dissociation of CH3COOH = 4.4 kJ/mol
(D) As we know
H+ + OH–  H2O H = –57
+ –
 2H + 2OH  2H2O H = –57× 2
 2H2O  2H+ + 2OH– H = 114 kJ
 Option A, B, and D are correct.
BORN HABER CYCLE

Ionisation Energy :-
The minimum amount of energy required to remove one electron form the outermost shell of an
isolated gaseous atom is called ionisation energy of the element.
Electron affinity:-
Amount of energy released when an extra electron is added to an isolated gaseous atom.
Lattice Energy :
Amount of energy released when 1 mole of gaseous cation and 1 mole gaseous anion combine to
each other and form 1 mole of ionic compound is called lattice energy.
Na+(g) + Cl–(g)  NaCl(s) + heat

Lattice energy
q1q 2
Hlattice  2
r 
 r 
Ex.13 The born-Haber cycle for formation of rubidium chloride ((RbCl) is given bellow (the
enthalpies are in kcal mol–1)
1 105
Rb(s)  Cl2 (g)   RbCl(b)
2
+20.5 –159.5
28.5
+
Rb (g)
Rb(g)
Cl(g)  Cl(g)
X
96.0
find the value of X?
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Class Room Problems
Problems : 1 Find the heat of formation of ethyl Problems : 7 One mole of naphthalene was burnt in
alcohol from following data. (Ans. – 65 kcal/ oxygen gas at constant volume to give CO2 gas and
mol) water at 250C. The heat evolved was found to be
5138.8 kJ. Calculate heat of reaction at constant
C(s) + O2(g)  CO2(g) ; H = –94 kcal
pressure.
1
H2(g) + O (g)  H2O(l) ; H = –68 kcal
2 2
Problems : 8 Calculate the heat of combustion of
benzene(l) at standard conditions. Given that the
C2H5OH (l) + 3O2(g)  2CO2(g) + 3 H2O (l) ;
standard enthalpies of formation of C6H6(l), H2O(l)
H = –327 kcal
and CO2(g) are 49, 286.2 and 393.5 Kcal/mole
respectively.
Problem : 2 Find Hf of HCl(g) if bond energies of

H2, Cl2 and HCl are 104, 58, 103 kcal/mol respectively
Problems : 9 0.6 gm of carbon was converted into
CO2 producing 4800 calorie of heat. When 0.6 gm of
Problems : 3 Find H of the following reaction : C converted to CO 1450 calories of heat was
OF2(g) + H2O(g)  O2(g) + 2 HF (g) ; average bond produced. What will be heat produced when 1.4 gm
energies of, O – H, O = O, H – F , O – F, are 44, 111, of CO is converted to CO2.
118 and 270 kcal/mol respectively.
Problems : 10 Calculate standard heat of formation

of CS2. Given that standard heat of combustion of C,
Problem : 4 The heat of formation of ethane is
S and CS2 are -393.3, -293.72 and -1108.76 KJ/mole.
–19.46 kcal. Bond energies of H – H, C – H and C – C
bonds are 104.18, 99.0 and 80.0 kcal respectively.
Calculate the heat of atomisation of graphite.
Problems : 11 Calculate the mass of mercury which
can be liberated from HgO at 250C by the treatment
Problem : 5 From Na atoms of an element A, when
of excess of HgO with 41.85 KJ of heat at (a) constant
half atoms transfer one electron to another atom,
pressure and (b) constant volume conditions : Given
405 kJ/mol of energy was found to be consumed. An
o
additional energy of 745 kJ was further required to  Hf [HgO(s)] = -90.8 KJ/mole, M(Hg) = 200.6 gm/
convert all the A– ions to A+. Calculate the ionisation mole.
energy and the electron affinity of atom A in eV.
Problems : 12 The enthalpy change involved in the

Problems : 6 Enthalpy of neutralisation of acetic oxidation of glucose is -2880 KJ/mole. Twenty five
acid by NaOH is –50.6 kJ/mol. Calculate H for percent of this energy is available for muscular work.
io nis ation of CH 3 COOH. Giv en, th e heat of If 100 KJ of muscular work is needed to walk one
neutralisation of a strong acid with a strong base is kilometer, what is the maximum distance that person
–55.9 kJ/mol. will be able to walk after eating 120 gm of glucose.
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Problems : 13 15.5 gm carbon is treated with 25 Problems : 19 A 150 ml of 0.5N HCl is neutralised
litre of air at 250C and 5.5 atm (air contain 19% by with an excess of NH4OH in a vessel with a rise of
volume O 2). Determine the heat evolved under temperature 2.360C. If the heat capacity of vessel
constant pressure if after reaction carbon and oxygen and its content after the reaction is 315 cal/deg.
o
are completely consumed.  Hf [CO2(g)] = -94.05 KJ/mole Calculate heat of neutralisation in cal./mole.
o
 H [CO(g)] = -26.71 KJ/mole.
f
Problems : 14 Estimate H for 2C4H10 (g) CH 8

(g)
18 Problems : 20 The molar heat capacities for H2O(s)
+ H2(g). Given bond energy of CC, CH are 347.3 and H2O(l) are 37.7 J mole1 K1 and 75.3 J mole1 K1
and 414.2 KJ/mole. The heat of formation of H atom respectively. The enthalpy of fusion of ice at -100C is
is 217.55 KJ/mole. 5.627KJ/mole. Calculate the enthalpy of fusion of ice
Problems : 15 Calculate H for th e f ollowing at 0oC. Assuming that molar heat capacities are
homogeneous gaseous reaction CH3COCH3 + 2O2  independent of temperature in this range.
CH3COOH + CO2 + H2O. Given Bond energy : CH :
99 Kcal CC : 83 Kcal, C = O : 173 Kcal O=O : 118
Kcal ; CO : 84 ; OH : 110 Kcal. Problems : 21 3.5 gm of a fuel (mo. wt. = 28) was
burnt in a calorimeter and raised the temperature of
Problems : 16 The heat of combustion of acetylene
1 gm water from 250C to 67.30C. If all the heat
is 312 Kcal. If the heat of formation of CO2 is 94.38
Kcal and that of water is 68.38 Kcal. Calculate C  C generated was used in heating water, calculate heat
bond energy assuming that the bond energy of CH of combustion of fuel.
is 93.6 Kcal. heat of atomisation of carbon and
hydrogen are 150 and 51.5 Kcal respectively.
Problems : 17 Calculate the resonance energy of
C6H6 from the following data (a) Hof for C6H6 = -358.5
KJ/mole (b) Heat of atomisation of C : 716.8 KJ/mole
(c) Bond energies of CH, CC, C=C, and HH are
490, 340, 620 and 436.9 KJ/mole respectively.
Problems : 18 Calculate the lattice energy of AH3(s)

o
from the following data :  Hformation [AH3(s)] = 52
o
Kc al/mo l,  Hsub limation [A l( s)] = 15 Kc al/ mo l,
o o
 Hfusion [Iodine(s)] = 10 Kcal/mol,  Hvapourization [Iodine(l)
o
= 6 Kcal/mol],  HEA [Iodine(g) = 28.67 Kcal/mol],
B.E. of (II) = 5 Kcal/mol]. The sum of first two
ionization energies and 3 times the third is 74 Kcal/
mol. The sum of the first and third ionization energies
along with twice the second ionization energy is 54
Kcal/mol, while three times the first ionization energy
added to five times the third ionization energy
subtracted by the second ionization energy given 98
Kcal/mol.
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Exercise - I (only one option is correct)

7. If x1, x2 and x3 are enthalpies of H – H, O = O and
1. For which of the following change H  E ?
O – H bonds respectively, and x4 is the enthalpy of
(A) H2(g) + I2(g)  2HI (g) vaporisation of water, estimate the standard enthalpy
(B) HCl (aq) + NaOH (aq)  NaCl(aq) + H2O (l) of combustion of hydrogen
(C) C(s) + O2(g)  CO2(g) x2 x2
(A) x1 + – 2x3 + x4 (B) x1 + – 2x3 – x4
(D) N2(g) + 3H2(g)  2NH3(g) 2 2
x2 x2
(C) x1 + – x3 + x4 (D) 2x3 – x1 – – x4
2. rH of which of the following reactions is zero ? 2 2
(A) H2(g)  2H+(g) + 2e–
8. NH3(g) + 3Cl2(g) NCl3(g) + 3HCl(g) ; – H1
(B) 2H(g) + aq  2H+(aq) + 2e–
N2(g) + 3H2(g) 2NH3(g) ; H2
(C) 2H(g)  2H+(g) + 2e–
(D) H2(g) + aq  2H+(aq) + 2e– H2(g) + Cl2(g) 2HCl(g) ; H3
The heat of formation of NCl3 (g) in the terms of H1,
H2 and H3 is
3. How much heat will be required at constant pressure
to form 1.28 kg of CaC2 from CaO(s) & C(s) ? H2 3
(A) Hf  – H1  – H3
Given : f H°(CaO, s)= –152 kcal/mol 2 2
f H°(CaC2, s) = –14 kcal/mol H2 3

(B) Hf  H1  – H3
f H°(CO, g) = –26 kcal/mol 2 2
(A) +112 kcal (B) 224 kcal H2 3
(C) Hf  H1 – – H3 (D) None
(C) 3840 kcal (D) 2240 kcal 2 2
9. The enthalpy of neutralisation of HCl and NaOH is

