Thermodynamics and Thermochemistry 195

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Thermodynamics and Thermochemistry

(A) THERMODYNAMICS (4) Homogeneous system : A system is said to be
homogeneous when it is completely uniform throughout. A
Thermodynamics (Greek word thermo means heat and homogeneous system is made of one phase only. Examples are as
dynamics means motion) is the branch of science which deals with pure single solid, liquid or gas, mixture of gases and a true
the study of different forms of energy and the quantitative solution.
relationships between them. (5) Heterogeneous system : A system is said to be
The complete study of thermodynamics is based upon three heterogeneous when it is not uniform throughout, i.e., it consist of
generalizations called first, second and third law of two or more phases. Examples are : ice in contact with water, two
thermodynamics. These laws have been arrived purely on the basis or more immiscible liquids, insoluble solid in contact with a liquid,
of human experience and there is no theoretical proof for any of a liquid in contact with vapour, etc.
these laws. (6) Macroscopic system : A macroscopic system is one in
which there are a large number of particles (may be molecules,
1. Basic Concepts atoms, ions etc. )
1.1. System, surroundings and boundary : A specified 1.3. Macroscopic properties of the system
Thermodynamics deals with matter in terms of bulk (large
part of the universe which is under observation is called the system
number of chemical species) behaviour. The properties of the
and the remaining portion of the universe which is not a part of the
system which arise from the bulk behaviour of matter are called
system is called the surroundings.
macroscopic properties. The common examples of macroscopic
The system and the surroundings are separated by real or properties are pressure, volume, temperature, surface tension,
imaginary boundaries. The boundary also defines the limits of the viscosity, density, refractive index, etc.
system. The system and the surroundings can interact across the The macroscopic properties can be subdivided into two
boundary. types,
1.2. Types of systems (1) Intensive properties : The properties which do not
(1) Isolated system : This type of system has no depend upon the quantity of matter present in the system or size of
interaction with its surroundings. The boundary is sealed and the system are called intensive properties. Its examples are
insulated. Neither matter nor energy can be exchanged with pressure, temperature, density, specific heat, surface tension,
surrounding. A substance contained in an ideal thermos flask is an refractive index, viscosity, melting point, boiling point, volume per
example of an isolated system. mole, concentration etc.
(2) Closed system : This type of system can exchange (2) Extensive properties : The properties whose magnitude
depends upon the quantity of matter present in the system are
energy in the form of heat, work or radiations but not matter with
called extensive properties. Its examples are total mass, volume,
its surroundings. The boundary between system and surroundings
internal energy, enthalpy, entropy etc. These properties are
is sealed but not insulated. For example, liquid in contact with
additive in nature.
vapour in a sealed tube and pressure cooker. Any extensive property if expressed as per mole or per
(3) Open system : This type of system can exchange gram becomes an intensive property.
matter as well as energy with its surroundings. The boundary is (3) Path functions : The quantities which depend on the
neither sealed nor insulated. Sodium reacting with water in an path by which the state has been achieved e.g. work done and
open beaker is an example of open system. heat supplied.
 196 Thermodynamics and Thermochemistry
1.4. State of a system and State Variable p
Macroscopic properties which determine the state of a
system are referred to as state variables or state functions or
thermodynamic parameters. The change in the state properties
depends only upon the initial and final states of the system, but it is (a)
independent of the manner in which the change has been brought
about. In other words, the state properties do not depend upon a
path followed. Examples are : Pressure, volume, temperature
enthalpy, entropy, free energy etc.
1.5. Thermodynamic equilibrium : “A system is said to Vf Volume (V) Vi
have attained a state of thermodynamic equilibrium when it shows
no further tendency to change its property with time”. p

The criterion for thermodynamic equilibrium requires that

the following three types of equilibrium exist simultaneously in a
system, (b)
(1) Chemical Equilibrium : A system in which the
composition of the system remains fixed and definite.
(2) Mechanical Equilibrium : No chemical work is done
between different parts of the system or between the system and
surrounding. It can be achieved by keeping pressure constant. Volume (V) Vi
Vf
(3) Thermal Equilibrium : Temperature remains constant
i.e. no flow of heat between system and surrounding. Fig. 1
1.6. Thermodynamic processes : When the (a) P-V plot when pressure changes in finite steps (irreversible
thermodynamic system changes from one state to another, the condition) during compression from Vi to Vf.
operation is called a process. The various types of the processes (b) P-V plot when pressure changes in infinite steps (reversible
are condition) during compression from Vi to Vf. For both cases,
(1) Isothermal process : In this process operation is done the shaded area represents the work done on the gas.
at constant temperature. dT = 0 thus ∆E = 0 .
(2) Adiabatic process : In this process no exchange of (8) Thermodynamic cycle : It involves a process in which
heat takes place between the system and surroundings. The system initial state is regained.
is thermally isolated, i.e., dQ = 0 and its boundaries are insulated.
2. Internal Energy, Heat and Work
(3) Isobaric process : In this process the pressure remains
constant throughout the change i.e., dP = 0. 2.1. Internal energy (E) : “Every system having some
(4) Isochoric process : In this process volume remains quantity of matter is associated with a definite amount of energy.
constant throughout the change, i.e., dV = 0. This energy is known as internal energy.”
(5) Cyclic process : When a system undergoes a number
E = E translational + E rotational + E vibrational + E bonding + Eelectronic + ......
of different processes and finally returns to its initial state, it is
termed cyclic process. For a cyclic process dE = 0 and dH = 0. (1) Characteristics of internal energy
(6) Reversible process : A process which occurs
(i) Internal energy of a system is an extensive property.
infinitesimally slowly, i.e. opposing force is infinitesimally smaller
than driving force and when infinitesimal increase in the opposing (ii) Internal energy is a state property.
force can reverse the process, it is said to be reversible process. (iii) The change in the internal energy does not depend on
(7) Irreversible process : When the process occurs from the path by which the final state is reached.
initial to final state in single step in finite time and cannot be (iv) There is no change in internal energy in a cyclic process.
reversed, it is termed as irreversible process. Amount of entropy (v) The internal energy of an ideal gas is a function of
increases in irreversible process. temperature only.
Irreversible processes are spontaneous in nature. All natural (vi) Internal energy of a system depends upon the quantity
processes are irreversible in nature of substance, its chemical nature, temperature, pressure and
Graphical representation of four basic thermodynamic volume.
processes. (vii) The unit of E is ergs in CGS or joules in SI
Isobaric
1 Joule = 10 7 ergs.
Pressure

Isochoric

Isothermal
(2) Change in internal energy ( ∆E ) : It is neither
Adiabatic possible nor necessary to calculate the absolute value of internal
energy of a system then, ∆E = E f − Ein ; ∆E is positive if
E f > Ein and negative if E f < Ein .
Volume
 Thermodynamics and Thermochemistry 197
2.2. Heat (q) and work (w) : The energy of a system may All these form of energy can be converted into heat as well
increase or decrease in several ways but two common ways are as into one another.
heat and work. Note : Unit of heat is calorie. 1 Nutritional calorie (or 1 Cal)
Heat is a form of energy. It flows from one system to is actually 1 K Cal.
another because of the difference in temperature between them.
Heat flows from higher temperature to lower temperature.
3. Zeroth Law of Thermodynamics
Therefore, it is regarded as energy on the move. This law forms the basis of concept of temperature. This law
Work is said to be performed if the point of application of can be stated as follows,
force is displaced in the direction of the force. It is equal to the “If a system A is in thermal equilibrium with a system C and
force multiplied by the displacement (distance through which the if B is also in thermal equilibrium with system C, then A and B are
force acts). in thermal equilibrium with each other whatever the composition
There are three main types of work which we generally of the system.”
come across. These are gravitational work, electrical work and
A C B C
mechanical work.
Mechanical work = Force × displacement = F.d
A B
Electrical work = potential difference × charge = V.q
Gravitational work = mgh 4. First Law of Thermodynamics
(1) Units of heat and work : The heat changes are Helmholtz and Robert Mayer proposed first law of
measured in calories (cal), Kilo calories (kcal), joules (J) or kilo thermodynamics. This law is also known as law of conservation of
joules (kJ). These are related as, 1 cal = 4.184 J; 1kcal = 4.184kJ energy. It states that,
The S.I. unit of heat is joule (J) or kilo joule. The Joule (J) is “Energy can neither be created nor destroyed although it
equal to Newton-metre (1 J= 1 Nm). can be converted from one form into another.”
Work is measured in terms of ergs or joules. The S.I. unit of E 2 − E1 = ∆E = q + w
work is Joule.
i.e. (Change in internal energy) = (Heat added to the
1 Joule = 10 7 ergs = 0.2390 cal. system) +(Work done on the system)
1 cal > 1 joule > 1 erg If a system does work (w) on the surroundings, its internal
(2) Sign conventions for heat and work energy decreases. In this case, ∆E = q + (−w) = q − w
Heat absorbed by the system = q positive i.e.(Change in internal energy)=(Heat added to the system)
Heat evolved by the system = q negative – (work done by the system)
Work done on the system = w positive The relationship between internal energy, work and heat is a
Work done by the system = w negative. mathematical statement of first law of thermodynamics.
2.3. Energy : Energy is the capacity of doing work. Its S.I. 5. Enthalpy and Enthalpy change
unit is Joule.
Heat content of a system at constant pressure is called
Some forms of energy are :
enthalpy denoted by ‘H’.
(1) Kinetic Energy : It is the energy possessed by a
system by virtue of its motion. From first law of thermodynamics, q = E + PV …….(i)
(2) Potential Energy : It is the energy possessed by a Heat change at constant pressure can be given as
system by virtue of its position. e.g. energy due to structure of the ∆q = ∆E + P∆V …….(ii)
body or due to configuration w.r.t. other bodies. At constant pressure heat can be replaced by enthalpy.
(3) Electric Energy : It is equal to the product of potential
∆H = ∆E + P∆V ……(iii)
and charge.
∴∆H = Heat change or heat of reaction (in chemical
(4) Radiant Energy : The energy associated with the
photon of light. process) at constant pressure
(5) Chemical Energy : The energy stored in all substances ∆E = Heat change or heat of reaction at constant volume.
and which appears when system or substance undergo In case of solids and liquids participating in a reaction,
transformation. ∆H = ∆E (P∆V ≈ 0)
(6) Mass Energy : It is the energy due to conversion of
Difference between ∆H and ∆E is significant when gases
mass into energy, which can be calculated from the relation,
are involved in chemical reaction.
E = mc 2 .
∆H = ∆E + P∆V
(7) Nuclear Energy : The energy liberated during nuclear
∆H = ∆E + ∆nRT
transformation.
(8) Heat energy : The energy transferred from one body to P∆V = ∆nRT
another is a result of temperature difference. Here, ∆n = nP – nR
 198 Thermodynamics and Thermochemistry

6. Specific and Molar Heat Capacity Pext

Pext – dP
6.1. Specific heat (or specific heat capacity) of a
substance is the quantity of heat (in calories, joules, kcal, or kilo
joules) required to raise the temperature of 1g of that substance
dV
through 1o C . It can be measured at constant pressure (c p ) and at
constant volume (c v ) .
Pgas
6.2. Molar heat capacity of a substance is the quantity of Pgas
heat required to raise the temperature of 1 mole of the substance
by 1o C . Fig. 2
∴ Molar heat capacity = Specific heat capacity × Molecular Since the system is in thermal equilibrium with the
weight, i.e., Cv = cv × M and C p = c p × M . surroundings, the infinitesimally small cooling produced due to
6.3. Since gases on heating show considerable tendency expansion is balanced by the absorption of heat from the
towards expansion if heated under constant pressure conditions, surroundings and the temperature remains constant throughout the
an additional energy has to be supplied for raising its temperature expansion.
The work done by the gas in each step of expansion can be
by 1o C relative to that required under constant volume
conditions, i.e., given as, dw = −(Pext − dP )dV = − Pext .dV − dP . dV
C p > Cv or C p = Cv + Work done in expansion, P∆V (= R) [Link] , the product of two infinitesimal quantities, is neglected.
where, C p = molar heat capacity at constant pressure The total amount of work done by the isothermal reversible
expansion of the ideal gas from volume V1 to volume V2 is, given
Cv = molar heat capacity at constant volume.
V2 V
6.4. Some useful relations of Cp and Cv as, w = −nRT log e or w = −2.303nRT log 10 2
C p − Cv = R = 2 calories = 8.314 J V1 V1
At constant temperature, according to Boyle’s law,
Table 1 : Relationship between Molar Heat Capacities for
V P P
Different Type of Gases P1 V1 = P2 V2 or 2 = 1 So, w = −2.303nRT log 10 1
V1 P2 P2
Molar Heat Molar Heat Cp
=γ Isothermal compression work of an ideal gas may be derived
Capacity at Capacity at Cv similarly and it has exactly the same value with positive sign.
Type of Gas
Constant Constant (Poisson’s V P
Pressure (Cp) Volume (Cv) wcompression = 2.303nRT log 1 = 2.303nRT log 2
Ratio) V2 P1
Monoatomic 5/2 R= 5 cal. 3/2 R= 3 cal. 5/3= 1.66 (2) Work done in irreversible isothermal expansion :
Two types of irreversible isothermal expansions are observed, i.e.,
Diatomic 7/2 R= 7 cal. 5/2 R= 5 cal. 7/5= 1.4
(a) Free expansion and (b) Intermediate expansion. In free
Polyatomic 4 R= 8 cal. 3 R= 6 cal. 4/3= 1.33 expansion, the external pressure is zero, i.e., work done is zero
when gas expands in vacuum. In intermediate expansion, the
7. Expansion of an Ideal Gas external pressure is less than gas pressure. So, the work done when
volume changes from V1 to V2 is given by
7.1. Isothermal expansion : For an isothermal V2
expansion, ∆T = 0 ; ∆E = 0.
According to first law of thermodynamics,
w=−
∫V1
Pext × dV = − Pext (V2 − V1 )

∆E = q + w ∴q = −w Since Pext is less than the pressure of the gas, the work
This shows that in isothermal expansion, the work is done done during intermediate expansion is numerically less than the
by the system at the expense of heat absorbed. work done during reversible isothermal expansion in which Pext is
Since for isothermal process, ∆E and ∆T are zero almost equal to Pgas .
respectively. Hence, ∆H = 0
7.2. Adiabatic expansion : In adiabatic expansion, no
(1) Work done in reversible isothermal expansion :
heat is allowed to enter or leave the system, hence, q = 0 .
Consider an ideal gas enclosed in a cylinder fitted with a weightless
and frictionless piston. The cylinder is not insulated. The external According to first law of thermodynamics,
pressure, Pext is equal to pressure of the gas, Pgas . ∆E = q + w ∴ ∆E = w

Pext = Pgas = P work is done by the gas during expansion at the expense of
internal energy. In expansion, ∆E decreases while in compression
If the external pressure is decreased by an infinitesimal ∆E increases.
amount dP, the gas will expand by an infinitesimal volume, dV. As
The molar specific heat capacity at constant volume of an
a result of expansion, the pressure of the gas within the cylinder
ideal gas is given by
falls to Pgas − dP , i.e., it becomes again equal to the external
 dE 
pressure and, thus, the piston comes to rest. Such a process is Cv =   or dE = Cv .dT
repeated for a number of times, i.e., in each step the gas expands  dT  v
by a volume dV. and for finite change ∆E = Cv ∆T So, w = ∆E = Cv ∆T
 Thermodynamics and Thermochemistry 199

The value of ∆T depends upon the process whether it is 8. Joule-Thomson Effect

reversible or irreversible. The phenomenon of producing lowering of temperature
(1) Reversible adiabatic expansion : The following when a gas is made to expand adiabatically from a region of high
relationships are followed by an ideal gas under reversible pressure into a region of low pressure, is known as Joule-Thomson
adiabatic expansion. effect.
Porous plug
γ
PV = constant DT ∝ DP
where, P = External pressure, V = Volume V1 V2
Cp
γ =
Cv P2 P2
T1 T2
where, C p = Molar specific heat capacity at constant
pressure, Cv = Molar specific heat capacity at constant volume.
γ γ −1 1− γ
 T1  P  P  X Y
  = 1  =  2 
T  P  Fig. 4
 2   2  P1 
During this process, enthalpy remains constant. It is,
knowing γ , P1 , P2 and initial temperature T1 , the final
therefore, called isoenthalpic process.
temperature T2 can be evaluated. The actual change in temperature on expansion of the gas
(2) Irreversible adiabatic expansion : In free expansion, is expressed in terms of Joule–Thomson coefficient (µ), defined
the external pressure is zero, i.e., work done is zero. Accordingly, as
∆E which is equal to w is also zero. If ∆E is zero, ∆T should be  ∂T 
µ = 
zero. Thus, in free expansion (adiabatically), ∆T = 0 , ∆E = 0 ,  ∂P  H
w = 0 and ∆H = 0 . i.e. it is the temperature change in degrees produced by a
In intermediate expansion, the volume changes from V1 to drop of one atmospheric pressure when the gas expands under
conditions of constant enthalpy.
V2 against external pressure, Pext .
(1) For cooling, µ = +ve (because dT and dP both will
 RT RT  be – ve)
w = − Pext (V2 − V1 ) = − Pext  2 − 1 
P
 2 P1  (2) For heating, µ = −ve (because dT = +ve, dP = – ve)
 T P − T1 P2  (3) µ = 0 means dT = 0 for any value of dP, i.e., there is
= − Pext  2 1 × R

 P1 P2  neither cooling nor heating.
The temperature at which a real gas shows no cooling or
 T P − T1 P2 
or w = Cv (T2 − T1 ) = − RPext  2 1  heating effect on adiabatic expansion (i.e. µ = 0), is called
P1 P2 
  Inversion temperature. Below this temperature it shows cooling
effect while above this temperature, it shows heating effect.
Comparison between Isothermal and Adiabatic Process
Most of the gases have inversion temperature above room
If a gas expands isothermally and adiabatically from volume temperature. H 2 and He have low inversion temperatures (being
Vi to Vf then from the slope of the graph it is clear that graph 1 – 80°C and –240°C respectively). That is why they show heating
represent isothermal process and graph 2 represent adiabatic effect at room temperature.
process.
9. Spontaneous and Non-spontaneous Processes
Work done Wisothermal > Wadiabatic
A process which can take place by itself under the given set
Final pressure Pisothermal > Padiabatic of conditions once it has been initiated if necessary, is said to be a
spontaneous process. In other words, a spontaneous process is a
Final temperature Tisothermal > Tadiabatic process that can occur without work being done on it. The
spontaneous processes are also called feasible or probable
P processes.
On the other hand, the processes which are forbidden and
are made to take place only by supplying energy continuously from
outside the system are called non-spontaneous processes. In other
1 words, non spontaneous processes can be brought about by doing
2 work.
Examples of Spontaneous and Non-spontaneous processes
V (1) The diffusion of the solute from a concentrated solution
Vi Vf
to a dilute solution occurs when these are brought into contact is
Fig. 3 : Isothermal and Adiabatic Process spontaneous process.
 200 Thermodynamics and Thermochemistry
(2) Mixing of different gases is spontaneous process. Thus, the larger the temperature difference between high
(3) Heat flows from a hot reservoir to a cold reservoir is and low temperature reservoirs, the more the heat converted into
spontaneous process. work by the heat engine.
(4) Electricity flows from high potential to low potential is T − T1
spontaneous process. Since 2 < 1 , it follows that w < q . This means that
T2
(5) Expansion of an ideal gas into vacuum through a
only a part of heat absorbed by the system at the higher
pinhole is spontaneous process.
temperature is transformed into work. The rest of the heat is given
All the above spontaneous processes become non-
spontaneous when we reverse them by doing work. out to surroundings. The efficiency of the heat engine is always less
than 1. This has led to the following enunciation of the second law
Spontaneous process and Enthalpy change : A
spontaneous process is accompanied by decrease in internal of thermodynamics.
energy or enthalpy, i.e., work can be obtained by the spontaneous “It is impossible to convert heat into work without
process. It indicates that only exothermic reactions are compensation.”
spontaneous. But the melting of ice and evaporation of water are Note :
endothermic processes which also proceed spontaneously. It • Efficiency of steam engine is 8–15%.
means, there is some other factor in addition to enthalpy change
• Efficiency of petrol engine is 40%.
(∆H ) which explains the spontaneous nature of the system. This
• Efficiency of Diesel engine is 50–55%.
factor is entropy.
• Efficiency of Heat engine is more at the top of a hill than a
10. Second Law of Thermodynamics plane since, Thill < Tplane .
All the limitations of the first law of thermodynamics can be
11. Entropy and Entropy Change
removed by the second law of thermodynamics. This law is
generalisation of certain experiences about heat engines and 11.1. Definition : Entropy is a thermodynamic state
refrigerators. It has been stated in a number of ways, but all the quantity which is a measure of randomness or disorder of the
statements are logically equivalent to one another. molecules of the system.
10.1. Statements of the law Entropy is represented by the symbol “S”. It is difficult to
define the actual entropy of a system. It is more convenient to
(1) Kelvin statement : “It is impossible to derive a
define the change of entropy during a change of state.
continuous supply of work by cooling a body to a temperature
The entropy change of a system may be defined as the
lower than that of the coldest of its surroundings.”
integral of all the terms involving heat exchanged (q) divided by
(2) Clausius statement : “It is impossible for a self acting the absolute temperature (T) during each infinitesimally small
machine, unaided by any external agency, to transfer heat from change of the process carried out reversibly at constant
one body to another at a higher temperature or Heat cannot itself temperature.
pass from a colder body to a hotter body, but tends invariably 1 q
towards a lower thermal level.” ∫ds =
T ∫ δqrev ⇒ ∆S = S final − Sinitial = rev
T
(3) Ostwald statement : “It is impossible to construct a If heat is absorbed, then ∆S = +ve and if heat is evolved,
machine functioning in cycle which can convert heat completely then ∆S = −ve.
into equivalent amount of work without producing changes
elsewhere, i.e., perpetual motions are not allowed.” Qrev/T is a measure of increase in disorder of the system. This
(4) Carnot statement : “It is impossible to take heat from can be explained on the basis that absorption of heat into a
a hot reservoir and convert it completely into work by a cyclic system leads to the vigourous movement of the molecules due
process without transferring a part of it to a cold reservoir.” to increased kinetic energy. Moreover, if heat is absorbed at
10.2. Proof of the law : No rigorous proof is available for low temperature, it becomes more disordered than when the
same amount of heat is added at higher temperature (as T is
the second law. The formulation of the second law is based upon
placed in denominator in the equation).
the observations and has yet to be disproved. No deviations of this
law have so far been reported. However, the law is applicable to
11.2. Units of entropy : Since entropy change is
cyclic processes only.
expressed by a heat term divided by temperature, it is expressed in
10.3 The Carnot Cycle terms of calorie per degree, i.e., cal deg–1. In SI units, the entropy is
Carnot, a French engineer, in 1824 employed merely
expressed in terms of joule per degree Kelvin, i.e., JK −1 entropy is
theoretical and an imaginary reversible cycle known as carnot cycle
also extensive property, i.e., it depends on mass of substance;
to demonstrate the maximum convertibility of heat into work.
hence units of entropy are expressed as cal deg −1 mol −1 or
The system consists of one mole of an ideal gas enclosed in
a cylinder fitted with a piston, which is subjected to a series of four ( JK −1mol −1 ).
successive operations. 11.3. Characteristics of entropy : The important
For cyclic process, the essential condition is that net work characteristics of entropy are summed up below
done is equal to heat absorbed. This condition is satisfied in a (1) Entropy is an extensive property. Its value depends upon
carnot cycle. the amount of the substance present in the system.
w T2 − T1 (2) Entropy of a system is a state function. It depends upon
= = Thermodynamic efficiency
q T2 the state variables (T , P , V , n) .
 Thermodynamics and Thermochemistry 201
(3) The change in entropy in going from one state to (1) When T and V are two variables,
another is independent of the path. T2 V
(4) The change in entropy for a cyclic process is always zero. ∆S = nCv ln + nR ln 2 . Assuming Cv is constant
T1 V1
(5) The total entropy change of an isolated system is equal
to the entropy change of system and entropy change of the (2) When T and P are two variables,
surroundings. The sum is called entropy change of universe. T p
∆S = nCP ln 2 − nR ln 2 . Assuming C p , is constant
∆Suniverse = ∆Ssys + ∆SSurr T1 p1
(i) Thus, for an isothermal process (T constant),
(i) In a reversible process, ∆Suniverse = 0 and, therefore
V p
∆S = nR ln 2 or = −nR ln 2
∆Ssys = − ∆SSurr V1 p1
(ii) In an irreversible process, ∆Suniverse > 0 . This means that (ii) For isobaric process (p constant),
there is increase in entropy of universe in spontaneous changes. T V
∆S = n C p ln 2 = nC p ln 2
(6) Entropy is a measure of unavailable energy for useful T1 V1
work. (iii) For isochoric process (V constant),
Unavailable energy = Entropy × Temperature T p
∆S = n Cv ln 2 = nCv ln 2
11.4. Entropy changes in system & surroundings and T1 p1
total entropy change for Exothermic and Endothermic (iv) Entropy change during adiabatic expansion : In such
reactions : Heat increases the thermal motion of the atoms or process q=0 at all stages. Hence ∆S = 0 . Thus, reversible
molecules and increases their disorder and hence their entropy. In adiabatic processes are called isentropic process.
case of an exothermic process, the heat escapes into the
12. Free Energy and Free Energy change
surroundings and therefore, entropy of the surroundings increases
on the other hand in case of endothermic process, the heat enters Gibb's free energy (G) is a state function and is a measure of
the system from the surroundings and therefore, the entropy of the maximum work done or useful work done from a reversible
surroundings decreases. reaction at constant temperature and pressure.
In general, there will be an overall increase of the total 12.1. Characteristics of free energy
entropy (or disorder) whenever the disorder of the surroundings is (1) The free energy of a system is the enthalpy of the system
greater than the decrease in disorder of the system. The process minus the product of absolute temperature and entropy i.e.,
will be spontaneous only when the total entropy increases. G = H − TS
11.5. Entropy change during phase transition : The
(2) Like other state functions E, H and S, it is also expressed
change of matter from one state (solid, liquid or gas) to another is
as ∆G . Also ∆G = ∆H − T∆Ssystem where ∆S is entropy change for
called phase transition. Such changes occur at definite temperature
such as melting point (solid to liquid), boiling point (liquid to system only. This is Gibb's Helmholtz equation.
vapours) etc and are accompanied by absorption or evolution of (3) At equilibrium ∆G = 0
heat. (4) For a spontaneous process decrease in free energy is
When a solid changes into a liquid at its fusion temperature, noticed i.e., ∆G = −ve .
there is absorption of heat (latent heat). Let ∆H fusion be the molar (5) At absolute zero, T∆S is zero. Therefore if ∆G is – ve,
heat of fusion. The entropy change will be ∆H should be – ve or only exothermic reactions proceed
spontaneously at absolute zero.
∆H fusion
∆S f = (6) ∆Gsystem = T∆Suniverse , where ∆H = 0
Tf
Similarly, if the latent heat of vaporisation and sublimation (vii) The standard free energy change,
are denoted by ∆H vap and ∆H sub , respectively, the entropy of ∆G o = −2.303 RT log 10 K, where K is equilibrium constant.
vaporisation and sublimation are given by (i) Thus if K > 1, then ∆G o = −ve thus reactions with
∆H vap ∆H sub equilibrium constant K >1 are thermodynamically spontaneous.
∆Svap = and ∆Ssub =
Tb Ts
(ii) If K<1, then ∆G o = +ve and thus reactions with
Since ∆H f , ∆H vap and ∆H Sub are all positive, these equilibrium constant K<1 are thermodynamically spontaneous in
processes are accompanied by increase of entropy and the reverse reverse direction.
processes are accompanied by decrease in entropy. 12.2. Criteria for spontaneity of reaction : For a
11.6. Entropy change for an ideal gas : In going from spontaneous change ∆G = −ve and therefore use of
initial to final state, the entropy change, ∆S for an ideal gas is ∆G = ∆H − T∆S, provides the following conditions for a change to
given by the following relations, be spontaneous.
 202 Thermodynamics and Thermochemistry

Table 2 : Criteria for spontaneity of reaction

∆H ∆S ∆G Reaction characteristics Example

– + Always negative Reaction is spontaneous at all temperatures 2O3( g ) → 3O2( g )

+ – Always positive Reaction is non spontaneous at all temperatures 3O2( g ) → 2O3( g )

– – Negative at low temperature but Reaction is spontaneous at low temperature but CaO(s ) + CO2( g ) → CaCO3(s )
positive at high temperature becomes non spontaneous at high temperature

+ + Positive at low temperature but Reaction is non spontaneous at low temperature CaCO3(s) → CaO(s ) + CO2(g)
negative at high temperature but becomes spontaneous at high temperature

Table 3 : Value of Parameters in Different Types of Expansion of an Ideal Gas

Process ∆H ∆T ∆E(∆U ) ∆Q ∆S W

Reversible Isothermal Work done

Expansion V2
(W) = − nRT ln
Change in V1
Change in Change in Change in
Change in Internal Entropy
Enthalpy temperature Heat
Irreversible Isothermal Energy ( ∆E ) = 0 V W= 0
( ∆ Q ) = –W ∆S = nR ln 2
Expansion- Free ∆H = 0 ( ∆T ) = 0 V1
Irreversible Isothermal W = − P (V2 − V1 )
Expansion- Intermediate

Reversible Adiabatic ∆H= nCp∆T ∆T < 0 ∆E = W W=

nR
(T2 − T1 )
Expansion γ −1

Irreversible Adiabatic ∆H = 0 ∆T = 0 ∆E = 0 W= 0
Expansion- Free ∆Q = 0 ∆S = 0

Irreversible Adiabatic ∆H= nCp∆T ∆T < 0 ∆E = W T T 

Expansion- Intermediate W = − RPext  2 − 1 
 P2 P1 

13. Third Law of Thermodynamics (2) Solids having mixtures of isotopes do not have zero
entropy at 0 K. For example, entropy of solid chlorine is not zero at
This law was first formulated by German chemist Walther
0 K.
Nernst in 1906. According to this law,
(3) Crystals of CO, N2O, NO, H2O, etc. do not have perfect
“The entropy of all perfectly crystalline solids is zero at the order even at 0 K thus their entropy is not equal to zero.
absolute zero temperature. Since entropy is a measure of disorder,
(B) THERMOCHEMISTRY
it can be interpreted that at absolute zero, a perfectly crystalline
“Thermochemistry is a branch of physical chemistry which is
solid has a perfect order of its constituent particles.”
concerned with energy changes accompanying chemical
The most important application of the third law of transformation. It is also termed as chemical energetics. It is based
thermodynamics is that it helps in the calculation of absolute on the first law of thermodynamics.”
entropies of the substance at any temperature T.
1. Exothermic and Endothermic Reactions
T Cp T Cp
∆S = ST − S0 = ∫ 0 T
dT ; Since S0 = 0 ⇒ ST = ∫ 0 T
dT = C p ln T 1.1. Exothermic reactions : The chemical reactions
which proceed with the evolution of heat energy are called
Where CP is the heat capacity of the substance at constant
exothermic reactions. The heat energy produced during the
pressure and is supposed to remain constant in the range of 0 to T. reactions is indicated by writing +q or more precisely by giving the
Limitations of the law : actual numerical value on the products side. In general exothermic
(1) Glassy solids even at 0 K have entropy greater than zero. reactions may be represented as, A + B → C + D + q (heat energy)
 Thermodynamics and Thermochemistry 203
In the exothermic reactions the enthalpy of the products will 2.1. Factors which influence the heat of reaction :
be less than the enthalpy of the reactants, so that the enthalpy There are a number of factors which affect the magnitude of heat
change is negative as shown below of reaction.
∆H = H p − H r ; H p < H r ; ∆H = − ve (1) Physical state of reactants and products : Heat
energy is involved for changing the physical state of a chemical
Examples : (i) C(s ) + O2( g ) → CO2( g ) + 393.5kJ
substance. For example in the conversion of water into steam, heat
(at constant temperature and pressure) is absorbed and heat is evolved when steam is condensed.
or C(s ) + O2( g ) → CO2( g ) ; ∆H = −393.5kJ Considering the following two reactions
1
1 H 2( g ) + O2( g ) = H 2O( g ) ; ∆H = − 57.8 kcal
(ii) H 2( g ) + O2 → H 2O(l ) ; ∆H = −285.8kJ 2
2 ( g)
1
(iii) Fermentation is also an example of exothermic H 2( g ) + O2 = H 2 O(l ) ; ∆H = − 68.32 kcal
reaction. 2 (g )
Reactant Products It is observed that there is difference in the value of ∆H if
Hp
Hr water is obtained in gaseous or liquid state. ∆H value in second
∆H=Hp–Hr = – ve ∆H=Hp–Hr = + ve case is higher because heat is evolved when steam condenses.
H (Hp<Hr) H (Hp>Hr) Hence, physical state always affects the heat of reaction.

