Chapter Contents: Chemical Thermodynamics

Chapter 6
Thermodynamics
Chapter Contents
z Chemical Thermodynamics CHEMICAL THERMODYNAMICS
z System and Surroundings The branch of science which deals with the study of the quantitative
z Thermodynamic Process relationship between heat and other forms of energy is known as
z Reversible and Irreversible Thermodynamics. When the study is confined to chemical changes
Process only, the branch is known as Chemical Thermodynamics.
z Internal Energy
SYSTEM AND SURROUNDINGS
z First Law of Thermodynamics
A system in thermodynamics refers to that part of universe in which
z Pressure-volume Work
observations are made and remaining universe constitutes the
z Free Expansion surroundings. The surroundings include everything other than the system.
z Enthalpy System and the surroundings together constitute the universe.
z Heat Capacity The universe = The system + The surroundings.
z Enthalpy Change, rH of a z Types of system : Depending on the interactions between system and
Reaction - Reaction Enthalpy its surroundings, three kinds of system are distinguishable.
z Bond Energy (i) Isolated system : A system which neither exchanges energy nor
z Hess’s Law of Constant Heat matter with its surroundings is called an isolated system. For
Summation example a liquid in contact with its vapour in an insulated closed
z Spontaneous Processes vessel is an isolated system.
z Second Law of (ii) Closed system : A system which may exchange energy but not
Thermodynamics matter with its surroundings is called a closed system. If in the
z Entropy Change during Phase above example the vessel containing liquid in contact with its vapour
is closed one but is not insulated. It is a closed system.
Transformations
z Gibb's Free Energy (iii) Open system : A system which may exchange both energy and
matter with its surrounding is called an open system. The
z Third Law of Thermodynamics
evaporation of water in an open vessel is an example of open
system. Water absorbs heat from the surroundings and escapes
into surroundings as water vapour.
z State of a system : The system is said to have a definite state when
it is in such a condition where all of its macroscopic properties have
definite values. When the value of any one of its macroscopic properties
changes, the system is said to have a different state. Thus the state of
a system is defined when its macroscopic properties are specified.
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140 Thermodynamics NEET
z State variables : The macroscopic properties of a system are often called state variables, since the state
of a system changes with the change in any of the macroscopic properties. Of all the macroscopic properties
(state variables) pressure, volume, temperature and composition, assume particular importance in
thermodynamics, since they can be controlled more easily.
z State function : A state function is a property of the system whose value depends only upon the state of
the system and is independent of the path or manner by which the state is reached. The change in the value
of these properties (state functions) depends only upon the initial and final states of the system and not on
the path by which the change from initial to final state is brought about. Some common state functions are
pressure (P), volume (V), temperature (T), internal energy (E), enthalpy (H), entropy (S) etc.
z Intensive & Extensive Properties
The properties of the system can be classified into two types:
(i) Intensive properties : The properties of the system whose value is independent of the amount of
substance present in the system are called intensive properties. For example : temperature, pressure,
viscosity, etc. are intensive properties.
(ii) Extensive properties : The properties of the system whose value depends upon the amount of
substance present in the system are called extensive properties. For example : mass, volume, surface
area and energy are extensive properties.
THERMODYNAMIC PROCESS
Let us consider a system having P1V1 and T1 state functions if T1 is changed to T2 then the resulting system
is characterized by state functions P1V1 and T2 and the process of changing state is called as thermodynamic
process that is thermodynamic process can be defined as a process having change in state of system. These
are of following types.
Isothermal Process : The thermodynamic process in which temperature remains constant throughout are
called isothermal process.
Adiabatic Process : The thermodynamic process in which heat exchange between system and surrounding
is not possible.
Isobaric Process : The thermodynamic process occurring at constant pressure are called isobaric process.
Isochoric Process : The thermodynamic process occurring at constant volume are called isochoric process.
Cyclic Process : The thermodynamic process having same initial and final state are called cyclic process.
REVERSIBLE AND IRREVERSIBLE PROCESS

(i) Reversible process : Process where change is carried out so slowly that system and surrounding are
always in equilibrium.
(ii) Irreversible process : Process other than reversible process are irreversible process.
Differences between Reversible and Irreversible Processes
S.No. Reversible process Irreversible process
1. It takes place in infinite number of infinitesimally It takes place in a single step.