4. 50.0 mL of 0.10 M HCl is mixed with 50.0 mL of 0.10 –57 kJ mol–1. The heat evolved at constant pressure
M NaOH. The solution temperature rises by 3.0°C (in kJ) when 0.5 mole of H2SO4 react with 0.75 mole
Calculate the enthalpy of neutralization per mole of of NaOH is equal to
HCl. [take proper assumptions] 3
(A) 57 × (B) 57 × 0.5 (C) 57 (D) 57 × 0.25
(A) –2.5 × 10 kJ2
(B) –1.3 × 10 kJ2 4
(C) –8.4 × 101 kJ (D) –6.3 × 101 kJ 10. Reaction involving gold have been of particular
interest to a chemist. Consider the following reactions.
Au(OH)3 + 4 HCl  HAuCl4 + 3H2O, H = – 28 kcal
5. The enthalpy of neutralisation of a weak acid in 1 Au(OH)3 + 4 HBr  HAuBr4 + 3 H2O, H = –36.8 kcal
M solution with a strong base is –56.1 kJ mol–1. If the
In an experiment there was an absorption of 0.44
enthalpy of ionization of the acid is 1.5 kJ mol–1 and kcal when one mole of HAuBr4 was mixed with 4 moles
enthalpy of neutralization of the strong acid with a of HCl. What is the percentage conversion of HAuBr4
strong base is –57.3 kJ equiv–1, what is % ionization into HAuCl4 ?
of the weak acid in molar solution (assume the acid (A) 0.5 % (B) 0.6 % (C) 5 % (D) 50%
to be monobasic) ?
11. (i) Cis - 2 - butene  trans – 2 – butene, H1
(A) 10 (B) 15 (C) 20 (D) 80
(ii) Cis – 2 – butene  1 – butene, H2
6. For the allotropic change represented by the (iii) Trans – 2 – butene is more stable than cis – 2 –
equation C (graphite)  C (diamond), H = 1.9 kJ. If butene.
6 g of diamond and 6 g of graphite are separately (iv) Enthalpy of combustion of 1 - butene, H = –
burnt to yield CO2, the heat liberated in first case is 649.8 kcal/mol
(v) 9H1 + 5 H2 = 0
(A) less than in the second case by 1.9 kJ
(vi) Enthalpy of combustion of trans 2 – butene, H =
(B) more than in the second case by 11.4 kJ –647.0 kcal/mol
(C) more than in the second case by 0.95 kJ The value of H1 & H2 in Kcal/mole are
(D) less than in the second case by 11.4 kJ (A) –1.0, 1.8 (B) 1.8, –1.0 (C) –5,9 (D) –2, 3, 6
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12. The reaction CH4(g) + Cl2(g)  CH3Cl(g) + HCl(g) (i)The value of CP of N2 & H2O will be (in cal. deg–1 mol–1)
has H = –25 kCal. (A) 8.3, 8.3 (B) 8.3, 11.3(C) 11.3, 11.3(D) 11.3, 8.3
(ii) What will be the maximum temperature attained
Bond if the process occurs in adiabatic container.
Bond Energy
kCal (A)  2940 K (B)  2665 K (C)  1900 K (D)  298 K
(iii) What will be the final pressure in atm.
c – Cl 84 (A)  8.5 (B)  7.6 (C)  5.46 (D)  0.85
(iv) If at initial temperature T1, E1 is initial internal
energy & at higher final temperature T2, E2 is the final
 H – Cl 103
internal energy, then which option is true
(A) E1 > E2 (B) E2 > E1 (C) E1 = E2
C – H x
(D) can't be compared from the given data
16. Match the column
 Cl – Cl y Column I Column II
(A) N2(g) + O2(g)  2NO(g) (P) S > 0
x:y=9:5 (B) 2KI(g) + Hgl2(aq)  K2[HgI4](aq.) (Q) S < 0
From the given data, what is the bond energy of Cl – (C) PCl3(g) + Cl2(g)  PCl5(g) (R) H > 0
Cl bond (D) NH3(g) + HCl(g)  NH4Cl(s) (S) H < 0
(A) 70 kCal (B) 80 kCal (C) 67.75 kCal (D) 57.75 kCal 17. Match the column
Column I Column II
13. From the following data at 25°C d
Reaction rH° kJ/mol (A) Kirchoff's equation (P) ( H)  C p
dt
½ H2(g) + ½O2(g)  OH (g) 42 (B) H (Q) U + n RT
H2(g) + ½O2(g)  H2O (g) –242
H2(g)  2H(g) 436 qrev
(C) (R) S
O2(g)  2O(g) 495 T
Which of the following statement(s) is/are correct :
H2 – H1
Statement(a) : rH° for the reaction H2O(g)  2H(g) (S)  C p
T
+ O(g) is 925 kJ/mol
Statement(b) : rH° for the reaction OH(g)  H(g) COMPREHENSION - I
+ O(g) is 502 kJ/mol Heat of reaction is the change in enthalpy or internal
Statement(c) : Enthalpy of formation of H(g) is – energy as represented by a balanced thermochemical
218 kJ/mol equation. The amount of energy released during a
chemical change depends upon the state of reactants
Statement(d) : Enthalpy of formation of OH(g) is 42
and products, the conditions of pressure and volume
kJ/mol
at which reaction is carried out, and temperature.
(A) Statement c (B) Statement a, b, d
The variation of heat of reaction (H or E) with
(C) Statement b,c (D) Statement a, d
temperature is given as H2 – H1 = Cp[T2 – T1] or
E2 – E1 = Cv(T2 – T1). Standard heat enthalpy of
14. The standard molar enthalpies for formation of
cyclohexane (l) & benzene (l) at 25°C are –156 & + elements in their most stable state is assumed to be
49 kJ/mol respectively. The standard enthalpy of zero whereas standard heat enthalpy of compound is
hydrogenation of cyclohexane (l) at 25° is –119 kJ referred as heat of formation of that compound at 1
mol–1. Use these data to estimate the magnitude of atm pressure and 25°C. Oxidation of N2 to N2O, NO,
the resonance energy of benzene. NO2 shows absorption of energy whereas heat of
(A) 252 kJ mol–1 (B) 240 kJ mol–1 combustion of N2 is exothermic like other heat of
–1
(C) 152 kJ mol (D) None of these combustion.
15. A mixture of hydrogen gas and the theoretical 18. Standard heat enthalpy has been assumed to be
amount of air at 25°C and a total pressure of`1 atm, zero for :
is exploded in a closed rigid vessel. If the process (A) Graphite (B) Diamond (C) Charcoal (D)Lamp black
occurs under adiabatic condition then using the given
datas answer the questions that follow : 19. Which statements regarding the formation of NO
Given (i) CP = 8.3 cal deg–1 mol–1 ; and NO2 respectively from N2 and O2 are correct :
(ii) CP = 11.3 cal deg–1 mol–1; Hf [H2O(g)] = –57.8 K cal (A) Heat of formation of NO is exothermic
[Take air as 80% N2, 20% O2 by volume] (B) Heat of formation of NO2 is exothermic
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(C) The oxidation of N2 to NO and NO2 is favoured at Select the correct statements :
high temperature. (1) Heat liberated in each of the two reactions is 274 cal.
(D) If heat of formation of NO and NO2 are 21.55 and (2) Heat liberated in I is 274 cal and in II is 137 cal
8.50 kcal, heat of reaction for (3) Temperature rise in I reaction is more than the
NO + ½O2  NO2 is –13.05 kcal temperature rise in II.
(A) 1,2 (B) 3, 4 (C) 1, 2, 4 (D) 1, 2, 3 (4) Temperature rise in I reaction is equal to the
temperature rise in II.
20. Heat of combustion of carbon in diamond and (A) 1, 3 (B) 2, 4 (C) 2, 3 (D) 1, 4
amorphous form are –94.3 and –97.6 kcal/mole. The
heat required to convert 6 g carbon from diamond to COMPREHENSION - III
amorphous form is : Hess's law of heat of summation is based on law of
(A) –1.65 kcal (B) +1.65 kcal conservation of energy. It has found significance in
(C) –3.3 kcal (D) +3.3 kcal deriving heats of many reactions which either do not
take place or if take place, than other side reactions
21. Heat of vaporisation of H2O is 627.78 cal/g. If also accompany it. For example heat of reaction for C
heat of formation of H2O(l) is –68.3 kcal, heat of + ½ O2  CO can not be studied directly as it occurs
formation of H2O(g) is : with simultaneous reaction of oxidation of CO to CO2.
(A) –57.0 kcal (B) 559.5 kcal Bond energy is referred as heat enthalpy when a bond
(C) 676.73 kcal (D) Can not be calculated is broken to produce isolated gaseous atoms. In case
of breaking up of bonds between unlike atoms e.g., C
22. The specific heat of I2 in vapour and solid state – H bond in CH4, bond energy is referred as average
are 0.031 and 0.055 cal/g-°C respectively. If heat of bond energy as four C – H bonds are broken up.
sublimation of iodine is 6.096 kcal mol–1 at 200°C, the 26. Which of the following statements are correct :
heat of sublimation of I2 at 250°C is : (1) The dissociation of bond is always endothermic.
(A) 5.8 kcal mol–1 (B) 2.28 kcal mol–1 (2) The formation of a bond is always exothermic.
(C) 4.8 kcal mol–1 (D) 3.8 kcal mol–1 (3) Heat of formation of an atom = ½ × bond energy
like atoms covalent bond
COMPREHENSION - II (4) The heat enthalpy change in a chemical reaction
Heat of neutralisation is amount of heat evolved or is equal but opposite to the heat enthalpy if reaction
absorbed when 1 g-equivalent of an acid reacts with is reversed.
1 g-equivalent of a base in dilute solution. If weak (5) Hess's law can be verified experimentally.
acid or weak base are neutralised, the heat released (A) 1, 2, 3, 4 (B) 1, 2, 3, 4, 5
during neutralisation is some what lesser than –13.7 (C) 2, 3, 4, 5 (D) 3, 4, 5
kcal or –57.27 kJ. Heat of neutralisation is also referred
as heat of formation of water from H+ and OH– ions 27. Heat of dissociation of CH4 and C2H6 are 360 and
i.e., 620 kcal mol–1. The C – C bond energy would be :
H+ + OH–  H2O ; H = –13.7 kcal. (A) 60 kcal (B) 80 kcal (C) 100 kcal (D) 40 kcal
23. Heat of neutralisation of HF and acetic acid
respectively are (in kcal) : 28. If C + ½ O2  CO(g) ; H = – 110 kJ.
(A) > –13.7, < –13.7 (B) > –13.7 C + H2O(g)  CO(g) + H2(g) ; H = 132 kJ The mole
(C) < –13.7 (D) < –13.7, > –13.7 composition of mixture of steam and O2 and steam on
being passed over coke at 1273 K so that temperature
24. Which of the following statements are correct : remains constant is :
(1) H = U + nRT (A) 0.6 : 1 (B) 1.67 : 1 (C) 0.3 : 1 (D) 0.4 : 1
(2) Heat changes measured by bomb calorimeter give
change in heat enthalpy during the reaction.
29. The heat of fusion for water is +1.44 kcal. The
(3) H = U for the reaction : heat required to change 27 g ice at 0°C to water is :
C(s) + O2(g)  CO2(g) (A) 2.16 kcal (B) 0.72 kcal
(4) Heat of formation for C6H6 can be directly measured (C) 25.92 kcal (D) 2.88 kcal
(A) 2, 3 (B) 1, 4 (C) 1, 2, 3 (D) 1, 3
25. 200 mL of 0.1 M NaOH is mixed with 100 mL of

