Ideal 21st Century Competitions www.21stideal.

com 1
Chemistry - Chemical Thermodynamics and energetic
[Time : 90 Mins] SOLUTION OF ASSIGNMENT [Max. Marks : 35]

Note : 1 Chemical Thermodynamics and energetic. Properties chapter Weightage total 8 marks.
2. All questions are compulsory.
3. Draw neat and labelled diagram wherever necessary.
4. Figure to the right indicates full marks.
5. Answer to every new question must begin on a new page.

I. Objective Type Questions
I. Choose the correct answer:
1. Thermochemistry is the study of relationship between heat energy and
(a) Chemical energy (b) Binding energy
(c) Gravitational energy (d) all of these.
Solution : (a)

2. An exothermic reaction is one in which heat content of
(a) Products is more than that of reactants
(b) Reactants is more than that of products
(c) Reactants and products is same
(d) None of these
Solution : (b)

3. The standard heat of combustion of C is -94.0 Kcals. What is H
f
of CO?
(a) -94.0 Kcals (b) -46.0 Kcals (c) +94.0 Kcals (d) -26.0 Kcals
Solution : (a)

4. In an adiabatic process
(a) pressure is maintained constant
(b) the gas is isothermally expanded



Ideal 21st Century Competitions www.21stideal.com 2
(c) there is perfect heat insulation
(d) the system exchanges heat with surroundings
Solution : (c)

5. Which of the following processes is reversible?
(a) Evaporation of water at 100C and 1 atm pressure
(b) Melting of ice at 10C
(c) Mixing of two gases by diffusion
(d) None of these
Solution : (d)

6. Enthalpy is same as
(a) Entropy (b) Heat
(c) Heat content (d) Volume
Solution : (c)

7. In an isothermal expansion of an ideal gas
(a) w = 0 (b) U = 0 (c) q = 0 (d) V = 0
Solution : (b)

II. Short Answer Type Questions-II
1. What do you mean by the law of conservation of energy? Derive the mathematical relationship of
heat, internal energy and work.
Solution : Law of conservation of energy states that energy can neither be created nor be destroyed. It can
change from one form to another. The total energy of universe remains constant.
Let E1 be initial internal energy, 'q' is heat supplied to the system, 'w' is work done on the system,
then final internal energy
U
2
= U
1
+ q + w
U
2
- U
1
= q + w [2 Marks]




Ideal 21st Century Competitions www.21stideal.com 3
2. What is the basic difference between enthalpy of formation and enthalpy of reaction? Illustrate with
suitable examples.
Solution : Enthalpy of formation is defined as enthalpy change when 1 mole of substance is formed from the
constituting elements in their standard states, e.g.,
H
2(g)
+ - O
2(g)
H
2
O
(l)

f
H = 286kJ/mol [1 Mark]
Enthalpy of reaction is defined as enthalpy change when reactants react completely to form products
according to balanced chemical reaction, e.g.,
N
2(g)
+ 3H
2(g)
2NH
3(g)
H = - 92.0 kJ
-1
[1 Mark]

3. Using the bond energy of H
2
= 435 kJ mol
-1
, Br
2
= 192 kJ mol-1, H
-
Br = 368 kJ mol
-1
Calculate
enthalpy change for the reaction : H
2(g)
+ Br
2(g)
2HBr
(g)

Solution :
r
H = bond enthalpies
reactants
- bond enthalpies
procducts

= [E
0
H-H
+ E
0
Br-Br
] - [2[E
0
H-Br
]
= (435 kJ mol
-1
+ 192 kJ mol
-1
) - 2 368 kJ mol
-1

= 627 mol
-1
- 736 kJmol
-1

= -109 kJmol
-1
[2 Marks]