small steps and it would take infinite time to
occur.
2. It is imaginary as it assumes the presence of It is real and can be performed actually.
frictionless and weightless piston.
3. It is in the state of equilibrium at all the stages It is in equilibrium state only at the initial and
of operation. final stages of the operation.
NEET Thermodynamics 141
S.No. Reversible process Irreversible process
4. All changes are reversed when the process is After the occurring of the process changes do
carried out in reversible direction. not return to the initial state by themselves.
5. It is extremely slow. It proceeds at measurable speed.
6. Work done by a reversible process is greater Work done in irreversible process is smaller
than the corresponding irreversible process. than the corresponding reversible process.
INTERNAL ENERGY (U)

The inherent energy which is possessed by a substance by virtue of its existence is called its Internal Energy.
The total energy possessed by a substance is known as internal or intrinsic energy. In case of a molecule,
it is equal to the sum of kinetic energy, [translational (Et), rotational (Er), vibrational (Ev)], potential energy (Ep),
chemical bond energy (Ec), electronic energy (Ee), and nuclear energy (En). Thus
U = Et + Er + Ev + Ep + Ec + Ee + En
The internal energy of a system is a state function, i.e., it depends only on the state of the system and is
independent of the path or the manner in which the state is reached.
z U) : It may be mentioned that the absolute value of internal energy of a substance
Internal Energy Change (
cannot be determined. When a system undergoes a change of state, the change in internal energy, U is given
by:
U = U2 – U1
Where U1 and U2 are internal energies in the initial and final states respectively.
During a reaction taking place at constant temperature and at constant volume (i.e., in a closed vessel), the
internal energy change is equal to the amount of heat evolved or absorbed (qv) in it, i.e.
U = qv = Heat absorbed in a reaction at constant temperature and volume.
z Heat : The change in internal energy of a system can be brought about by the transfer of heat from the
surroundings to the system or vice-versa. This exchange of energy between the system and surroundings is
possible as a result of the temperature difference between them. This energy called heat is represented by q.
FIRST LAW OF THERMODYNAMICS

(i) Energy can neither be created nor be destroyed.
(ii) The total energy of universe is constant.
(iii) The mass and energy of an isolated system remains constant.
(iv) The total energy of a system and its surrounding must remain constant, although it may be changed from
one form to other.
Mathematically, U  q  W …(1)
Sign Convention :
W = +ve, work done on the system
W = –ve, work done by the system
q = +ve, heat is absorbed by the system

q = –ve, heat is evolved by the system.
Example 1 : A system gives out 20 J of heat and also does 40 J of work. What is the internal energy change?
Solution : U = q + w
= –20 J + (–40) J
= –60 J
PRESSURE-VOLUME WORK
It is the work done when the gas expands or contracts against the external pressure (usually atmospheric
pressure). To understand this, consider a cylinder containing one mole of an ideal gas fitted with a frictionless
and weightless piston. Pressure of the gas inside is p. Let the external pressure acting on the piston is pex.
If the external pressure pex is slightly greater than p(i.e., pex > p), piston moves downward till the pressure
inside the cylinder becomes equal to pex. During this compression, suppose the piston moves a very small
distance l.
Cross-section
pex area of
piston A
pex
Vi
Pressure, p
pex
Area = pex × V
V = Vf – Vi l
Vi, p Vf
Vf, p
Vf Vi
Fig. : (a) Fig. : (b) Fig. : (c)
Initial status Final status Work done on an ideal gas in a cylinder
when it is compressed by a constant
Pressure-Volume work external pressure, pex (in a single step)
is equal to the shaded area
It, w is the work done on the sytem by the movement of the piston, then
Work, w = force × displacement
= pex × A × l
= pex × (–V)
= –pex V
= –pex(Vf – Vi)
For irreversible isothermal process : W = –Pext.V
V2
For reversible isothermal process : W = –2.303nRT log
V1
FREE EXPANSION
Expansion of a gas in vacuum (where pex = 0) is called free expansion. No work is done during free expansion
of an ideal gas whether the process is reversible or irreversible.
wirrev = –pex V
= 0 × V = 0
Vf
and wrev =  pex dV  0