0.1 M H2SO4 in 1 experiment. In II experiment 100 mL
of 0.1 M NaOH is mixed with 50 mL of 0.1 M H2SO4.
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Exercise - II (One or more than one option correct)

5. The heat of reaction depends upon :
1. Which of the following pairs are correctly
(A) The manner by which the reaction is carried out
matched ?
(B) Temperature at which the reaction is carried out
(A) Arrhenius equation : Variation of enthalpy of a (C) Physical state of reactant and products
reaction with temperature
(D) Whether the reaction is carried out at constant
(B) Kirchoff equation : Variation of rate constant with pressure or at constant volume
temperature
(C) Second law of : Entropy of an isolated system
6. The enthalpy of formation of UF(g) is 22 kcal mol–1
tends to increase and reach a maximum value
and that of U(g) is 128 kcal mol–1. The bond energy
thermodynamics
of the F – F bond is 37 kcal mol–1. The bond
(D) Hess's law of constant : Enthalpy change in a dissociation energy of UF(g) is (are) :
reaction is always constant and independent of the
(A) 124.5 kcal mol–1 (B) 131.1 kcal mol–1
heat summation manner in which the reaction occurs
(C) 521 kJ mol–1 (D) 623 kJ mol–1
2. Which of the following statements is (are) correct

7. The standard heat of formation of a compound is
(A) The heat of neutralization of a strong acid with the :
a strong base is always the same
(A) Change in enthalpy for the production of 1 mole of
(B) The enthalpy of combustion is always negative the compound at STP
(C) A spontaneous change involves a lowering of (B) Change in enthalpy for the formation of 1 mole of
free energy the compound form its elements
(D) The enthalpy of an element in the standard (C) Change in enthalpy for the formation of 1 mole of
state is assumed to be unity at 298 K the compound form its elements at 298 K and 1 atm
pressure
(D) Change in enthalpy for the formation of 1 mole of
3. Which is (are) correct for ideal gas ? the compound form its elements at 25°C and 760 mm
of Hg pressure
 U   U 
(A)    0 (B)    0
T P T H 8. The heat of neutralization of a strong acid by a
strong base is a constant because :
(A) The strong acid and strong base react completely
 E   U 
(C)    0 (D)    0 (B) The strong acid and strong base dissociate
V T P T
completely and only H+ and OH– ions react in every
case
(C) The salt formed do not hydrolyse
4. Which of the following are applicable for a (D) There is no side reaction during neutralization
thermochemical equation ? It tells :
(A) A bout the physical state of reactants and
products 9. Which of the following statements is (are) true ?
(A) The evaporation of water is an endothermic change
(B) A bout the allotropic form (if any) of the
reactants (B) The conversion of white phosphorus to red
phosphorus is an exothermic reaction
(C) Whether the reaction is exothermic or
endothermic (C) The heat of neutralisation of a strong acid with a
strong base is always the same
(D) Whether a particular reaction is spontaneous or
not (D) H is negative for endothermic reactions
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10. The standard heat of formation of U3O8 is –853.5
kcal mol–1 and standard heat of the reaction, 3UO2 +
O2  U3O8 is –76.01 kcal. The standard heat of
formation of UO2 is (are) :
(A) –1083 kJ mol–1 (B) –1102 kJ mol–1
(C) –259 kcal mol–1 (D) –302 kcal mol–1
11. For which of the following substances is the heat

of formation in the standard state zero ?
(A) Aluminium (B) Cdiamond (C) Zinc (D) Cgraphite
12. Which of the following statements is (are) true ?
(A) H is –ve for exothermic reactions
(B) H is +ve for endothermic reactions
(C) The heat of neutralization of strong acid and strong
bases is constant
(D) The enthalpy of fusion is +ve
13. The heat of combustion of ethanol was

determined in a bomb calorimeter and was found to
be –670.48 kcal mol–1 at 25°C. What will be U for
the same reaction at 298 K ?
(A) –2802.6 kJ (B) –669.28 cal
(C) –670.48 kcal (D) –280.26 × 104 J
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Exercise - III Subjective Level-I

Heat of reaction & it's type 9. The heat of reaction ½H2(g) + ½Cl2(g)  HCl
1. For urea NH2CONH2(S) ; f H°298 = –333.5 kJ/mol. (g) at 27° C is –22.1 k cal. Calculate the heat of
Find f U°298 of urea. reaction at 77°C. The molar heat capacities at
constant pressure at 27° for hydrogen, chlorine & HCl
are 6.82, 7.70 & 6.80 cal mol–1 respectively.
2. On the basis of following data,
Evaluate the standard enthalpy of formation of
tungsten carbide (WC) 10. Calculate the enthalpy change when infinitely
3 dilute solutions of CaCl2 and Na2CO3 are mixed Hf
(i) W(s) + O2(g) WO3(s) rH° = – 837 for Ca2+ (aq), CO32– (aq) and CaCO3 (s) are –129.80,
2
kJ/mol –161.65, –288.5 kcal mol–1 respectively.
5
(ii) WC(s) + O2(g) WO3 (s) + CO2(g)
2
rH° = – 1196 kJ/mol
11. The enthalpies of neutralization of NaOH & NH4OH
(iii) C(graphite) + O2(g) CO2(g) rH° = –
by HCl are –13680 calories and –12270cal respectively.
393.5 kJ/mol
What would be the enthalpy change if one gram
equivalent of NaOH is added to one gram equivalent
3. Calculate r H° for Fe2O 3(s) + 3CO(g) of NH4Cl in solution? Assume that NH4OH and NaCl are
2Fe(s) + 3CO2(g) quantitatively obtained.
Given : fH° (Fe2O3) = –822.2 kJ/mol
fH° (CO, g) = –110.5 kJ/mol, fH° (CO2, g) 12. The heat of solution of anhydrous CuSO4 is –15.9
= – 393.5 kJ/mol kcal and that of CuSO4. 5H2O is 2.8 kcal. Calculate
the heat of hydration of CuSO4
4. The standard heats of formation of CH4(g), CO2(g)

and H2O(l ) are –76.2, –398.8, –241.6 kJ mol–1. 13. The standard enthalpy of neutralization of KOH
Calculate amount of heat evolved by burning 1 m3 of with (a) HCN (b) HCl in dilute solution is –2480 cal.
methane measured at 1 atm & 273 K. geq–1 and –13.68 kcal geq–1 respectively. Find the
enthalpy of dissociation of HCN at the same
5. A cylinder of gas supplied by a company contains
temperature.
14 kg of butane. The heat of combustion of butane is
2658 kJ/mol. A normal family requires 20 MJ of energy
per day for cooking. If the cylinder lasts for 26 days, 14. If the enthalpy of formation of HCl (g) and Cl–
what percentage of gas is wasted due to inefficient (aq) are –92.3 kJ/mole and –167.44 kJ/mol, find the
combustion. enthalpy of solution of hydrogen chloride gas.
6. A cylinder of gas is assumed to contain 11.2 kg of Calorimeter