Hr (2) Allotropic forms of the element : Heat energy is also

Hp
Products Reactant involved when one allotropic form of an element is converted into
Reaction path
another. Thus, the value of ∆H depends on the allotropic form
Reaction path
Enthalpy change during an Enthalpy change during an used in the reaction. For example, the value of ∆H is different
exothermic reaction endothermic reaction when carbon in the form of diamond or in amorphous form is
1.2. Endothermic reactions : The chemical reactions used.
which proceed with the absorption of heat energy are called C (diamond) +O2( g ) → CO2( g ) ; ∆H = − 94.3 kcal
endothermic reactions. Since the heat is added to the reactants in
C (amorphous) +O2( g ) → CO2( g ) ; ∆H = − 97.6 kcal
these reactions, the heat absorbed is indicated by either putting (–)
or by writing the actual numerical value of heat on the reactant side The difference between the two values is equal to the heat
absorbed when 12g of diamond is converted into 12g of
A + B → C + D − q (heat energy)
amorphous carbon. This is termed as heat of transition.
The heat absorbed at constant temperature and constant
C (diamond) → C (amorphous); ∆H = 3.3Kcal
pressure measures enthalpy change. Because of the absorption of
heat, the enthalpy of products will be more than the enthalpy of (3) Temperature : Heat of reaction has been found to
the reactants. Consequently, ∆H will be positive (+ve ) for the depend upon the temperature at which reaction is occurring. The
variation of the heat of reaction with temperature can be calculated
endothermic reactions.
by using Kirchhoff's equation.
∆H = H p − H r ; H p > H r ; ∆H = +ve
∆H T2 − ∆H T1
Example : (i) N 2( g ) + O2( g ) → 2 NO( g ) ; ∆H = +180.5 kJ = ∆CP
T2 − T1
(ii) C( s) + 2S(s) → CS2(l ) ∆H = +92.0kJ Kirchhoff's equation at constant volume may be given as,
(iii) Preparation of ozone by passing silent electric ∆ET2 − ∆ET1
= ∆Cν
discharged through oxygen is the example of endothermic T2 − T1
reaction.
(4) Reaction carried out at constant pressure or
(iv) Evaporation of water is also the example of constant volume : When a chemical reaction occurs at constant
endothermic reaction. volume, the heat change is called the internal energy of reaction at
For exothermic reaction : ∆H or ∆E = −ve constant volume. However, most of the reactions are carried out at
For endothermic reaction : ∆H or ∆E = +ve constant pressure; the enthalpy change is then termed as the
enthalpy of reaction at constant pressure. The difference in the
2. Heat of Reaction or Enthalpy of Reaction values is negligible when solids and liquids are involved in a
Heat of reaction is defined as the amount of heat evolved or chemical change. But, in reactions which involve gases, the
absorbed when quantities of the substances indicated by the difference in two values is considerable.
chemical equation have completely reacted. The heat of reaction ∆E + ∆nRT = ∆H or qv + ∆nRT = q p
(or enthalpy of reaction) is actually the difference between the ∆E = q v = heat change at constant volume;
enthalpies of the products and the reactants when the quantities of
the reactants indicated by the chemical equation have completely ∆H = q p = heat change at constant pressure,
reacted. Mathematically, ∆n = Total number of moles of gaseous products
Enthalpy of reaction (heat of reaction) = ∆H = ΣH P − ΣH R – Total number of moles of gaseous reactants.
 204 Thermodynamics and Thermochemistry

2.2. Types of heat of reaction (ii) Enthalpies of formation : Enthalpies of formation of

(1) Heat of formation : It is the quantity of heat evolved various compounds, which are not directly obtained, can be
or absorbed (i.e. the change in enthalpy) when one mole of the calculated from the data of enthalpies of combustions easily by the
substance is formed from its constituent elements under given application of Hess's law.
conditions of temperature and pressure. It is represented by ∆H f . Heat of reaction = Σ Heat of combustion of reactants
– Σ Heat of combustion of products.
When the temperature and pressure are as 25°C and
1 atmospheric pressure, the heat of formation under these (3) Heat of neutralisation : It is the amount of heat
conditions is called standard heat of formation. It is usually evolved (i.e., change in enthalpy) when one equivalent of an acid
is neutralised by one equivalent of a base in fairly dilute solution,
represented by ∆H of . e.g., Neutralisation reactions are always exothermic reaction and
The standard heat of formation of 1 mole of NH 3( g ) and the value of ∆H is (−ve ) .

1 mole of HCl (g ) . HCl(aq.) + NaOH (aq.) → NaCl(aq.) + H 2O

∆H = − 13.7 kcal
1 3
N 2 (g) + H 2 (g) → NH 3 (g); ∆H f = −11kcal The heat of neutralisation of a strong acid against a strong
2 2
1 1 base is always constant (13.7 kcal or 57 kJ mole −1 ) . It is because
H 2 (g) + Cl 2 (g) → HCl ; ∆H f = −22 kcal
2 2 in dilute solutions all strong acids and bases ionise completely and
It may be calculated by thus the heat of neutralisation in such cases is actually the heat of
formation of water from H + and OH − ions, i.e.,
∆H 0 = [Σ∆H 0(products) – Σ∆H 0(Reactants) ]
H + + OH − → H 2 O; ∆H = − 13 .7 kcal
(2) Heat of combustion : It is the amount of heat evolved
or absorbed (i.e. change in enthalpy) when one mole of the In case of neutralisation of a weak acid or a weak base
against a strong base or acid respectively, since a part of the
substance is completely burnt in air or oxygen. For example
evolved heat is used up in ionising the weak acid or base, it is
CH 4 ( g ) + 2O2( g ) → CO2( g ) + 2H 2O(l ) ; ∆H = − 192 kcal
always less than 13 .7 kcal mole −1 (57 kJ mole −1 ) . For example,
C2 H 6( g ) + 3.5 O2( g ) → 2CO2( g ) + 3 H 2O(l ) ; ∆H = − 372.8 kcal HCN + NaOH → NaCN (aq.) + H 2O
(aq.) (aq.)
It may be calculated by ∆H = − 2.9 kcal
∆H 0 = [Σ∆H 0f (Products) – ΣH 0f (Reactants) ] HCN H + CN ; ∆H = 10.8 Kcal
+ –
(aq.)

The enthalpy or heat of combustion has a number of 10.8 KCal of heat is absorbed for ionisation of HCN . It is
applications. Some of these are described below, heat of dissociation or ionisation
(i) Calorific value of foods and fuels : Energy is needed for (4) Heat of solution : It is the amount of heat evolved or
the working of all machines. Even human body is no exception. absorbed (i.e., change in enthalpy) when one mole of the solute is
Coal, petroleum, natural gas etc. serve as the principal sources of dissolved completely in excess of the solvent (usually water). For
energy for man-made machines, the food which we eat serves as a example,
source of energy to our body. NH 4 Cl(s ) + H 2O(l ) → NH 4 Cl(aq.) ; ∆H = + 3.90 kcal
The energy released by the combustion of foods or fuels is BaCl 2(s ) + H 2O(l ) → BaCl 2(aq.) ; ∆H = − 2.70 kcal
usually compared in terms of their combustion energies per gram.
(5) Heat of hydration : It is the amount of heat evolved or
It is known as calorific value. The amount of heat produced in
absorbed (i.e. change in enthalpy) when 1 mole of an anhydrous
calories or Joules when one gram of a substance (food or fuel) is
or a partially hydrated salt combines with the required number of
completely burnt or oxidised.
moles of water to form a specific hydrate. For example,
When methane burns, 890.3 kJ mol–1 of energy is released. CuSO4 (s ) + 5 H 2 O(l ) → CuSO4 . 5 H 2 O(s ) ; ∆H = − 18.69 [Link].
CH 4(g ) + 2O2(g ) → CO2( g) + 2H 2O(l ) ; ∆H CH 4 = −890.3 kJ
1 mole (16g)
(6) Heat of vapourisation : When a liquid is allowed to
evaporate, it absorbs heat from the surroundings and evaporation
890.3
So, the calorific value of methane = − = −55.6kJ / g is accompanied by increase in enthalpy. For example: 10.5 kcal is
16
the increase in enthalpy when one mole of water is allowed to
Calorific values of some fuels
evaporate at 25 o C . When the vapours are allowed to condense to
Calorific value liquid state, the heat is evolved and condensation of vapour is
Fuel (solid)
(B. Th. U. Per lb) accompanied by decrease in enthalpy.
Cellulose 7500 The evaporation and condensation can be represented as,
Wood (dry) 8600 H 2O(l ) → H 2O( g ) ; ∆H = + 10.5 kcals (+43.93 kJ )
Peat 9000 H 2O( g ) → H 2O(l ) ; ∆H = − 10.5 kcals (−43.93 kJ )
Lignite (Brown coal) 11700
Thus the change in enthalpy when a liquid changes into
Bituminous coal 14950 vapour state or when vapour changes into liquid state is called heat
Welch steam coal 15720 of vapourisation.
 Thermodynamics and Thermochemistry 205
(7) Heat of fusion : When a solid is allowed to melt, it 3.2. Hess's law (the law of constant heat summation) :
changes into liquid state with the absorption of heat (increase in This law was presented by Hess in 1840. According to this law “If a
enthalpy) and when a liquid is allowed to freeze, it changes into chemical reaction can be made to take place in a number of ways
solid with the evolution of heat (decrease in enthalpy). The change in one or in several steps, the total enthalpy change (total heat
in enthalpy of such type of transformations is called enthalpy of change) is always the same, i.e. the total enthalpy change is
fusion. For example, independent of intermediate steps involved in the change.” The
H 2O(ice ) → H 2O(liquid) ; ∆H = + 1.44 kcals (+ 6.02 kJ ) enthalpy change of a chemical reaction depends on the initial and
final stages only. Let a substance A be changed in three steps to D
H 2O → H 2O (ice ); ∆H = − 1.44 kcals (− 6.02 kJ )
(liquid)
with enthalpy change from A to B, ∆H1 calorie, from B to C, ∆H 2
(8) Heat of precipitation : It is defined as the amount of calorie and from C to D, ∆H 3 calorie. Total enthalpy change from
heat liberated in the precipitation of one mole of a sparingly
soluble substance when solutions of suitable electrolytes are mixed, A to D will be equal to the sum of enthalpies involved in various
for example steps. Total enthalpy change ∆H steps = ∆H1 + ∆H 2 + ∆H 3

Ba2 + + SO42−(aq) → BaSO4(s) : ∆H = − 4.66 kcal Now if D is directly converted into A, let the enthalpy
change be ∆H direct . According to Hess's law ∆H steps + ∆H direct = 0,
(9) Heat of sublimation : Sublimation is the process in
which a solid on heating changes directly into gaseous state below i.e. ∆H steps must be equal to ∆H direct numerically but with
its melting point. opposite sign. In case it is not so, say ∆H steps (which is negative) is
Heat of sublimation of a substance is the amount of heat
more that ∆H direct (which is positive), then in one cycle, some
absorbed in the conversion of 1 mole of a solid directly into vapour
phase at a given temperature below its melting point. energy will be created which is not possible on the basis of first law
I 2( s) → I 2( g ) ; ∆H = + 62.39 kJ of thermodynamics. Thus, ∆H steps must be equal to ∆H direct
numerically.
Most solids that sublime are molecular in nature e.g. iodine
and naphthalene etc. (1) Experimental verification of Hess's law
(i) Formation of carbon dioxide from carbon
∆H sub. = ∆H fusion + ∆H vaporisation
First method : carbon is directly converted into CO2( g ) .
2.3. Experimental determination of the heat of
reaction: The heat evolved or absorbed in a chemical reaction is C(s ) + O2( g ) = CO2( g ) ; ∆H = −94.0 kcal
measured by carrying out the reaction in an apparatus called Second method : Carbon is first converted into CO(g ) and
calorimeter. The principle of measurement is that heat given out is then CO(g ) into CO2(g ) , i.e. conversion has been carried in two
equal to heat taken, i.e., Q = (W + m) × s × (T2 − T1 ),
steps,
Where Q is the heat of the reaction (given out), W is the
1
water equivalent of the calorimeter and m is the mass of liquid in C( s) + O2 = CO( g ) ; ∆H = −26.0 kcal
2
the calorimeter and s its specific heat, T2 is the final temperature
1
and T1 the initial temperature of the system. Different types of CO( g ) + O2 = CO2( g ) ; ∆H = − 68.0 kcal
2
calorimeters are used but two of the common types are,
Total enthalpy change C(s) to CO2( g ) ; ∆H = −94.0 kcal
(1) Water calorimeter
(2) Bomb calorimeter (ii) Formation of ammonium chloride from ammonia and
Bomb calorimeter : This is commonly used to find the hydrochloric acid:
heat of combustion of organic substances. First method
Since the reaction in a bomb calorimeter proceeds at constant NH 3( g ) + HCl = NH 4 Cl( g ) ; ∆H = − 42.2 kcal
volume, the heat of combustion measured is ∆E NH4Cl(g)+aq= NH4Cl(aq); ∆H = + 4.0 kcal
(W + m) (T2 − T1 ) × s NH 3( g ) + HCl( g ) + aq = NH 4 Cl(aq) ; ∆H = −38.2 kcal
∆E = × M kcal
w1
Second method
Where M is the molecular mass of the substance, w 1 is the NH 3( g ) + aq = NH 3(aq) ; ∆H = −8.4 kcal
weight of substance taken, W is the water equivalent of calorimeter, HCl( g ) + aq = HCl(aq) ; ∆H = −17.3 kcal
m is the mass of liquid in the calorimeter and s is the specific heat
of liquid. NH 3(aq) + HCl(aq) = NH 4 Cl(aq) ; ∆H = −12.3 kcal
∆H can be calculated from the relation, ∆H = ∆E + ∆nRT NH 3( g ) + HCl( g ) + aq = NH 4 Cl(aq) ; ∆H = −38.0 kcal
3. Laws of Thermochemistry (2) Applications of Hess's law
3.1. Lavoisier and Laplace law : According to this law (i) For the determination of enthalpies of formation of those
enthalpy of decomposition of a compound is numerically equal to compounds which cannot be prepared directly from the elements
the enthalpy of formation of that compound with opposite sign, easily using enthalpies of combustion of compounds.
For example, (ii) For the determination of enthalpies of extremely slow
C(s ) + O2 → CO2( g ) ; ∆H = −94.3 kcal reactions.
(iii) For the determination of enthalpies of transformation of
CO2( g ) → C( s) + O2( g ) ; ∆H = +94.3kcal one allotropic form into another.
 206 Thermodynamics and Thermochemistry
(iv) For the determination of bond energies.
∆H reaction = Σ Bond energies of reactants – Σ Bond
energies of products. Critical Points
(v) For the determination of resonance energy. Scan QR Code to Read & Revise
(iv) For the determination of lattice energy. Critical Points on the Phone App
4. Bond Energy or Bond Enthalpies
When a bond is formed between atoms, energy is released.  ∂T 

Joule Thomson coefficient µ =  
Obviously same amount of energy will be required to break the  ∂p  H
bond. The energy required to break the bond is termed bond
For cooling µ = +ve
dissociation energy. The more precise definition is,
“The amount of energy required to break one mole of bond For Heating µ = −ve
of a particular type between the atoms in the gaseous state, i.e., to Neither cooling nor heating µ = 0
separate the atoms in the gaseous state under 1 atmospheric
The temperature at which a real gas shows neither cooling nor
pressure and the specified temperature is called bond dissociation heating effect on adiabatic expansion (i.e., µ = 0 ) is called
energy.”
inversion temperature.
For example, H − H( g ) → 2 H( g ) ; ∆H = + 433 kJ mol −1

Hydrogen has highest calorific value.
Cl − Cl( g ) → 2Cl ( g ); ∆H = + 242 .5 kJ mol −1
13.7 kcal / mol = 57 kJ / mol (Because of 1 cal =4.2 Joule)
H − Cl( g ) → H( g ) + Cl( g ) ; ∆H = + 431 kJ mol −1
Enthalpy of fusion of ice per mole is 6kJ .
The bond dissociation energy of a diatomic molecule is also
Order of bond energy in halogen Cl 2 > Br2 > F2 > I 2 .
called bond energy. However, the bond dissociation energy
depends upon the nature of bond and also the molecule in which
Heat of vapourisation of water per mole is 10.5 kCal.
the bond is present. When a molecule of a compound contains
The heat of reaction is independent of the time consumed
more than one bond of the same kind, the average value of the in the process.
dissociation energies of a given bond is taken. This average bond
∆H =∆E +P∆V. In bomb calorimeter, ∆V=0, hence we
dissociation energy required to break each bond in a compound is have ∆H=∆E. However this is not true. This is because the
called bond energy.
relation ∆H=∆E+P∆V holds good only at constant pressure.
Bond energy is also called, the heat of formation of the
bond from gaseous atoms constituting the bond with reverse sign.
Heat of neutralisation of HF is about 68kJ i.e., more than
57.1kJ. This is due to very high hydration energy of fluoride
H( g ) + Cl( g ) → H − Cl ( g ); ∆H = − 431 kJ mol −1
ions.
Bond energy of H − Cl = − (enthalpy of formation)
It appears that, during stretching of rubber band entropy
= −(−431) = + 431 kJ mol −1 increases while on hard boiling of egg, entropy decreases but
Consider the dissociation of water molecule which consists actually the results are reverse.
of two O − H bonds. The dissociation occurs in two stages.
During the stretching of rubber band, the long flexible
H 2O( g ) → H( g ) + OH( g ) ; ∆H = 497 .89 kJ mol −1 macromolecules get uncoiled. The uncoiled arrangement has
more specific geometry and more order. Thus entropy
OH( g ) → H( g ) + O( g ) ; ∆H = 428 .5 kJ mol −1
decreases.
The average of these two bond dissociation energies gives

On hard boiling of egg denaturation of protein occur in
the value of bond energy of O − H.
which protein form helical changes unit random coiled form,
Bond energy of O − H bond entropy increases.
497.8 + 428.5
= = 463.15 kJ mol −1
Gibb's energy criteria is better than entropy criteria in
2 determining the spontaneity. This is because the former refers to
Similarly, the bond energy of N − H bond in NH3 is equal system only while the latter refers to both system and
to one – third of the energy of dissociation of NH 3 and those of surroundings .
C − H bond in CH4 is equal to one – fourth of the energy of
∆Go= – nFEo
dissociation of CH4 . n= No. of moles of electrons, F=Faraday and Eo= standard emf.

1664

Standard enthalpy of formation and standard free energy of
Bond energy of C − H = = 416 kJ mol −1 formation of an element is taken as zero but standard entropy of
4
even an element is not zero.
[CH 4 ( g ) → C( g ) + 4 H( g ) ; ∆H = 1664 kJ mol −1 ]

∆Hcombustion is always negative. There are certain reactions
Applications of bond energy : which involve combination with oxygen undergoing partial
(1) Heat of a reaction = Σ Bond energy of reactants – combustion and ∆H is +ve e.g., N 2 + O2 → 2 NO, ∆H = +ve
Σ Bond energy of products.
(2) Determination of resonance energy : When a
Spontaneous dissolution of gases in liquid in an exothermic
compound shows resonance, there is considerable difference process. For such a process, ∆S is always –ve. As such for the
between the heat of formation as calculated from bond energies process to be spontaneous (∆G to be –ve); ∆H has to be –ve
and that determined experimentally. i.e., process is exothermic.
 NCERT BASED QUESTIONS
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Scan to Practice the Questions On the Go with Mobile App

Basic Concepts 11. Which one of the following is not a unit of energy
(a) Nm (b) kg. ms −2
1. Heat produced in calories by the combustion of one gram of
carbon is called (c) lit-atm (d) kg m 2 s −2
(a) Heat of combustion of carbon
12. Identify an extensive property amongst the following
(b) Heat of formation of carbon
(c) Calorific value of carbon (a) Viscosity (b) Heat capacity
(d) Heat of production of carbon (c) Density (d) Surface tension
2. Conditions of standard state used in thermochemistry is 13. In an isothermal process
(a) 0 o C and 1 atm (b) 20 o C and 1 atm (a) q = 0 and ∆E = 0 (b) q ≠ 0 and ∆E = 0
o
(c) 25 C and 1 atm (d) 0 K and 1 atm (c) q = 0 and ∆E ≠ 0 (d) q ≠ 0 and ∆E ≠ 0
3. The temperature of the system decreases in an 14. The heat change at constant volume (qv ) is equal to
(a) Adiabatic compression (b) Isothermal compression
(a) ∆U (b) ∆H
(c) Isothermal expansion (d) Adiabatic expansion
4. Changes in a system from an initial state to the final state (c) RT (d) ∆G
were made by a different manner that ∆H remains same 15. An ideal gas at constant temperature and pressure expands,
but q changes because then its
(a) ∆H is a path function and q is a state function (a) Internal energy remains same
(b) ∆H is a state function and q is a path function (b) Internal energy decreases
(c) Internal energy increases
(c) Both ∆H and q are state functions
(d) Entropy first increases and then decreases
(d) Both ∆H and q are path functions
16. Internal energy is sum of
5. The cooling in refrigerator is due to
(a) Kinetic energy and potential energy
(a) Reaction of the refrigerator gas
(b) Expansion of ice (b) All types of energy of the system
(c) The expansion of the gas in the refrigerator (c) Energy of internal system
(d) The work of the compressor (d) None of these
6. Mark the correct statement 17. ∆E is always positive when
(a) For a chemical reaction to be feasible, ∆G should be (a) System absorbs heat and work is done on it
zero
(b) System emits heat and work is done by it
(b) Entropy is a measure of order in a system
(c) System emits heat and no work is done on it
(c) For a chemical reaction to be feasible, ∆G should be
positive (d) System absorbs heat and work is done by it
(d) The total energy of an isolated system is constant 18. Five moles of a gas is put through a series of changes as
7. Among them intensive property is shown graphically in a cyclic process the A → B , B → C
(a) Mass (b) Volume and C → A respectively are
(c) Surface tension (d) Enthalpy
A B
8. An adiabatic process occurs in
Volume

(a) Open system (b) Closed system

(c) Isolated system (d) In all the given systems C
9. Which of the following is true for an adiabatic process
Temperature
(a) ∆H = 0 (b) ∆W = 0
(c) ∆Q = 0 (d) ∆V = 0 (a) Isochoric, Isobaric, Isothermal
10. For a cyclic process (b) Isobaric, Isochoric, Isothermal
(a) W = 0 (b) ∆E = 0 (c) Isothermal, Isobaric, Isochoric
(c) ∆H ≠ 0 (d) ∆E ≠ 0 (d) Isochoric, Isothermal, Isobaric
 208 Thermodynamics and Thermochemistry

19. Thermodynamics is not concerned about

First Law of Thermodynamics and Hess Law
(a) Energy changes involved in a chemical reaction
(b) The extent to which a chemical reaction proceeds 1. The relation between ∆E and ∆H is
(c) The rate at which a reaction proceeds (a) ∆H = ∆E − P ∆V (b) ∆H = ∆E + P ∆V
(d) The feasibility of a chemical reaction
(c) ∆E = ∆V + ∆H (d) ∆E = ∆H + P ∆V
20. Which of the following statement is correct
(a) The presence of reacting species in a covered beaker is 2. At constant T and P, which one of the following statements
an example of open system 1
is correct for the reaction, CO(g) + O2 (g) → CO2 (g)
(b) There is an exchange of energy as well as matter 2
between the system and the surroundings in a closed (a) ∆H is independent of the physical state of the
system reactants of that compound
(c) The presence of reactants in a closed vessel made up of (b) ∆H > ∆E
copper is an example of a closed system
(c) ∆H < ∆E
(d) The presence of reactants in a thermos flask or any
other closed insulated vessel is an example of a closed (d) ∆H = ∆E
system 3. For the reaction N 2 + 3H 2 2 NH 3 ; ∆H =
21. The state of a gas can be described by quoting the (a) ∆E − RT (b) ∆E − 2RT
relationship between
(c) ∆E + RT (d) ∆E + 2RT
(a) Pressure, volume, temperature
4. If ∆H is the change in enthalpy and ∆E the change in
(b) Temperature, amount, pressure
internal energy accompanying a gaseous reaction
(c) Amount, volume, temperature
(a) ∆H is always greater than ∆E
(d) Pressure, volume, temperature, amount
(b) ∆H < ∆E only if the number of moles of the products is
22. The volume of gas is reduced to half from its original
greater than the number of the reactants
volume. The specific heat will be
(a) Reduce to half (c) ∆H is always less than ∆E
(b) Be doubled (d) ∆H < ∆E only if the number of moles of the products is
(c) Remain constant less than the number of moles of the reactants
(d) Increase four times 5. Consider the reaction : N 2 + 3 H 2 → 2 NH 3 carried out at
23. Which of the following are not state functions constant temperature and pressure. If ∆H and ∆U are the
(I) q + w (II) q enthalpy and internal energy changes for the reaction, which
(III) w (IV) H – TS of the following expression is true
(a) (I), (II) and (III) (b) (II) and (III) (a) ∆H = 0 (b) ∆H = ∆U
(c) (I) and (IV) (d) (II), (III) and (IV) (c) ∆H < ∆U (d) ∆H > ∆U
24. Consider the Born– Haber cycle for the formation of an 6. During an isothermal expansion of an ideal gas its
ionic compound given below and identify the compound (Z) (a) Internal energy increases
formed. (b) Enthalpy decreases
∆H 1 ∆H 2
 M(s )  → M( g )  → M(+g )  (c) Enthalpy remains unaffected
  