4. Calculate the heat of reaction of the following reaction :
CO
2(g)
+ H
2(g)
CO
(g)
+ H
2
O
(g)
Given that the H
f
0
CO = - 110.5 kJ, H
f
0
CO
2
= - 393.8 kJ, H
f
0
H
2
O
(g)
= - 241.8 kJ respectively.
Solution : CO
2(g)
+ H
2(g)
CO
(g)
+ H
2
O
(g)

H = H
f

product
-H
f reactants

= H
f
CO
(g)
+ H
f
H
2
O(g) - CO
2(g)
- H
f
H
2(g)

= - 110.5 kJ - 241.8 kJ - (- 393.8 kJ
= - 352.3 kJ + 393.8 kJ = 41.5 kJ. [2 Marks]

5. Define
1. Isothermal Process
2. Adiabatic process



Ideal 21st Century Competitions www.21stideal.com 4
Solution : 1. Isothermal Process: When temperature of the system remains constant (i.e., T = 0) throughout the
process whether heat enters or leaves the system is called as isothermal process. Change of state e.g.,
freezing, melting, evaporation and condensation are the examples of isothermal process.
[1 Mark]
2. Adiabatic process: When heat change is zero (Q = 0) i.e., no heat enters or leaves the system
during any step of the process is known as adiabatic process. A reaction carried out in an isolated
system is an example of adiabatic process. [1 Mark]

6. Write Hesss Law of Constant Heat Summation
Solution : Hesss Law of Constant Heat Summation
When a chemical reaction gets completed directly in one step or indirectly in two or more steps, the
total energy change in the reaction remains same. i.e., the change does not depend on the path of a
chemical reaction. [1 Mark]
Reactant ,
Example Combustion of carbon
Method 1: C
(s)
+ O
2 (g)
CO
2 (g)
+ 94 Kcal H = 94 Kcal
Method 2: C
(s)
+1/2 O
2(g)
CO
(g)
+ 16.4 Kcal .......... [1]
CO
(s)
+ O
2 (g)
CO
2 (g)
+ 67.6 Kcal ........ [2]
On summing up equations [1] and [2], H = 94 Kcal [1 Marks]

III. Four sub-questions of 3 marks each (Attempt any THREE)
1. Explain the concept of maximum work.
Solution : Concept of Maximum work (Wmax)
Maximum work can be obtained only during isothermal and reversible process. It is denoted by W
max

In isothermal process, temperature of system remains constant at every stage.
Hence for such process change in internal energy of system remains constant
i.e E = 0.
Hence first law of thermodynamics which is mathematically expressed as, q = E - W becomes
q = -W. Thus all the heat supplied in isothermal process is used to perform work, hence work is
maximum. The value of work done by the system also depends on the magnitude of external opposing
pressure. The external opposing pressure has maximum possible value only in case of reversible


Ideal 21st Century Competitions
process because in such process, the driving and opposing forces differ by an infinitesimally small
value. Graphical representation of maximum work done

From the above graph it is evident th
steps.

2. Derive the expression for maximum work done in an
Solution : Mathematical expression for maximum work done in an
The a small amount of work done in a single step of small expansion of gas is
dw = PdV
In reversible process, an infinite number of such steps are involved. Henc
these steps is the maximum work. It is obtained by intergrating abovs equation in limits of initial
volume V1 to final volume V2.

(As per IUPAC conventions, work done in expansion is shown by negative sign)
Where, n = No. of moles of gas.

R = Molar gas constant.
T = Constant temperature in K. V
The unit of work depends upon the unit of molar gas constant, R.
In the compression of gas, work is positive
w
ecause in such process, the driving and opposing forces differ by an infinitesimally small
Graphical representation of maximum work done is as follow.
From the above graph it is evident that work done is maximum if the process is carried out in infinite

Derive the expression for maximum work done in an isothermal reversible process.
Mathematical expression for maximum work done in an isothermal reversible process :
The a small amount of work done in a single step of small expansion of gas is
In reversible process, an infinite number of such steps are involved. Henc
these steps is the maximum work. It is obtained by intergrating abovs equation in limits of initial
volume V1 to final volume V2.