butane. If a normal family needs 20,000 kJ of energy
per day for cooking, how long will the cylinder last if 15. 0.16 g of methane was subjected to combustion
the enthalpy of combustion, H = –2658 kJ/mole for at 27° C in a bomb calorimeter. The temperature of
butane. calorimeter system (including water) was found to
rise by 0.5°C. Calculate the heat of combustion of
methane at (i) constant volume (ii) constant pressure.
7. The molar enthalpy of vaporization of benzene at The thermal capacity of calorimeter system is 17.7
its boiling point (353 K) is 30.84 kJ mol–1 What is the kJK–1 (R = 8.313 mol–1K–1)
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 ? 16. 1.00 l sample of a mixture of CH4(g) & O2(g)
measured at 25° C & 740 torr was allowed to react at
constant pressure in a calorimeter which together
8. When 12.0 g of carbon reacted with oxygen to with its contents had a heat capacity of 1260 cal/K.
form CO & CO2 at 25°C & constant pressure, 75.0 The complete combustion of the methane to CO2 &
kcal of heat was liberated and no carbon remained. H2O caused a temperature rise in the calorimeter of
Calculate the mass of oxygen which reacted. 0.667 K. What was the mole percent of CH4 in the
H0f (CO 2 ) = –95 kcal mol–1, H0f (CO) = –24 kcal mol– original mixture ? H°comb(CH4) = –215 kcal mol–1.
1
.
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17. A quantity of 1.92 of methanol was burnt in a 24. Using the given data calculate enthalpy of
constant pressure calorimeter. The temperature of formation of acetone (g). [All values in kJ mol–1]
water increased by 4.2°C. If the quantity of water binding energy of ; C – H = 413.4 ; C – C = 347.0 ;
surrounding the inner vessel was 2000 ml and the C = O = 728.0 ; O = O = 495.0 ; H – H = 435.8
heat capacity of the inner vessel was 2.02 kJ/°C. ; Hsub of C = 718.4
Calculate the heat of combustion of methanol.
[Specific heat of capacity of H2O = 4.18 J/g°C]
25. Find the enthalpy of S – S bond from the following
Bond energy data.
18. The enthalpy of dissociation of PH3 is 954 kJ/mol (i) C2H5 – S – C2H5(g) H0f  –147.2 kJ / mol
and that of P2H4 is 1.48 M J mol–1. What is the bond (ii) C2H5 – S – S – C2H5(g) H0f  –201.9 kJ / mol
enthalpy of the P – P bond ? (iii) S (g) Hf0  222.8 kJ / mol
19. Using the bond enthalpy data given below, Resonance Energy
calculate the enthalpy change for the reaction. 26. The enthalpy of formation of ethane, ethylene
C2H4(g) + H2(g)  C2H6 (g) and benzene from the gaseous atoms are –2839.2, –
Data : 2275.2 and –5506 KJ mol–1 respectively. Calculate the
Bond C–C C=C C–H H–H resonance energy of benzene. The bond enthalpy of
C – H bond is given as equal to +410.87 KJ/mol.
Bond Enthalpy 336.81 kJ/mol 606.68 kJ/mol 410.87
kJ/mol 431.79 kJ/mol
27. Calculate the heat of combustion of methyl alcohol
at 298 K from the following data
20. The enthalpy change for the following process at Bond C–H C–O O–H O=O C=O
25°C and under constant pressure at 1 atm are as Energy kJ mol–1 414 351.5 464.5 494 711
follows : Resonance energy of CO2 = –143 kJ mol–1
CH4(g)  C(g) + 4H(g) rH = 396 kcal/mole Latent heat of vaporisation of methyl alcohol = 35.5
C2H6(g)  2C(g) + 6H(g) rH = 676 kcal/mole kJ mol–1
Calculate C – C bond energy in C2H6 & heat of formation Latent heat of vaporisation of water = 40.6 kJ mol–1.
of C2H6 (g)
Given : subC(s) = 171.8 kcal/mole Born Haber cycle
28. Calculate the electron gain enthalpy of fluorine
B.E. (H – H) = 104.1 kcal/mole
atom using the following data. Make Born – Haber's
cycle. All the values are in kJ mol–1 at 25°C. Hdiss (F2)
21. The polymersiation of ethylene to linear = 160, H0f (NaF(s)) = –571, I.E.
polyethylene is represented by the reaction nCH2 = [Na(g)] = 494, Hvap [Na(s)] = 101. Lattice energy of
CH2  (–CH2 – CH2)n where n has a large integral NaF(s) = –894.
value. Given that the average enthalpies of bond
dissociation for C = C & C – C at 298 K are +590 & 29. Cesium chloride is formed according to the
+331 kJ mol–1 respectively. Calculate the enthalpy of following equation
polymerisation per mole of ethylene at 298 K. Cs(s) + 0.5 Cl2(g)  CsCl(s).
The enthalpy of sublimation of Cs, enthalpy of
22. From the following data : Enthalpy of formation dissociation of chlorine, ionization energy of Cs &
of CH3CN = 87.86 kJ/mol, Enthalpy of formation of electron gain enthalpy of chlorine are 81.2, 243.0,
C2H6 = –83.68 kJ/mol 375.7 and –348.3 kJ mol–1. The energy change
Enthalpy of sublimation of graphite = 719.65 kJ/mol involved in the formation of CsCl is –388.6 kJ mol–1.
Calculate the lattice energy of CsCl.
Enthalpy of dissociation of nitrogen = 945.58 kJ/mol;
Enthalpy of dissociation of H2 = 435.14 kJ/mol
30. The Born-Haber cycle for rubidium chloride (RbCl)
C – H bond enthalpy = 414.22 kJ/mol
is given below (the energies are in kcal mol–1)
Calculate the (i) C–C ; (ii) C  N
23. The heat of combustion of acetylene is 312 kcal.

If heat of formation of CO2 & H2O are –94.38 & –68.38
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 k cal respectively. Find the value of X.
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Exercise - IV Subjective Level-II

(b) For CO2, a = 5.0, b = 15 × 10–5. Find the heat
1. From the following data, required (for one mole) to raise its temperature from
C(s, graphite) + O2(g)  CO2(g) 300 K to 500 K in case (i) and case (ii). Case (ii) gives
a more accurate value. Find the percent error in case
1
H2 ( g)  O 2 ( g)  H2 O(l ) Hreaction  –286 kJ / mole (i).
2
2C2H6(g) + 7O2(g)  4CO2 (g) + 6H2O (l) 6. An intimate mix of ferric oxide & Al is used as solid
rocket fuel. Calculate the fuel value per gm & fuel
Hreaction  –3120 kJ / mole
value per CC of the mixture. Heats of formation &
Calculate the standard enthalpy of formation of C2H6 densities are :
(g) (in kJ/mole) Hf° (Al2O3) = –399 k cal/mole ; H°f (Fe2O3) = – 199
kcal/mole,
2. Calculate the mass of mercury which can be
density of Fe2O3 = 5.2 g/cc; density of Al = 2.7 g/cc.
liberated from HgO at 25ºC by the treatment of excess
HgO with 41.84 kJ of heat at
(a) constant pressure (b) constant volume 7. A person takes 15 breaths per minute. The volume
conditions of air inhaled in each breath is 448 ml and contains
21% of oxygen by volume. The exhaled air contains
Given : Hºf (HgO, s)  90.8 kJmol 1 & M (Hg) = 200.6 g 16% of oxygen by volume. If all the oxygen is used in
mol–1. the combustion of sucrose, how much of the latter is
burnt in the body per day & how much heat is evolved.
3. For reduction of ferric oxide by hydrogen, Hcom of sucrose is = – 6000 kJ mol–1. Take temperature
Fe2 O 3 (s)  3 H2 ( g)  2 Fe( s)  3 H2 O ( l ) ; Hº 298 = – 35.1 to be 300 K throughout.
kJ. The reaction was found to be too exothermic to 8. The enthalpies of neutralization of weak acid HA &
be convenient. It is desirable that Hº should be at a weak acid HB by NaOH are –6900 cal/equivalent &
the most – 26 kJ. At what temperature is it possible ? –2900 cal/equivalent & –2900 cal/equivalent
Cp[Fe2O3] = 104.5, Cp[Fe(s)] = 25.5, Cp[H2O(l)] = 75.3, respectively. When one equivalent of NaOH is added
C p [H 2 (g)] = 28.9 to a solution containing one equivalent of HA & one
(all in J/mol) equivalent of HB, the enthalpy change was –3900
calories. In what ratio is the base distributed
4. From the following data of H of the following between HA & HB ?
reactions
C(s) + ½O2(g)  CO(g) ; H = –110 KJ
9. Calculate the heat produced when 3.785 litre of
and C(s) + H2O(s)  CO(g) + H2(g) ; H = 132 KJ octane (C8H18) reacts with oxygen to form CO & water
Calculate the mole composition of the mixture of steam vapour at 25° C. The density of octane is 0.7025 gm/
and oxygen on being passed over coke at 1273 K, ml. Heat of combustion of C8H18 is –1302.7 kcal/mol.
keeping the reaction temperature constant. H°f CO2(g) = –94.05 k cal mol–1 ;H°f CO(g) = –26.41 k cal
mol–1
5. Although CP is usually assumed to be constant, for
H°f H2O (l) = –68.32 k cal mol–1 ;H°f H2O(g) = –57.79 k
more accurate calculations we must consider its
cal mol–1
variation with temperature as well. This relation is
given by :
10. Using the data (all values are in kJ/mole at 25°C)
CP = a + bT + cT2 + dT3 mol–1 K–1 given below
(a) Find the expression for the amount of heat H°combustion(ethane) = –1559.8 ; H°combustion(ethene)
required to raise the temperature of 1 mole of gas = –1410.9
from T1K to T2K, while
H° combustion (acetylene) = –1299.7 ; H° combustion
(i) keeping the first term [i.e. CP = a](ii) keeping the (acetaldehyde) = –1192.3
first two terms.
H°f CO2(g) = –393.5 ; H°f of H2O (l) = –285.8
(ii) keeping all the terms of the above expression.
H° for C(s) (graphite)  C(g) = + 716.68 ;
Note that each successive term introduces higher
accuracy. Bond energy of H – H = 435.94
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Bond energy of O = O = 498.94 16. Calculate the proton gain enthalpy of NH3(g) from
Calculating the following bond energies : the following data (in kJ/mole)
(i) C – C (ii) C – H (iii) C = 0 (iv) C = C (v) C = C H°dissociation : H2(g) = 218 ; H dissociation : Cl 2 (g) =
124
H°formation : NH3(g) = –46 ; H°f : NH4Cl(s) = –314
11. Using bond energy data, calculate heat of Lattice energy of NH4Cl(s) = –683
formation of isoprene. Ionization energy of H = 1310
Electron affinity of Cl = 348
5 C(s)  4H2 ( g)  H2 C  C – C  CH2 (g)
| | 17. Heat of combustion of gaseous isoprene (C5H8)
CH3 H CH2  CH – C  CH2 to CO2 (g) & H2O (l) is –3186 kJ/
|
Given : C – H = 98.8 k cal ; H – H = 104 kcal ; CH3
C – C = 83 k cal ; C = C = 147 k cal & mole.