∆H 5
→ Z
 1 X 2( g ) ∆H 3 ∆H 4
→ X( g )  → X(−g )  (d) Enthalpy reduces to zero
 2  7. Which of the following expressions represents the first law
of thermodynamics
(a) MX (b) M + X(g− )
(a) ∆E = −q + W (b) ∆E = q − W
(c) M + X −(s ) (d) M − X(s− ) (c) ∆E = q + W (d) ∆E = −q − W
25. The internal energy change when a system goes from state 8. For a gaseous reaction at 300 K , ∆H − ∆U = −4.98 kJ ,
A to B is 40 kJ/mole. If the system goes from A to B by a
assuming that R = 8.3 JK −1mol −1, ∆n( g ) is
reversible path and returns to state A by an irreversible path
what would be the net change in internal energy (a) 1 (b) 2
(a) 40 kJ (b) > 0 kJ (c) –2 (d) 0
(c) < 40 kJ (d) Zero 9. For the reaction
26. Among the quantities, density (ρ ) , temperature (T) , CH 3 COOH (l) + 2O 2 (g ) 2CO 2 (g) + 2 H 2 O(l) at 25o C
enthalpy (H) , heat capacity (C p ) , volume (V ) and and 1 atm. pressure, ∆H = −874 kJ . Then the change in
pressure (P ) , a set of intensive variables are internal energy (∆E) is ….
(a) (ρ, T, H ) (b) (H, T, V ) (a) – 874 kJ (b) – 871.53 kJ
(c) (V , T, C p ) (d) (ρ , T, P) (c) – 876.47 kJ (d) + 874 kJ
 Thermodynamics and Thermochemistry 209
10. In a closed insulated container, a liquid is stirred with a 20. Molar heat capacity of aluminium is 25 JK −1mol −1 . The
paddle to increase its temperature. In this process, which of
heat necessary to raise the temperature of 54g of aluminium
the following is true
(Atomic mass 27 g mol −1 ) from 30º C to 50º C is
(a) ∆E = W = Q = 0 (b) ∆E ≠ 0, Q = W = 0
(a) 1.5 kJ (b) 0.5 kJ
(c) ∆E = W ≠ 0, Q = 0 (d) ∆E = Q ≠ 0, W = 0
(c) 1.0 kJ (d) 2.5 kJ
11. For the reaction,
C 3 H 8 (g ) + 5O 2 (g ) → 3CO 2 (g ) + 4 H 2 O(l) (e) 2.0 kJ
at constant temperature, ∆H − ∆E is 21. A 1.0 g sample of substance A at 100°C is added to 100 mL
(a) – RT (b) + RT of H 2O at 25°C. Using separate 100 mL portions of H 2O,
(c) – 3RT (d) + 3RT the procedure is repeated with substance B and then with
12. The work done by a system is 8 joule, when 40 joule heat is substance C. How will the final temperature of the water
supplied to it. What is the increase in internal energy of compare
system Substance Specific Heat
(a) 25 J (b) 30 J A 0.60 Jg −1 °C −1
(c) 32 J (d) 28 J
B 0.40 Jg −1 °C −1
13. Under which of the following condition is the relation
∆H = ∆E + P∆V valid for a closed system C 0.20 Jg −1 °C −1
(a) Constant pressure (a) TC > TB > TA (b) TB > TA > TC
(b) Constant temperature
(c) TA > TB > TC (d) TA = TB = TC
(c) Constant temperature and pressure
(d) Constant temperature, pressure and composition 22. Mass and energy are conserved is demonstrated by
14. The volume of a gas decreases from 500 cc to 300 cc when (a) First law of thermodynamics
(b) Law of conservation of energy
a sample of gas is compressed by an average pressure of 0.6
(c) Law of conservation of mass
atm. During this process 10 J of heat is liberated. The
(d) Modified form of Ist law of thermodynamics
change in internal energy is
23. A mixture of two moles of carbon monoxide and one mole
(a) – 2.16 J (b) 12.156 J
of oxygen, in a closed vessel is ignited to convert the carbon
(c) 2.16 J (d) 101.3 J
monoxide to carbon dioxide. If ∆H is the enthalpy change
15. For the reaction A(g) + 2B(g) → 2C(g) + 3D(g) , the value of
and ∆E is the change in internal energy, then
∆E at 27 o C is 19.0 kcal. The value of ∆H for the reaction (a) ∆H > ∆E
would be (R = 2.0 cal K −1mol −1 ) (b) ∆H < ∆E
(a) 20.8 kcal (b) 19.8 kcal (c) ∆H = ∆E
(c) 18.8 kcal (d) 20.2 kcal (d) The relationship depends on the capacity of the vessel
16. If one mole of ammonia and one mole of hydrogen chloride 24. The standard enthalpy of formation of which of the
are mixed in a closed container to form ammonium chloride following is zero
gas, then (a) CH3OH (b) HF
(a) ∆H < ∆U (b) No relationship (c) H 2O (d) F2
(c) ∆H > ∆U (d) ∆H = ∆U
25. ∆E o of combustion of isobutylene is − X kJ mol −1 . The
17. According to the first law of thermodynamics which of the
following quantities represents change in a state function value of ∆H o is
(a) qrev (b) qrev − wrev (a) = ∆E o (b) > ∆E o
(c) qrev / wrev (d) wrev (c) = 0 (d) < ∆E o
(e) qrev + wrev 26. The work done by the gas liberated when 50 g of iron
18. The molar heat capacity of water at constant pressure is (molar mass 55 . 85 g mol −1 ) reacts with hydrochloric acid in
75 JK −1 mol −1 . When 1.0 kJ of heat is supplied to 100 g of an open beaker at 25º C
water which is free to expand then increase in temperature (a) Zero (b) −2.2 kJ
of water is (c) 2.2 kJ (d) 0.22 kJ
(a) 6.6 K (b) 1.2 K
27. For isothermal expansion of an ideal gas, the correct
(c) 2.4 K (d) 4.8 K
combination of the thermodynamic parameters will be
19. For the process dry ice → CO 2 (g)
(a) ∆U = 0, Q = 0, w ≠ 0 and ∆H ≠ 0
(a) ∆H is positive while ∆P is negative
(b) ∆U ≠ 0, Q ≠ 0, w ≠ 0 and ∆H ≠ 0
(b) Both ∆H and ∆P are negative
(c) Both ∆H and ∆P are positive (c) ∆U = 0, Q ≠ 0, w = 0 and ∆H ≠ 0
(d) ∆H is negative while ∆P is positive (d) ∆U = 0, Q ≠ 0, w ≠ 0 and ∆H = 0
 210 Thermodynamics and Thermochemistry
28. Pressure-volume (PV) work done by an ideal gaseous 36. Enthalpy change for a reaction does not depend upon
system at constant volume is (where E is internal energy of (a) The physical states of reactants and products
the system) (b) Use of different reactants for the same product
(a) − ∆P / P (b) Zero (c) The nature of intermediate reaction steps
(c) −V ∆P (d) −∆E (d) The differences in initial or final temperatures of
29. A sample of liquid in a thermally insulated container is involved substances
stirred for 1 hr by a mechanical attachment to a motor in 37. On the basis of theromochemical equations (i), (ii) and (iii),
the surroundings, which of the following thermodynamic find out which of the algebraic relationships given in options
quantity for the system is zero (a) to (d) is correct
(a) Work (W) (i) C (graphite) + O 2 ( g ) → CO 2 ( g ); ∆ r H = xkJ mol −1
(b) Change in internal energy (∆E) 1
(ii) C (graphite ) + O2 (g) → CO(g); ∆ r H = y kJ mol −1
(c) Change in enthalpy (∆H ) 2
(d) None of these 1
(iii) CO(g) + O2 (g) → CO2 (g); ∆ r H = zkJ mol −1
30. Hess's law of constant heat summation is based on 2
(a) E = mc 2 (a) z = x + y (b) x = y − z
(b) Conservation of mass (c) x =y+z (d) y = 2z − x
(c) First law of thermodynamics 38. For the reactions A → B; ∆H = +24 kJ/mol and
(d) None of the above
B → C; ∆H = −18kJ/mol , the decreasing order of enthalpy
31. According to Hess’s law, the heat of reaction depends upon
(a) Initial condition of reactants of A, B, C follows the order
(b) Initial and final conditions of reactants (a) A, B, C (b) B, C, A
(c) Intermediate path of the reaction (c) C, B, A (d) C, A, B
(d) End conditions of reactants 39. The enthalpy of neutralization of HCN by NaOH is
32. On the basis of following equations the heat of dimerisation − 12.13 kJ mol −1 . The enthalpy of ionisation of HCN will
of NO2 will be be
(i) N 2 + 2O2 → 2NO2 ∆H = 67.9 kJ (a) 4.519 kJ (b) 54.10 kJ
(c) 451.9 kJ (d) 45.19 kJ
(ii) N 2 + 2O2 → N 2O4 ∆H = 09.3 kJ
40. One mole of magnesium in the vapour state absorbed
(a) +77.2 kJ (b) −77.2 kJ
1200 kJ mol −1 of energy. If the first and second ionization
(c) −58.6 kJ (d) +58.6 kJ
energies of Mg are 750 and 1450 kJ mol −1 respectively, the
33. If ∆H of for H 2 O2 and H 2 O are −188 kJ / mole and final composition of the mixture is
−286 kJ / mole . What will be the enthalpy change of the (a) 31 % Mg + + 69 % Mg 2 + (b) 69 % Mg + + 31 % Mg 2 +
reaction 2H 2 O2 (l) → 2H 2 O(l) + O2 (g) (c) 86 % Mg + + 14 % Mg 2+ (d) 14 % Mg + + 86 % Mg 2 +
(a) −196 kJ / mole (b) 146 kJ / mole (e) 13 % Mg + + 87 % Mg 2 +
(c) −494 kJ / mole (d) −98 kJ / mole 41. For the allotropic change represented by equation
34. The sublimation energy of I 2( s ) is 57.3 kJ / mol and the C(diamond) → C(graphite) ; the enthalpy change is
enthalpy of fusion is 15.5 kJ/mol. The enthalpy of ∆H = −1.89 kJ . If 6 g of diamond and 6 g of graphite are
vaporisation of I 2 is separately burnt to yield carbon dioxide, the heat liberated
(a) 41.8 kJ / mol (b) − 41.8 kJ / mol in the first case is
(a) Less than in the second case by 1.89 kJ
(c) 72.8 kJ / mol (d) −72.8 kJ / mol
(b) More than in the second case by 1.89 kJ
35. The following thermochemical reactions are given
1 (c) Less than in the second case by 11.34 kJ
M + O 2 → MO + 351.4 kJ
2 (d) More than in the second case by 0.945 kJ
1
X + O 2 → XO + 90.8 kJ 42. Given R = 8.314 JK −1 Mol −1 , the work done during
2
combustion of 0.090 kg of ethane
It follows that the heat of reaction for the following process
M + XO MO + X is given by (molar mass =30 )at 300 K is
(a) 422.2 kJ (b) 268.7 kJ (a) –18.7 kJ (b) 18.7 kJ
(c) – 442.2 kJ (d) 260.6 kJ (c) 6.234 kJ (d) – 6.234 kJ
 Thermodynamics and Thermochemistry 211
43. Work done during isothermal expansion of one mole of an 52. For an ideal gas, which of the following is true
ideal gas from 10 atm. to 1 atm at 300K is  ∂E   ∂P 
(a) 4938.8 J (b) 4138.8 J (a)   >0 (b)   =0
 ∂V  T  ∂V  T
(c) 5744.1 J (d) 6257.2 J
 ∂E   ∂(PV ) 
44. An ideal gas expands in volume from 1 × 10−3 m3 to (c)   =0 (d)   >0
 ∂V  T  ∂V  T
1 × 10−2 m3 at 300 K against a constant pressure of
−2 53. In an isobaric process, the ratio of heat supplied to the
1 × 10 Nm . The work done is
5
system (dQ) and work done by the system (dW ) for
(a) 270 kJ (b) –900 kJ
(c) –900 J (d) 900 kJ diatomic gas is
45. In an adiabatic process, no transfer of heat takes place (a) 1 : 1 (b) 7 : 2
between system and surroundings. Choose the correct (c) 7 : 5 (d) 5 : 7
option for free expansion of an ideal gas under adiabatic 54. The entropy change in the isothermal reversible expansion
condition from the following of 2 moles of an ideal gas from 10 to 100 L at 300 K is
(a) q = 0, ∆T ≠ 0, W = 0 (b) q ≠ 0, ∆T = 0, W = 0
(a) 42.3 J K −1 (b) 35.8 J K −1
(c) q = 0, ∆T = 0, W = 0 (d) q = 0, ∆T < 0, W ≠ 0
(c) 38.3 J K −1 (d) 32.3 J K −1
46. One mole of an ideal gas is allowed to expand reversibly
55. For the isothermal reversible expansion of an ideal gas
and adiabatically from a temperature of 27o C . If the work
(a) ∆H > 0 and ∆U = 0 (b) ∆H > 0 and ∆U < 0
done during the process is 3 kJ , then final temperature of
(c) ∆H = 0 and ∆U = 0 (d) ∆H = 0 and ∆U > 0
the gas is (CV = 20 J / K)
(a) 100 K (b) 150 K IInd & IIIrd Law of Thermodynamics and Entropy
(c) 195 K (d) 255 K
1. An engine operating between 150 o C and 25 o C takes 500 J
47. One mole of an ideal gas at 300K is expanded isothermally
heat from a higher temperature reservoir if there are no
from an initial volume of 1 litre to 10 litres. The change in
frictional losses, then work done by engine is
energy for this process is ( R = 2 cal mol −1 K −1 )
(a) 147.7 J (b) 157.75 J
(a) 163.7 cal (b) 850.2 cal (c) 165.85 J (d) 169.95 J
(c) 1381.1 cal (d) Zero
2. For a carnot engine, the source is at 500 K and the sink at
48. To calculate the amount of work done in joules during
300 K . What is efficiency of this engine
reversible isothermal expansion of an ideal gas, the volume
must be expressed in (a) 0.2 (b) 0.4
(c) 0.6 (d) 0.3
(a) m 3 only (b) dm 3 only
3. When you freeze water in your freezer to make ice cubes,
(c) cm3 only (d) Any one of them the amount of order in the molecules of water increases.
49. Two moles of an ideal gas expand spontaneously into a However, second law of thermodynamics says that the
vacuum. The work done is amount of order in an isolated system can only stay constant
(a) 2 Joule (b) 4 Joule or decrease with time. How can this making of ice violates
(c) Zero (d) Infinite second law
50. Which expression is correct for the work done in adiabatic (a) Because water expands during ice formation
reversible expansion of an ideal gas
(b) Because ice formation takes place at 0°C
V T
(a) W = nRT ln 2 (b) W = ne ln 2 (c) Because ice is solid
V1 T1
(d) Because ice cubes do not constitute isolated system
2
(c) W = P∆V (d) W = − ∫ 1
PdV 4. The entropy values (in JK-1 mol-1) of H2(g) = 130.6,
Cl2(g) = 223.0 and HCl(g) = 186.7 at 298 K and 1 atm
51. The pressure-volume work for an ideal gas can be calculated pressure. Then entropy change for the reaction
Vf
H 2( g) + Cl 2( g ) → 2HCl( g) is
∫
by using the expression W = − Pex dV . The work can also
Vi (a) + 540.3 (b) + 727.3
be calculated from the pV − plot by using the area under (c) – 166.9 (d) + 19.8
the curve within the specified limits. When an ideal gas is 5. Choose the reaction with negative ∆S value
compressed (a) reversibly or (b) irreversibly from volume Vi (a) 2 NaHCO3(s ) → Na2CO3(s ) + CO2( g ) + H 2O( g )
to Vf . Choose the correct option (b) Cl 2( g ) → 2Cl( g )
(a) W (reversible) = W (irreversible) (c) 2SO2( g ) + O2( g ) → 2SO3( g )
(b) W (reversible) < W (irreversible)
(d) 2KClO3(s ) → 2KCl(s ) + 3O2( g)
(c) W (reversible) > W (irreversible)
(d) W (reversible) = W (irreversible) + Pex .∆V (e) H 2O(l ) → H 2O( g )
 212 Thermodynamics and Thermochemistry
6. Which of the following is zero during adiabatic expansion of 14. The unit of entropy is
the gas
(a) J mol −1 (b) JK mol −1
(a) ∆T (b) ∆S
(c) ∆E (d) None of these (c) J mol −1 K −1 (d) J −1 K −1mol 1

7. 9.0 g of H 2 O is vaporised at 100o C and 1 atm pressure. If 15. H + (aq) + OH − (aq) → H 2O(l)
So (298 K ) JK −1mol −1 −10.7 J / mol / K +70 J / mol / K
the latent heat of vaporisation of water is x J / g , then ∆S
is given by Standard entropy change for the above reaction is

x 18x (a) 60.3 JK −1mol −1 (b) 80.7 JK −1mol −1

(a) (b)
373 100
(c) − 70 JK −1mol −1 (d) + 10.7 JK −1mol −1
18x 1 18 x
(c) (d) × 16. Which is the correct expression, that relates changes of
373 2 373
entropy with the change of pressure for an ideal gas at
8. If the enthalpy of vaporization for water is 186.5 kJ mol −1 ,
constant temperature in the following
the entropy of its vaporization will be
P2
(a) 0.5 JK −1mol −1 (b) 1.0 JK −1mol −1 (a) ∆S = nRT ln (b) ∆S = T (P2 − P1 )
P1
−1 −1 −1 −1
(c) 1.5 JK mol (d) 2.0 JK mol
P1 P1
9. Which of the following statement is true. The entropy of the (c) ∆S = nR ln (d) ∆S = 2.303 nRT ln
P2 P2
universe
(a) Increases and tends towards maximum value 17. One mole of which of the following has the highest entropy
(b) Decreases and tends to be zero (a) Mercury (b) Diamond
(c) Remains constant (c) Liquid nitrogen (d) Hydrogen gas
(d) Decreases and increases with a periodic rate 18. Predict the sign/value of ∆S° for the following reaction
10. Which of the following is correct
2H 2 S( g ) + 3O2( g ) → 2H 2 O( g ) + 2SO2( g )
(a) Evaporation of water causes an increase in disorder of
the system (a) +ve (b) −ve
(b) Melting of ice causes a decrease in randomness of the (c) Zero (d) Can not be predicted
system
19. Enthalpy of vaporization of benzene is +35.3 kJ mol–1 at its
(c) Condensation of steam causes an increase in disorder
of the system boiling point, 80o C . The entropy change in the transition of
(d) There is practically no change in the randomness of the the vapour to liquid at its boiling point [in JK −1mol −1 ] is …..
system when water is evaporated
(a) − 441 (b) − 100
11. Identify the correct statement regarding entropy
(c) + 441 (d) + 100
(a) At 0 o C , the entropy of a perfectly crystalline substance
is taken to be zero 20. Entropy change in a process where 1 litre of liquid He is
(b) At absolute zero of temperature, the entropy of a poured into ice cold water is
perfectly crystalline substance is +ve
(a) Finite and positive (b) Finite and negative
(c) At absolute zero of temperature, the entropy of all
(c) Zero (d) Infinity
crystalline substances is taken to be zero
(d) At absolute zero of temperature, the entropy of a 21. The change of entropy (dS) is defined as
perfectly crystalline substance is taken to be zero (a) dS = δq / T (b) dS = dH / T
12. The entropy change, in the conversion of one mole of liquid
(c) dS = δqrev / T (d) dS = (dH − dG) / T
water at 373 K to vapour at the same temperature is (Latent
heat of vaporization of water, ∆H vap = 2.257 kJ / g) 22. In which of the following entropy decreases
(a) Crystallization of sucrose from solution
(a) 105.9 JK −1 (b) 107.9 JK −1
(b) Rusting of iron
(c) 108.9 JK −1 (d) 109.9 JK −1
(c) Melting of ice
13. Entropy will not change for the reaction
(d) Vaporization of camphor
(a) Crystallization of sucrose from the solution
23. For conversion C (graphite) → C (diamond) the ∆S is
(b) Corrosion of iron
(c) Conversion of ice into water (a) Zero (b) Positive
(d) Vaporisation of Camphor (c) Negative (d) Unknown
 Thermodynamics and Thermochemistry 213
24. If for a given substance melting point is TB and freezing 32. Considering entropy (S) as a thermodynamic parameter, the
point is T A , then correct variation shown by graph between criterion for the spontaneity of any process is

entropy change and temperature is (a) ∆Ssystem > 0 only

(b) ∆Ssurroundings > 0 only

TB
TB ∆S (c) ∆Ssystem + ∆Ssurroundings > 0
(a) ∆S (b)
TA TA (d) ∆Ssystem − ∆Ssurroundings > 0

T T 33. Entropy changes for the process, H 2O(l ) → H 2O( s) at normal

pressure and 274 K are given below ∆Ssystem = −22.13,
(c) (d)
TA TB
∆S
TA
TB ∆S ∆Ssurr = +22.05, the process is non-spontaneous because

(a) ∆Ssystem is – ve (b) ∆Ssurr is +ve

T T (c) ∆Su is – ve (d) ∆Ssystem ≠ ∆Ssurr
25. Which of the following would be expected to have the
(‘surr’ stands for surrounding and ‘u’ stands for universe)
largest entropy per mole
34. For an exothermic reaction, which is true
(a) SO2Cl 2 (s) (b) SO2Cl 2 (g)
(a) ∆Ssys > 0 (b) ∆Ssurr > 0
(c) SO2Cl 2 (l) (d) SO2 (g )
(c) ∆Stotal > 0 (d) None of these
26. Mixing of non-reacting gases is generally accompanied by
(a) Decrease in entropy (b) Increase in entropy 35. The entropy change can be calculated by using the
(c) Change in enthalpy (d) Change in free energy q
expression ∆S = rev when water freezes in a glass beaker,
27. An irreversible process occurring isothermally in an isolated T
system leads to choose the correct statement amongst the following
(a) Zero entropy (a) ∆S (system) decreases but ∆S (surroundings) remains
(b) An increase in the total entropy of the system the same
(c) A decrease in the total entropy of the system (b) ∆S (system) increases but ∆S (surroundings)
(d) None of these decreases
28. For chemical reactions, the calculation of change in entropy (c) ∆S (system) decreases but ∆S (surroundings)
is normally done increases
(a) At constant pressure (d) ∆S (system) decreases but ∆S (surroundings) also
(b) At constant temperature decreases
(c) At constant temperature and pressure both 36. For an isolated system, ∆U = 0, then
(d) At constant volume (a) ∆S = 0
29. For which of the processes is ∆S negative
(b) ∆S < 0
(a) H 2 (g ) → 2 H (g )
(c) ∆S ≥ 0
(b) N 2 (g )1atm → N 2 (g) 8 atm (d) The value of ∆S cannot be predicted
(c) 2SO3 (g ) → 2SO2 (g ) + O2 (g ) 37. Under equilibrium conditions, which of the following is true
(d) C(diamond) → C( graphite) (a) ∆S = 0 (b) ∆H > 0

30. A container has hydrogen and oxygen mixture in ratio of 4 (c) ∆S > 0 (d) ∆H < 0
: 1 by weight, then 38. A concentrated solution of copper sulphate, which is dark
(a) Internal energy of the mixture decreases blue in colour, is mixed at room temperature with a dilute
solution of copper sulphate, which is light blue. For this
(b) Internal energy of the mixture increases
process
(c) Entropy of the mixture increases
(a) Entropy change is positive, but enthalpy change is
(d) Entropy of the mixture decreases
negative
31. For the gas phase reaction s
(b) Entropy and enthalpy changes are both positive
PCl 5 (g ) PCl 3 (g ) + Cl 2 (g )
(c) Entropy change is positive and enthalpy does not
Which of the following conditions are correct change
(a) ∆H < 0 and ∆S < 0 (b) ∆H > 0 and ∆S < 0 (d) Entropy change is negative and enthalpy change is
(c) ∆H = 0 and ∆S < 0 (d) ∆H > 0 and ∆S > 0 positive
 214 Thermodynamics and Thermochemistry
39. As isolated box, equally partitioned contains two ideal gases then the enthalpy of formation of H 2 SO4 at 298K will be
A and B as shown (a) − 433.7 kJ (b) − 650.3 kJ
(c) + 320.5 kJ (d) − 813.9 kJ
A B
1 atm, 25ºC 1 atm, 25ºC 5. An exothermic reaction is one in which the reacting
substances
When the partition is removed, the gases mix. The changes (a) Have more energy than the products
in enthalpy (∆H ) and entropy (∆S) in the process, (b) Have less energy than the products
respectively, are (c) Are at a higher temperature than the product
(a) Zero, positive (b) Zero, negative (d) None of the above
(c) Positive, zero (d) Negative, zero 6. The enthalpy of combustion at 25°C of H2, cyclohexane
40. For a process to occur spontaneously (C6H12) and cyclohexene (C6H10) are –241, –3920 and
(a) Only the entropy of the system must increase –3800 KJ / mole respectively. The heat of hydrogenation of
(b) Only the entropy of the surroundings must increase cyclohexene is
(c) Either the entropy of the system or that of the (a) – 121 KJ / mole (b) + 121 KJ / mole
surroundings must increase (c) – 242 KJ / mole (d) + 242 KJ / mole
(d) The total entropy of the system and the surroundings 7. Heat of neutralization of NH 4 OH and HCl is
must increase
(a) 13.7 kcal (b) > 13.7 kcal
41. The latent heat of melting of ice at 0 o C is 6 kJ mol −1 . The
entropy change during the melting in JK −1 mol −1 is closest (c) < 13.7 kcal (d) None of the above
to 8. The energy released on combustion of 1 mole of C(s) with
(a) 22 (b) 11 gaseous oxygen is
(c) −11 (d) −22
(a) ∆H combustion
º
(b) ∆H formation
º
of CO 2

Heat of Reaction (c) Both are true (d) None is true

9. In the reaction for the transition of carbon in the diamond
1. One gram sample of ammonium nitrate is decomposed in a
form to carbon in the graphite form, ∆H is − 453.5 cal .
bomb calorimeter. The temperature of calorimeter increases
by 6.12 K. The heat capacity of the system is 1.23 kJ/g/deg. This points out that
What is the molar heat of decomposition of NH 4 NO3 (a) Graphite is chemically different from diamond
(b) Graphite is as stable as diamond
(a) – 7.53 kJ mol–1 (b) – 398.1 kJ mol–1
(c) Graphite is more stable than diamond
(c) – 16.1 kJ mol–1 (d) – 602 kJ mol–1
(d) Diamond is more stable than graphite
2. The standard enthalpy of formation of H 2( g ) and Cl2( g ) and
10. The difference between heats of reaction at constant
HCl(g ) are 218 kJ/mol, 121.68 kJ/mol and −92.31kJ / mol pressure and at constant volume for the reaction
respectively. Calculate standard enthalpy change in kJ for 2C6 H 6 (l ) + 15O 2 (g ) → 12CO 2 (g ) + 6 H 2 O(l ) at 25 o C in kJ is
1 1 (a) –7.43 (b) +3.72
H 2( g ) + Cl 2( g ) → HCl( g )
2 2 (c) –3.72 (d) +7.43
(a) + 431 .99 (b) − 262.14 11. Based on the following thermochemical equations
(c) − 431.99 (d) + 247.37 H 2 O(g ) + C(s) → CO(g ) + H 2 (g ); ∆H = 131 kJ

3. In which of the following neutralisation reactions, the heat 1

CO(g) + O2 (g) → CO2 (g); ∆H = −282 kJ
of neutralisation will be highest 2
(a) NH 4 OH and CH 3COOH 1
H 2 (g ) + O2 (g) → H 2 O(g); ∆H = −242 kJ
2
(b) NH 4 OH and HCl
C(s) + O 2 (g ) → CO 2 (g ); ∆H = X kJ
(c) NaOH and CH 3COOH
The value of X is
(d) NaOH and HCl (a) −393 kJ (b) − 655 kJ
4. If S + O2 → SO2 ; (∆H = −298.2)
(c) + 393 kJ (d) +655 kJ
1
SO2 + O2 → SO3 ; (∆H = −98.2) 12. For an exothermic reaction
2 (a) H of the products is less than H of the reactants
SO3 + H 2O → H 2 SO4 ; (∆H = −130.2) (b) H of the products is more than H of the reactants
1 (c) H of the products is equal to H of the reactants
H2 + O2 → H 2O; (∆H = −287.3)
2 (d) ∆H is always positive
 Thermodynamics and Thermochemistry 215

13. The standard enthalpy of formation of H 2O(l ) and Fe2O3(s ) 21. When the aqueous solution of 0.5 mole HNO3 is mixed
are respectively − 286 kJ mol −1 −1
and − 824 kJ mol . What is with the 0.3 mole of OH − solution, then what will be the
the standard enthalpy change for the following reaction liberated heat (Enthalpy of neutralization is = 57.1 kJ)
Fe 2O3(s ) + 3H 2( g ) → 3 H 2O(l ) + 2Fe( s) (a) 28.5 kJ (b) 17.1 kJ
(c) 45.7 kJ (d) 1.7 kJ
(a) − 538 kJ mol −1 (b) + 538 kJ mol −1
(e) 2.85 kJ
(c) − 102 kJ mol −1 (d) + 34 kJ mol −1
22. A cylinder of gas is assumed to contain 11.2 kg of butane
(e) − 34 kJ mol −1 (C 4 H 10 ) . If a normal family needs 20000 kJ of energy per
14. Calculate the standard heat of formation of carbon day. The cylinder will last: (Given that ∆H for combustion
disulphide (l ) , given that the standard heat of combustion of of butane is – 2658 kJ)
carbon (s) , sulphur (s) and carbon disulphide (l ) are (a) 20 days (b) 25 days
−1
−393.3, − 293.72 and − 1108.76 kJ mol respectively (c) 26 days (d) 24 days
−1 −1
(a) − 128.02 kJ mol (b) + 12.802 kJ mol 23. Compounds with high heat of formation are less stable
−1 because
(c) + 128.02 kJ mol (d) − 12.802 kJ mol −1
(a) High temperature is required to synthesise them
15. When 0.5 g of sulphur is burnt to SO2 , 4.6 kJ of heat is
(b) Molecules of such compounds are distorted
liberated. What is the enthalpy of formation of sulphur (c) It is difficult to synthesis them
dioxide
(d) Energy rich state leads to instability
(a) + 147.2 kJ (b) – 147.2 kJ
24. Which of the following reactions is not exothermic
(c) – 294.4 kJ (d) + 294.4 kJ
16. The standard heats of formation of CH 4 , H 2 O and (a) C(s) + O 2 (g) → CO 2 (g)