(As per IUPAC conventions, work done in expansion is shown by negative sign)
of moles of gas.
weight of substance
n
molecular weight
| |
=
|
\


T = Constant temperature in K. V
1
= Initial volume of the gas. V
2
= Final volume of the gas.
The unit of work depends upon the unit of molar gas constant, R.
compression of gas, work is positive

1
max 10
2
V
W 2.303nRt log
V
=

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ecause in such process, the driving and opposing forces differ by an infinitesimally small
[2 Marks]

at work done is maximum if the process is carried out in infinite
[1 Mark]
isothermal reversible process.
isothermal reversible process :
The a small amount of work done in a single step of small expansion of gas is
In reversible process, an infinite number of such steps are involved. Hence, the totel work done in
these steps is the maximum work. It is obtained by intergrating abovs equation in limits of initial

(As per IUPAC conventions, work done in expansion is shown by negative sign)
= Final volume of the gas.
[2 Mark]



Ideal 21st Century Competitions www.21stideal.com 6
In terms of initial pressure P
1
and final pressure, P
2
the expression for maximum work is,

2
max 10
1
P
W 2.303 nRt log
P
=
(In expansion, work has -ve sign.)
In compression of a gas, work has positive sign.

2
max 10
1
P
W 2.303 nRt log
P
= [1 Mark]
3. Derive the Mathematical expression of first law of thermodynamics.
Solution : Mathematical form of first law of thermodynamics
E = q + W i.e., change in internal energy = heat change + work done
The following sign conventions are used for this equation
(i) Heat absorbed by the system = +q
(ii) Heat released by the system = q
(iii) Work done on the system by the surroundings = +W
(iv) Work done by the system on the surroundings = W [1 Mark]
(a) For isothermal process T = 0, hence E = 0
0 = q + W
q = W
(b) For isochoric process V=0, hence W = 0
E = q
i.e., heat given to system at constant volume changes into internal energy. [1 Mark]
(c) For adiabatic process q = 0
E = 0 + W
E = W
i.e., work done on system changes into internal energy
(d) For isobaric process
(i) When a gas expands against a constant pressure P such that P 0, the work done by
the system.
W = PV
E = q PV



Ideal 21st Century Competitions www.21stideal.com 7
(ii) If a gas expands in vacuum, the work done, W = 0, because P = 0.
E = q [1 Mark]

IV. Two sub-questions of 7 marks each (Attempt any ONE)
1. Derive a relation, q
p
= q
v
+ H = U + nRT.
Solution : Consider a reaction in which n
1
moles of gaseous reactant in initial state change to n
2
moles of
gaseous product in the final state.
Let H
1
, U
1
, P
1
, V
1
and H
2
, U
2
, P
2
, V
2
represent enthalpies, internal energies, pressures and volumes in
the initial and final states respectively then,

( ) ( )
T
1 2 g g
n A n B

[1 Mark]
H
1
, U
1
, P
1
, V
1
H
2
, U
2
, P
2
, V
2
The heat of reaction is given by enthalpy change H as,
H = H
2
H
1

By definition, H = U + PV
H
1
= U
1
+ P
1
V
1
and H
1
= U
2
+ P
2
V
2
H = (U
2
+ P
2
V
2
) (U
1
+ P
1
V
1
) [2 Mark]
Now, U = U
2
U
1

Since PV = nRT,
For initial state, P
1
V
1
= n
1
RT
For Final state, P
2
V
2
= n
2
RT
P
2
V
2
- P
1
V
1
= n
2
RT - n
1
RT
= (n
2
n
2
) RT
= nRT [2 Marks]
Where n =
Number of moles
of gaseous products
(
(

-
Number of moles
of gaseous reactants
(
(


H = U + nRT
If q
p
and q
v
are the heats involved in the reaction at constant pressure and constant volume
respectively, then since q
p
= H and q
v
= U.
q
p
= q
v
nRT