Calculate the heat of formation and compare with bond
C(s)  C(g) = 171 k cal.
energies. Calculate the resonance energy of isoprene.
Given : fH (CO2, g) = –393.5 kJ/mol ; f H (H2O, l) =
12. Compute the heat of formation of liquid methyl –285.84 kJ/mol
alcohol in kJ mol–1, using the following data. Heat of Bond energies of C – H, C – C & C = C are 413, 348
vaporisation of liquid CH3OH = 38 kJ/mol. Heat of and 615 kJ.
formation of gaseous atoms from the elements in their Heat of atomization of carbon and H2 are 718.4 and
standard states ; H, 218 KJ/mol ; C, 715 KJ/mol ; 435.8
O, 249 KJ/mol Average Bond energies C – H, 415 KJ/
mol ; C – O, 356 KJ/mol ; O – H, 463 KJ/mol
18. The enthalpy of formation of C2H5OH(l) is –66k
cal/mol. The enthalpy of combustion of CH3 – O – CH3
is –348 k cal/mol. Given that the enthalpies of
13. Calculate the enthalpy change for the reaction
formation of CO2(g) and H2O (l) are –94 kcal/mol & –
XeF4  Xe+ + F– + F2 + F. The average Xe – F bond
68 k cal/mol respectively, calculate H for the
energy is 34 kcal/mol, first I.E. of Xe is 279 kcal/mol,
isomerisation of ethanol to methoxymethane. All data
electron affinity of F is 85 kcal/mol & bond dissociation
are at 25°C.
energy of F2 is 38 kcal/mol.
19. What is the ratio of the energy yield on
combustion of hydrogen atoms to steam to the yield
14. By using the following data draw an appropriate on combustion of an equal mass of hydrogen molecules
energy cycle & calculate the enthalpy change of to steam ?
hydration of (i) the chloride ion ; (ii) the iodide ion. Given ; H2(g) + ½O2(g)  H2O (g) ; H = –242 kJ
comment on the difference in their values. B.E. (H – H) = 436 kJ
• enthalpy change of solution of NaCl(s) = – 2 kJ/mol
20. FexO4 a mixed oxide of iron consists of only Fe+2
• enthalpy change of solution of Nal (s) = +2 kJ/mol
& Fe+3 ions, with the ratio of Fe+2 : Fe+3 = 1 : 2 in the
• enthalpy change of hydration of Na+(g) = –390 kJ/ mixed oxide. From the data given below,
mol Enthalpy of formation, Hf(FexO4) = –1092 kJ/mol.
• lattice energy of NaCl = – 772 kJ/mol Enthalpy of sublimation. Hsub (Fe) = 390 kJ/mol
• lattice energy of NaI = –699 kJ/mol. B.D.E of O2 = 490 kJ/mol
I.E1 of Fe = 760 kJ/mol
15. The standard enthalpy of combustion of sucrose I.E2 of Fe = 1560 kJ/mol
is –5645 kJ mol–1. What is the advantage (in kJ mol–1 I.E3 of Fe = 2960 kJ/mol
of energy released as heat) of complete aerobic I.E1 of O2– = –844 kJ/mol
oxidation compared to anaerobic hydrolysis of sucrose I.E2 of O2– = 142 kJ/mol.
to lactic acid ? H°f for lactic acid, CO2 and H2O is –
Lattice Energy of FexO4 = 18930 kJ/mol.
694, –395.0 and –286.0 respectively
Prove that value of x is 3 with the help of given data.
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Exercise - V JEE-Problems
OBJECTIVE
7.Estimate the average S – F bond energy in SF6. The
1.Which of the following reactions defines H f ?
(A) C(diamond) + O2(g) CO2(g) (B) ½ H2(g) + ½ F2(g)  Hf values of SF6(g), S(g), and F(g) are –1100, 275
HF (g)
(C) N2(g) + 3H2(g)  2NH3 (D) CO(g) + ½O 2(g)  and 80 kJ/mol respectively. [JEE99,5]
CO2(g) [JEE 2003]
8.In a constant volume calorimeter, 3.5 g of a gas

2. H f for CO2(g), CO(g) and H2O(g) are –393.5, –
with molecular weight 28 was burnt in excess oxygen
110.5 and –241.8 kJ mol–1 respectively. The standard
enthalpy change (in kJ) for the reactionCO 2 (g) + at 298.0 K. The temperature of the calorimeter was
H2(g)  CO(g) + H2O (g) is found to increase from 298.0 K to 298.43 K due to
(A) 524.1 (B) 41.2 (C) –262.5 (D) –41.2 the combustion process. Given that the heat capacity
[JEE 2000] of the calorimeter is 2.5 kJ K–1, the numerical value
for the enthalpy of combustion of the gas in KJ mol–1
3. Which of the following is not an endothermic reaction ?
(A) Combustion of methane is [JEE 2009]
(B) Decomposition of water
(C) Dehydrogenation of ethene to ethylene
(D) Conversion of graphite to diamond [JEE 1999] 9.Using the data provided, calculate the multiple bond
4.The bond energy (in kcal mol–1) of a C–C single energy (kJ mol–1) of a C C bond in C2H2. That energy
bond is approximately [JEE 2010] is (take the bond energy of a C–H bond as 350 kJ
(A) 1 (B) 10 (C) 100 (D) 1000 mol–1)
5.The species which by definition has zero standard 2C(s) + H2(g) C2H2(g) H = 225 kJ mol–1
molar enthalpy of formation at 298 K is [JEE 2010] 2C(s) 2C(g) H = 1410 kJ mol–1
(A) Br2 (g) (B) Cl2 (g) (C) H2O (g) (D) CH4 (g)
H2(g) 2H(g) H = 330 kJ mol–1
SUBJECTIVE
(A) 1165 (B) 837 (C) 865 ( D) 815
6.Diborane is potential rocket fuel which undergoes
combustion according to the reaction, [JEE 2012]
B2H6(g) + 3O2(g)  B2O3(s) + 3H2O (g)
From the following data, calculate the enthalpy change
for the combustion of diborane :
3
2B(s) + O2(g)  B2O3(s) ; H = –1273 kJ
2
1
H2(g) + O (g)  H2O(l) ; H = –286 kJ
2 2
H2O (l)  H2O(g) ; H = 44 kJ
2B(s) + 3H2(g)  B2H6(g) ; H = 36 kJ
[JEE 2000]
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Answer-Key
Exercise-I
1. D 2. D 3. D 4. A 5. C 6. C 7. B 8. A
9. A 10.C 11. A 12. D 13. D 14. C
15. (i) B (ii) A (iii) A (iv) C 16. A  (P,R), B  (Q,S), C  (Q,S), D  (Q,S)
17. A  (P,S), B  (Q), C  (R) 18. A 19. B 20. B 21. A 22. A
23. A 24. D 25. B 26. A 27. B 28. B 29. A
Exercise-II
1. C,D 2. A,B,C 3. C,D 4. A,B,C 5. B,C,D 6. A,Ca 7. C,D 8. B,C,D

9. A,B,C 10. A,C 11. A,C,D 12. A,B,C,D 13. A,C,D
Exercise-III
1. –324.8 kJ/mol 2. –34.5 kJ/mol 3. –26.8 kJ/mol 4. 35.973 MJ

5. 18.95% 6. 25.66 days 7. E = 27.91 KJ mol–1, t = 514 sec.
8. 27.43 g O2 9. –22.123 k cal 10. 2.95 kcal 11. –1410 cal 12. –18.7 kcal
13. 11.2 Kcal 14. –75.14 kJ/mol 15. (i) –885 kJ/mol (ii) –889.980 kJ/mol
16. 10.0 mol% CH4 17. –726.6 kJ/mol 18. 208 kJ/mol 19. –120.08 J/ml
20. B.E. (C – C) = 82 kcal/mole; fH [C2H6(g)] = – 20.1 kcal/mole 21. –72 kJmol–1
22. (i) 343.08 ; (ii) 891.2 23. EC  C = 160.86 k cal 24. –192.3 kJ mol–1 25. 277.5 kJ/mol
26. –23.68 KJ/mol 27. –669.7 kJ mol 28. –352 kJ mol–1 29. –618.7 kJ mol–1 30. –90.75 kcal mol–1
Exercise-IV
1. –85 kJ/mole 2. (a) 92.435 g (b) 93.72 g 3. 404 K

4. mole % O2(g) = 37.5, H2O (g) = 62.5
b
5. (a) (i) aT (ii) aT + (T 2 – T12) (b) 1000cal, 1012cal, 1.1858% error
2 2
6. 0.9346 k cal g–1, 3.94 kcal cm–3 7. 9.822 MJ/day evolved
8. 1 : 3 9. –666.81 k cal mol–1, 15.55 Mcal
10. C – C = 97.81 kJ, C – H = 454.64 kJ, C = O = 804.26 kJ, C = C = 434.3 kJ, C = C = 733.48 kJ
11. +20.6 kcal 12. –266 kJ mol–1 13. 292 kcal/mol
14. for Cl – 384 kJ mol , for I – 307 kJ mol–1
– –1 –
15. advantage = 5393 kJ mol–1
16. –718 kJ/mol 17. –30.06 kJ/mol 18. 22 kcal mol–1
19. 2.80 : 1
Exercise-V
1. B 2. B 3. A 4. C 5. B 6. –2035 kJ mol–1 7. 309.6 kJ/mol
8. 9 9. D
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Page # 1 Solution Slot - 2 (Chemistry)
THERMOCHEMISTRY
EXERCISE – I SINGLE CORRECT (OBJECTIVE QUESTIONS)
1. If  ng = 0  H =E 8. N2(g) + 3Cl2 (g) 2NCl3(g) ;  rH
n
above eq can be get after
2  Rxn 1 + Rxn 2 – 3  Rxn 3
2.  rH= 0 ; If all the reactants & products have 1
zero  f H.   f H (NCl3,g) =  rH
2
3. CaO(S) + 3C(S)  CaC2 + CO 1

= [–2  H1 +  H2 – 3  H3]
 r  = – 14 – 26 + 152 = 112 per mole 2
for 1.28 Kg = 112  20 = 2240 Kcal
H 2 3
= –  H1 + – H
2 2  3
50  0.1
4. HCl = NaOH = = 5  10–Mole
1000 9. H+ = 1 Mole ; OH– = 0.75 Mole
H = 0.75  (–57)
100
q = 4.2  3  = 1.26 KJ. Heat enolved = 57  3/4
1000
1.26 10. By Rxn .....1 – Rxn .....2

per mole  4 AuBr4+4 HCl HA4Cl4 + 4HBr
5 10 – 3
H = – 28 + 36.8 = 8.8 KCal/mol
KJ = 2.5  102 KJ/Mole But H = 0.44 K Cal
5. HA BOH 0.44
  = = 0.05
8 .8
 ionH
% dissociation = 5%
H+ A– + B+ OH– H2O + BA
11. By
 – 57.3
– 56.1 =  ionH 
Eq ....2 – Eq....1
 1.5  = 1.2   = 0.8 t – 2–butene 1 – butene
 H2 –  H1 > 0
6. C (graphite) (diamond) ;  H1 –  H2 By
Eq ....6 – Eq....7
1.9 1
 H1 –  H2 = 2 (6g º Mole) t – 2 – butene 1– butene
2
 H2 –  H1 > 0
= 0.95
  H = – 647 + 649.8 = 2.8
  H2 –  H1 = 2.8 and
1
7. H2 + O H2O (l) 9  H1+5  H2= 0
2 2
  H2 = 1.0 and  H2 =1.8
1
H–H+ 0=0 H20(g) H20 (l)
2 12. – 25 = (4x +y ) – (3x + 84 + 103)
X2 x 9
 x + y = 162 and y =
X = X1 +
2
– 2X3 – X4 5
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Solution Slot - 2 (Chemistry) Page # 2
 y = 57.85 2x x
0 0 2x
Heat =  rU = – 57.8  2x
1 1
13. H2 + O OH(g) ; 42 ....(1) In container after reaction 2x mole H2O and 4x
2 2 2 mole N2 will be present
1  {2x  Cv(H2O,g)+4xCv(N2,g)}  T = 57.8  2x