CH 3 OH are –76, –242 and –266 kJ/mole respectively. The (b) C(s) + 2S(s) → CS 2 (g)
enthalpy change for the following reaction is (c) CH 4 (g) + 2O 2 (g) → CO 2 (g) + 2H 2 O(l)
CH 3 OH(l ) + H 2( g) → CH 4( g) + H 2 O(l )
1
(d) CO(g) + O 2 (g) → CO 2 (g)
(a) – 4 kJ/mole (b) –556 kJ/mole 2
(c) –318 kJ/mole (d) –52 kJ/mole 25. The heat of combustion of carbon to CO2 is
17. The heat of formation of methane C(s) + 2 H 2 (g ) → CH 4 (g )
−393.5 kJ / mol . The heat released upon formation of 35.2
at constant pressure is 18500 cal at 25 o C . The heat of
g of CO2 from carbon and oxygen gas is
reaction at constant volume would be
(a) 17904 cal (b) 18202 cal (a) + 315 kJ (b) − 31.5 kJ
(c) 18798 cal (d) 19096 cal (c) −315 kJ (d) +31.5 kJ
18. When 400 mL of 0.2 N solution of a weak acid is
26. If (i) C + O2 → CO2 , (ii) C + 1 / 2O2 → CO ,
neutralized by a dilute aqueous solution of sodium
hydroxide under standard conditions, 4.4 kJ amount of heat (iii) CO + 1 / 2O2 → CO2 , the heats of reaction are
is liberated. Therefore, the standard enthalpy of Q, − 12, − 10 respectively. Then Q =
neutralization of this weak acid in kJ eq −1 is
(a) – 2 (b) 2
(a) −11 (b) − 44
(c) – 22 (d) – 16
(c) −55 (d) −22 3
19. The values of ∆H for the combustion of ethene and ethyne 27. Given : 2Fe + O2 → Fe 2O3 , ∆H = −193.4 kJ ;
2
are – 341.1 and – 310.0kcal respectively. Which of the
1
following is a better fuel Mg + O2 → MgO, ∆H = −140.2 kJ
2
(a) C 2 H 2 (b) C 2 H 4
What is the ∆H for the reaction
(c) Both of these (d) None of these
3 Mg + Fe 2 O3 → 3 MgO + 2 Fe
20. In which of the following reactions, the heat liberated is
known as “heat of combustion” (a) – 1802 kJ (b) +1802 kJ
+ − (c) – 800 kJ (d) – 228 kJ
(a) H (aq) + OH (aq) → H 2 O(l ) + heat
28. If 27 g of water is formed during complete combustion of
1
(b) C(graphite) + O 2 ( g ) → CO( g ) + heat pure propene (C3 H 6 ), the mass of propene burnt is
2
(a) 42 g (b) 21 g
(c) CH 4 ( g ) + 2O 2 ( g ) → CO 2 ( g ) + 2H 2 O(l ) + heat
(c) 14 g (d) 56 g
(d) H 2 SO4 (aq) + H 2 O(l ) → H 2 SO4 (aq) + heat (e) 40 g
 216 Thermodynamics and Thermochemistry
29. Which of the following reactions corresponds to the 35. ∆ f U of formation of CH 4 (g ) at certain temperature is
definition of enthalpy of formation
− 393 kJ mol −1 . The value of ∆ f H is
(a) C( g ) + O2( g ) → CO2( g ) (b) C(s ) + O2(l ) → CO2( g )
(a) Zero (b) < ∆ f U
(c) C( s) + O2( g ) → CO2( g ) (d) C(l ) + O2(s ) → CO2( g )
(c) > ∆fU (d) Equal to ∆ f U
30. Heat of neutralization of strong acid against strong base is 36. Enthalpy of sublimation of a substance is equal to
constant and is equal to (a) Enthalpy of fusion + enthalpy of vaporisation
(a) 13.7 kcal (b) 57 kJ (b) Enthalpy of fusion
(c) 5.7 × 10 J4
(d) All of the above (c) Enthalpy of vaporisation
(d) Twice the enthalpy of vaporisation
31. The enthalpies of formation of Al 2 O3 and Cr2 O3 are
37. The enthalpy of a certain reaction at 273 K is –20.75 kJ.
−1596 kJ and −1134 kJ respectively. ∆H for the reaction The enthalpy of same reaction at 373 K (if heat capacities of
2 Al + Cr2 O3 → 2Cr + Al 2 O3 is reactants and products is same) will be
(a) –20.75 kJ (b) –2075 kJ
(a) −2730 kJ (b) −462 kJ
373
(c) Zero (d) − 20.75 × kJ
(c) −1365 kJ (d) + 2730 kJ 273
32. Sodium chloride is soluble in water but not in benzene 38. 0.06 mole of KNO3 solid is added to 100 cm3 of water at
because 298 K. The enthalpy of KNO3 aq solution is 35.8 kJ mol–1.
After the solute is dissolved the temperature of the solutions
(a) ∆H hydration < ∆H lattice energy in water and will be
∆H hydration > ∆H lattice energy in benzene (a) 293 K (b) 298 K
(c) 301 K (d) 304 K
(b) ∆H hydration > ∆H lattice energy in water and
39. The average molar heat capacities of ice and water are
∆H hydration < ∆H lattice energy in benzene 37.8 J mol −1 and 75.6 J mol −1 respectively and the enthalpy
(c) ∆H hydration = ∆H lattice energy in water and of fusion of ice is 6.012 kJ mol −1 . The amount of heat
required to change 10 g of ice at −10º C to water at 10ºC
∆H hydration < ∆H lattice energy in benzene would be
(d) ∆H hydration < ∆H lattice enery in water and (a) 2376 J (b) 4752 J
(c) 3970 J (d) 1128 J
∆H hydration = ∆H lattice energy in benzene
(e) 1985 J
33. One mole of NaCl (s) on melting absorbed 30.5 kJ of heat 40. The enthalpy of solution of sodium chloride is 4 kJ mol −1
and its entropy is increased by 28.8 JK −1 . The melting and its enthalpy of hydration of ions is − 784kJ mol −1.
point of NaCl is Then the lattice enthalpy of NaCl (in kJ mol −1 ) is
(a) 1059 K (b) 30.5 K (a) +788 (b) +4
(c) 28.8 K (d) 28800 K (c) +398 (d) +780
34. During complete combustion of one mole of butane, (e) +394
2658 kJ of heat is released. The thermochemical reaction for 41. If C + O2 → CO2 + 94.2 kcal
above change is 1
H2 + O2 → H 2O + 68.3 kcal
(a) 2C4 H10 (g) + 13O2 (g ) → 3CO2 (g) + 10 H 2 O(l) 2
CH 4 + 2O2 → CO2 + 2 H 2O + 210.8 kcal
∆ r H = −2658.0 kJ mol −1
then the possible heat of formation of methane will be
13
(b) C4 H10 (g) + O2 (g) → 4 CO2 (g) + 5 H 2 O(l); (a) 47.3 kcal (b) 20.0 kcal
2 (c) 45.9 kcal (d) – 47.3 kcal
∆ r H = −1129.0kJ mol −1 42. The standard enthalpies of combustion of C6 H6(l ) , C(graphite)
13 and H 2( g ) are respectively − 3270 kJ mol −1 , − 394 kJ mol −1
(c) C4 H10 (g) + O2 (g) → 4 CO2 (g) + 5 H 2 O(l),
2
and − 286 kJ mol −1 . What is the standard enthalpy of
∆ r H = −2658.0kJ mol −1
formation of C6 H6(l ) in kJ mol −1
13
(d) C4 H10 (g) + O2 (g) → 4 CO2 (g) + 5 H 2O (l); (a) – 48 (b) + 48
2
(c) – 480 (d) + 480
∆r H = +2658.0 kJ mol −1 (e) – 72
 Thermodynamics and Thermochemistry 217
43. The standard molar heat of formation of ethane, CO2 and 51. Four grams of graphite is burnt in a bomb calorimeter of
water (l) are respectively – 21.1, – 94.1 and – 68.3 kcal. The heat capacity 30 kJ K −1 in excess of oxygen at
standard molar heat of combustion of ethane will be 1 atmospheric pressure. The temperature rises from 300 to
(a) – 372 kcal (b) 162 kcal 304 K. What is the enthalpy of combustion of graphite (in
(c) – 240 kcal (d) 183.5 kcal kJ mol −1 )
44. Which of the following fuels will have the highest calorific
(a) 360 (b) 1440
value (kJ/kg)
(c) – 360 (d) – 1440
(a) Charcoal (b) Kerosene
(e) – 520
(c) Wood (d) Dung
52. Given,
45. The heat of neutralization of a strong acid and a strong alkali
is 57.0 kJ mol −1 . The heat released when 0.5 mole of NH3( g ) + 3Cl2( g ) NCl 3( g ) + 3 HCl( g ) ; − ∆H1

HNO3 solution is mixed with 0.2 mole of KOH is N 2( g ) + 3H 2( g) 2 NH 3( g ) ; − ∆H 2

(a) 57.0 kJ (b) 11.4 kJ H 2( g ) + Cl2( g ) 2HCl( g ) ; ∆H 3
(c) 28.5 kJ (d) 34.9 kJ
The heat of formation of NCl3( g ) in the terms of ∆H1 , ∆H 2
46. Which of the following is an endothermic reaction and ∆H 3 is
(a) 2 H 2 + O 2 → 2 H 2 O
∆H 2 3
(b) N 2 + O2 → 2 NO (a) ∆H f = − ∆H1 + − ∆H 3
2 2
(c) 2 NaOH + H 2 SO 4 → Na 2 SO 4 + 2 H 2 O ∆H 2 3
(b) ∆H f = ∆H1 + − ∆H 3
(d) 3O 2 + C 2 H 5 OH → 2CO 2 + 3 H 2 O 2 2
∆H 2 3
47. The heat of combustion of benzene determined in a bomb (c) ∆H f = − ∆H1 − − ∆H 3
2 2
calorimeter is − 870 kcal mol −1 at 25 o C . The value of ∆E
(d) None of these
for the reaction is
(a) − 1740 kcal (b) − 870 kcal 53. The lattice enthalpy and hydration enthalpy of four
compounds are given below
(c) − 872 kcal (d) − 874 kcal
Lattice Hydration
48. In the complete combustion of butanol C4 H 9 OH (l) , if ∆H Compound enthalpy enthalpy
is enthalpy of combustion and ∆E is the heat of combustion (in kJ mol–1) (in kJ mol–1)
at constant volume, then
P +780 – 920
(a) ∆H < ∆E
(b) ∆H = ∆E Q +1012 – 812

(c) ∆H > ∆E R +828 – 878

(d) ∆H , ∆E relation cannot be predicted S +632 – 600
49. Which of the following compounds will absorb the The pair of compounds which is soluble in water is
maximum quantity of heat when dissolved in the same
(a) P and Q (b) Q and R
amount of water ? The heats of solution of these
(c) R and S (d) Q and S
compounds at 25 o C in kJ/mole of each solute is given in
brackets (e) P and R

(a) HNO 3 (∆H = −33) 54. For an endothermic reaction where ∆H represents the
enthalpy of the reaction in kJ/mole, the minimum value for
(b) KCl(∆H = +17.64) the energy of activation will be
(c) NH 4 NO 3 (∆H = +25.5) (a) Less than ∆H (b) Zero
(d) HCl (∆H = −74.1) (c) More than ∆H (d) Equal to ∆H
50. Which one of the following is always not negative 55. A Beckmann thermometer is used to measure
(a) Enthalpy of combustion (a) High temperature
(b) Enthalpy of formation (b) Low temperature
(c) Enthalpy of neutralisation (c) Normal temperature
(d) Lattice enthalpy (d) All temperature
 218 Thermodynamics and Thermochemistry
56. The heat liberated when 1.89 g of benzoic acid is burnt in a 63. The heat of combustion of carbon is –94 kcal at 1 atm
o
bomb calorimeter at 25 C increases the temperature of pressure. The intrinsic energy of CO2 is

18.94 kg of water by 0.632o C .If the specific heat of water (a) +94 kcal (b) − 94 kcal
o
at 25 C is 0.998 cal/g-deg, the value of the heat (c) +47 kcal (d) − 47 kcal
combustion of benzoic acid is (in per mole)
64. A solution of 500mL of 0.2 M KOH and 500 mL of
(a) 771.1 kcal (b) 871.2 kcal
0.2 M HCl is mixed and stirred; the rise in temperature is
(c) 881.1 kcal (d) 981.1 kcal
T1 . The experiment is repeated using 250 mL each of
57. The standard enthalpies of formation of
solution, the temperature raised is T2 . Which of the
A( NH 3 ), B(CO 2 ), C(HI ) and D(SO 2 ) are respectively –
following is true
46.19, –393.4, +24.94 and –296.9 kJ mol −1 . The (a) T1 = T2 (b) T1 = 2T2
increasing order of their stability is
(c) T1 = 4T2 (d) T2 = 9T1
(a) B < D < A < C (b) C < A < D < B
(c) D<B<C< A (d) A < C < D < B 65. When 50 cm 3 of a strong acid is added to 50 cm 3 of an

58. C(graphite) + O2 (g) → CO2(g) ; ∆H = −94.05 kcal mol −1 alkali, the temperature rises by 5 o C . If 250 cm 3 of each
liquid are mixed, the temperature rise would be
C(diamond) + O 2 (g) → CO 2 (g); ∆H = −94.50 kcal mol −1
(a) 5 o C (b) 10 o C
therefore
(c) 25 o C (d) 20 o C
−1
(a) C(graphite) → C(diamond) ; ∆H 298
o
K = −450 cal mol 66. The enthalpy of neutralization of oxalic acid by a strong
−1
base is –25.4 kcal mol–1. The enthalpy of neutralization of
(b) C(diamond) → C(graphite) ; ∆H 298
o
K = +450 cal mol
strong acid and strong base is –13.7 kcal equiv–1. The
(c) Graphite is the stabler allotrope enthalpy of dissociation of H 2 C 2 O4 2 H + + C2 O42− is
(d) Diamond is harder than graphite (a) 1.0 kcal mol–1 (b) 2.0 kcal mol–1
3 3 –1
59. When 50cm of 0.2 N H 2SO4 is mixed with 50cm of (c) 18.55 kcal mol (d) 11.7 kcal mol–1
1 N KOH , the heat liberated is 67. Which of the following salt on dissolution in water absorbs
heat
(a) 11.46 kJ (b) 57.3 kJ
(a) NH 4 Cl (b) CaO
(c) 573 kJ (d) 573 J
(c) Na2 SO4 (d) Na2CO3
60. The amount of heat evolved when 500cm 3 of 0.1M HCl is

mixed with 200cm 3 of 0.2 M NaOH is .......... Bond Energy

(a) 2.292 kJ (b) 1.292 kJ 1. A system is changed from state A to state B by one path and
from B to A another path. If E1 and E 2 are the
(c) 0.292 kJ (d) 3.392 kJ
corresponding changes in internal energy, then
61. The enthalpy of the reaction,
(a) E1 + E 2 = −ve (b) E1 + E 2 = +ve
1
H 2 (g ) + O2 (g) → H 2 O(g) is ∆H 1 and that of (c) E1 + E 2 = 0 (d) None of these
2
1 2. Energy required to dissociate 4 gm of gaseous hydrogen into
H 2 (g ) + O2 (g) → H 2 O(l ) is ∆H 2 . Then
2 free gaseous atoms is 208 kcal at 25 o C . The bond energy
(a) ∆H 1 < ∆H 2 (b) ∆H 1 + ∆H 2 = 0 of H − H bond will be
(a) 104 kcal (b) 10.4 kcal
(c) ∆H 1 > ∆H 2 (d) ∆H 1 = ∆H 2
(c) 1040 kcal (d) 104 cal
62. The enthalpies of elements in their standard states are taken 3. The first ionization energy for Li is 5.4 eV and electron
as zero. The enthalpy of formation of a compound affinity of Cl is 3.61eV. The ∆H (in kJ/mol) for the reaction
(a) Is always negative Li(g) + Cl(g) → Li + + Cl − is (if resulting ions do not combine
(b) Is always positive with each other) (1 eV = 1.6 × 10 −19 J )
(c) May be positive or negative (a) 70 (b) 100
(d) Is never negative (c) 170 (d) 270
 Thermodynamics and Thermochemistry 219

4. Bond dissociation enthalpy of H 2 ,Cl2 and HCl are 434, 11. From the following bond energies :

242 and 431 kJmol −1 respectively. Enthalpy of formation of H − H bond energy : 431.37 kJ mol–1
HCl is C = C bond energy : 606.10 kJ mol–1

(a) − 93kJmol −1 (b) 245kJmol −1 C – C bond energy : 336.49 kJ mol–1

C – H bond energy : 410.50 kJ mol–1
(c) 93kJmol −1 (d) − 245kJmol −1
Enthalpy for the reaction,
5. If enthalpies of methane and ethane are respectively 320
H H H H
and 360 calories then the bond energy of C − C bond is | | | |
C = C + H − H → H − C − C − H will be
(a) 80 calories (b) 40 calories | | | |
H H H H
(c) 60 calories (d) 120 calories
(a) 1523.6 kJ mol–1 (b) –243.6 kJ mol–1
6. Given that ∆H f (H ) = 218 kJ/mol, express the H−H bond –1
(c) –120.0 kJ mol (d) 553.0 kJ mol–1
energy in kcal/mol 12. Given that bond energies of H − H and Cl − Cl are 430 kJ
(a) 52.15 (b) 911 mol–1 and 240 kJ mol–1 respectively and ∆ f H for HCl is
(c) 104 (d) 52153 − 90kJ mol −1 . Bond enthalpy of HCl is
7. Given the bond energies N ≡ N , H − H and N − H bonds
(a) 290 kJ mol −1 (b) 380 kJ mol −1
−1
are 945, 436 and 391 kJ mole respectively, the enthalpy
(c) 425 kJ mol −1 (d) 245 kJ mol −1
of the following reaction N 2 (g) + 3 H 2 (g) → 2 NH 3 (g) is
13. For the reaction 2H 2 + O2 → 2H 2 O, ∆H = −571 . Bond
(a) −93 kJ (b) 102 kJ
energy of H − H = 435, O = O = 498, then calculate the
(c) 90 kJ (d) 105 kJ average bond energy of O − H bond using the above data
8. The enthalpy change (∆H ) for the process (a) 484 (b) – 484

N 2 H 4 (g) → 2 N(g) + 4 H(g) is 1724 kJ mol −1

. If the bond (c) 271 (d) – 271

energy of N − H bond in ammonia is 391kJ mol −1 . What 14. The heat of atomization of PH 3 (g) is 228 k cal mol −1 and that

is the bond energy of N − N bond in N 2 H 4 of P2 H 4 (g) is 355 k cal mol −1 . The energy of the P − P bond
is
(a) 160 kJ mol −1 (b) 391kJ mol −1
(a) 102 k cal mol −1 (b) 51 k cal mol −1
−1 −1
(c) 1173 kJ mol (d) 320 kJ mol
(c) 26 k cal mol −1 (d) 204 k cal mol −1
9. Enthalpy of formation of HF and HCl are − 161 kJ and
15. Consider the reactions given below. On the basis of these
− 92 kJ respectively. Which of the following statements is reactions find out which of the algebraic relationship given
incorrect in options (a) to (d) is correct

(a) HCl is more stable than HF (i) C (g) + 4 H (g ) → CH 4 (g ); ∆ r H = x k J mol −1

(b) HF and HCl are exothermic compounds (ii) C (graphite ) + 2 H 2 (g) → CH 4 (g ); ∆ r H = y k J mol −1
(c) The affinity of fluorine to hydrogen is greater than the
(a) x = y (b) x = 2y
affinity of chlorine to hydrogen
(c) x>y (d) x < y
(d) HF is more stable than HCl
10. If the bond dissociation energies of XY, X 2 and Y2 (all Free Energy and Work Function
diatomic molecules) are in the ratio of 1 : 1 : 0.5 and ∆ f H 1. Which of the following conditions will always lead to a non-
−1 spontaneous change
for the formation of XY is − 200 kJ mole . The bond
dissociation energy of X 2 will be (a) Positive ∆H and positive ∆S
(b) Negative ∆H and negative ∆S
(a) 100 kJ mol −1 (b) 800 kJ mol −1
(c) Positive ∆H and negative ∆S
−1 −1
(c) 300 kJ mol (d) 400 kJ mol (d) Negative ∆H and positive ∆S
 220 Thermodynamics and Thermochemistry

2. The reaction, Zn(s) + CuSO4 (aq) → ZnSO4 (aq) + Cu(s) is 9. A spontaneous process is one in which the system suffers
an example for a (a) No energy change
(a) Spontaneous process (b) Non-spontaneous process (b) A lowering of free energy
(c) Isobaric process (d) Reversible process (c) A lowering of entropy
3. The condition of spontaneity of process is (d) An increase in internal energy
(a) Lowering of entropy at constant temperature and
10. The ∆H and ∆S for a reaction at one atmospheric
pressure
pressure are +30.558 kJ and 0.066 kJk −1 respectively. The
(b) Lowering of Gibbs free energy of system at constant
temperature and pressure temperature at which the free energy change will be zero and
below of this temperature the nature of reaction would be
(c) Increase of entropy of system at constant temperature
and pressure (a) 483 K, spontaneous (b) 443 K, non-spontaneous
(d) Increase of Gibbs free energy of the universe at (c) 443 K, spontaneous (d) 463 K, non-spontaneous
constant temperature and pressure (e) 463 K, spontaneous
4. Mixing of two different ideal gases under isothermal 11. The occurrence of a reaction is impossible if
reversible condition will lead to
(a) ∆H is +ve ; ∆S is also + ve but ∆H < T∆S
(a) Increase of Gibbs free energy of the system
(b) ∆H is – ve ; ∆S is also – ve but ∆H > T∆S
(b) No change of entropy of the system
(c) Increase of entropy of the system (c) ∆H is – ve ; ∆S is + ve
(d) Increase of enthalpy of the system (d) ∆H is + ve ; ∆S is – ve
5. For a spontaneous change, free energy change ∆G is 12. When enthalpy and entropy change for a chemical reaction
(a) Positive are − 2.5 × 10 3 cal and 7.4 cal deg −1 respectively. Predict
(b) Negative the reaction at 298 K is
(c) Zero
(a) Spontaneous (b) Reversible
(d) Can be positive or negative
(c) Irreversible (d) Non-spontaneous
6. For the reaction,
CaCO3 (s) CaO(s) + CO2 (g) 13. For the reaction at 298K, A( g ) + B( g ) → C( g )

partial pressure of CO2 at 1000 K is 0.003 atm. ∆E = −5 cal and ∆S = −10 cal K −1
∆Gº = 27.2 kcal. Calculate the value of ∆G (a) ∆G = +2612 cal (b) ∆G = −2612 cal
(a) 12.6 kcal (b) 15.6 kcal
(c) ∆G = +261.2 cal (d) ∆G = 2379 cal
(c) 13.4 kcal (d) 14.2 kcal
7. What is the free energy change ∆G when 1.0 mole of 14. The free energy of formation of NO is 78 kJ mol −1 at the

water at 100 o C and 1 atm pressure is converted into steam temperature of an automobile engine (1000 K). What is the
equilibrium constant for this reaction at 1000 K
at 100 o C and 1 atm pressure
1 1
N 2 ( g ) + O2 ( g ) NO(g)
(a) 540 cal (b) −9800 cal 2 2
(c) 9800 cal (d) 0 cal (a) 8.4 × 10 −5 (b) 7.1 × 10 −9
8. The free energy change for the following reactions are given (c) 4.2 × 10−10 (d) 1.7 × 10−19
below,
15. A chemical reaction is spontaneous at 298 K but non-
5
C2 H 2 (g) + O2 (g) → 2CO2 (g ) + H 2O(l); ∆Go = −1234 kJ spontaneous at 350 K. Which one of the following is true
2
for the reaction
C(s) + O 2 (g) → CO 2 (g) ∆G o = −394 kJ
∆G ∆H ∆S
1
H 2 (g) + O 2 (g) → H 2 O(l ) ∆G o = −237kJ (a) – – +
2
What is the standard free energy change for the reaction (b) + + +
H 2 (g ) + 2 C ( s ) → C2 H 2 ( g ) (c) – + –

(a) – 209 kJ (b) – 2259 kJ (d) + – +

(c) + 2259 kJ (d) 209 kJ (e) – – –
 Thermodynamics and Thermochemistry 221
16. Identify the correct statement from the following in a 23. A reaction occurs spontaneously if
chemical reaction
(a) T∆S < ∆H and both ∆H and ∆S are +ve
(a) The entropy always increases
(b) The change in entropy along with suitable change in (b) T∆S > ∆H and both ∆H and ∆S are +ve
enthalpy decides the fate of a reaction (c) T∆S = ∆H and both ∆H and ∆S are +ve
(c) The enthalpy always decreases
(d) T∆S > ∆H and ∆H is +ve and ∆S is –ve
(d) Both the enthalpy and the entropy remain constant
17. The standard Gibbs free energy change (∆G0 ) at 25º C for 24. The standard Gibbs free energy change ∆G o is related to
the dissociation of N 2O4 (g) to NO2 (g) is (given, equilibrium equilibrium constant K p as

constant = 0.15, R = 8.314 JK −1mol −1 ) ∆Go

 e 
(a) 1.1 kJ (b) 4.7 kJ (a) K p = − RT ln ∆G o
(b) K p =  
 RT 
(c) 8.1 kJ (d) 38.2 kJ
∆Go
∆G o −
18. For the reaction, X 2O4 (l) → 2 XO2 (g) ∆U = 2.1 kcal, (c) K p = − (d) K p = e RT
RT
∆S = 20 cal K −1 at 300 K Hence, ∆G is
25. Which of the following is not correct
(a) 9.3 kcal (b) –9.3 kcal
(a) ∆G is zero for a reversible reaction
(c) 2.7 kcal (d) –2.7 kcal
19. ∆G in Ag 2 O → 2 Ag + 1 / 2O2 at a certain temperature is (b) ∆G is positive for a spontaneous reaction
−10 kJ / mole. Pick the correct statement (c) ∆G is negative for a spontaneous reaction
(a) Ag 2 O decomposes to Ag and O 2 (d) ∆G is positive for a non-spontaneous reaction
(b) Ag and O 2 combines to form Ag 2 O 26. Standard entropy of X 2 , Y2 and XY3 are 60, 40 and 50
(c) Reaction is in equilibrium
JK −1mol −1, respectively. For the reaction,
(d) Reaction does not take place
1 3
20. As O2 is cooled at 1 atm pressure, it freezes to form solid I X 2 + Y2 → XY3 , ∆H = −30kJ , to be at equilibrium, the
2 2
at 54.5 K. At a lower temperature, solid I rearranges to solid
II, which has a different crystal structure. Thermal temperature will be
measurements show that for the phase transition solid I to (a) 500 K (b) 750 K
solid II, ∆H = −743.1 J mol −1 and ∆S = −17.0 JK −1 mol −1 . (c) 1000 K (d) 1250 K
At what temperature are solids I and II in equilibrium
27. If an endothermic reaction is non-spontaneous at freezing
(a) 2.06 K (b) 31.5 K
point of water and becomes feasible at its boiling point then
(c) 43.7 K (d) 53.4 K
21. Which of the following statements is true (a) ∆H is −ve, ∆S is + ve
(a) The total entropy of the universe remains constant
(b) ∆H and ∆S both are + ve
(b) The total entropy of the universe is continuously
decreasing (c) ∆H and ∆S both are – ve
(c) The total energy of the universe is continuously (d) ∆H is + ve, ∆S is – ve
decreasing
28. A process is taking place at constant temperature and
(d) The total energy of the universe remains constant
pressure. Then
22. Values of ∆H and ∆S for five different reactions are given
below. (a) ∆H = ∆E (b) ∆H = T∆S
−1 −1 −1
Reactions ∆H (kJ mol ) ∆S (JK mol ) (c) ∆H = 0 (d) ∆S = 0
I +98.0 +14.8 29. If an endothermic reaction occurs spontaneously at constant
II – 55.5 –84.6 temperature T and pressure P, then which of the following is
III +28.3 –17.0 true
IV – 40.5 +24.6
(a) ∆G > 0 (b) ∆H < 0
V + 34.7 0.0
On the basis of these values predict which one of these will (c) ∆S > 0 (d) ∆S < 0
be spontaneous at all temperature 30. Thermodynamically the most stable form of carbon is
(a) Reaction I (b) Reaction II
(a) Diamond (b) Graphite
(c) Reaction III (d) Reaction IV
(e) Reaction V (c) Fullerenes (d) Coal
 222 Thermodynamics and Thermochemistry
31. The equilibrium concentration of the species in the reaction
Statement Type Questions
A+B C + D are 3, 5, 10 and 15 mole L−1 respectively
1. Read the following statements carefully and choose the
at 300 K the ∆G o for the reaction is correct option
(a) 13.81 cal (b) – 1381.8 cal (i) The state of the system is specified by state functions or
(c) – 138.18 cal (d) 1391.6 cal state variables.
32. For a reversible reaction: X(g ) + 3Y( g ) 2 Z( g ) , ∆H= – 40kJ, (ii) Variables like P, V and T are called state variables or
state functions.
the standard entropies of X, Y and Z are 60, 40 and 50 JK–
1 (iii) Their values depend only on the state of the system and
mol–1 respectively. The temperature at which the above
not on how it is reached.
reaction attains equilibrium is about
(a) (i) and (ii) are correct
(a) 400 K (b) 500 K
(b) (ii) and (iii) are correct
(c) 273 K (d) 373 K
(c) (i) , (ii) and (iii) are correct
33. For the reversible reaction :
(d) Only (iii) is correct
A(s) + B(g ) C(g ) + D(g ) : ∆G
= − 350 kj . 2. Read the following statements carefully and choose the
Which one of the following statements is true correct option
(a) The entropy change is negative (i) Internal energy U, of the system is a state function.
(ii) –w shows, that work is done on the system.
(b) Equilibrium constant is greater than one
(iii) +w shows, that work is done by the system.
(c) The reaction should be instantaneous
(a) (i) and (ii) are correct (b) (ii) and (iii) are correct
(d) The reaction is thermodynamically not feasible
(c) (i) and (iii) are correct (d) Only (i) is correct
34. In which of the following reactions, standard reaction
3. Which of the following statement(s) is/are correct
entropy change (∆Sº ) is positive and standard Gibb’s
(i) In case of expansion maximum amount of work can be
energy change (∆Gº ) decreases sharply with increasing
obtained under isothermal conditions by reversibly
temperature carrying out the process rather than through irreversible
1 route.
(a) C graphite + O2 (g) → CO(g)
2 (ii) In case of compression, minimum amount of work can
1 be done on system by carrying out the process
(b) CO(g) + O2 (g) → CO2 (g)
2 irreversibly than reversibly.
1 (a) (i) and (ii) (b) Only (i)
(c) Mg(s) + O2 (g) → MgO(s) (c) Only (ii) (d) Neither (i) nor (ii)
2
1 1 1 4. Read the following statements carefully and choose the
(d) C graphite + O2 (g) → CO2 (g) correct option
2 2 2
(i) In case of diatomic molecules the enthalpy of
35. Following reaction occurring in an automobile
atomization is also the bond dissociation enthalpy.
2C8 H18 (g) + 25O2 (g) → 16CO2 (g) + 18 H 2O(g). The sign of
(ii) In case polyatomic molecules, bond dissociation
∆H, ∆S and ∆G would be enthalpy is different for different bonds within the same
(a) +, –, + (b) –, +, – molecule.
(c) –, +, + (d) +, +, – (a) Both (i) and (ii) are correct
36. The densities of graphite and diamond at 298 K are 2.25 (b) (i) is correct but (ii) is incorrect
and 3.31 g cm–3, respectively. If the standard free energy (c) (ii) is correct but (i) is incorrect
−1
difference (∆G ) is equal to 1895 J mol , the pressure at
o (d) Both (i) and (ii) are incorrect
which graphite will be transformed diamond at 298 K is 5. Which of the following statement is incorrect
(a) The standard enthalpy of reaction is the enthalpy
(a) 9.92 × 10 5 Pa (b) 1.1 × 10 9 Pa
change for a reaction when all the participating
(c) 9.92 × 10 7 Pa (d) 9.92 × 10 6 Pa substances are in their standard states.
37. The equilibrium constant of a reaction at 298 K is 5 × 10 −3 (b) The standard state of a substance at a specified
−5
temperature is its pure form at 1 bar.
and at 1000 K is 2 × 10 . What is the sign of ∆H º for the
(c) The standard state of solid iron at 298 K is pure iron at
reaction 1 bar
(a) ∆H º = 0 (b) ∆H º is negative (d) Standard conditions are denoted by adding the
(c) ∆H º is positive (d) None of these superscript
to the symbol ∆H e.g., −∆H

 Thermodynamics and Thermochemistry 223
4. Match the columns
Matching Type Questions
1. Match the columns Column I Column II

Column I Column II (A) ∆H = −ve; ∆S = −ve (p) Reaction will be non-

∆G = −ve spontaneous at high

(A) pext = 0 (p) Free expansion of an
ideal gas temperature

(B) q = pext (V f − Vi ) (q) Adiabatic change (B) ∆H = −ve; ∆S = −ve (q) Reaction will be non-

∆G = +ve spontaneous at low

(C) q = 2.303 nRT log (r) Isothermal reversible temperature
change
(V f / Vi )
(C) ∆H = +ve; ∆S = +ve (r) Reaction will be
(D) ∆U = Wad (s) Isothermal ∆G = +ve spontaneous at low
irreversible change temperature