H2 (g) + O (g)
2 2
H2O(g) ; –242 ....(2)  103
 {(11.3 – 2) + 2 (8.3 –2)}
H2(g) 2H(g) ; 436 ....(3)
O2(g) 2O(g) ; 495 ....(4)  T = 57800
  T = 2639.27  Tf = 2639.27 + 298
= 2937.3 K
1
(a) Eq-----3 + Eq -----4 Eq 2
2
(iii) Close container  Constant Volume
495 P1 P2
  242 + 436 + = 925.5 ; True
rue
2 n1T1 =
n 2 T2
1 n 1 n n1 = 2x + x + 4x = 7x
(b) Eq 3 + Eq 4 – Eqn 1
2 2 n2 = 2x + 4x = 6x
436 495 n2 6 1 P2
H = –42+   423.5 , false  n = 6/7   =
2 2 1 7 298 2940
(c) H2 2H ;  rH = 2  fH (H,g)
 P2 = 8.46
436
 fH(H,g) = 2
= 218 ; False (iv) E1 = E2
because : w = 0 (Rigid vessel)
(d) First reaction is  rH =  f H(OH,g) q = 0 (Adiabatic)
= 42 ; True
 E=0
14.
16. If ng > 0 : S > 0
17. Kirchaff’s equation

+ 3H2
d(  rH) =  rCpdt
  H =  U +  ngRT
 rH =fH (cyclohexane) –fH(Benzene)
= – 156 – 49 q rev
 s =
T
 rH = 3  (– 19) + R.E
 R.E = – 156 – 49 + (3  119) = 152 KJ/
Mole 18. Stable state had zero standard molar enthalpy
15. (i) As atomicity decreases ; CpM 19. N2 + O2 2NO ;  rH > O

increases N2 + 2O2 2NO2 ;  rH > O
(ii) for maximum temp  H2 and O2react Endothermic reactions are favourable High
completely reaction is in closed container  temperature.
volume = constant
2H2 + O2 2H2O 20. (diamond) +O2 CO2 ; – 94.3
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(Amorphous) + O2 CO2; – 97.6 27.

(diamond) (amorphous) ;  rH
H
 rH = –94.3 +97.6 =3.3 KCal / Mole
1 H C H
for 6g C  Mole C
2
H
3. 3
 rH = 2 = 1.65 KCal 360
EC–H = = 90
4
21. H2O (l) H2O(g)
H H
 18  0.62778 =  fH(H2O, g) –  fH(H2O,l)
=  fH(H2O, g) + 68.3
H C C H
  fH(H2O, g) = – 68.3 + 11.3
= –57.0 KCal H H
620 = 90  6 + EC–C
22. I2(s) I2(g)
 EC–C = 80
 H2 –  H1 =  Cp (T2 –T
T1)
50 28. To Keep the temp. constant  H

 H2 – 6.096 = (0.031 – 0.055) 1000  254
overall = 0
Let x mole O2 and y mole steam
 H2 = – 0.3048 + 6.092
= 5.78  110  2x = 132 y
x no2
23. Acetic acid ; weak acid (Less than 13.7)  y = n = 0.6
And HF is the exceptional case having langer steam
value for Heat of neutradiazation than 13.7

no2 1
= = 1.666
24. (i) True nsteam 0 .6
(ii) Due to cont. volume it measure  U
(iii)  ng = 0   H =  U
(iv) False (due to involvement of R.E) 29.
H2O (s) H2O (l) ; 1.44 KCal
+
25. Case I ; H = 0.1  100  2 = 20 m.eq.
OH– = 0.1  100  2 = 20 m.eq.
1.44
For 27 g  27 = 2.16
Case II ; H+ = 50  0.1  2 = 10 m.eq. 18
OH– = 100  0.1 = 10 m.eq.
 2 HII =  HI
HI = 274 cal ;  HII = 137
TI = TII (Because amount of subsances in
case I is double than case II)
26. 1 True 2 True 3 True 4 True 5 False
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Exercise - II (One or more than one option correct)
1. Arrhenius equation ; K = Ae–Ea/RT

8. Follow the theory
Kirchaff’s Equation ;
d (  rH) =  r CpdT
9. Pwhite < Pred (Stability)
 Exothermic
2.  G < 0 for spontaneous
(D) Assumed to zero not unity
10. 3UO2 +O2 U3O8
– 76.01 = – 853.5 – (3   fH(UO2)
3. Internal Energy depend on only temperature
 If temp. is constant than dU or dE = 0  853.5  76.01

  fH =
3
4. Thermochemical reaction equation does not = – 259.16 Kcal /Mole
give information about  rG or spontanity
11. C (diamond) ;  fH  0
5.  rH does not depend on the manner cause it
is the state function. 12. Solid liquid
Endthemic ;  H > 0
1
6. Uf(g) U(g) + F (g)
2 2
 rH =  fH (U,g) –  fH(UF,g)
,g)
= 128 – 22 = 106
or
1
 rH = E U–F – 2 EF–F = 106
1
 E U–F = 106 +  37
2
= 124.5 KCal /Mole
or
521 KJ/Mole
7. Enthalpy of formation : follow the definition
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Exercise - III Subjective Level-I
1 7.
1. N2(g) + 2H2(g) + C(s) + O (g)  U =  H –  ngRT = 30.84 –
2 2
NH2CONH2(s)  1 8.314  353 
 
7  1000 
ng = – = 27.905 KJ / Mole
2 For 7.8 g º 0.1 Mole benzene
 fU°298 =  fH°–ngRT  H = 3.084 KJ = VIt
7 8.314  298 3.084  103
= – 333.5 + 
2 1000  t=
12  0.5
= 514 Sec.
= –324.8
2. By Eq (1) – (2)+(3) 1
w(s) +c(gr) wc(s) 8. C + O CO ; – 24 KCal/Mole
2 2
rH° = – 837 + 1196 – 393.5
1 0.5 1
=34.5
1
C + O CO2 ;
3.  rH = 3(–393.5) – 3  (–110.5) – (–822.2) 2 2
= –26.8 KJ/Mole – 95 + 24 = –71 Kcal/mole
Heat evolved in first reaction = 24 Kcal
4. CH4 +2O2(g) CO2(g) + 2H2O(l) Heat evolved in Second reaction = 71  2y
1000  24 + 71  2y = 75
Mole
22.4 51
 2y =  y = 0.359 Mole
 rH = 2  (–241.6) + (–398.8) – (76.2) 71
= 805.8KJ/Mole total O2 Mole = 0.5 + 0.359 = 0.859
mass of O2 = 0.859  32 = 27.4g
1000
For Mole CH4 ; Heat evolved
22.4 9.  rHT2 –  rHT1 =  rCp (T2 –T
T1)
1000   rHT2 – (–22.1) =
= 805.8  = 35.97  103 KJ
22.4  1 
 6 . 8  (6.82  7.7) 
2
14000 
1000
  50
5. C4H10 = Mole  
58  
14000   rHT2 = –22.123 KCal
Total energy produced = 2658  103
58
= 641.58 MJ 10. CaCl2 (aq.) + Na2(CO3(aq.)  CaCO3(s) + 2NaCl(aq.)
Total energy used = 20  26 = 520 MJ overall reaction
Ca2+ (aq.) + CO32–(aq) CaCO3(s)
641.58  520 H = – 288.5– (–129.8 – 161.65)
% waste =  100 r
641.58 = 2.95 Kcal
= 18.05%
11. NaOH + HCl NaCl + H2O ;
– 13680 ------(1)
2658 11.2  1000 NaOH + HCl NH4Cl + H2O ;
6. Energy formed =
58 – 12270 ------(2)
From Eq (1) --- (2)
2658 11.2  1000 NH4Cl + NaOH NH4OH + NaCl
no. of days =
58  20000
= 25.66 days
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Solution - 2 (Chemistry) Page # 6
  rH = – 13680 + 12270 0.004
= – 1410 Cal % Mole ot CH4 =  100 = 10%
0.04
12. CuSO4 + aq. CuSO4(aq.) ; – 15.9 4.18J
CuSO4 . 5H2O + aq. CuSO4(aq.) ; 2.8 17. q = 4.2  2.02 KJ + 2000  4.2
CuSO4 CuSO4.5H2O gc 
 rH =  H Hydration = – 15.9 – 2.8 = 43.596 KJ by 1.92 g of CH3OH
= – 18.7 Kcal
 43.596
13. HCl + KOH
 1.92  KJ/mole
 Comb H (CH3OH =  
H 1  32 
KJ
= 726.6
H+ + OH– H2O Mole
H H
 – 13.68  103 +  H1 = –2480 18.
P–P
  H1 = 11200 Cal H H
= 11.2 Kcal ; 1.48  103 = 4EP–H + E P–P
H+ (aq.) + Cl– (aq.) H
14. HCl (g)
H–P 954
 Sol H (HCl , g) = { 0 + ( – 167.44 ) } – {– ; EP–H =
H 3
92.3 }
= 74.14 KJ / Mole 4
E P–P = 1480 –  954
15. At Constant Pressure 3
= 208 KJ / Mole
1
q evolved = 17.7  = 8.85 KJ
2 Ec  c E C  C 
For 0.01 Mole     
 8.85 19.  rH =   + E H H  –   
 U = q = 0.01 = – 885 KJ / Mole 4E c h  6 E C  H 
At Constant Pressune = – 120.08 kJ/mole
 H = q =  U +  ngRT 20. H2(g) 2H (g) ; 104.1 ...(1)
CH4 + 2O2 CO2 + 2H2O (l) ;  ng = –2 (s) (cg) ; 171.8 ...(2)
2  8.314  300 CH4(g) (cg) + 4 H(g) ; 396 ...(3)
 H = –885 – C2H6 (g) 2C(cg) 6H(g) ; 676 ...(4)
1000 For Heat of formation
= 2889.98 KJ / Mole 2C(s) + 3H2(g) C2H6(g) ...(5)
eq (5) = 2×(2)+8×(1)–(4)
16. CH4 = x mole   fH(C2H6) = 171.8  2 + 104.1  3 – 676
CH4 + 2O2 CO2 + H2O (l) = – 20.1 KCal / Mole
q = 1260 Cal/ k  0.667 = 840 Cal
 fH (C2H6) = 2   Hsub (c,s) + 3EH–H)
 HCombustion (CH4) = – 215  1000 Cal /Mole – (6EC–H + EC – C)
840 396
CH4(mole) = = 0.004 mole
215  1000 From (3) EC–H =
4
= 99
for total mole
 – 20.1 = (2  171.8) + (3  104.1) – (6  99)
PV – Ec – c
PV = nRT  n =
RT  Ec – c =82 KCal / Mole
 740  21. n CH2 = CH2 (CH2 – CH2)n
  1
n total =  760  r H = nEC=C
– 2n EC – C
= 0.0397 0.04
= – 72 n
0.0821  298
For n mole  rH = – 72 n
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For 1 mole  rH = – 72 KJ / Mole From eq. 1 & 2