(a) A – (p), B – (s), C – (r), D – (q) (D) ∆H = +ve; ∆S = +ve (s) Reaction will be
(b) A – (p), B – (q), C – (r), D – (s) ∆G = −ve spontaneous at high
(c) A – (p), B – (r), C – (s), D – (q) temperature

(d) A – (p), B – (r), C – (q), D – (s)

(a) A – (q), B – (r), C – (p), D – (s)
2. Match the columns
(b) A – (r), B – (p), C – (q), D – (s)
Column I Column II
(c) A – (r), B – (q), C – (s), D – (p)
(A) 13 (p) Enthalpy of
C4 H10 + O2 → (d) A – (q), B – (s), C – (p), D – (r)
2 atomisation
5. Match the columns
4 CO2 + 5 H 2O ; ∆H = −w
Column I Column II
(B) CH 4 → C + 4 H ; ∆H = x (q) Enthalpy of
(A) H 2 (g ) + Br2 (g ) → (p) ∆H = ∆U − 2RT
formation
2 HBr (g)
(C) H 2 + Br2 → 2 HBr ; ∆H = y (r) Enthalpy of
combustion (B) PCl5 (g ) → (q) ∆H = ∆U + 3RT

(D) Na − (s) → Na(g) ; ∆H = z (s) Enthalpy of PCl3 (g ) + Cl2 (g )

sublimation
(C) N 2 (g ) + 3 H 2 (g) → (r) ∆H = ∆U
(a) A – (s), B – (p), C – (q), D – (r)
2 NH 3 (g)
(b) A – (q), B – (r), C – (p), D – (s)
(c) A – (r), B – (p), C – (q), D – (s)
(D) 2 N 2O5 (g ) → (s) ∆H = ∆U + RT

(d) A – (p), B – (q), C – (s), D – (r) 4 NO2 (g) + O2 (g)

3. Match the columns
(a) A – (r), B – (p), C – (q), D – (s)
Column I Column II
(b) A – (r), B – (s), C – (p), D – (q)
(A) Exothermic (p) ∆H = 0, ∆E = 0 (c) A – (q), B – (p), C – (s), D – (r)
(d) A – (s), B – (q), C – (p), D – (r)
(B) Spontaneous (q) ∆G = 0

(C) Cyclic process (r) ∆H is negative Numerical Value type questions

(D) Equilibrium (s) ∆G is negative 1. An athlete is given 100 g of glucose (C6 H12 O6 ) of energy
equivalent to 1560 kJ . He utilizes 50 percent of this gained
(a) A – (q), B – (r), C – (p), D – (s)
energy in the event. In order to avoid storage of energy in
(b) A – (s), B – (p), C – (r), D – (q)
the body, calculate the weight of water he would need to
(c) A – (p), B – (q), C – (s), D – (r)
perspire. The enthalpy of evaporation of water is
(d) A – (r), B – (s), C – (p), D – (q) 44 kJ / mol
 224 Thermodynamics and Thermochemistry

2. Estimate the average S—F bond energy in SF6 . The 7. Calculate standard heat of formation of CS2 . Given that
standard heat of formation values of SF6 (g ), S (g) and standard heat of combustion of C, S and CS2 are −393.3,

−293.72 and − 1108.76 kJ mol −1

–1
F (g ) are : – 1100, 275 and 80 kJ mol respectively

3. 2 mol of an ideal gas at 27°C is expanded reversibly from 8. The heat evolved in the conversion of 1g-atom of
2 lit to 20 lit. Find entropy change (R = 2 cal/mol K) β − sulphur into α − sulphur is 82 cal at 25°C. If the
4. One mole of an ideal monoatomic gas is mixed with 1 mole specific heats of α − and β − sulphur are 0.163 and
of an ideal diatomic gas. The molar specific heat of the 0.171 cal / g, calculate the heat of transition for β − sulphur
mixture at constant volume is
into α − sulphur at 50°C
5. When 1 mol of CO2 (g ) occupying a volume of 10 L at
9. When a certain amount of ethylene was burnt 6226 kJ heat
27°C is allowed to expand under adiabatic conditions,
was evolved. If heat of combustion of ethylene is 1411kJ ,
temperature falls to −123°C. Hence, final volume of the gas
will be the volume of O2 (at NTP) that entered into the reaction is

6. When 12.0 g of carbon reacted with oxygen to form CO 10. Heat evolved in the reaction, H 2 + Cl 2 → 2 HCl is
and CO2 at 25°C and constant pressure, 75.0 k cal of 182 kJ . Bond energies of H — H and Cl — Cl are
heat was liberated and no carbon remained. Calculate the 430 and 242 kJ / mol respectively. The H − Cl bond
mass of oxygen which reacted
energy is
∆H °f (CO2 ) = −95 kcal mol −1 , ∆H °f (CO) = −24 kcal mol −1
 PAST YEARS QUESTIONS
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1. Among the following, the set of parameters that represents 8. The enthalpy change for the following processes are listed
path function is [JEE (Main) 2019] below
(A) q + w (B) q
Cl2 (g) = 2 Cl(g), 242 .3 kJ mol −1
(C) w (D) H − TS
(a) (A) and (D) (b) (A), (B) and (C) I 2 (g) = 2I (g), 151 .0 kJ mol −1
(c) (B) and (C) (d) (B), (C) and (D)
2. Assuming that water vapour is an ideal gas, the internal ICl(g) = I (g) + Cl(g), 211 .3 kJ mol −1
energy (∆U) when 1 mol of water is vapourised at 1 bar I 2 (s) = I 2 (g), 62 . 76 kJ mol −1
pressure and 100°C, (Given : Molar enthalpy of
vapourization of water at 1 bar and 373 K = 41 kJ mol–1 Given that the standard states for iodine and chlorine are
and R = 8.3 J mol–1K–1) will be [AIEEE 2007] I 2 (s) and Cl2 (g), the standard enthalpy of formation for
(a) 4.100 kJ mol −1 (b) 3.7904 kJ mol −1 ICl(g) is [AIEEE 2006]
(c) 37.904 kJ mol −1 (d) 41.00 kJ mol −1
(a) − 14 .6 kJ mol −1 (b) − 16 .8 kJ mol −1
3. The heat required to raise the temperature of a body by 1 K
is called [AIEEE 2002] (c) + 16 .8 kJ mol −1 (d) + 244 .8 kJ mol −1
(a) Specific heat (b) Thermal capacity
(c) Water equivalent (d) None of these 9. Molar heat capacity of water in equilibrium with ice at
4. For which one of the following reactions, ∆H is not equal constant pressure is [IIT JEE 1997]
to ∆E [IIT JEE 1995] (a) Zero (b) Infinity (∞)
(a) H 2( g ) + I 2( g ) 2HI ( g ) −1 −1
(c) 40 . 45 kJ K mol (d) 75 .48 J K −1
(b) C( s) + O2( g ) CO2( g )
10. The enthalpies of combustion of carbon and carbon
(c) N 2( g ) + 3 H 2( g ) 2 NH 3( g)
monoxide are –393.5 and –283 kJ mol–1 respectively. The
(d) HCl(aq) + NaOH(aq) NaCl(aq) + H 2 O enthalpy of formation of carbon monoxide per mole is
5. For the reaction, 2CO + O2 → 2CO2 ; ∆H = 560kJ . Two [AIEEE 2004; MP PET 2013; JEE (Main) 2016]
moles of CO and one mole of O2 are taken in a container of (a) −676.5 kJ (b) 676.5 kJ
volume 1L. They completely form two moles of CO2, the
gases deviate appreciably from ideal behaviour. If the (c) 110.5 kJ (d) −110.5 kJ
pressure in the vessel changes from 70 to 40 atm, find the
11. An ideal gas is allowed to expand both reversibly and
magnitude (absolute value) of ∆U at 500 K (1 L atm = 0.1
kJ) [IIT JEE 2006] irreversibly in an isolated system. If Ti is the initial
(a) 563 (b) 575 temperature and Tf is the final temperature, which of the
(c) 585 (d) 595
following statements is correct [AIEEE 2006]
6. (∆H − ∆U) for the formation of carbon monoxide
(CO) from its elements at 298 K is ( R = 8.314 JK −1
mol −1
) (a) (Tf )irrev > (Tf )rev

[AIEEE 2006] (b) Tf > Ti for reversible process but Tf = Ti for irreversible
(a) − 1238 . 78 J mol −1 (b) 1238 . 78 J mol −1
process
(c) − 2477 .57 J mol −1 (d) 2477 .57 J mol −1
(c) (Tf )rev = (Tf )irrev
7. A piston filled with 0.04 mol of an ideal gas expands
(d) Tf = Ti for both reversible and irreversible processes
reversibly from 50.0 mL to 375mL at a constant temperature
of 37.0ºC. As it does so, it absorbs 208 J of heat. The values 12. Two mole of an ideal gas is expanded isothermally and
of q and w for the process will be reversibly from 1 litre to 10 litre at 300K . The enthalpy
(R = 8.314 J/mol K) (ln 7.5 = 2.01) [JEE (Mains) 2013]
change (in kJ ) for the process is [IIT Screening 2004]
(a) q = +208 J, w = − 208 J (b) q = − 208 J, w = − 208 J (a) 11.4 kJ (b) –11.4 kJ
(c) q = −208 J, w = + 208 J (d) q = + 208 J, w = + 208 J (c) 0 kJ (d) 4.8 kJ
 226 Thermodynamics and Thermochemistry
13. When one mole of monoatomic ideal gas at T K undergoes 19. For a diatomic ideal gas in a closed system, which of the
adiabatic change under a constant external pressure of 1 following plots does not correctly describe the relation
atm changes volume from 1 litre to 2 litre. between various thermodynamic quantities
The final temperature in Kelvin would be [IIT JEE 2005]
[JEE (Mains) 2019]
T 2
(a) (b) T +
2(2 / 3) 3 × 0.0821
CP CV
2
(c) T (d) T − (a) (b)
3 × 0.0821
14. ∆U equal to [JEE (Main) 2017]
(a) Isobaric work (b) Adiabatic work P V
(c) Isothermal work (d) Isochoric work
15. The combustion of benzene (l ) gives CO 2 (g ) and H 2 O(l) .
(c) CV (d) U
Given that heat of combustion of benzene at constant
volume is − 3263.9 kJ mol −1 at 25 o C ; heat of combustion
(in kJ mol–1) of benzene at constant pressure will be T T
(R = 8.314 JK–1 mol–1) [JEE (Main) 2018]
20. The combination of plots which does not represent
(a) 3260 (b) – 3267.6
isothermal expansion of an ideal gas is : [JEE (Mains) 2019]
(c) 4152.6 (d) – 452.46
16. Consider the reversible isothermal expansion of an ideal gas
in a closed system at two different temperatures T1 and P P
T2 (T1 < T2 ) . The correct graphical depiction of the
(A) (B)
dependence of work done (W ) on the final volume (V ) is :
[JEE (Mains) 2019]
T2 T2 O 1/Vm O Vm
|W| |W|
T1
T1
(a) (b) PVm

(C) (D) U
O O
In V In V
T2 T2 O P O Vm
|W| |W|
T1 T1 (a) (B) and (C) (b) (A) and (C)
(c) (d)
(c) (A) and (D) (d) (B) and (D)
21. 5 moles of an ideal gas at 100 K are allowed to undergo
O O
In V In V
reversible compression till its temperature becomes 200 K .
17. The entropy change associated with the conversion of
If CV = 28 J K −1mol −1 , calculate ∆U and ∆pV for this
1kg of ice at 273 K to water vapours at 383K is :
(Specific heat of water liquid and water vapour are process. (R = 8.0 J K −1mol −1 ) [JEE (Main) 2019]
4.2 k J K −1kg −1 and 2.0k J K −1k g −1 ; heat of liquid fusion (a) ∆U = 14 kJ ; ∆( pV ) = 4 kJ
and vaporisation of water are 334 kJ kg −1 and
(b) ∆U = 14 kJ ; ∆( pV ) = 18kJ
2491 kJ kg −1 , respectively). (log 273 = 2.436,
(c) ∆U = 14 J ; ∆( pV ) = 0.8 J
log 373 = 2.572, log 383 = 2.583) [JEE (Mains) 2019]
(a) 8.49kJ kg −1 K −1 (b) 9.26 kJ kg −1 K −1 (d) ∆U = 2.8 kJ ; ∆( pV ) = 0.8kJ

(c) 2.64kJ kg −1 K −1 (d) 7.90kJ kg −1 K −1 22. Which one of the following equations does not correctly
represent the first law of thermodynamics for the given
18. An ideal gas undergoes isothermal compression from 5m 3
processes involving an ideal gas (Assume non-expansion
to 1m 3 against a constant external pressure of 4 Nm −2 .
Heat released in this process is used to increase the work is zero) [Kerala PET 2006; KCET 2010;
temperature of 1 mole of Al . If molar heat capacity of Al JEE (Main) 2019]
is 24 J mol −1 K −1 , the temperature of Al increases by : (a) Isothermal process : q = −w
[JEE (Mains) 2019] (b) Isochoric process : ∆U = q
3 2
(a) K (b) K (c) Adiabatic process : ∆U = −w
2 3
(c) 1K (d) 2K (d) Cyclic process : q = −w
 Thermodynamics and Thermochemistry 227

23. For silver, C p ( JK −1mol −1 ) = 23 + 0.01T . If the temperature 31. For the process
H 2 O(ℓ) → H 2 O(g)
(T ) of 3 moles of silver is raised from 300 K to 1000 K at
1 atm pressure, the value of ∆H will be close to at T = 100 C and 1 atmosphere pressure, the correct
0

[JEE (Main) 2019] choice is [JEE (Advanced) 2014]

(a) 13 kJ (b) 16 kJ (a) ∆Ssystem > 0 and ∆Ssurroundings > 0
(c) 62 kJ (d) 21 kJ (b) ∆Ssystem > 0 and ∆Ssurroundings < 0
24. During compression of a spring the work done is 10 kJ and (c) ∆Ssystem < 0 and ∆Ssurroundings > 0
2 kJ escaped to the surrounding as heat. The change in
(d) ∆Ssystem < 0 and ∆Ssurroundings < 0
internal energy, ∆U (in kJ ) is [JEE (Main) 2019]
32. A process will be spontaneous at all temperature if
(a) 8 (b) −12
[JEE (Main) 2019]
(c) 12 (d) −8
(a) ∆H > 0 and ∆S > 0 (b) ∆H < 0 and ∆S < 0
25. An ideal gas is allowed to expand from 1 L to 10 L against
(c) ∆H < 0 and ∆S > 0 (d) ∆H > 0 and ∆S < 0
a constant external pressure of 1 bar. The work done in kJ 33. The process with negative entropy change is :
is [JEE (Main) 2019]
[JEE (Mains) 2019]
(a) −0.9 (b) −9.0 (a) Sublimation of dry ice
(c) −2.0 (d) +10.0 (b) Dissolution of iodine in water
26. A heat engine absorbs heat Q1 at temperature T1 and heat (c) Dissociation of CaSO4 (s) to CaO(s) and SO3 (g)
Q2 at temperature T2 . Work done by the engine is
(d) Synthesis of ammonia from N 2 and H 2
(Q1 + Q 2 ) . This data [AIEEE 2002]
34. Two blocks of the same metal having same mass and at
(a) Violates Ist law of thermodynamics temperature T1 and T2 , respectively, are brought in contact
(b) Violates Ist law of thermodynamics if Q1 is –ve
with each other and allowed to attain thermal equilibrium at
(c) Violates Ist law of thermodynamics if Q 2 is –ve constant pressure. The change in entropy, ∆S, for this
(d) Does not violate Ist law of thermodynamics process is : [JEE (Mains) 2019]
27. The enthalpy of vaporization of a liquid is 30 kJ mol −1 and  1

 T + T2  (T + T2 ) 2
−1
entropy of vaporization is 75 J mol K . The boiling point of (a) 2C p ln  1 
 (b) 2C p ln  1 
 4 T1 T2   T1T2 
the liquid at 1 atm is [IIT Screening 2004]
 
(a) 250K (b) 400K  (T + T2 ) 2   T + T2 
(c) C p ln  1  (d) 2C p ln  1 
(c) 450K (d) 600K
 4 T1 T2   2T1 T2 
28. The direct conversion of A to B is difficult, hence it is carried
35. Which of the following equations correctly represents the
out by the following shown path
C D standard heat of formation (∆H of ) of methane
Given ∆S( A→ C) = 50 e.u.
[IIT Screening 1992; UPSEAT 2004]
∆S(C → D) = 30 e.u. (a) C(diamond ) + 2 H 2 (g) → CH 4 (g )

∆S( B→ D) = 20 e.u. A B (b) C(graphite ) + 2 H 2 (g ) → CH 4 (l)

(c) C(graphite ) + 2 H 2 (g) → CH 4 (g )
where e.u. is entropy unit then ∆S( A → B) is [IIT JEE 2006]
(d) C(graphite ) + 4 H → CH 4 (g )
(a) + 100 e.u. (b) + 60 e.u.
36. Standard molar enthalpy of formation of CO 2 is equal to
(c) – 100 e.u. (d) – 60 e.u.
[IIT JEE 1997; BHU 2001]
29. The entropy change involved in the isothermal reversible
(a) Zero
expansion of 2 moles of an ideal gas from a volume of
(b) The standard molar enthalpy of combustion of gaseous
10 dm3 to a volume of 100 dm3 at 27o C is [AIEEE 2011] carbon
(a) 38.3 J mol −1 K −1 (b) 35.8 J mol −1 K −1 (c) The sum of standard molar enthalpies of formation of
CO and O2
(c) 32.3 J mol −1 K −1 (d) 42.3 J mol −1 K −1
(d) The standard molar enthalpy of combustion of carbon
30. One mole of an ideal gas at 300 K in thermal contact with (graphite)
surroundings expands isothermally from 1.0 L to 2.0 L
37. The ∆H of for CO 2 (g ), CO(g) and H 2 O(g ) are – 393.5,
against a constant pressure of 3.0 atm. In this process, the
–110.5 and – 241.8kJmol–1 respectively. The standard
change in entropy of surroundings (∆SSurr ) in JK −1 is
enthalpy change (in kJ) for the reaction CO2 (g ) + H 2 (g) →
(1 L atm = 101.3 J ) [JEE (Advanced) 2016]
CO(g) + H 2O(g ) is [IIT Screening 2000]
(a) 5.763 (b) 1.013 (a) 524.1 (b) 41.2
(c) –1.013 (d) –5.763 (c) – 262.5 (d) – 41.2
 228 Thermodynamics and Thermochemistry

38. Which of the reaction defines ∆H of [IIT Screening 2003] (a) − 1366.95 kJ mol −1 (b) − 1361.95 kJ mol −1
(a) C(diamond ) + O 2 (g) → CO 2 (g) (c) − 1460.50 kJ mol −1 (d) − 1350.50 kJ mol −1
1 1 44. The enthalpy of solution of BaCl 2 (s) and BaCl 2 .2 H 2 O(s)
(b) H 2 (g) + F2 (g) → HF (g)
2 2
are −20.6 and 8.8 kJ mol −1 respectively. The enthalpy
(c) N 2 (g) + 3 H 2 (g) → 2 NH 3 (g)
change for the reaction BaCl 2 (s) + 2 H 2O → BaCl 2 .2 H 2O is
1
(d) CO(g) + O 2 (g) → CO 2 (g) [Roorkee Qualifying 1998]
2
39. The species which by definition has ZERO standard molar (a) 29.4 kJ (b) – 11.8 kJ
enthalpy of formation at 298 K is [IIT JEE 2010] (c) – 20.6 kJ (d) – 29.4 kJ
(a) Br2 (g) (b) Cl 2 (g) 45. Given
(c) H 2O(g) (d) CH 4 (g) C( graphite) + O2 (g) → CO2 (g); ∆ r H º = −393.5 kJ mol −1 ;
40. The standard enthalpies of formation of CO 2 (g ), H 2O(l)
1
and glucose(s) at 25º C are − 400 kJ / mol , −300 kJ / mol H 2 (g ) + O2 (g) → H 2 O(l); ∆ r H º = −285.8 kJ mol −1 ;
2
and −1300 kJ / mol , respectively. The standard enthalpy of
CO2 (g) + 2H 2 O(l) → CH 4 (g) + 2O2 (g); ∆ r H º = +890.3 kJ mol −1
combustion per gram of glucose at 25º C is
[JEE (Advanced) 2013] Based on the above thermochemical equations, the value of
(a) +2900 kJ (b) −2900 kJ ∆ r H º at 298 K for the reaction
(c) −16.11 kJ (d) +16.11 kJ C(graphite) + 2H 2 (g) → CH 4 (g)
will be [JEE (Main) 2017]
41. On the basis of the following thermochemical data :
−1
(a) + 144 .0 kJ mol (b) − 74 .8 kJ mol −1
(∆ f G H (+aq ) = 0)
o

(c) − 144 .0 kJ mol −1 (d) + 74 .8 kJ mol −1

H 2O(l ) → H + (aq) + OH −(aq) ; ∆H = 57.32 kJ
1 46. Given :
H 2( g ) +O2 → H 2 O(l ) ; ∆H = −286.20 kJ
2 (g ) (i) C(graphite) + O2 (g) → CO2 (g); ∆rH ° = xkJ mol −1
The value of enthalpy of formation of OH − ion at 25°C is 1
[AIEEE 2009] (ii) C(graphite) + O2 (g) → CO(g); ∆rH ° = y kJ mol − 1
2
(a) −22.88 kJ (b) −228.88 kJ
1
(c) +228.88 kJ (d) −343.52 kJ (iii) CO(g) + O2 (g) → CO2 (g); ∆rH ° = z kJ mol −1
2
42. Oxidising power of chlorine in aqueous solution can be
determined by the parameters indicated below : Based on the above thermochemical equations, find out
1 - - which one of the following algebraic relationships is correct
1 ∆ diss H ∆ H
Cl2 (g)  
2 → Cl(g) eg→ Cl − (g) [JEE (Mains) 2019]
2
- (a) x = y − z (b) y = 2z − x
∆
→ Cl − (aq)
H
hyd (c) x =y+z (d) z = x + y
The energy involved in the conversion of 47. The difference between ∆H and ∆U (∆H − ∆U ) when the
1
Cl 2 (g ) to Cl − (aq) combustion of one mole of heptane (l ) is carried out at a
2 temperature T is equal to [JEE (Main) 2019]
(Using the data, (a) − 4 RT (b) 4 RT
Θ
∆ diss HCl 2 = 240kJmol −1 , (c) − 3 RT (d) 3 RT
Θ
−1
∆ eg HCl = −349kJmol , 48. Enthalpy of sublimation of iodine is 24 cal g −1 at 200°C . If
Θ
specific heat of I 2 (s) and I 2 (vap) are 0.055 and
∆ hyd HCl = −381kJmol −1 ) will be [AIEEE 2008]
−1 −1
0.031 cal g K respectively, then enthalpy of sublimation
(a) − 610 kJ mol −1 (b) − 850 kJ mol −1
of iodine at 250°C in cal g −1 is [JEE (Main) 2019]
(c) + 120 kJ mol −1 (d) + 152 kJ mol −1
(a) 5.7 (b) 22.8
43. For complete combustion of ethanol, C2 H 5 OH (l) + 3O2 (g )
(c) 2.85 (d) 11.4
→ 2CO2 (g ) + 3 H 2O(l ), the amount of heat produced as
49. The bond dissociation energy needed to form benzyl radical
measured in bomb calorimeter, is 1364.47 kJ mol −1 at from toluene is ..... than the formation of the methyl radical
25° C . Assuming ideality the Enthalpy of combustion. from methane [IIT JEE 1994]
∆ C H , for the reaction will be (R = 8.314 kJ mol −1 ) (a) Less (b) More
[JEE (Mains) 2014] (c) Equal (d) None of the above
 Thermodynamics and Thermochemistry 229

50. The standard enthalpy of formation of NH 3 is 57. For a particular reversible reaction at temperature T , ∆H
− 46.0kJ mol . If the enthalpy of formation of H 2 from its
1− and ∆S were found to be both +ve. If the temperature Te is
at equilibrium, the reaction would be spontaneous when
atoms is − 436kJ mol −1 and that of N 2 is − 712kJ mol −1 , [AIEEE 2010]
the average bond enthalpy of N − H bond in NH 3 is (a) T = Te (b) Te > T
[AIEEE 2010] (c) T > Te (d) Te is 5 time T
(a) − 1102 kJ mol −1
(b) − 964 kJ mol −1 58. Adsorption of gases on solid surface is generally exothermic
because [IIT Screening 2004]
−1
(c) + 352 kJ mol (d) + 1056 kJ mol −1 (a) Enthalpy is positive (b) Entropy decreases
(c) Entropy increases (d) Free energy increase
51. The bond energy (in kcal mol–1) of a C – C single bond is
59. The incorrect expression among the following is
approximately [IIT JEE 2010]
[AIEEE 2012]
(a) 1 (b) 10 ∆Gsystem
(c) 100 (d) 1000 (a) = −T
∆Stotal
52. Using the data provided, calculate the multiple bond energy
Vf
(kJ mol −1 ) of a C ≡ C bond in C2 H 2 . That energy is (take (b) In isothermal process, Wreversible = −nRT ln
Vi
the bond energy of a C − H bond as 350 kJ mol −1 )
∆H o − T∆S o
(c) ln K =
2C(s) + H 2 (g ) → C 2 H 2 (g ) ∆H = 225 kJ mol −1 RT
o / RT
2C(s) → 2C(g) ∆H = 1410 kJ mol −1 (d) K = e − ∆G
60. A schematic plot of lnK eq versus inverse of temperature for
H 2 (g ) → 2 H (g) ∆H = 330kJ mol −1
a reaction is shown below
[IIT JEE 2012]
6.0
(a) 1165 (b) 837
(c) 865 (d) 815

ln Keq
53. The standard enthalpy of formation (∆H f °) at 298 K for
methane, CH 4 (g), is – 74.8 kJ mol–1 The additional
2.0
information required to determine the average energy for 1.5×10–3 1/T (K–1) 2.0×10–3
C − H bond formation would be [AIEEE 2006] The reaction must be [AIEEE 2005]
(a) The dissociation energy of H 2 and enthalpy of (a) Exothermic
sublimation of carbon (b) Endothermic
(c) One with negligible enthalpy change
(b) Latent heat of vapourization of methane
(d) Highly spontaneous at ordinary temperature
(c) The first four ionization energies of carbon and electron
61. In a fuel cell methanol is used as fuel and oxygen gas is used
gain enthalpy of hydrogen as an oxidizer. The reaction is
(d) The dissociation energy of hydrogen molecule, H 2 3
CH 3 OH (l) + O2 (g ) → CO 2 (g) + 2 H 2 O(l)
54. For the process H2O(l) (1 bar, 373 K) H2O (g) (1 bar, 2
373 K), the correct set of thermodynamic parameters is At 298K standard Gibb's energies of formation for
[IIT JEE 2007] CH 3 OH(l), H 2 O(l) and CO2 (g) are –166.2, –237.2 and
(a) ∆G = 0, ∆S = +ve (b) ∆G = 0, ∆S = −ve –394.4 kJ mol–1 respectively. If standard enthalpy of
(c) ∆G = +ve, ∆S = 0 (d) ∆G = −ve, ∆S = +ve combustion of methanol is − 726 kJ mol −1 , efficiency of the
55. The value of log 10 K for a reaction A B is fuel cell will be [AIEEE 2009]
−1 (a) 80% (b) 87%
(Given : ∆ r H ° 298 K = −54.07kJ mol ,
(c) 90% (d) 97%
∆ r S° 298 K = 10 JK −1 mol −1 and 62. The following reaction is performed at 298 K.
2NO(g) + O2 (g) 2 NO2(g)
R = 8.314 JK −1mol −1 ; 2.303 × 8.314 × 298 = 5705)
The standard free energy of formation of NO(g ) is
[IIT JEE 2007]
86.6 kJ / mol at 298 K. What is the standard free energy of
(a) 5 (b) 10
(c) 95 (d) 100 formation of NO2 (g) at 298 K (K p = 1.6 × 1012 )
56. In an irreversible process taking place at constant T and P [JEE (Main) 2015]
and in which only pressure-volume work is being done, the (a) R(298) ln(1.6 × 10 12 ) − 86600
change in Gibbs free energy (dG) and change in entropy (b) 86600 + R(298) ln(1.6 × 10 12 )
(dS) , satisfy the criteria [AIEEE 2003]
ln(1.6 × 1012 )
(a) (dS) V , E < 0, (dG)T , P < 0 (b) (dS) V , E > 0, (dG) T , P < 0 (c) 86600 −
R(298)
(c) (dS) V , E = 0, (dG) T , P = 0 (d) (dS) V , E = 0, (dG) T , P > 0 (d) 0.5[2 × 86600 − R(298) ln(1.6 × 10 12 )]
 230 Thermodynamics and Thermochemistry
63. The standard Gibbs energy change at 300 K for the reaction 69. At 298.2 K the relationship between enthalpy of bond
2A B + C is 2494.2 J. At a given time, the
dissociation (in kJ mol −1 ) for hydrogen ( E H ) and its isotope,
1
composition of the reaction mixture is [ A] = , [ B] = 2 and deuterium ( E D ), is best described by [JEE (Main) 2021]
2
1 1
[C] = . The reaction proceeds in the − E D − 7. 5
(a) E H ~ (b) E H = ED
2 2
[R = 8.314 J / K / mol, e = 2.718] [JEE (Main) 2015] (c) EH = 2ED (d) E H = E D
(a) Forward direction because Q > K C
70. At 25 o C and 1 atm pressure, the enthalpies of combustion
(b) Reverse direction because Q > K C are as given below :
(c) Forward direction because Q < K C
Substance H2 C (graphite) C 2 H 6 (g)
(d) Reverse direction because Q < K C
∆c H
– 286.0 –394.0 –1560.0
64. A process has ∆H = 200 J mol −1 and ∆S = 40 JK −1mol −1 . −1
kJ mol
Out of the values given below, choose the minimum
temperature above which the process will be spontaneous : The enthalpy of formation of ethane is [JEE (Main) 2022]
[JEE (Mains) 2019]
−1
(a) + 54.0 kJ mol (b) − 68.0 kJ mol −1
(a) 5 K (b) 12K
(c) 4 K (d) 20 K (c) − 86.0 kJ mol −1 (d) + 97.0 kJ mol −1
65. The standard reaction Gibbs energy for a chemical reaction
at an absolute temperature T is given by
∆Go = A − BT Numerical Questions :
Where A and B are non-zero constants. Which of the
71. The standard heat of formation (∆ f H 298
0
) of ethane
following is TRUE about this reaction [JEE (Mains) 2019]
(a) Endothermic if A > 0 (in kJ / mol ) , if the heat of combustion of ethane, hydrogen
(b) Exothermic if B < 0 and graphite are −1560, − 393.5 and −286 kJ / mol,
(c) Exothermic if A > 0 and B < 0 respectively is [JEE (Mains) 2020]
(d) Endothermic if A < 0 and B > 0 72. For a given chemical reaction A → B at 300 K the free
66. The reaction, MgO(s) + C(s) → Mg(s) + CO(g) , for which
energy change is − 49.4 kJ mol −1 and the enthalpy of
−1 −1 −1
∆rH ° = +491.1 kJ mol and ∆rS° = 198.0 JK mol , is
reaction is 51.4 kJ mol −1 . The entropy change of the
not feasible at 298 K . Temperature above which reaction
reaction is________ J K −1mol −1 [JEE (Main) 2021]
will be feasible is [JEE (Mains) 2019]
(a) 2380.5 K (b) 1890.0 K 73. If the standard molar enthalpy change for combustion of
graphite powder is − 2.48 × 10 2 kJ mol −1 , the amount of
(c) 2040.5 K (d) 2480.3 K
heat generated on combustion of 1 g of graphite powder
67. Lattice enthalpy and enthalpy of solution of NaCl are
is________ kJ . (Nearest integer) [JEE (Main) 2021]
788 kJ mol −1 and 4 kJ mol −1 , respectively. The hydration
74. A system does 200 J of work and at the same time absorbs
enthalpy of NaCl is [JEE (Mains) 2020]
150 J of heat. The magnitude of the change in internal
(a) − 780 kJ mol −1 (b) 780 kJ mol −1
energy is________J. (Nearest integer) [JEE (Main) 2021]
(c) − 784 kJ mol −1 (d) 784 kJ mol −1
75. For the reaction 2 NO2 (g ) N 2 O4 (g ),
68. During which of the following processes, does entropy
decrease [JEE (Main) 2021] when ∆S = −176.0 J K −1 and ∆H = −57.8 kJ mol −1 , the
(A) Freezing of water to ice at 0 o C magnitude of ∆G at 298 K for the reaction
−1
(B) Freezing of water to ice at − 10 C o
is________ kJ mol . (Nearest integer) [JEE (Main) 2021]
(C) N 2 (g ) + 3 H 2 (g ) → 2 NH 3 (g )
76. The ionization enthalpy of Na + formation from Na(g ) is
(D) Adsorption of CO(g) on lead surface
495.8 kJ mol −1 , while the electron gain enthalpy of Br is
(E) Dissolution of NaCl in water
− 325.0 kJ mol −1 . Given the lattice enthalpy of NaBr is
Choose the correct answer from the options given below
(a) (A), (C) and (E) only (b) (A), (B), (C) and (D) only − 728.4 kJ mol −1 . The energy for the formation of NaBr
(c) (A) and (E) only (d) (B) and (C) only ionic solid is (–) _______ × 10 −1 kJ mol −1 . [JEE (Main) 2021]
 Thermodynamics and Thermochemistry 231

77. For a chemical reaction A + B C+D 81. For independent processes at 300K
−1
(∆ r H

= 80 kJ mol ) the entropy change ∆ r S

depends Process ∆H/kJ mol–1 ∆S/JK–1
−1 −1
on the temperature T (in K) as (∆ r S

= 2T( JK mol ) A –25 –80
Minimum temperature at which it will become spontaneous
B –22 40
is ______K. (Integer) [JEE (Main) 2021]
C 25 –50
78. At 25°C, 50g of iron reacts with HCl to form FeCl2. The
evolved hydrogen gas expands against a constant pressure D 22 20
of 1 bar. The work done by the gas during this expansion is
The number of non-spontaneous processes from the
_______ J. (Round off to the nearest integer)
following is ………… [JEE (Main) 2023]
[Given : R = 8.314 J mol −1 K −1 . Assume, hydrogen is an
82. One mole of an ideal monoatomic gas is subjected to
ideal gas] changes as shown in the graph. The magnitude of the work
[Atomic mass of Fe is 55.85u] [JEE (Main) 2021] done (by the system or on the system) is ………… J
79. The enthalpy of combustion of propane, graphite and (nearest integer)
dihydrogen at 298 K are : − 2220.0 kJ mol −1 ,
1 2
− 393.5 kJ mol −1 and − 285.8 kJ mol −1 respectively. The 1.0
magnitude of enthalpy of formation of propane (C3 H 8 ) is

Pressure (bar)
…… kJ mol −1 . (Nearest integer) [JEE (Main) 2022]

80. While performing a thermodynamics experiment, a student

made the following observations. 0.5 3

HCl + NaOH → NaCl + H 2 O ; ∆H = −57.3 kJ mol −1

CH 3 COOH + NaOH → CH 3 COONa + H 2 O

; ∆H = −55.3 kJ mol −1 . 20 40
Volume (L)
The enthalpy of ionization of CH 3 COOH as calculated by
the student is ……….. kJ mol −1 . (Nearest integer) Given : log 2 = 0.3

[JEE (Main) 2022] ln10 = 2.3 [JEE (Main) 2023]

 Answers Key

56 a 57 b 58 c 59 d 60 a
Basic Concepts
61 a 62 c 63 b 64 a 65 a
1 c 2 c 3 d 4 b 5 c
66 b 67 a
6 d 7 c 8 c 9 c 10 b
11 b 12 b 13 b 14 a 15 a Bond Energy
16 b 17 a 18 a 19 c 20 c 1 c 2 a 3 c 4 a 5 d
21 d 22 c 23 b 24 c 25 d 6 c 7 a 8 a 9 a 10 b
26 d 11 c 12 c 13 a 14 b 15 c

First Law of Thermodynamics and Hess Law Free Energy and Work Function
1 c 2 a 3 b 4 c 5 b
1 b 2 c 3 b 4 d 5 c
6 b 7 d 8 d 9 b 10 d
6 c 7 c 8 c 9 a 10 c
11 d 12 a 13 d 14 a 15 e
11 c 12 c 13 a 14 c 15 d
16 b 17 b 18 d 19 a 20 c
16 a 17 e 18 c 19 c 20 c
21 d 22 d 23 b 24 d 25 b
21 c 22 d 23 b 24 d 25 d
26 b 27 b 28 b 29 c 30 b
26 b 27 d 28 b 29 d 30 c
31 b 32 b 33 b 34 a 35 b
31 b 32 c 33 a 34 a 35 d
36 b 37 b
36 c 37 c 38 b 39 d 40 b
41 d 42 b 43 c 44 c 45 c
Statement Type Questions
1 c 2 d 3 a 4 a 5 c
46 b 47 d 48 d 49 c 50 c
51 b 52 c 53 b 54 c 55 c Matching Type Questions
1 a 2 c 3 d 4 b 5 b
IInd & IIIrd Law of thermodynamics and Entropy
1 a 2 b 3 d 4 d 5 c Numerical Value type questions
6 b 7 d 8 a 9 a 10 a 1 319 2 309.16 3 9.2 4 4 5 80
11 d 12 c 13 b 14 c 15 b 6 27.49 7 128.02 8 88.4 9 296.5 10 245
16 c 17 d 18 b 19 b 20 a
Past Years Questions
21 c 22 a 23 c 24 a 25 d
1 c 2 c 3 b 4 c 5 a
26 b 27 b 28 c 29 b 30 c
6 b 7 a 8 c 9 b 10 d
31 d 32 c 33 c 34 b 35 c
11 a 12 c 13 d 14 b 15 b
36 c 37 a 38 c 39 a 40 d
16 c 17 b 18 b 19 a 20 d
41 a
21 a 22 c 23 c 24 a 25 a
Heat of Reaction 26 d 27 b 28 b 29 a 30 c

1 d 2 b 3 d 4 d 5 a 31 b 32 c 33 d 34 c 35 c

6 a 7 c 8 c 9 c 10 a 36 d 37 b 38 b 39 b 40 c

11 a 12 a 13 e 14 c 15 c 41 b 42 a 43 a 44 d 45 b

16 d 17 d 18 c 19 b 20 c 46 c 47 a 48 b 49 a 50 c

21 b 22 c 23 d 24 b 25 c 51 c 52 d 53 a 54 a 55 b

26 c 27 d 28 b 29 c 30 d 56 b 57 c 58 b 59 c 60 a

31 b 32 b 33 a 34 c 35 b 61 d 62 d 63 b 64 a 65 a

36 a 37 a 38 a 39 c 40 a 66 d 67 c 68 b 69 a 70 c

41 b 42 b 43 a 44 b 45 b 71 192.5 72 336 73 21 74 50 75 5

46 b 47 b 48 c 49 c 50 b 76 5576 77 200 78 2218 79 104 80 2

51 c 52 c 53 e 54 c 55 b 81 2 82 620
 Answers & Solutions

19. (c) Thermodynamics is not concerned with the rate at

NCERT Based Questions which a reaction proceeds. Thermodynamics deals with
Basic Concepts the energy change, feasibility and extent of a reaction,
but not with the rate and mechanism of a process.
1. (c) It is the definition of calorific value.
20. (c) For a closed vessel made of copper, no matter can
2. (c) Factual exchange between the system and the surroundings but
3. (d) An adiabatic system is thermally isolated. Upon energy exchange can occur through its walls.
expansion, the work is done by the system so internal Presence of reaction species in a covered beaker-closed
energy or temperature of the system will decrease. system and exchange of matter as well as energy-open-
4. (b) By definition system. Presence of reactant in a closed vessel closed
5. (c) This is based on Joule-Thomson effect. system and presence of reactant in thermos flask-
isolated system.
6. (d) There is no energy or matter transfer for an isolated
21. (d) The state of a gas can be described by quoting the
system i.e. total energy is constant.
relationship between pressure, volume temperature and
7. (c) Surface tension is an intensive property which does not amount. The ideal gas equation is
depend upon the quantity of matter present in the
pV = nRT
system.
Thus p, V , T and n describe the state of the system.
8. (c) If a process is carried out under such a condition that
no exchange of heat takes place between the system 22. (c) The volume of gas is reduced to half from its original
and surroundings, the process is termed adiabatic. The volume the specific heat will be remain constant.
system is thermally isolated i.e., dq = 0. In adiabatic Specific heat is an intensive property depending only
process, the temperature of the system varies. on the nature of the gas.
9. (c) For adiabatic process ∆Q = 0 . 23. (b) Work done and heat energy of the system are path
functions.
10. (b) For a cyclic process dE = 0 and dH = 0 .
24. (c) The energy released when the requisite numbers of
11. (b) E = mc 2 ⇒ kg(ms −1 )2 = kgm 2 s −2 positive and negative ions are condensed into crystal to
form one mole of the compound is called lattice energy
So [Link] −2 is not the unit of energy. ∆H 5
M (+g ) + X (−g ) → MX (s ) ; ∆H 5 → Lattice energy.
12. (b) Molar heat capacity is intensive property but heat (Z)
capacity of a given matter is an extensive property. 25. (d) Change in internal energy in a cyclic process is zero
13. (b) For an isothermal process : whether the process is reversible or irreversible.
∆T = 0 and ∆E = 0 and q ≠ 0 . 26. (d) Density (ρ ) , temperature (T ) and pressure (P ) are
14. (a) At constant volume, the work done W = 0 so heat intensive properties because they do not depend upon
change ∆Q = ∆U (Change in internal energy). mass.

15. (a) At constant T and P internal energy of ideal gas remains

unaffected.
First Law of Thermodynamics and Hess Law
16. (b) Internal energy is the energy associated with every 1. (b) ∆H = ∆E + P∆V .
substance, depending on the chemical nature, 3 −1
temperature, pressure and volume. It is the sum of 2. (c) ∆ng = 1 − = , As ∆ng is negative, thus ∆H < ∆E .
2 2
many types of energies such as translational energy,
3. (b) N 2( g ) + 3 H 2( g ) 2 NH 3( g )
rotational energy, vibrational energy, electronic energy
and bonding energy of the molecule. ∆H = ∆E + ∆ng RT
U = U trans + Urot + U vib + U bonding + Uelectronic . ∆n = np − nr = 2 − 4 = −2
17. (a) When system absorbs heat then q > 0 and when work ∴ ∆H = ∆E − 2RT .
is done on the system then w > 0 so ∆E = q + w > 0 . 4. (d) If ∆n = −ve than ∆H < ∆E .
18. (a) A → B , volume is not changing (Isochoric) 5. (c) At constant P or T
B → C Isobaric ∆H = ∆U + ∆ng RT ⇒ ∆ng = n p − nR = 2 − 4 = −2

C → A Temperature is constant (Isothermal). ∴ ∆H < ∆U .

 234 Thermodynamics and Thermochemistry

6. (c) During isothermal expansion of ideal gas, ∆T = 0 19. (c) For the conversion of solid to gas, both ∆H and ∆P
∆H = ∆E + P∆V = ∆E + ng R∆T = 0 + 0 = 0 . will be positive.
54
7. (c) ∆E = q + w . 20. (c) Q = nC∆T, n = =2
27
8. (c) ∆H = ∆E + ∆ng RT
= 2 × 25 × 20 = 1000 J
∆ng RT = ∆H − ∆E
Q = 1.0 kJ .
∆ng × 8.3 × 300 = − 4.98 × 10 3
21. (c) Substance A has more value of specific heat than B
∆ng = −2 . and C so it will raise the temperature of water more
than B and C .
9. (a) ∆ng = 2 (from CO 2 ) − 2 (from O2 ) = 0
22. (d) It is a modified form of 1st law of thermodynamics. It is
So work done W = 0 a conservation law of mass and energy.
Thus ∆E = ∆H = −874 kJ . 23. (b) Formation of CO 2 from CO is an exothermic reaction;
10. (c) As the system is closed and insulated no heat enters or heat is evolved from the system, i.e., energy is lowered.
leaves the system, i.e. q = 0 . Thus, exothermic reactions occur spontaneously on
account of decrease in enthalpy of system. Thus,
∴ ∆E = q + W = W .
∆E > ∆H .
11. (c) ∆H − ∆E = ∆ng RT ; ∆ng = −3 24. (d) For elements, enthalpy of formation is zero.
so, ∆H − ∆E = −3 RT . 25. (d) (CH 3 ) 2 C = CH 2 (g) + 6O2 (g) → 4 CO2 (g) + 4 H 2 O(l)
12. (c) q = 40 J ∆n g = 4 − 6 = −2 (i.e., negative)
w = −8 J (work done by the system) we know that ∆H = ∆E + ∆n g RT
∆E = q + w = 40 − 8 = 32 J . = ∆E − (∆n g )RT ( ∵∆n g = −ve)
13. (a) H = E + PV
∴ ∆H < ∆E .
∴ ∆H = ∆E + P∆V + V∆P
26. (b) Fe(s) + 2HCl(aq) → FeCl 2 (aq) + H 2 (g )
At constant P, ∆H = ∆E + P∆V .  50   50 
 moles   moles 
 55.85   55.85 
14. (c) Here: Change in
Volume (V ) = 500 − 300 = 200cc = 0.2 litre, Moles of iron = Moles of hydrogen gas
50
Pressure (P ) = 0.6 atm and heat liberated (q) = 10J = = ∆ng
55.85
Work done (W ) = P∆V = (0.2 × 0.6) = 0.12 litre − atm
R = 8.314 J mole −1 K −1
But 1litre − atm = 101.3 J . T = 25 + 273 = 298 K
hence W = 0.12 × 101.3 = 12.156 J . We also know that Work done by H 2 gas W = − ∆ng RT
heat is liberated, therefore it would be negative. Thus −50
change in ∆E = q + W = −10 + 12.16 = 2.16 J . = × 8.314 × 298 × 10 − 3 kJ
55.85
15. (d) Use ∆H = ∆E + ∆ng RT = − 2.2kJ .
27. (d) For isothermal process, ∆T = 0 . From first law of
∆H = 19 + 2 × 2 × 10 −3 × 300 = 20.2 kcal ; ∆ng = 2 .
thermodynamics
16. (a) NH 3( g ) + HCl( g ) → NH 4 Cl( g ) ∆U = Q + W
∆n =no. of moles of product – no. of moles of reactant ∴ ∆U = nCv ∆T = 0 As ∆U = 0
=1− 2
∆H = nC p ∆T = 0 ∴Q =W ≠ 0
∆n = −1
28. (b) From 1st law of thermodynamic
Now, ∆H = ∆E + ∆ng RT ; ∆H = ∆E − RT or
∆E = q + w. Now w = P∆V . for ∆V = 0
∆E = ∆H + RT
w=0.
∴ ∆E > ∆H (∆E = ∆U ) = change in internal energy.
29. (d) For a thermally insulated container, ∆q = 0 But work
17. (e) ∆E = q + ω , ∆E is a state function.
(W ), change in internal energy (∆E) and change in
75
18. (c) Heat capacity of water per gram = = 4.17 J enthalpy (∆H ) are non zero.
18
30. (c) Hess’s law is an application of first law of
Q = mst ; 1000 = 100 × 4.17 × ∆T
thermodynamics.
1000 (b) According to Hess’s law. The heat of reaction depends
∆T = = 2.4 K . 31.
100 × 4.17 upon initial and final conditions of reactants.
 Thermodynamics and Thermochemistry 235
32. (c) Our desirable equation is 38. (b) A → B, ∆H = + 24 kJ / mol
2 NO2 → N 2O4 …..(iii) ⇒ H B − H A = + 24 …. (i)
Given B → C, ∆H = −18 kJ/mol
2 NO2 → N 2 + 2O2 ∆H = −67.9 kJ …..(i)
⇒ H C − H B = −18
N 2 O4 → N 2 + 2O2 ∆H = −09.3 kJ …..(ii) ⇒ H B − H C = + 18 ... (ii)
On subtracting equation (ii) from (i) we will get From Eqs. (i) and (ii), we have
equation (iii)
HC − H A = 6
2 NO2 − N 2 O4 → 0
∴ H B > HC > H A .
2 NO2 → N 2O4 …..(iii) 39. (d) −57.4 + x = −12.13
So Heat of dimerisation of NO2 = −67.9 − (−09.3) kJ x = 45.2 .
= −67.9 + 9.3 40. (b) Number of moles of 1 g of Mg = 1 / 24 = 0.0417
= −58.6 kJ 1200
1 g of Mg (g) absorbs = = 50 kJ
24
33. (a) H 2 (g) + O2 (g) → H 2 O2 (l) ∆H = −188
∴ Energy required to convert Mg (g) to Mg + (g)
1
H 2 (g) + O2 (g) → H 2 O(l) ∆H = −286 = 0.0417 × 750 = 31.275 kJ.
2
By Lavoisier and Laplace Law : ∴ Remaining energy = 50 – 31.275 = 18.725 kJ
2H 2 O2 (l) → 2H 2 (g) + 2O2 (g), ∆H = + 376 18.725
Number of moles of Mg 2 + formed = = 0.013
1450
2H 2 (g) + O2 (g) → 2H 2 O(l), ∆H = −572
Thus remaining Mg + will be = 0.0417 – 0.013 = 0.0287
Adding the above two equations by using Hess’ Law :
0.0287
2H 2 O2 (l) → 2H 2 O(l) + O2 (g) ∆H = −196. ∴ % Mg + = × 100 = 68.82%
0.0417
34. (a) I 2 (s) → I 2 (g), ∆H1 = +57.3 kJ / mol % Mg 2 + = 100 − 68.82 = 31.18% .
I 2 (s) → I 2 (l), ∆H 2 = +15.5 kJ / mol 41. (d) C (diamond) → C (graphite), ∆H = −1.89 kJ / mole
Hence, for the conversion – C (diamond) +O2 (g) → CO2 (g), ∆H = ∆H1 …(i)
I 2 (l) → I 2 (g) ∆H = ∆H1 − ∆H 2
C (graphite) +O2 (g) → CO2 (g), ∆H = ∆H 2 …(ii)
= 57.3 − 15.5 = +41.8 kJ / mol .
By Lavoisier and Laplace Law :
1 CO2 (g) → C (graphite) +O2 (g), ∆H = − ∆H 2 …(iii)
35. (d) M + O2 → MO + 351.4 kJ …(i)
2
Adding equation (i) and (iii) using Hess’ Law :
1
X+ O2 → XO + 90.8 kJ …(ii) C (diamond) → C (graphite), ∆H = ∆H1 − ∆H 2
2
Subtract (i) – (ii) Thus ∆H1 − ∆H 2 = −1.89 kJ / mole
1 Both ∆H1 and ∆H 2 are negative so the value of ∆H1
M+ O2 → MO + 351.4 kJ
2 is more negative (more exothermic reaction) than that
1 of ∆H 2
X + O2 → XO + 90.8 kJ
2 1 mole of C = 12 g. of C
M + XO → MO + X 260.6 kJ .
So the enthalpy difference per 6 g. of diamond and
36. (c) According to Hess law, enthalpy change for a reaction −1.89
does not depend on the nature of intermediate reaction graphite = = −0.945 kJ .
2
steps.
42. (b) 2C2 H 6( g ) + 7O2(l ) → 4 CO2( g ) + 6 H 2 O(l )
37. (c) The algebraic relationships of the given reaction is
equation (a) – equation (b) = equation (c) 7
C2 H 6 + O2 → 2CO2 + 3 H 2 O
−1 2
(a) C(graphite) + O2 (g) → CO2 (g); ∆ r H = xkJ mol
 7
1 ∆ng = n p − nr =  2 − 1 −  = −2.5
(b) C (graphite) + O2 (g) → CO(g); ∆r H = ykJ mol −1  2
2
− P∆v = ∆ng RT
1
CO(g) + O2 (g) → CO2 (g); ∆r H = zkJ mol −1
2 W = − ∆ng RT = −2.5 × 8.314 × 300
Hence, x − y = z or x = y + z . W = −(−2.5 × 8.314 × 300) = 6235.5 J
 236 Thermodynamics and Thermochemistry
For one mole combustion we get work done 51. (b) The correct option is W (reversible) < W (irreversible).
= 6235.5 J This is because area under the curve is always more in
irreversible compression as can be seen from given
1000 figure.
∴ for 0.090 kg = 0.090 × moles
30 P P
= 3 moles
For 3 moles the work done = 3 × 6235.5 J
= 18706.5
= 18.7 kJ .
43. (c) Given that
P1 = 10 atm , P2 = 1 atm , T = 300 K , n = 1 Vf Volume (V) Vi Vf Volume (V) Vi
pV-plot when pressure is not pV-plot when pressure is not
R = 8.314 J / K / mol constant and changes in initial constant and changes in initial
steps during compression steps (reversible conditions)
Now, by using from initial volume Vi to final during compression from initial
P2 volume Vf , work done on the volume Vi to final volume Vf ,
W = −2.303 nRT log 10 gas is represented by the work done on the gas is
P1 shaded area. represented by the shaded area.
1 52. (c) There is no change in internal energy with change in
= −2.303 × 1 × 8.314 × 300 log 10
10 volume at constant temperature for an ideal gas. As
W = 5744.1 Joule . there is no force of attraction operating in between the
molecules, there is no work during change in volume
44. (c) W = − P∆V = −1 × 10 5 (1 × 10 −2 − 1 × 10 −3 )
and hence no change in internal energy.
= −1 × 10 5 × 9 × 10 −3 = −900 J . dQ dQ
53. (b) − = ; dE = dW + dQ ; −dW = dQ − dE
45. (c) Free expansion, W = 0 dW dQ − dE
Adiabatic process q = 0 nc p dT cp
= =
∆U = q + W = 0 this means that internal energy nc p dT − ncv dT (c p − c v )

remains constant. Therefore, ∆T = 0 ideal gas there is =

7R
{for diatomic of gas c p =
7R
}.
no intermolecular attraction. 2R 2
Hence, when such a gas expands under adiabatic nRT v2
54. (c) ∆S = ln
conditions into a vacuum, no heat is absorbed or T v1
evolved since no external work is done to separate the
v2 v
molecules. = nR ln = 2.303 nR log 2
v1 v1
46. (b) Given number of moles =1
= 2.303 × 2 × 8.314 × 1 = 38.3 J / K.
Initial temperature = 27 o C = 300 K
55. (c) Isothermal means ∆T = 0
Work done by the system = 3 kJ = 3000 J
If temperature is constant, means ∆U = 0 as whole
It will be (−) because work is done by the system. energy is used in work done and due to reversible
Heat capacity at constant volume (CV ) = 20 J / K expansion ∆H = 0 .

We know that work done IInd & IIIrd Law of thermodynamics and Entropy
W = −nCV (T2 − T1 ) ; 3000 = −1 × 20 (T2 − 300)
1. (a) T2 = 150 + 273 = 423 K ; T1 = 25 + 273 = 298 K
3000 = −20T2 + 6000
Q = 500 K
3000
20T2 = 3000 ; T2 = = 150 K . W T2 − T1  423 − 298 
20 = ; W = 500  = 147.7 J .
Q T2  423 
47. (d) For isothermal expansion of ideal gas, ∆E = 0 .
2. (b) Given that, T1 = 500 K, T2 = 300 K
V2 V2
48. (d) w = 2.303 RT log . As it involves the ratio ,
V1 V1 T1 − T2 500 − 300 200
By using, η = = = = 0.4 .
volume can be used in any units. (R should be in T1 500 500
joules). 3. (d) Ice cubes are in contact with freezer so it does not
49. (c) An ideal gas under going expansion in vacuum shows, constitute isolated system.
∆E = 0, W = 0 and q = 0 . 4. (d) ∆S o = 2SHCl
o
− (SHo 2 + SCl
o
2
)
50. (c) W = P∆V . = 2 × 186.7 − (130.6 + 223.0) = 19.8 JK −1mol −1 .
 Thermodynamics and Thermochemistry 237

5. (c) ∆S has negative value if ∆n g = −ve i.e. number of And entropy decreases on going from vapour to liquid.
gaseous moles decreasing during a reaction. i.e., ∆H = T∆S

∆ng = 2 − 0 = 2 ∆H 35300
For (a), ∆S = − =− = − 100 JK −1mol −1 .
T 80 + 273
For (b), ∆ng = 2 − 1 = 1
20. (a) The temperature of liquid He is very low compared to
For (c), ∆ng = 2 − 3 = −1 (∆S negative) ice cold water thus the entropy will increase.
δ qrev
For (d), ∆ng = 3 − 0 = 3 21. (c) dS = for reversible reaction and
T
For (e), ∆ng = 1 − 0 = 1 . dS > δ qirr /T for irreversible reaction.
6. (b) For adiabatic expansion q = 0 then according to 22. (a) Because decreases of randomness of molecules during
q crystallization, entropy decreases.
following relation ∆S = , ∆S = 0 .
T 23. (c) Conversion of graphite into diamond is an endothermic
∆H vapourisation reaction. So, heat of diamond is higher than that of
7. (d) ∆Svapourisation = graphite. But ∆S would be negative for the conversion
Tb
of graphite into diamond.
entropy change for conversion of 1 mol i.e. 9 g H 2 O of
24. (a) For a pure substance TA and TB represent the same
x
liquid into vapour at 373 K is ∆Svapourisation i.e. . temperature. Hence A is a correct choice.
373
25. (d) Suppose the no. of gm, 1gm for each case so the max.
1 18 x no. of mole expected for SO2 (g) which has to
So, entropy change for .5 mole is × .
2 373 expected maximum entropy.
8. (a) ∆S = 186.5 / 373 = 0.5 JK −1 mol −1 . 26. (b) Mixing of non-reacting gases increases randomness and
vap
so increase entropy.
9. (a) The entropy of the universe is continuously increasing
27. (b) Entropy of the system increases as the process occur
due to continuously happening spontaneous reactions.
irreversibly and isothermally in an isolated system.
10. (a) Randomness or entropy order is
28. (c) Calculation of change in entropy is done at constant
gas > liquid > solid temperature and pressure both.
H 2 O(l )  → H 2 O( g )
Evaporation
∆S increases 29. (b)
(a) H 2 (g) → 2H (g) ∆ng > 0 ⇒ ∆S > 0
H 2 O(s ) 
→ H 2 O(l )
Melting
∆S increases
(b) N 2 (g)1atm → N 2 (g) 8 atm
H 2 O( g )   → H 2 O(l )
Condensation
∆S decreases
As pressure increases, the motion of gas molecules
11. (d) This is the statement of third law of thermodynamics. decreases and thus disorder decreases. ∆S < 0
2.257 × 10 3 J (c) 2 SO3 (g) → 2SO2 (g) + O2 (g) ∆ng > 0 ⇒ ∆S > 0
12. (c) ∆H vap =
(1/18) mole
(d) C(diamond ) → C( graphite ) This is an exothermic reaction
∆H vap 2257 J × 18 thus ∆S is positive.
∆Svap = = = 108.9 JK −1 .
T 373 K-mole 30. (c) A small amount of water will be formed in an
13. (b) The change in entropy in going from one state to exothermic reaction. Thus it will increase entropy of the
another is independent of the path. mixture.
qrev 31. (d) This is an endothermic reaction,
14. (c) ∆S = ∴unit of S is JK −1mol −1 .
T So, ∆H > 0 .
+ −
15. (b) H (aq) + OH (aq) → H 2 O(l ) Since, number of moles in the product side is more
So ( 298 K ) JK −mol −1 − 10.7 J / mol / K + 70 J / mol / K So, ∆S > 0 .
∆S o (298 K ) = ∆SP − ∆SR = 70 − (−10.7 + 0) 32. (c) ∆Ssystem + ∆Ssurroundings > O (for spontaneity)

80.7 JK −1 mol −1 . Because of ∆S = R ln

V2
V1
16. (c) By formula.
17. (d) Entropy of a gas is greater than liquid and solid because Here the volume of gas increases from V1 to V2 at
gaseous particles are quite apart from each other and constant temperature T.
are in random motion. The total increase in entropy of the system and its
18. (b) Less volume on the product side. surrounding during the spontaneous process of
19. (b) According to Gibb's formula, ∆G = ∆H − T∆S V 
expansion considered above is, thus R ln  2  since
At equilibrium, ∆G = 0  V1 
 238 Thermodynamics and Thermochemistry

V2 > V1 it is obvious that the spontaneous (irreversible) 3. (d) Heat of neutralization between strong acid and a strong
isothermal expansion of a gas is accompanied by an base is about −13.7 kcal.
increase in the entropy of the system and its
4. (d) S + O2 → SO2 ; ∆H = −298.2
surrounding considered together.
∆Ssystem + ∆Ssurroundings > 0 . 1
SO2 + O2 → SO3 ; ∆H = −98.2
33. (c) ∆Su = ∆Ssystem + ∆Ssurrounding = −22.13 + 22.05 = −0.08 2