2839.2= 6EC – H  E C – C  E C – C = 373.98
3 1 2275.2 = 4EC – H + EC = C  EC = C = 631.72
22. 2(Cs) + H2 (g) + N (g) CH3CN ;
2 2 2  C6H6 6C(g) + 6 H (g) ; 5506
87.86 ...(1) then
2(Cs) + 3H2(g) C2H6 ; – 83.68 ...(2) 5506 = |R.E| + 6EC – H + 3 E C – C + 3EC = C
C(s) C(g) ; 719.65 ...(3)
 |R.E| = 23.68
N2(g) 2N(g) ; 945.58 ...(4)
H2(g) 2H(g) ; 435.14 ....(5)  R.E = – 23. 68
From Eq. 2  3 + 3  5 .....(2)
27. R.E = – 143
C2H6 2(g) + 6H(g) ;  H1
 1H = (2  719.65) +(3  435.14) + 83.68 = 3
CH3OH (l) + O (g) CO2 (g) +2H2O(l)
2828.4 2 2
 2828.4 = 6EC–H + EC–C= 6  414.22 + EC – C rH =  Comb. H = {(35.5) + 3EC–H + EO – C + EO – H}
 EC  C  343.08 3 
   EO  O  – 143  3 EC  O 
1 3 2 
Form Eqn 2  2 + 4 +  (5) ...(1) – { (40.6  2 ) + 4EO–H}
2 2 After puting the data
CH3CN 2(g) + 3 H (g) + N (g) ; 2476.94
 rH = – 66.97
 2476.94 = 3EC–H + E C– C + EC  N
 EC  N = 2476.9 – (3  414.22) – 343.08
= 891.2 1
28. Na(S) + F NaF(S) ; – 571
5 2 2
23. C2H2 + O2 2CO2 + H2O (l) ; –312 KCal
2 160 = 80
101
– 312 = [2  (– 94.38) + (– 68.381] – [  fH(C2H2)] 2
  f H (C2H2) = 54.86 Kcal / Mole Na(g) F(g)
 2(Cs) + H2 (g) C2H2 ; 54.86
494 H
 54.86 = [ 2   aton (c) + EH – H] –
H
[2  EC – H + ECC]
 EC C = (403 – 54.86) – 2  93.64 Na+ + F–
= 106.86  101 + 494 + 80 +  H – 894 = – 571
24. H3C – C – CH3 (mol. formula C3H6O)   H = – 352 KJ / Mole
O 1
29. Cs(s) + Cl (g) CsCl (g) ; – 388.6
1 2 2
3C(s) + 3H2(g) + O2 (g) C3H6O
2 243
81.2
1 2
fH = [(3  718 ) + (3  435.8 ) +  495 ]
2 Cs(g) Cl(g)
– [(6  413.4 ) + ( 2  347) + 728]
= –193.5
375.7 –348.3
25. C2H5 – S – C2H5+S(g) C2H5–S –S – C2H5
rH = – 201.9 – (– 147.2 +222.8) = – 277.5 Cs+ Cl–
L.E. = 618.7
 rH = – ES – S = 277.5
 ES – S = – 277.5 30. X = – 105 + 159.5 – 96 – 20 .5 – 28.75
X = – 90.75
26. 2C(g) + 6H (g) C2H6 ; – 2839.2.... (1)
2C(g) + 4H (g) C2H4 ; – 2275.2....(2)
6C(g) + 6H (g) C6H6 ; – 5506....(3)
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Exercise - IV Subjective Level-II
1 x n O2 132
2. Hgo  Hg + O (g)  rH = –  fH°
 2 2  y =
n Steam = = 0.6
220
(HgO) = 90.38 KJ / Mole
0 .6 60
% of O2 (by mole ) =  100 = =37.5
1 .6 1.6
cos t.P
At % of steam (by mole) = 62.5%
Heat
Let n mole Hgo get decomposed T2
5.(a) (i) q = a  dT = a  T
41.84 T1
 90.8  n = 41.84  n =
90.8
41.84 T2 b
mole of Hg =  mass of Hg (ii) q =  (a  bT)dT = a  T + (T22 – T12)
90.8 T1 2
41.84 T2
=
90.8
 200.6 (iii) q =  (a  bT  CT 2  dT 3 )dT
T1
= 92.435g
b 2 c
q = aT + (T2 – T12) + (T23 – T13) +
const.volume 2 3
b. At
Heat  rU   rH =  rU +  ng RT
d 4
1 8.314  298 (T – T14)
 rU = 90.8 – ( 2  ) 4 2
1000
= 90.8 – (1.238) b. for CO2 ; a = 5 ; b = 15  10 –5
= 89.561 KJ/mole (i) q = a ( T2 – T1) = 5  (500 – 300) = 1000
 89.561  n = 41.84
b 2
41.84 (ii) q = a ( T2 – T1) + (T – T12)
2 2
n= = mole of Hgo
89.561
15  10 –5
41.84 = 1000 + (250000 – 90000)
 mass of Hg =  200.6 = 93.71g 2
89.561 = 1000 + 12 = 1012
3. Kirchoff’s Eq 12
% error =  100 = 1.1858%
 r HT2 –  rHT1 =  rCP(T2 – T1) 1012
At  r HT2 = – 26 KJ ;  r HT1 = –35.1 KJ 6. Fe2O3 + 2Al Al2O3 + 2Fe
 rCP =(3  75.3 + 2  25.5)–(104.5+3  28.9) = 85.77  rH =  fH (Al2O3)  fH (Fe2O3)
= – 399 – (–199)
 rCP = 0.0857 KJ
– 26 – (–35.1) = 0.0857 (T2 – 298) = –200 KCal / Mole
Fuel value per gm (for given rxn 1 mole Fe2O3,2
9 .1 mole Al)
 T2 – 298 = = 106
0.0857 Total mass of fuel = mass of Fe2O3 + mass of
Al
 T2= 298 + 106 = 404 K = 160 + 2  27 = 214 g
4. To Keep the temperature constant  H overall 200

fuel value per gm = = 0.9346 KCal/g
=0 214
Let x mole O2 & y mole steam
 110  2  x = 132  y
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 160 2  27   rH = x
Total volume ot fuel =    cc =
 5 .2 2 .7 
25
50.77 cc C8 H18 + O 8CO2 + 9H2O (l) ....(1)
2 2
200 H2O(l) H2O(g) ....(2) ;
Fuel value per cc = = 3.94 KCal /cc
50.77 – 57.59 – (–68.32) = 10.53
21 1
7. In single breath O2 contain = 448  ml CO + O CO2 ....(3) ; –94.05 –
100 2 2
O2 Contain inhaled per M minute = (–26.4) = – 67.64 ....3
1 + 9  2 – 8  3 = Eq. A
448  21 15 x = – 1302.7 + (9  10.53) – 8  (– 67.64) = –
ml
100 666.81 =  rH KJ / Mole
mass of octaine = 3.785  103  0.7025 g
448  16  15
O2 exhaled per mehute = ml = 2659g
100
2659
448  15 448  15  5 =
114
Mole = 23.325 mole
O2 remain = (21 –16) = ml
100 100 Heat evolved = 666.81  23.325 =
C12H22 O11+12O2 12CO2 +11H2O 15553.3Kcal
= 15.55 Mcal
 448  15  5 
  11.
moleof O2 M inhaled =  100  1000   1 by
0.0821  300 5 (CS) + 4 H2 (g) H2C = C – C = CH2
PV = nRT
= 0.013642 mole in one minute CH3 H
 In one minute Sucrose burnt
 rH = {(5  171) +4  EH – H} – { 8  EC – H +
0.013642 2E C = C + 2 EC – C}
= mole = (5  171 + 4  104) – ( 8  98.8 + 2  147 +
12 2  147 + 2  83 )
0.013642 = 1271 – (1250.4)
per day sucrose burnt =  24  60 = 20.6 KCal
12
= 1.637 mole 12. Desired eq.
energy evolved = 1.63  6000 KJ per day
= 9822 KJ / day 1
C( grap) +2H2(g) + O (g) CH3OH (l) :
= 9.822 MJ / day 2 2
8. Let the of HA = xeq & HB = yeq.  rH
reacted reacted given
CH3OH (l) CH3OH (g) ; 38KJ
 69 x + 29y = 39 x + y = eq. of NaOH
H2(g) 2H(g) ; 218  2
x+y=1
C(grap) C(g) ; 715
10 O2 2O (g) ; 249  2
x = = 0.25
40 1
y = 0.75  rH = {  vap.H(C,grap) + 2  EH–H + 2 Eo =
x 0.25 1 0} –{ H (CH3OH,l)+3EC – H+EC – O + EO – H }
ratio = = =
y 0.75 3 1
= { 715 + 2  (218  2) +  (249  2)}
2
17 – ( 38 + 3  415 + 356 +463}
9. C8 H18 + O 8CO+ 9 H2O (g) = – 266 KJ / Mole
2 2
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13. XeF4 Xe+ + F– + F2 + F , g) –  fH (NH4Cl)
 rH = 4  Exe – F – {– IExe + E.AF + EF– F
= 34 ×4 – {– 279 + (85 ) + 38} From (4) & (6)
= 136 + 279 – 85 – 38 Cl2 2Cl– (g) ;  H = – 2  348 + 124
= 292 KCal / Mole
+ – = – 572
XeF4 Xe + F + F2 + F
+279 –85 –38