For a spontaneous process, ∆Su must be positive i.e., SO3 + H 2O → H 2 SO4 ; ∆H = −130.2

∆Su = ∆Ssystem + ∆Ssurrounding > 0 . 1

H2 + O2 → H 2O; ∆H = −287.3
34. (b) For an exothermic reaction, ∆Ssurr > 0 as heat is 2

released. On adding all the equations

35. (c) The entropy change can be calculated by using the S + 2O2 + H 2 → H 2 SO4 ; ∆H = −813.9 kJ .
q
expression ∆S = rev 5. (a) For exothermic reactions H p < H R .
T
When water freezes in a glass beaker, ∆S (system) For endothermic reactions H p > H R .
decreases because molecules in solid ice are less
1
random than in liquid water. However, when water 6. (a) (i) H 2 + O2 → H 2O, ∆H = −241 kJ
freezes to ice, heat is released which is absorbed by the 2
surroundings. 17
(ii) C6 H10 + O2 → 6CO2 + 5 H 2O, ∆H = −3800 kJ
Hence, entropy of the surrounding increases. 2
36. (c) For isolated system q = 0, if ∆U = 0 then w = 0,
(iii) C6 H12 + 9O2 → 6CO2 + 6 H 2O, ∆H = −3920 kJ
∆T = 0 so if something is going on inside the system
then the process is spontaneous ( ∆S > 0), otherwise C6 H10 + H 2 → C6 H12
∆S = 0 . By Eq. (i) + Eq. (ii) – Eq. (iii)
37. (a) Factual.
∆H = −241 − 3800 − (−3920)
38. (c) Colour changes from dark blue to light blue means
randomness of particles increases results entropy = −4041 + 3920 = −121 kJ .
change positive. No chemical bond cleavage and bond
7. (c) NH 4 OH is a weak base. Heat of neutralisation <
formation takes place therefore no enthalpy change.
39. (a) According to kinetic theory of gases 13.7kcal.
Force of attraction and repulsion amongst molecules of 8. (c) Heat of combustion of 1 mole of carbon is equal to heat
ideal gas are negligible of formation of 1 mole of CO2 gas.
so, ∆H = 0
9. (c) C D → CG , ∆H = −453.5 cal.
And randomness increases due to increase in volume so
∆S = + ve . The enthalpy of CG is less than that of CD . Thus it is
40. (d) (∆S)system + (∆S)surrounding > 0 (irreversible process). more stable.
∆H melting 6 × 1000 J 10. (a) ∆H − ∆E = ∆nRT −3 × 8.314 × 298
41. (a) ∆S = =
TF.P. 273 K
= −7432 J = −7.43 kJ .
= 21.978 ≈ 22 J/K .
11. (a) H 2O(g) + C(s) → CO(g) + H 2 (g); ∆H1 = 131kJ …(i)
Heat of Reaction 1
CO(g) + O2 (g) → CO2 (g); ∆H 2 = −282kJ …(ii)
1. (d) ∆U = −6.12 × 1.23 × GMM NH4 NO3 2
1
= −6.12 × 1.23 × 80 = −602 kJ / mol. H 2 (g ) + O2 (g) → H 2O(g); ∆H 3 = −242kJ …(iii)
2
2. (b) ∆ r H = ∆H products − ∆H reactants By adding eq. (i), (ii) and (iii)
H 2O + C + CO + O2 + H 2 → CO + H 2 + CO2 + H 2O
 218 121.68 
= −92.3 −  + = −92.3 − [109 + 60.84] C + O2 → CO2
 2 2 
∴ ∆H1 + ∆H 2 + ∆H 3 = 131 − 282 − 242 = −393kJ .
= −262.14 kJ / mol .
 Thermodynamics and Thermochemistry 239

12. (a) H product < H reactant for exothermic reaction. 23. (d) Compounds with high heat of formation are less stable
because energy rich state leads to instability.
13. (e) Fe 2 O3(s ) + 3 H 2( g ) → 3 H 2 O(l ) + 2Fe( s)
24. (b) This reaction absorbed heat, so it is endothermic
∆ r H = Σ∆ f H
o o
(Products) − Σ∆ f H (Reactants)
o
reaction.
25. (c) C + O2 → CO2 ∆H = −393.5 kJ / mol
⇒ ∆ r H o = 3(−286) − (−824)
∵ 44 gm of CO2 form by which heat released
[∵ ∆ f H o for Fe( s) , H 2( g ) = 0]
= −393. 5 kJ
= −858 + 824 = −34 kJ mol −1 .
393.5
14. (c) C + 2S → CS2 ∆H = ? ∴ 1gm of CO2 form by which heat released = −
44
C + O2 → CO2 ∆H = −393.3 kJ …..(i) ∴ 35.2 gm (given) of CO2 form by which heat released
S + O2 → SO2 ∆H = −293.72 kJ .....(ii)
393.5
=− × 35.2 = −315 kJ .
CS2 + 3O2 → CO2 + 2SO2 ∆H = −1108.76 kJ …..(iii) 44
eq. (ii) ×2+ eq. (i) – eq. (iii) – and find required result. 26. (c) C + O2 → CO2 ; ∆H = q
15. (c) S + O2 → SO2 , ∆H f = − 4.6 kJ C + 1 / 2O2 → CO ; ∆H = −12 …..(i)
∵ 0.5 g. of sulphur on burning produce 1g of SO2 CO + 1 / 2O2 → CO2 ; ∆H = −10 …..(ii)
∴ 32 g of sulphur on burning produce 64 g of SO2 adding equation (i) and (ii) we can get
∴ ∆H = ( − 4.6 kJ ) × 64 = − 294.4 kJ . ∆H = −12 + (−10) = −22 .
16. (d) ∆H = Σ∆H of (products) − Σ∆H of (reactants) 3
27. (d) 2Fe + O 2 → Fe 2 O 3 ; ∆H = −193.4 kJ .....(i)
2
∆H = (−242 − 76) − (−266 + 0) = −52 kJ .
1
17. (d) ∆H = 18500 = ∆E + ∆ng RT Mg + O 2 → MgO; ∆H = −140.2 kJ .....(ii)
2
or 18500 = ∆E + (−1) × 2 × 298 = 19096 cal .
On multiplying eq. (ii) by 3
18. (c) No. of equivalents of weak acid 0.4 × 0.2 = 0.08 3
3 Mg + O 2 → 3 MgO; ∆H = −420.6 kJ ......(iii)
So, amount of heat liberated per equivalent 2
4.4 Resulting equation can be obtained by subtracting eq.
= = −55kJ .
0.08 (i) from (iii)
19. (b) ∆H for C 2 H 4 = −341.1 K cal 3
3 Mg + O 2 → 3 MgO; ∆H = −420.6 kJ
−341.1 2
its calorific value = = −12.1 kcal / g .
28 3
2Fe + O 2 → Fe 2 O 3 ; ∆H = −193.4 kJ
∆H for C2 H 2 = −310.0 kcal 2

−310.0 Subtraction :
its Calorific value = = −11.92,
26 3 Mg + Fe 2 O3 → 2Fe + 3 MgO; ∆H = −227.2 kJ .
hence C2 H 4 is a better fuel.
28. (b) CH 3 CH = CH 2 + 9 / 2O2 → 3CO2 + 3 H 2 O
20. (c) By definition 42 g 3 ×18
= 54 g
−
21. (b) 0.3 mole OH , neutralize 0.3 mole of HNO3
54 g of H 2O ≡ 42 g of propene
Evolved heat, = 57.1 × 0.3 = 17.13kJ .
42
22. (c) 1 mole of butane (C4 H10 ) ≡ 58 g. ∴ 27 g of H 2 O = × 27 = 21 g.
54
58g. of butane ≡ 2658 kJ 29. (c) Heat of formation is the quantity of heat exchanged
2658 when one mole of a substance is formed from its
11200g. of butane ≡ × 11200 ≡ 513269 kJ constituent elements under given condition of
58
temperature and pressure. Under normal conditions,
20000 kJ of energy required = 1 day.
carbon is found in solid form and oxygen is found in
513269 gaseous form.
513269 kJ of energy required = = 25.66 days
20000
30. (d) 13.7 kcal = 57 kJ = 5.7 × 10 4 J .
≈ 26 days (approx).
 240 Thermodynamics and Thermochemistry

3 Total heat absorbed Q = 35.8 × 0.06 kJ

31. (b) 2 Al + O2 → Al 2O3 , ∆H = −1596 kJ …..(i)
2
Specific heat of water Cv = 4.18 × 10 −3 kJ/g
3
2Cr + O2 → Cr2O3 , ∆H = −1134 kJ …..(ii) Q = [Link] .∆T
2
By (i) – (ii) 35.8 × 0.06 = 4.18 × 10 −3 kJ / g K × 100 g. × ∆T
2 Al + Cr2O3 → 2Cr + Al 2 O3 , ∆H = −462 kJ . [Mass of 100 cm 3 (100mL.) of water = 100 g. ]
32. (b) For a substance to dissolve, the energy evolved when 35.8 × 0.06 kJ
∆T = = 5.13 K
the ions are hydrated (hydration energy) must be larger 4.18 × 10 −3 × 100 kJ/K
than the energy required to break the crystal lattice
Final temperature of the solution
(lattice energy). Conversely if the solid is insoluble, the
= 298 K − 5.13 K ≈ 293 K .
hydration energy is less than the lattice energy.
33. (a) NaCl(s) NaCl (l ) 39. (c) The entire process of changing of 10 g. of ice at
− 10 o C to water at + 10 o C can be divided into:
Given that : ∆H = 30.5 kJ mol −1
∆H ∆H
Ice (−10 º C) 
1
→ Ice(0º C) 
2 → Water (0 º C)
∆S = 28.8 JK −1 = 28.8 × 10 −3 kJ K −1
∆H
∆H 30.5 
3 → Water (10º C )

By using ∆T = = = 1059 K .
∆S 28.8 × 10 − 3 10
∆H1 = mCp .∆T = × 37.8 × 10 = 210 J
34. (c) Given that, the complete combustion of one mole of 18
butane is represented by thermochemical reaction as 10
∆H 2 = × 6.012 × 10 3 J = 3340J
13 18
C4 H10( g ) + O2 (g) → 4 CO2 (g) + 5 H 2 O(l)
2 10
∆H 3 = × 75.6 × 10 = 420 J
We have to take the combustion of one mole of C4 H10 18
Total heat required = 210 + 3340 + 420 = 3970 J .
and ∆ E H should be negative and have a value of
40. (a) ∆H sol = ∆H lattice + ∆H hydration
2658 kJ mol −1 .
4 − (−784) = ∆H lattice ⇒ ∆H lattice = +788 .
35. (b) The reaction is
41. (b) C + O2 → CO2 + 94.2 kcal . …..(i)
C(s) + 2 H 2 (g) → CH 4 (g)
1
∆ng = 1 − 2 = −1 H2 + O2 → H 2O + 68.3 kcal. ….(ii)
2
∆ f H = ∆ f U + ∆ng RT On multiplication of eq. (ii) by 2 and than adding in eq. (i)
As ∆n g = − 1 C + 2H 2 + 2O2 → CO2 + 2H 2O + 230.8 kcal …(iii)

∴ ∆ f H < ∆fU . On subtracting eq. (iii) by following eq.

CH 4 + 2O2 → CO2 + 2H 2O + 210.8 kcal. we get,
36. (a) Enthalpy of sublimation of a substance is equal to
enthalpy of fusion + enthalpy of vaporisation C + 2H 2 → CH 4 ∆H = 20 kcal.
Sublimation is direct conversion of solid to vapour, solid 15
42. (b) C6 H 6(l ) + O2( g ) → 6CO2( g ) + 3 H 2O(l ) ,
→ vapour 2
Writing in two step, we have solid → liquid → vapour ∆H = −3270 kJ mol −1 ...(i)
Solid → liquid requires enthalpy of fusion
C( gr ) + O2( g ) → CO2( g ) , ∆H = −394 kJ mol −1 ...(ii)
Liquid → vapour requires enthalpy of vaporisation.
1
37. (a) By Kirchhoff’s equation : H 2( g ) + O2( g ) → H 2O(l ) , ∆H = −286 kJ mol −1 ...(iii)
2
∆H T2 − ∆H T1
= C p (Product) − C p (Reactant) Formation of C6 H 6
T2 − T1
6C( gr ) + 3 H 2( g ) → C6 H 6(l ) ; ∆H = ? ...(iv)
∆H T2 − (−20.75)
= 0 ⇒ ∆H T2 = −20.75 KJ . By multiplying eq. (ii) with 6 and eq. (iii) with 3 and
∆T
adding we get,
38. (a) Enthalpy of solution of KNO3 is endothermic reaction
3
6C( gr ) + 6O2( g ) + 3 H 2( g ) + O2( g ) →
KNO3 (s) + H 2 O(l) → KNO3(aq) , 2
∆H = + 35.8 kJ/mol 6CO2( g ) + 6 H 2O(l ) ...(v)
 Thermodynamics and Thermochemistry 241

∆H = 6(−394) + 3(−286) = (−2364) + (−858) 53. (e) A compound is soluble in water when its hydration
= −3222 kJ / mol enthalpy is greater than its lattice enthalpy.

Now, by subtracting eq. (i), from (v) we get

6C( gr ) + 3 H 2( g ) → C6 H 6(l ) Ea Ea > ∆H

Enthalpy
54. (c)
∆H
∆H = −3222 − (−3270) = +48 kJ / mol .
43. (a) (i) 2 C(s) + 3 H 2 (g) → C 2 H 6 (g); ∆H = −21.1
(ii) C( s ) + O2 (g) → CO2 (g); ∆H = −94.1 Energy
1 55. (b) Beckmann thermometer is used to measure low
(iii) H 2 (g) + O2 (g) → H 2O(l); ∆H = −68.3
2 temperature.
3 × Eq.(iii) + 2 × Eq.(ii) − Eq.(i) : 56. (a) Heat evolved from 1.89 g. of benzoic acid
7 (C6 H 5 COOH ) = 18.94 × 10 3 × 0.632 × 0.998 cal.
C2 H 6 + O2 → 2CO2 + 3 H 2 O .
2
Combustion heat of benzoic acid (molecular mass
∆H = 3(−68.3) + 2 (−94 .1) − (−21.1) kcal . =122) per mole
∆H = −372 kcal . 18.94 × 10 3 × 0.632 × 0.998 × 122
= cal.
44. (b) Out of given substances, kerosene oil has maximum 1.89
calorific value. = 771.1 kcal .
45. (b) 0.2 mole will neutralize 0.2 mole of HNO3 , heat 57. (b) More negative the value of enthalpies of formation,
evolved = 57 × 0.2 = 11.4 kJ . more stable the products.
46. (b) Oxidation of N 2 (g) is endothermic reaction because of 58. (c) C(graphite) + O2 (g) → CO2 (g), ∆H = −94.05kcal/mole
high bond dissociation energy of N 2 molecule. C(diamond) + O2 (g) → CO2 (g), ∆H = −94.50kcal/mole
47. (b) Since the reaction happens in a bomb calorimeter at a C(graphite) → C(diamond), ∆H = −94 .05 + 94.50
constant volume so ∆E represents the heat of = + 450 cal/mol
combustion. ∆E = −870kcal .
So graphite is the stabler allotrope. Hardness of two
48. (c) In the complete combustion of butanol ∆H > ∆E . compounds cannot be predicted from the given
49. (c) NH 4 NO3 (s) → NH 4 NO3 (aq.); ∆H S = 25.5 equations.

NH 4 NO3 (aq.) NH 4 + (aq.) + NO3 − (aq.); ∆H diss. . 59. (d) For complete neutralization of strong acid and strong
base energy released is 57.32 kJ / mol
More +ve is ∆H S , more is the heat of dissociation.
0.2 × 50
50. (b) Enthalpy of formation for NO(g), CS2 (l) is positive. No. of g. eq. of H 2 SO4 = = 10 − 2
1000
M 12
51. (c) ∆E = C × ∆t × = 30 × 4 × =360 1
m 4 No. of g. eq. of KOH = × 50 = 5 × 10 − 2
1000
∆E = −360kJ mol −1. So = 57.32 × 10 −2 = 0.5732 kJ = 573.2 Joule .
52. (c) (i) NH 3 (g) + 3Cl 2 (g) NCl 3 (g) + 3 HCl(g) ; −∆H1 60. (a) Mili-equivalent of HCl = 500 × 0.1
(ii) N 2 (g) + 3 H 2 (g) 2 NH 3 (g); − ∆H 2 = 50 milli-moles = 0.05 moles
(iii) H 2 (g) + Cl 2 (g) 2HCl(g); + ∆H 3 Milli-equivalent of NaOH = 200 × 0.2

1 = 40 milli-moles = 0.04 moles

From eq.(ii), ∆ f H NH3 = − ∆H 2
2 When 1 mole of H + ions and 1 mole of OH − ions are
1 neutralized, 1 mole of water is formed and 57.1 kJ of
From eq.(iii) ∆ f H HCl = + ∆H 3 energy is released.
2
From eq.(i), 0.04 moles of H + ions react with 0.04 moles of OH −
∆ r H = ∆ f H NCl3 + 3∆ f H HCl − ∆ f H NH3 − 3 ∆ f H Cl2 ions to form 0.04 moles of water molecules. Heat
evolved = 0.04 × 57.1 = 2.29kJ .
1   1 
− ∆H1 = ∆ f H NCl3 + 3 ∆H 3  −  − ∆H 2  − 3(0) 61. (a) For reaction (i) ∆n1 = 0.5
2   2 
For reaction (ii) ∆n2 = 1.5
1 3
∆ f H NCl3 = −∆H1 − ∆H 2 − ∆H 3 .
2 2 So, ∆H1 < ∆H 2 .
 242 Thermodynamics and Thermochemistry
62. (c) Reaction of elements to form a compound can be
Bond Energy
exothermic or endothermic e.g.
1. (c) ∆E = 0 for a cyclic process.
C + O2 → CO2 is exothermic
2. (a) 4 g H 2 = 2 moles. Bond energy for 1 mole of
whereas C + 2S → CS2 is endothermic
H 2 = 208 / 2 = 104 kcal.
Hence, enthalpy of formation can be positive or 3. (c) First ionization potential of Li = 5.4 eV
negative.
Electron affinity of Cl = 3.61eV
63. (b) C(s) + O2 (g) → CO2 ( g ) ; ∆H = −94 Kkcal We have ∆H = I .P . − E. A.
∆ng = 1 − 1 = 0 = 5.4 − 3.61 = 1.80eV = 1.80 × 1.6 × 10 −22 kJ

∆H = ∆E + ∆ng RT ⇒ ∆E = −94 kcal . ∆H = 2.86 × 10 −22 kJ ,

for 1mol Avogadro’s number = 6.02 × 10 23 .

∆E = ECO2 − EC − EO2
∆H = 2.86 × 10 −22 × 6.02 × 10 23 = 170 kJ / mole.
−94 = ECO2 − 0 − 0 [Internal energy of elements = 0]
1 1
4. (a) H 2 + Cl 2 → HCl
ECO2 = −94kcal . 2 2

64. (a) No. of moles of KOH = 0.2 × 0.5 = 0.1 moles 1 1

∆H = × 434 + × 242 − 431
2 2
No. of moles of HCl = 0.2 × 0.5 = 0.1 moles
= 217 + 121 − 431 = −93 kJ / mole .
Heat evolved due to neutralization = Q1 5. (d) CH 4 has 4 C − H bond
When the experiment is repeated using half of the 320
solution then the no. of moles of both the solution will EC −H = = 80
4
be reduced to half of the original. Thus heat evolved
In C 2 H 6 there is
Q2 = Q1 / 2
6 ⇒ C − H bond and 1 ⇒ C − C bond
But in second case the volume of solution
360 = EC−C + 6 EC − H
(250mL + 250mL) also reduced to half of the original
360 = EC −C + 6 × 80
(500mL + 500mL) . So the increase in temperature will
be same i.e. T1 = T2 . E C − C = 120cal .

65. (a) No doubt heat evolved during neutralisation of 6. (c) ∆H f (H ) = 218kJ / mol

250 cm3 of each acid and base is five time the heat ∆H f (H 2 ) = 2 × 218 = 436kJ / mol

evolved during neutralisation of 50 cm 3 of each acid 1kcal = 4.184kJ

and base but the quantity if solution taking heat is also 1
436 kJ / mol = × 436 = 104 kcal / mol .
five time and thus same temperature rise is noticed. 4.184
7. (a) Enthalpy of reaction = Bond energy of reactants –
66. (b) H 2C2O4 2 H + + C2O42 − ; ∆H1 = Q
Bond energy of products
and 2H + + C2O42 − + 2 Na + + 2OH − → 2 Na + + C2O42 − = 945 + 3(436) − 2 × 3 × 391
+2H 2 O(l ) ; ∆H 2 = −13.7 × 2 = −93 kJ .

Adding both H H
| |
+
H 2C2O4 + Na + OH − +
Na + C2O42 − + H 2O 8. (a) H − N − N − H (So, 4 N − H bond present)
means their energy = 391 × 4 = 1564
∆H 3 = −25.4 kcal
so the bond energy of N − N in N 2 H 4
So, Q − 13.7 × 2 = −25.4 kcal = 1724 − 1564 = 160kJ / mol .
Q = 2 kcal mol −1 . 9. (a) Bond energy = – (Enthalpy of formation)
Bond energy of HF = 161 kJ
67. (a) Generally enthalpy of solution is positive but here in this
question, the three other compounds have -ve enthalpy Bond energy of HCl = 92 kJ
of solution. So HF is more stable than HCl .
 Thermodynamics and Thermochemistry 243

10. (b) XY( g ) → X( g ) + Y( g ) ; ∆H = + a kJ / mole ……….(i) 15. (c) Same bonds are formed in reaction (i) and (ii) but no
bonds are broken in reaction (i) whereas bonds in the
X 2( g ) → 2 X ( g ) ; ∆H = + a kJ / mole ………. (ii) reactant molecules are broken in reaction (ii). As energy
is absorbed when bonds are broken, energy released in
Y2( g ) → 2Y( g ) ; ∆H = +0.5 a kJ / mole ……….(iii) reaction (i) is greater than that in reaction (ii) hence,
x > y.
1 1
× (ii) + × (iii) − (i), gives
2 2 Free Energy and Work Function
1 1 (c) When ∆H = +ve and ∆S = −ve reaction is non-
X 2(g ) + Y2(g ) → XY(g ) ; 1.
2 2 spontaneous.
 a 0.5  2. (a) This is an example of spontaneous reaction because it
∆H =  + + a − a  kJ / mole
 2 2  occurs of its own and hence ∆G of the reaction must be
negative.
a 0.5a
⇒ + + − a = −200 3. (b) dGP , T = − ve is the criterion for spontaneity.
2 2
4. (c) Upon mixing each ideal gas has now excess to more
⇒ a = 800 .
volume of the container so the randomness of gas
11. (c) [(4 × 410.5) + 606.1 + 431.3] − [(6 × 410.5) + 336.49] molecules increases and so do the entropy of the system.
= −120.0 kJ mol −1 . 5. (b) For spontaneous change ∆G = −ve .
6. (b) CaCO3 (s) CaO(s) + CO2 (g)
1 1
12. (c) H 2 + Cl 2 → HCl K p = PCO2 = 0.003 atm
2 2
∆G = ∆Gº +2.303 RT log K p
1 
∆H f =  ∆H H − H + ∆H Cl − Cl  − [∆H H − Cl ]
1
2 2  = 27.2 + 2.303 × 2 × 1000 × log 0.003

1 1  = 15.6 kcal (R = 2 cal mol −1 K −1 ) .

− 90 =  × 430 + × 240 − ∆H H − Cl
2 2  7. (d) At equilibrium ∆G = 0 .
−90 = 215 + 120 − ∆H H − Cl 5
8. (d) (i) C2 H 2 (g) + O2 (g) → 2CO2 (g) + H 2 O(l);
2
∆H H −Cl = 335 + 90 = 425 kJ / mol .
∆Gº = −1234kJ
13. (a) 2H 2 + O2 → 2H 2O, ∆H = −571 (ii) C(s) + O2 (g) → CO2 (g); ∆Gº = −394kJ
∆H reaction = 2 × B.E (H 2 ) + B.E (O2 ) − 2 × B.E (H 2O) 1
(iii) H 2 (g) + O2 (g) → H 2 O(l); ∆Gº = −237kJ
∴ −571 = (2 × 435) + 498 − 2 × B.E (H 2O) 2
Eq.(iii) + 2 × Eq.(ii) − Eq.(i) :
or, 2 × B.E(H 2O) = 870 + 498 + 571
H 2 (g) + 2C(s) → C2 H 2 (g),
1939
B.E (H 2O) = = 969.5 . ∆Gº = −237 + 2(−394) − (−1234)kJ
2
∆Gº = + 209kJ .
969.5
B.E(O − H ) = = 484.75 . 9. (b) Negative value of ∆G indicates that the process is
2
spontaneous. Spontaneous process leads to the
14. (b) Bond dissociation energy of PH 3 (g) lowering of free energy (∆G) .
= 228 k cal mol −1 10. (d) ∆G = ∆H − T∆S = 0
∆H + 30.558 kJ mol −1
P − H bond energy =
228
= 76 k cal mol −1 ∴ T= = = 463 K
3 ∆S 0.066 kJK − 1mol −1

H H ∆G = ∆H − T∆S = (30.558 − T × 0.066) kJ mol −1

P−P at T < 463 K
H H 0.066 T < 463 × 0.066
Bond energy of 4(P − H ) + (P − P ) or 0.066 T < 30.558
= 355 k cal mol −1 or 0 < 30.558 − 0.066 T
or 0 < ∆G
or 4 × 76 + (P − P ) = 355 kcal mol −1
Thus, at T < 463 K, ∆G > 0
⇒ 51k cal mol −1 . i.e., process is non spontaneous.
 244 Thermodynamics and Thermochemistry

11. (d) + ve ∆H and − ve ∆S both oppose the reaction. 20. (c) At equilibrium ∆G = 0
12. (a) When ∆H = –ve, ∆S = +ve and ∆G = –ve than ∆H − T∆S = 0
reaction is spontaneous. ∆H −743.1
T= = = 43.7 K .
13. (d) A( g ) + B( g ) → C( g ) , ∆E = −5 cal ∆S − 17
21. (d) Factual.
∆ng = 1 − (1 + 1) = −1
22. (d) A spontaneous process is accompanied by decrease in
∆H = ∆E + ∆nRT = −5 − 1 × 2.0 × 298 = −601 enthalpy and increase in entropy means ∆H is
∆G = ∆H − T∆S = −601 − 298 × (−10) = 2379 cal . negative and ∆S is positive.
1 1 23. (b) For spontaneous reaction ∆G should be negative
14. (a) N 2 (g) + O2 (g) NO(g) ∆G = 78kJ/mol
2 2 ∆G = ∆H − T∆S = (+ve) − T(+ve)
At equilibrium ∆G = −2.303RT log 10 K If T∆S > ∆H then ∆G will be negative and reaction will
be spontaneous at high temperature.
78 × 10 3 = −2.303 × 8.314 × 1000 × log 10 K
o
24. (d) K p = e − ∆G / RT
.
log 10 K = −4.07
25. (b) ∆G gives a criteria for spontaneity at constant pressure
K = 8.4 × 10 −5 .
and temperature
15. (e) ∆G = ∆H − T∆S
(i) If ∆G is negative (< 0), the process is spontaneous
For first condition, reaction will be spontaneous at all
(ii) If ∆G is positive (> 0), the process is non-
temperatures.
spontaneous
For second option as ∆H = +ve and ∆S is +ve thus
∆G = ∆H − T∆S (iii) If ∆G is zero then reaction is equilibrium.
+ ve (− ve ) 1 3
26. (b) X 2 + Y2 → XY3
If temperature is high, T∆S will have higher negative 2 2
value and reaction will be spontaneous.  60 3 
∆S = 50 −  + × 40  = 50 − (30 + 60) = −40 J / Kmol
Thus not true for given reaction.  2 2 
In case (c), ∆G = always positive at equilibrium ∆G = 0
⇒ non-spontaneous at all temperatures ∆H − 30 × 10 3
∆H = T∆S ; T = = = 750 K .
In case (d), ∆H = −ve, ∆S = +ve ∆S − 40
⇒ spontaneous at all temperatures 27. (b) For a reaction to be spontaneous, ∆G must be
In case (e), ∆G = ∆H − T∆S negative. According to the equation –
− ve + ve ∆G = ∆H − T.∆S
At high temperature, second term will have high If ∆H and ∆S both are positive, than term T. ∆S will
positive value and reaction will be non-spontaneous; be greater than ∆H at high temperature and
thus case (e) is true for given example. consequently ∆G will be negative at high temperature.
16. (b) ∆G = ∆H − T∆S 28. (b) ∆G = ∆H − T∆S
For a reaction to be spontaneous ∆G should be at constant temperature and pressure ∆G = 0
negative. Thus ∆S and ∆H decides the fate of a 0 = ∆H − T∆S so ∆H = T∆S .
reaction. 29. (c) The thermodynamic quantity of the system, the
17. (b) ∆Gº = − RT ln K decrease in whose value during a process is equal to
useful work done by the system, i,e., ∆G = ∆H − T∆S ,
= −2.303 × 8.314 × 10 −3 × 298 × log 10 (0.15) = 4.7kJ .
where H = enthalpy, S= entropy and T= absolute
18. (d) X 2 O4 (l) → 2 XO2 (g) temperature. If an endothermic reaction occurs
∆ng = 2 − 0 = 2 spontaneously i.e. ∆H = +ve then for reaction to be
spontaneous ∆G should be negative that is only
∆H = ∆U + ∆ng RT possible when ∆S > 0 at constant temperature and
∆G = ∆H − T∆S pressure.
30. (b) The Gibbs free energy of graphite is lowest among all
= 2.1 kcal + (2 × 2 × 10 −3 × 300) − (300 × 20) kcal × 10 −3
the allotropes of carbon at standard temperature and
= −2.7 kcal . pressure. Thus graphite is the most stable form of
19. (a) ∆G = −ve means the process is spontaneous. carbon.
 Thermodynamics and Thermochemistry 245
31. (b) ∆G = −2.303 RT log K ′ , Here R = 2 cal, T = 300 K As K 2 < K1 and T2 > T1

10 × 15 K   1 1 
K′ = = 10 ; ∆G = −2.303 × 2 × 300 × log 10 10 So ln  2  < 0 and  −  > 0
3× 5 K T T
 1  1 2 
= −2.303 × 2 × 300 × 1 = −1381.8 cal .
So ∆H º must be negative.
32. (b) X( g ) + 3Y( g ) 2Z(g)

∆S°= 2S° (Z) – {S° (X) + 3S° (Y)} Statement Type Questions
= 2 × 50 – {60 + 3 × 40} =100 – 180 = – 80 J K–1 mol–1
1. (c) Variables like P, V and T which describes the state of
Given ∆H° = – 40 kJ = – 40,000 J, ∆G° = ∆H° – T∆S° system are called state variables or state functions
At equilibrium, ∆G° = 0 ∴ ∆H° = T∆S° because their values depend only on the state of the
∆H ° 40000 system and not on how it is reached.
or, T = = = 500 K .
∆S° 80 2. (d) The positive sign expresses when work is done on the
33. (b) ∆G has a negative value. So, the reaction is feasible in system. Similarly, negative sign expresses when work is
forward direction. So, equilibrium constant will have done by the system.
value greater than one.
3. (a)
1
34. (a) In the first reaction C(gr.) + O2(g) → CO(g) ∆Sº = +ve 4. (a)
2
5. (c) The standard enthalpy of reaction is the enthalpy
Therefore ∆Gº = ∆H º −T∆S that means the value of
change for a reaction when all the participating
∆G decrease on increase temperature.
substances are in their standard states. The standard
35. (b) For Combustion reaction, ∆H is negative,
state of a substance at a specified temperature is its pure
∆ng = (16 + 18) − (25 + 2) = +7 , so ∆S is +ve , reaction
form at 1 bar. For example, the standard state of liquid
is spontaneous, hence ∆G is –ve. ethanol at 298 K is pure liquid ethanol at 1 bar.
36. (b) Gibb’s free energy is the measure of useful work done Standard state of solid ion at 500 K is pure iron at 1
at constant temperature and pressure. bar. The standard conditions are denoted by adding the
∆G º = − P ∆V superscript
to the symbol ∆H e.g., −∆H
.
Volume difference (∆V ) for 12g of carbon (1mole)
Matching Type Questions
−12 g 12 g
= + 1. (a) A – (p), B – (s), C – (r), D – (q)
2.25 g/cm 3 3.31 g/cm 3
Expansion of a gas in vacuum ( pext = 0) is called free
∆V = −1.7cm3 = −1.7 × 10 −6 m 3 / mole
expansion.
− ∆G 1895 J/mole
P= = For isothermal irreversible change
∆V 1.7 × 10 − 6 m 3 /mole
q = −W = pext (V f − Vi )
= 1.1 × 10 9 Pa .
37. (b) ∆Gº = ∆H º −T∆Sº = − RT ln K For isothermal reversible change

T1 = 298 K, T2 = 1000 K, K 1 = 5 × 10 −3 , K 2 = 2 × 10 −5 q = −W = nRT ln (V f / Vi )

∆H º − T ∆S º = 2.303 nRT log V f / Vi

= − ln K
RT
For adiabatic change, q = 0, ∆U = Wad
∆H º −T1 ∆Sº
= − ln K1 …(i) 2. (c)
RT1
3. (d)
∆H º −T2 ∆Sº
= − ln K 2 …(ii) 4. (b)
RT2
Subtracting eq. (ii) from eq. (i) 5. (b) (A) ∆ng = 2 − 2 = 0 hence ∆H = ∆U

∆H º T1 ∆Sº ∆H º T2 ∆Sº (B) ∆ng = 2 − 1 = 1 hence ∆H = ∆U + RT

− − + = ln K 2 − ln K1
RT1 RT1 RT2 RT2
(C) ∆ng = 2 − 4 = −2 hence ∆H = ∆U − 2RT
∆H º  1 1  K 
 −  = ln 2 
R  T1 T2   K1  (D) ∆ng = 5 − 2 = 3 hence ∆H = ∆U + 3RT
 246 Thermodynamics and Thermochemistry

Numerical Value type questions 20 51

Using eqs. (i) and (ii), b = and a =
71 71
1560
1. (319) Energy left unutilized = kJ = 780 kJ 20 1 51 122
2 ∴ nO2 used = × + =
71 2 71 142
For losing 44 kJ of energy, water to be evaporated =
122
1 mole = 18 g or Mass of O2 used = × 32 = 27.49 g .
142
∴ For loosing 780 kJ of energy, water to be 7. (128.02) The desired chemical change is

evaporated =
18
× 780 g = 319 g . C + 2S → CS2 ; ∆H = ? …(i)
44
The data given is
1
2. (309.16) Aim : [SF6 (g ) → S (g) + 6 F (g )], ∆H = ? C + O2 → CO2 ; ∆H = −393.3 kJ …(ii)
6
For the reaction, SF6 (g ) → S (g) + 6 F (g) S + O2 → SO2 ; ∆H = −293.72 kJ …(iii)

CS2 + 3O2 → CO2 + 2SO2 ; ∆H = −1108.76 kJ …(iv)

∆ r H = ∆ f H ° [S (g)] + 6[∆ f H ° F (g)] − [∆ f H ° SF6 (g)]
Now performing the mathematical operation,
= 275 + 6 (80) − (−1100) kJ mol −1 = 1855 kJ mol −1
[(iii) × 2] + (i)
∴ Average S—F bond energy C + 2S + 3O2 → CO2 + 2SO2 ; ∆H = −980.74 kJ …(v)
1855
= = 309.16 kJ mol −1 . and (v) – (iv)
6
CS2 + 3O2 → CO2 + 2SO2 ; ∆H = −1108.76 kJ
3. (9.2) At constant temperature,
− − − − +
V V C + 2S → CS2 ; ∆H = +128.02 kJ
∆S = n RT ln 2 = 2.303 n RT log 2
V1 V1
∆H f (CS 2 ) = +128.02 kJ .
20
= 2.303 × 2 × 2 × log = 9.2 cal K − 1 mol − 1 . 8. (88.4) ⠍ sulphur → α  sulphur ; ∆H1 = 82 cal at 25°C
2
3 5 Using Kirchoff's equation
4. (4) Cv = R for monoatomic and Cv = R for diatomic
2 2 ∆H 2 − ∆H1 = ∆C p (T2 − T1 )
gases. Hence, for the mixture,
∆C p = C pα − S − C p β − S
3 5
R+ R
2 2 = 2 R = 4 cal . = 0.171 − 0.163 = 0.008 cal / g
Cv =
2
∆C p is per g and thus ∆H 2 and ∆H1 will be per g,
γ −1
T V 
5. (80) For adiabatic expansion, 2 =  1  i.e.,
T1  V2 
82
∆H1 = cal/g at 25°C
For CO2 (triatomic gas), γ = 1.33 32
0.33 1/ 3 ∆H 2 − ∆H1 = ∆C p × [T2 − T1 ]
150  10   10 
∴ =  =  
300  V2  
 V2  82
∆H 2 − = 0.008 × [323 − 298]
32
1/ 3
1  10  10 1
or =  or = or V2 = 80 L .  82
∴ ∆H 2 = 

+ 0.008 × 25 cal / g
2  V2  V2 8
 32 
6. (27.49) Using the data given
 82 
= + 0.008 × 25 × 32 cal / g  atom
1  32 
C + O2 → CO ; ∆H = −24 k cal
2
= 88.4 cal / g  atom .
C + O2 → CO2 ; ∆H = −95 k cal
9. (296.5) C 2 H 4 + 3O2 → 2 CO2 + 2 H 2 O
Total mass of carbon present = 12 g = 1 mole
6226 × 3 × 22.4
Let a mole forms CO and b mole forms CO2 Thus, VO2 used = = 296.5 litre .
1411
a+b =1 …(i) 10. (245) ∆H = −2 × e H − Cl + e H − H + e Cl − Cl
Also heat liberated = −75 = −95 × a + (−24 × b) ∴ 182 = −2 × a + 430 + 242
or 95 a − 24 b = 75 …(ii) ∴ a = 245 kJ mol −1 .
 Thermodynamics and Thermochemistry 247

10. (d) C(s) + O2 (g) → CO 2 (g)

Past Years Questions
∆H = −393.5 kJ mol −1 …..(i)
1. (c) w, q are path functions; q + w = ∆E , H − TS = G are
CO(g) + 1 / 2O2 (g) → CO2 (g)
state function.
∆H = −283 kJ mol −1 …..(ii)
2. (c) H 2O (l)  → H 2O (g)
vaporization

On subtracting equation (ii) from equation (i)

∆ng = 1 − 0 = 1 We get
∆H = ∆U + ∆ng RT C(s) + O2 (g) → CO(g) ; ∆H = −110.5 kJ mol −1
∆U = ∆H − ∆ng RT The enthalpy of formation of carbon monoxide per
= 41 − 8.3 × 10 −3
× 373 = 37.9 kJ mol −1
. mole = −110.5 kJ mol −1 .

3. (b) Heat required rising the temperature of a body by 1K 11. (a) In isolated system the expansion of gas is carried out
adiabatically. Since heat exchange between system and
called thermal capacity of the body.
surrounding is not possible i.e. q = 0 and secondary
4. (c) In this reaction ∆ng = 2 − 4 = −2 so ∆H ≠ ∆E .
wrev is always greater than wirr therefore for reversible
5. (a) ∆H = ∆U + ∆(PV ) process there must be comparatively higher decreases
∆H = ∆U + V∆P in internal energy i.e. ∆U for reversible process will be
∆U = ∆H − V∆P = −560 − 1 × 30 × 0.1 more negative. Hence final temperature in reversible
Absolute value = 563 kJ. process will be smaller than irreversible process.
∴ (Tf)irrev > (Tf)rev
1
6. (b) C(s) + O2(g)  → CO(g) 12. (c) ∆H = nCp ∆T
2
The process is isothermal therefore
∆H = ∆U + ∆ng RT  1 1
∆n = 1 − ⇒ + ∆G = 0 ; ∴ ∆H = 0 .
(∆H − ∆U ) = ∆ng RT  2 2
13. (d) Work done by the gas W = − P∆V .
1
= + × 8.314 × 298 = +1238.78 J mol−1. For irreversible adiabatic expansion.
2 W = CV (T2 − T1 ) ,CV = 3/2 R for monoatomic gas
7. (a) Method I : Thus − P∆V = CV (T2 − T1 )
The process is isothermal expansion Hence, q = −w
− 1 × ( 2 − 1) = (3/2) R ( T2 − T1 )
∆u = 0
q = + 208 J −2 2
T2 − T1 = ⇒ T2 = T1 − .
3R 3 × 0.0821
w = − 208 J (expansion work).
14. (b) For Adiabatic process, Q = 0
Method II :
Now, ∆U = Q + W ⇒ ∆U = W.
q = + 208 J (as it absorb heat)
15. (b) C6 H 6(l ) + 7.5O2( g ) → 6CO2( g ) + 3 H 2 O(l )
v 
wrev = −2.303 nRT log 10  2  ∆n( g ) = 6 − 7.5 = −1.5
 v1 
∆H = ∆E + ∆n( g ) RT
 375 
− 2.303 × 0.04 × 8.314 × 310 log 10   = −208 J . 1.5 × 8.314 × 298
 10  ∆H = −3263.9kJ − kJ = −3267.6 kJ .
1000
8. (c) 1/2I2(s) + 1/2Cl2(g) 
→ ICl(g); ∆Hf = ? V
16. (c) w = − nRTln 2
Cl2(g) → 2Cl(g); ∆H = 242.3 kJ mol −1
V1
I2(s) → I2(g); ∆H = 62.76 kJ mol−1 V
| w |= nRT ln (given final volume= V)
I2(g) → 2I(g); V1
∆H = 151.0 kJ mol−1
| w |= (nRT) ln V + (−nRT ln V1 )
2Cl(g) + 2I(g) → 2ICl(g); ∆H = −422.6 kJ mol−1
On comparing this graph with y = mx + c ; c = −nRT ln V1
I2(s) + Cl2(g) 
→ 2ICl(g);
If V = 1 litre, then 0 < V1 < 1 ;
∆H = −422.6 + 151 + 62.76 + 242.3 = 33.46 kJ
33.46 so at temperature T1 and T2 :
So heat of formation of ICl = = 16.73 kJ mol−1.
2 | w |T1 = −nRT1 ln V1 ; (n, R and T are positive and ln V1 is
9. (b) The amount of heat required to raise the temperature negative)
by ∆T of 1 mole of substance at constant pressure | w |T2 = −nRT2 ln V1
Q P = C p × ∆T
As T2 > T1 ⇒| w |T2 >| w |T1
Qp Hence intercept on y-axis will be positive at
Cp = and ∆T = 0 at equilibrium.
∆T ln V = 0 and the magnitude will be more for T2 . Only
Hence C p = ∞ (Infinity). given in option (c) is possible.
 248 Thermodynamics and Thermochemistry

334 373 2491 383 V2 V

17. (b) ∆S = + 4.2 ln + + 2 ln 29. (a) ∆S = nR ln = 2.303 nR log 2
273 273 373 373 V1 V1
= 1.2234 + 2.303 × 4.2(2.572 − 2.436) 100
= 2.303 × 2 × 8.314 × log
+ 6.678 + 2 × 2.303(2.583 − 2.572) 10
= 7.9014 + 1.315 + 0.05 = 9.267 kJkg −1 K −1 . = 38.3 J mol −1 K −1 .
18. (b) W = − P(∆V ) = − 4 [1 − 5] = 16 J 30. (c) From 1st law of thermodynamics
16 = 1 × 24 × ∆T q sys = ∆U − w = 0 − [− Pext .∆V ]
2 = 3.0 atm × (2.0 L − 1.0 L) = 3.0 L − atm
∆T = K .
3 (qrev )surr qsys
(a) C p should not change with pressure. ∴ ∆Ssurr = =−
19. T T
20. (d) Isothermal expansion PVm = K (Graph − C) 3.0 × 101.3 J
=− = −1.013 J / K.
K 300 K
P= (Graph – A)
Vm 31. (b) At 100 0 C and 1 atmosphere pressure
P U
H 2 O(l) H 2 O (g ) is at equilibrium. For
equilibrium ∆Stotal = 0 and ∆Ssystem + ∆Ssurrounding = 0

Vm ∴ ∆Ssystem > 0 and ∆Ssurroundings < 0.

Vm
32. (c) For spontaneous process ∆G = ∆H − T∆S
5 × 28 × 100
21. (a) ∆U = nCv ∆T = = 14 kJ ∵ ∆H < 0 ⇒ ∆S > 0 .
1000
33. (d) CO2 (s) → CO2 (g) ; ∆S = +ve
5 × 8 × 100
∆(PV ) = nR∆T = = 4 kJ . N 2 + 3 H 2 → 2 NH 3 ; ∆S = −ve
1000
CaSO4 → CaO + SO3 ; ∆S = +ve
22. (c) From FLOT ∆U = q + W
Dissolution of I 2 ; ∆S = +ve
for adiabatic process q = 0
T1 + T2
∴ ∆U = w . 34. (c) TFinal =
2
T2 1000
 Tf 
23. (c) ∆H = ∫
T1
nCpdT = n ∫ (23 + 0.01T)dT
300
∆SI = CP ln
 T1


1000  Tf 
 0.01T 2   2 × 23 × 700 + 9100  ∆SII = CP ln 
= 3 23T +  = 3   T2 
 2  300  2 
∆S = ∆SI + ∆SII
= 61950 J / mol ≈ 62 kJ / mol .
  T + T 2 
24. (a) q = −2 kJ  1 2
 
 Tf2   2  
= CP ln  = CP ln 
w = +10 kJ  T1T2  T1T2 .
   
∆U = q + w = −2 + 10 = + 8 kJ .  
25. (a) W = − Pext (V2 − V1 ) = −1(10 − 1) = −9 bar 35. (c) At 25 o C , the state of methane is gas and the
L = −900 J = −0.9 kJ . elementary form of carbon is graphite.

26. (d) According to first law of thermodynamics if ∆U = 0 the 36. (d) Standard molar heat enthalpy (H o ) of a compound is
work done can be equal to Q1 + Q2 but according to equal to its standard heat of formation from most stable
states of initial components.
second law of thermodynamic 100% efficiency is not 37. (b) CO2 (g) + H 2 (g) → CO(g) + H 2 O(g)
possible so it violates 2nd law of thermodynamics. o o o o
∆ r H º = ∆ f H CO + ∆ f H H 2O − ∆ f H CO2 − ∆ f H H 2
dQrev. 30 × 10 3
= −110.5 + (−241.8) − (−393.5) − 0
27. (b) dS = ; T= ; T = 400 K .
T 75
= 41.2kJ / mole .
28. (b) SC − S A = 50 e.u.
38. (b) Formation of one mole of its constituents elements is
SD − SC = 30 e.u. called enthalpy of formation.
SB − SD = −20 e.u. Which is satisfied by (b) option.
In (a) Cdiamond is not constituent element.
On addition of these equations we get
In (c) 2 mole NH 3 is formed instead of one mole.
SB − S A = 60 e.u.
In (d) CO is not constituent element, it should be
∆S A → B = 60 e.u.
carbon.
 Thermodynamics and Thermochemistry 249

39. (b) At standard conditions, chlorine is found in gaseous 45. (b) C( graphite) + O2 (g) → CO2 (g)
form and bromine as in liquid form. And ∆H ºf of ∆H r = −393.5 kJ / mol = ∆H f CO2 (g)
elements is taken as zero.
1
H 2 ( g) +O2 (g) → H 2O(l)
40. (c) C6 H12 O6 (s) + 6O2 (g) → 6CO2 (g) + 6 H 2 O(l) 2
∆ c H = 6 × ∆ f H (CO2 ) + 6 ∆ f H(H 2 O) − ∆ f H (C6 H12O6 ) ∆H r = −285.8 kJ / mol = ∆H f H 2 O(l)

−6∆ f H (O2 , g) CO2 (g) + 2H 2 O(l) → CH 4 (g) + 2O2 (g)

∆H r = ∆H f (CH 4 ) − ∆H f CO2 (g) − 2∆H f H 2 O(l) = 890.3
= 6 × (−400 − 300) − (−1300) − 0
⇒ ∆H f CH 4 + 393.5 + 2 × 285.8 = 890.3
= − 4200 + 1300
⇒ ∆H f CH 4 (g) = −74.8 kJ / mol.
= −2900 kJ / mol
46. (c) C(graphite) + O2 (g) → CO2 (g)∆, H ° = xkJ / mol …(i)
For one gram of glucose, enthalpy of combustion
1
2900 C(graphite) + O2 (g) → CO(g)∆ r H ° = ykJ / mol ...(ii)
=− = −16.11 kJ / g . 2
180
1
1 CO(g) + O2 (g) → CO2 (g)∆ r H ° = zkJ / mol …(iii)
41. (b) H 2 (g) + O2 (g) → H 2 O(l) ; ∆H = −286.20 kJ 2
2
(i) = (ii) +(iii)
1 x = y + z.
∆H r = ∆H f (H 2 O, l) − ∆H f (H 2 , g) − ∆H f (O2 , g)
2 47. (a) C7 H16 (l) + 11O2 (g) → 7CO2 (g) + 8 H 2O(l)
−286.20 = ∆H f (H 2 O(l))
∆ng = 7 − 11 = −4
So, ∆H f (H 2 O, l) = −286.20 ∆H = ∆U + ∆ng RT
+ −
H 2 O(l) → H (aq) + OH (aq) ; ∆H = 57.32 kJ ∆H − ∆U = −4 RT .
48. (b) I 2 (s) → I 2 (g )
∆H r = ∆H of (H + , aq) + ∆H of (OH − , aq) − ∆H of (H 2O, l)
(∆H )250 o C − (∆H )200 o C = ∆C p,m (T2 − T1 )
57.32 = 0 + ∆H of (OH − , aq) − (−286.20)
∆H 250 o C = 24 + (0.031 − 0.055)50 = 22.8 Cal g −1 .
∆H of (OH − , aq) = 57.32 − 286.20 = −228.88kJ .
49. (a) CH 4 → CH 3 + + H − ,∆H1
240
42. (a) ∆H = − 349 − 381 C6 H 5 − CH 3 → C6 H 5 CH 2 + + H − , ∆H 2
2
= 120 − 349 − 381 = − 610kJ / mol . The stability of benzyl radical is more than that of
methyl radical so the bond dissociation energy is less.
43. (a) C2 H 5 OH(ℓ) + 3O2 (g) → 2CO2 (g) + 3 H 2 O(ℓ) 1 3
50. (c) N 2 + H 2 → NH 3
∆U = −1364.47 KJ / mol 2 2
1 3
∆H = ∆U + ∆ng RT ∆H = H f ( NH 3 ) − H f ( N 2 ) − H f (H 2 )
2 2
∆n g = − 1 1 3
− 46 = H f ( NH 3 ) − (−712) − × (−436)
2 2
 −1 × 8.314 × 298  H f ( NH 3 ) = −46 − 356 − 654 = −1056 KJ
∆H = −1364.47 +  
 1000 
enthalpy of formation of NH 3 = −1056 KJ
= −1364.47 − 2.4776 Average bond enthalpy of N − H bond
= −1366.94 KJ / mol . 1056
= = 352
44. (d) (i) BaCl 2 (s) → BaCl 2 (aq); ∆H = −20.6 kJ/mol 3 .
51. (c) EC − C ≅ 100 KCal / mole.
(ii) BaCl 2.2 H 2 O(s) → BaCl 2 (aq) + 2H 2 O(l) ; ∆H ,
52. (d) 2C(s) + H 2 (g) → C 2 H 2 (g) ∆H = 225 KJ / mol
= 8.8 kJ/mol
Subtracting eq.(ii) from eq.(i)
− (2 E C − H + E C ≡ C )
BaCl 2 (s) + 2H 2 O(l) → BaCl 2 .2H 2 O(s)
2C(g) + 2H (g)
∆H = (−20.6 − 8.8)kJ / mol ∴ ∆H = +1410 + 330 − (350 × 2) − EC ≡ C = +225
∆H = −29.4kJ/mol . ∴ EC ≡ C = 1740 − 700 − 225 = +815 kJ / mol.
 250 Thermodynamics and Thermochemistry

53. (a) C( s) + 2H 2( g ) → CH 4( g ) ; ∆H of = −74.8 kJ/mol 62. (d) 2 NO(g) + O2 (g) 2 NO2 (g), ∆Gr
Bond energy of CH 4 will be the heat of formation of At equilibrium ∆Gro =0
the bond from gaseous atoms constituting the bond So ∆Gr = − RT ln K p
with reverse sign.
C( g ) + 4 H ( g ) → CH 4 ( g ) , ∆ r H = ? ∆Gr = 2G f ( NO2 ) − 2G f ( NO) − G f (O2 )
∆ r H = ∆ f H CH4 ( g ) − ∆ f H C( g ) − ∆ f H H ( g ) 2 G f ( NO2 ) = 2G f ( NO) + G f (O2 ) + ∆Gr
In this equation the first term is given but the second
G f ( NO2 ) = 0.5[2 × 86600 − R(298) ln(1.6 × 1012 )] .
 
term (∆H C(s) → C(g ) ) and third term  ∆H 1  are not 63. (b) 2 A B+C
 H2 → H 
 2 
[ B][C]
given. Q=
54. (a) Since, liquid is passing in to gaseous phase so entropy [ A]2
will increase and at 373 K the phase transformation 1
2×
remains at equilibrium. So ∆G = 0. 2 =4
Q=
55. (b) A B (1 / 2)2
∆G o = ∆H o − T ∆S o ; ∆G = − RT ln K c
∆G o = 0 − 2.303 RT log 10 K
2494.2 = −8.314 × 300 × ln K c
− 2.303 RT log 10 K = ∆H o − T∆S o ;
ln K c = −1
2.303 RT log 10 K = T∆S o − ∆H o
K c = C −1
T∆S − ∆H
o
298 × 10 + 54.07 × 1000
o
log 10 K = = = 10 . = 1 / 2.718 [Given e = 2.718 ]
2.303 RT 2.303 × 8.314 × 298
56. (b) (dS)V , E > 0,(dG)T ,P < 0 . = 0.36
As Q > K c , reaction move in reverse direction.
57. (c) At temperature T :
∆G = ∆H − T∆S 64. (a) ∆G = ∆H − T∆S = 0
At temperature Te : ∆H 200
T= = = 5K .
∆Ge = ∆H − Te ∆S = 0 ∆S 40
∆H = Te ∆S 65. (a) ∆G = A − BT
∆G = Te ∆S − T∆S = ∆H − T∆S
As ∆S is positive and T > Te then ∆G < 0 . A = ∆H
58. (b) Since adsorption is exothermic, ∆S is negative and free ∆H = A = +ve endothermic.
energy decreases. Due to randomness of particles 66. (d) ∆H − T∆S < 0
reduced so entropy will decreases. ∆H
59. (c) ∆G o = ∆H o − T∆S o T>
∆S
− RT ln K = ∆H o − T∆S o 491.1 × 1000
T>
∆H o − T∆S o 198
ln K = − .
RT T > 2480.3 K .
o
60. (a) At equilibrium ∆G = 0 ⇒ ∆G = − RT ln K eq 67. (c) ∆ Sol H o = ∆ lattice H o + ∆ Hyd. H o
∆H º −T∆Sº = − RT ln K eq
4 = 788 + ∆ Hyd. H o
= ln( K eq ) = ( − ∆H º /R)(1/T ) + ( ∆Sº /R)
∆ Hyd. H o = −784 kJ / mol .
Slope (−∆H º / R) > 0 ⇒ ∆H º < 0
o
Reaction is exothermic. 68. (b) (A) Water → ice; ∆S = −ve
0 C

3
(d) CH 3 OH(l) + O2 (g) → CO2 (g) + 2 H 2 O(l)
o
−10 C
61. (B) Water  
→ ice; ∆S = −ve
2
∆Gr = ∆G f (CO 2 (g) + 2∆G f (H 2 O(l)) − ∆G f (CH 3 OH(l)) (C) N 2 (g ) + 3 H 2 (g ) → 2 NH 3 (g ); ∆S = −ve
3 (D) Adsorption ; ∆S = −ve
− ∆Gf (O2 ( g))
2 (E) NaCl (s) → Na + (aq) + Cl − (aq); ∆S = +ve .
= −394.4 + 2(−237.2) − (−166.2) − 0
69. (a) Enthalpy of bond dissociation (kJ/mole) at 298.2K
= −394.4 − 474.4 + 166.2 = −868.8 + 166.2 For , hydrogen = 435.88
∆Gr = −702.6 kJ
For , Deuterium = 443.35
702.6
% efficiency = × 100 = 97% . ∴ EH ~
− E D − 7.5 .
726
 Thermodynamics and Thermochemistry 251

7 78. (2218) Fe + 2HCl → FeCl 2 + H 2

70. (c) C 2 H 6 (g) + O2 (g) → 2CO2 (g) + 3 H 2 O(ℓ)
2 50
∆ C H (C2 H 6 ) = 2∆ f H CO2 (g) + 3∆ f H(H 2 O, ℓ) moles
55.85
−∆ f H (C2 H 6 , g) 50
No. of H 2 produced = moles
−1560 = 2 (−394) + 3 (−286) − ∆ f H (C2 H 6 , g) 55.85
Work done = − Pext .∆V
∆ f H (C2 H 6 , g) = −86 kJ / mole .
= −∆ng RT
71. (192.5)
50
C2 H 6 (g) + 3.5O2 (g) → 2CO2 (g) + 3 H 2O(l) = × 8.314 × 298
55.85
From the given data ≃ 2218 J .
2 × (−286) + 3 × (−393.5) − (−1560) = −572 − 1180.5
79. (104) 3C(Graphite) + 4 H 2 (g) → C3 H 8 (g)
+1560 = −192.50 kJ / mol
∆H r0 = 3∆ H c0 (C, graphite) + 4 ∆ H c0 (H 2 , g) − ∆ H c0 (C3 H 8 , g)
72. (336) ∆G = −49.4kJ / mol
∆H = 51.4 kJ / mol = 3(−393.5) + 4(−285.8) − (−2220)
∆G = ∆H − T∆S = −1180.5 − 1143.2 + 2220
−49400 = 51400 − 300∆S = −2323.7 + 2220 = −103.7 kJ / mole
+100800 ≈ 104 kJ / mole .
∆S = = 336 JK −1mol −1 .
300 80. (2) HCl + NaOH → NaCl + H 2 O ∆H1 = −57.3 KJ mole −1
73. (21) C(graphite) + O2 → CO2 (g) ; ∆H = −2.48 kJ mole CH 3 COOH + NaOH → CH 3 COONa + H 2 O
1 gram
1 ∆H 2 = −55.3 KJ mole −1
Total heat released = 2.48 × × 10 2
12 CH 3 COOH CH 3 COO − + H + ∆H 3 = ?
= 20.67 = 21 . ∆H 3 = ∆H1 − ∆H 2 = +2.0 KJ mole −1 .
74. (50) q = 150 Joules
81. (2) ∆G = ∆H − T ∆S
W = −200 Joules 300(−80)
∆E = q + w (First law of thermodynamics) Process A = ∆G = −25 −
1000
∆E = 150 + (−200) = −25 + 24
∆E = −50 Joule. = −1 < 0
75. (5) ∆G = ∆H − T∆S 300(+40)
Process B : ∆G = −22 −
298(−176) 1000
∆G = 57.8 −
1000 <0
∆G = −5.352 kJ / mole 300(−50)
Process C : ∆G = 25 −
[Nearest integer value] = 5. 1000
>0
76. (5576) Na(s) → Na + (g) ∆H = 495.8
300(20)
1 Process D : ∆G = 22 −
Br2 (l) + e − → Br − (g) ∆H = 325 1000
2 = 22 − 6 = 16
Na + (g) + Br − (g) → NaBr (s) ∆H = −728.4 >0
1 ∴ Process C & D are non spontaneous
Na(s) + Br2 (l) → NaBr (s) ∆H = ? 82. (620)
2
1 → 2 ⇒ Isobaric process
∆H = 495.8 − 325 − 728.4
2 → 3 ⇒ Isochoric process
− 557.6 kJ = −5576 × 10 −1 kJ .
3 → 1 ⇒ Isothermal process
77. (200) A + B C+D W = W1→ 2 + W2→ 3 + W3 →1
For a reaction to be spontaneous    V  
∆r G < 0 =  − P (V2 − V1 ) + 0  − P1V1 ln  2   
   V1   

Or ∆ r G o < 0 (for the given case)
   20   
=  −1 × (40 − 20) + 0 +  −1 × 20 ln   
⇒ ∆ r H − T∆ r S < 0
o o
   40   
⇒ 80 × 1000 − T × 2T < 0 = −20 + 20 ln 2
⇒ T 2 > 40000 = −20 + 20 × 2.3 × 0.3
T > 200 = −6.2 bar L
∴ Tmin = 200 K . | W |= 6.2 bar 1 = 620 J .