 572
  fH (Cl–, g) = = – 286
2
Xe(g) + F(g) +2F(g)+F
 686 =  fH (NH4+, g) – 286 – (– 314)
14. NaCl (s) Na+(g) + Cl–(g)  H = 772  fH (NH4+ , g) = 686 + 286 – 314 = 655
Na+ (g) Na+ (aq.)  H = – 390 From (3) & (5)
– –
Cl (g) Cl (aq.)  H = x
H2 2H + (g) : rH = 1310  218 = 2838
NaCl (s) Na (aq) + Cl– (aq.) ;  H = x + 772
+
– 390 2838
NaCl (s) Na+(aq) + Cl–(aq) ; H=x  fH (H+, g) = 2
= 1419
+ 772 – 390
X + 772 – 390 = – 2  x = – 2 + 390 – 772 =
 for 1 eqn
– 384 KJ / Mole
 rH =  fH( NH4+ ,g) –  fH (NH3,g) –  fH (H+, g)
Similarly
For I– (g) I–(aq) = 655 – ( – 46) – (1419) = – 718 KJ/ Mole
 H = + 2 + 390 – 699 = – 307 KJ/ Mole
15.
C12 H22O11+12O2 12CO2+11H2O:rH = – 5645 17. CH2 = CH – C = CH2 + 7O2 5CO2 + 4H2O
– 5645 = 12   fH(CO2)+11   fH(H2O)
–  fH (sucrose) CH3
– 5645 = 12  (– 395 ) + 11  (–286) –
– ;  H = – 3186 KJ/mole
 fH (sucrose)
– 4740 – 3146 – fH (sucrose)
 H =–3186=5  fH (CO2)+4  fH (H2O)
  fH (sucrose) = – 2241
–  fH(Isoprene)
C12 H22O11+ H2O 4C3H6O3 (lache wod)
 fH = 4   fH (C3H6O3) – 3186=5  (–393.5)+4 (–285.84)–
–fH(Sucrose)–  fH(Isoprene)
 fH (H2O)
= 4  ( – 694) – (– 2241) – (– 286)  fH(Isoprene) = – 1967.5 – 1143.36 + 3186
= – 2776 + 2241 + 286 = – 249 KJ = 75.14
Advantage of energy = 5645 – 249 = 5396 KJ
– 3186={|R.E|+8EC – H +2EC – H+2EC=C+2 EC– C) +7EO–H}
16. NH3(g) + H +(g) NH4+(g) ;  rH = ?...(1)
NH4Cl (s) NH4 (g) + Cl – (g) ;
+
– 3186 = { |R.E| 8  413 + 2  615 + 2 
 H = 683 .....(2)
348) + 7  EO =O)} – {10  E C= O
+ 8EO–H}
H H + (g) ;  H = 1310 ....(3)
...(1)
Cl ;  H = – 248 ....(4)
H2 ; 218 .....(5) (CS) + O2 ; – 393.5
Cl2 ; 124 .....(6) – 393.5 (718.4 + EO = 0) – E ) ...(2)
C= O
From above eqn

From 2nd eqn 683 =  fH (NH4+ , g ) +  fH (Cl–
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1  rH1 = – 436 – 242 = /– 678

H2 + O H2O (l) ; – 285.84
2 2
 r H1  678
 r H 2 =  242 = 2.80
1
– 285.84 = (435.8 + E ) – (EO–H) ...(3)
2 O=O
20.

(Heat of atomisation of C(s)
E – 2E = – 1111.9  5 X Fe(s)+ 2O2 FexO4
O=O C=O =
If total Fe=x
and x×390 Fe2+ : x
3
3+
E – 4EO = H= – 1443.28  2 Fe : 2x
O=O
x 2x 3
Fe(g)  Fe(g) 4O
 7 E O = O – 4EC = O= – 8446.06 ...(4) 3 3
Putting the values of Eqn. 4 into Eqn

– 3186 - |R.E| 5230 – 8446.06 4O2–
x 2
Fe 2x 3
3 Fe
 |R.E| = – 3186 – 5260 + 8446.06 3
= 30.06
R.E always in – ve
–30.06
 fH (FeO4) = 390 x +  H1 +  H2 + ( 2  490)
+  H3 + L.E
18. C2H5OH CH3 – O – CH3  H = ?
CH3 – O – CH3 2CO2 + 3H2O ; – 348 x 2x

– 1092 = 390 x +  (760 + 1560) + (460
– 348 = 3   fH (H2O) + 2   fH (CO2) –  fH 3 3
(C2H6O) + 1560 + 2960) + ( 2  490) 4  (844 – 142) –
18930
= 3  (–68)+2  (– 94 )–  fH (CH3–O – CH3)
 fH(CH3–O–CH3)=–68  3– 94×2 +348 = – 44 2320x 10560 x

– 1092 = 290x + + – 15142
3 3
 for first reaction
 fH=  fH (CH3OCH3 ) –  fH (C2H5OH) 14050 x
– 1092 = – 15142
= – 44 – (– 66) 3
= + 22 KCal/ Mole
14050 x
 = 15142 – 1092
3
1
19. 2H + O H2O :  rH1 = 14050
2 2
1  x=3
H2 + O H2O :  rH2 ; – 242 KJ
2 2
H2 2H : 436
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Exercise - V JEE-Problems
1. A: C(diamond ) wrong  rH = 1855
B: Correct 1855 = 6ES–F
C: 2 Mole NH3 (wrong)
D: CO (g) not elemental stale
1855
 ES–F= = 309.16 KJ/Mole
6
2. CO2(g) + H2(g) CO(g) + H2O(g)
 r H =  fH (H2O) +  fH (CO) –  fH (CO2) 3. 5

8. Mole of gas =
= (– 241.8) + ( – 110.5) – (–393.5) 28
= 41.2 T = 0.43 K
3. Combustion : Exothermic KJ
q = 2.5  0.45 K
graphite is more stable than diamond K
= 1.125 KJ
4. Remenber the fact Heat evolved by 1 Mole
EC– C = 100 KCal / Mole
1.125
5.  fH (Br2,l) = 0 ;  fH (Br2,g)  0 = 
3.5  = 9 KJ / Mole

 28 
6. by performing (2) + 3  (4) + 3  (3) – (5)

9. C2H2 (g) 2C(s) + H2(g)
B2H6 (g) + 3O2(g) B2O3 (S) + 3H2O(g)
– 225 = 2 BE C–H + B.E. EC C – 1410 – 330
 rH = – 1273 + ( 3  44) – ( 3  286) – 36  BE C C = – 225 – 700 + 1740 = 815
= – 2035KJ/Mole
7. S(g) + 6F(g) SF6 (g)

 rH = – 1100 – (275 + 6  80)
= – 1855
Sf6(g) S(g) + 6 F(g) Sf6(g)
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Thermochemistry: Theory and Exercise Booklet

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Thermochemistry: Theory and Exercise Booklet

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S.NO. TOPIC PAGE NO.

1 THEORY WITH SOLVED EXAMPLES ..................................... 3 – 15

2 CLASS ROOM PROBLEMS .................................................. 16 - 20

3 EXERCISE - I (SINGLE CHOICE) ......................................... 21 – 26

4 EXERCISE - II (MULTIPLE CHOICE) .................................... 27 – 28

5 EXERCISE - III (SUBJECTIVE LEVEL - I) .............................. 29 – 35

6 EXERCISE - IV (SUBJECTIVE LEVEL - II) ............................. 36 – 37

7 EXERCISE - V (JEE PROBLEMS) ......................................... 38 – 39

8 ANSWER KEY ................................................................... 40

CLASSIFICATION OF MOLAR HEAT CAPACITY

Mass dependent properties are called extensive properties

* Two extensive property can be added or additive.

 dmix x(h1 + h2)A = d1h1A + d2h2A

d1h1A  d2h 2 A d1h1  d2h 2

 Enthalpy at cons tan t pressure.

Enthalpy at  Enthalpy at

After reaction  n changes

This gives the relation between enthalpy and temperature.

Molar heat capacity at

ENTHALPY AT STANDARD STATE :-(Hº)

Another example can be taken as

Ex.1 From the following data,

Hº = HCº (H2) = Hfº (H2O) – Hfº(H2) – 1/2Hfº (O2)

Hrº = Hcº (C3H8) + HCº (H2) – {Hcº(C2H6) + HCº(CH4) }

Problems Based on Both HOC and HOF :

CH4(g)  C(g) + 4 H(g)

H = 4  C  H =H ºC(g) + 4H ºH(g) – H º(CH )

Sol. rHº =  reac tant   product

Hrº = 606.68 + 4×410.87 + 431.79 –336.81 –6×410.87

 Hrº = Hº (Hydrogenation)

Ex.5 Compare the heat of hydrogenation of the following alkene

(more stable) (more stable as nothing is

of therefore decreasing order of heat of hydrogenation of alkene

 H  Cl = H ºH(g) + H ºCl(g) – H ºHCl(g)

bond enthalpy of C–H = 413.4, C – C = 347.0 (C = O) = 728.0

 C  C + 2  C  H = 2H ºC(g) + 2H ºH(g) – H º(CH  CH)

6C(g) + 6H(g)  C6H6 Hº = –5506

Heat evolved = mst + Ct

Heat capacity Heat capacity

INTEGRAL HEAT OF SOLUTION

dilute soln is called heat of neutralisation.

(C) 57–(x + y) = 48.1

 4.5 + y = 8.9  y = 4.4

BORN HABER CYCLE

Class Room Problems

Problem : 2 Find Hf of HCl(g) if bond energies of

118 and 270 kcal/mol respectively.

Problems : 10 Calculate standard heat of formation

Problems : 12 The enthalpy change involved in the

Problems : 14 Estimate H for 2C4H10 (g) CH 8

Problems : 17 Calculate the resonance energy of

Problems : 18 Calculate the lattice energy of AH3(s)

Exercise - I (only one option is correct)

f H°(CaC2, s) = –14 kcal/mol H2 3

9. The enthalpy of neutralisation of HCl and NaOH is

25. 200 mL of 0.1 M NaOH is mixed with 100 mL of

Exercise - II (One or more than one option correct)

2. Which of the following statements is (are) correct

11. For which of the following substances is the heat

13. The heat of combustion of ethanol was

Exercise - III Subjective Level-I

4. The standard heats of formation of CH4(g), CO2(g)