Vi
Example 2 : Calculate the amount of work done when one mole of an ideal gas contained in a bulb of 2 L
capacity at 1 atm is allowed to enter in evacuated bulb of 10 L capacity and in another case it
is allowed to expand from 1 L to 5 L against a pressure of 1 atm.
Solution : Case I
w = –pex V
As expansion is taking place in the evacuated bulb, i.e., against vacuum, pex = 0. Hence w = 0.
Case II
V = V2 – V1
=5L–1L
=4L
p = 1 atm
 w = –pV
= –1 × 4
= –4 L-atm
1 L-atm = 101.3 J
= –4 × 101.3 J
= –405.2 J
The negative sign implies that work is done by the system.
ENTHALPY (H)
Many of the reactions are carried out at constant pressure. To measure heat changes at constant pressure
it is useful to define new state function called enthalpy (H).
The thermodynamic quantity U + PV is called the heat content or enthalpy of the system denoted by H.
H = U + PV
For a reaction : H  U  ngRT
Where, ng = number of moles of gaseous product – number of moles of gaseous reactant.
Note : H is a state function and is an extensive property.
Example 3 : If water vapour is assumed to be a perfect gas, molar enthalpy change for vaporization of 1 mol
of water at 1 bar and 100°C is 41 kJ mol–1. Calculate the internal energy, when 1 mol of water
is vapourised at one bar pressure and 100°C.
Solution : The change H2O(l)  H2O(g)
H = U + ngRT
or U = H – ngRT
= 41 kJ mol–1 – 1 × 8.314 J mol–1 K–1 × 373 K
= 41 kJ mol–1 – 3101 J mol–1
= 41 kJ mol–1 – 3.101 kJ mol–1
= 37.9 kJ mol–1
HEAT CAPACITY
Heat capacity of a system is defined as the quantity of heat required to raise the temperature of the system
by one degree. Let a very small quantity of heat dq be given to a system and the temperature of the system
rises by dT.
dq
Thus, Heat capacity (C) =
dT
 Q = C T = mCsT = nCmT
Where C = Heat capacity (Cal °C–1)
Cs = Specific heat capacity (Cal gm–1°C–1)
Cm = Molar heat capacity (Cal mol–1°C–1)
Example 4 : Calculate the amount of heat required to raise the temperature of 13.5 g aluminium from 300 K
to 400 K, if specific heat of aluminium is 0.9 J (°C)–1 g–1.
Solution : q = C m T
= 0.9 × 13.5 × (T2 – T1)
= 0.9 × 13.5 × 100
= 1215 J
z Relation between Cp and Cv for an ideal gas

If the volume of the system is kept constant and heat is added to a system, then no work is done by the
system. Thus the heat absorbed by the system is used up completely to increase the internal energy of the
system. If the pressure of the system is kept constant and heat is supplied to the system, then some work
of expansion will be done by the system in addition to the increase in internal energy. Therefore, heat given
at constant pressure will be more than that of constant volume. And for one mole of gas and 1°C temperature
to increase that extra heat will be equal to the extra work done by the system and it is ‘R’. So the relation
between heat capacity at constant pressure and constant volume is
Cp – Cv = R
z Ratio of Molar Heat Capacity : It is represented by  and gives idea about atomicity of gas.
Cp

Cv
Cp
Value of Cp Value of C v = Atomicity
Cv
5R 3
R 1.66 Monoatomic
2 2
7 5
R R 1.40 Diatomic
2 2
4R 3R 1.33 Triatomic
z Kirchoff's equation :
U2  U1
Cv 
T2  T1
H2  H1
Cp 
T2  T1
EXERCISE
1. Which of the following is an example of open system?
(1) Human body (2) The earth
(3) Pond (4) All of these
2. Which of the following is not a state function?
(1) H (2) U
(3) q (4) G
3. Which of the following is intensive property?
(1) Temperature (2) Heat
(3) Mass (4) Volume
4. Closed system can exchange (with surroundings)
(1) Heat (2) Matter
(3) Heat and matter (4) Neither heat nor matter
5. System and surroundings together constitute
(1) The earth (2) The solar system
(3) Galaxy (4) Universe
6. E and H both are zero in
(1) Isobaric process (2) Adiabatic process
(3) Isochoric process (4) Cyclic process
7. The work done in an open vessel at 300 K, when 56 g iron reacts with dilute HCl is
(1) 600 cal (2) 300 cal
(3) 150 cal (4) 100 cal
8. Work done in reversible isothermal expansion is given by
V2 nR
(1) –2.303 RT log (2) (T2  T1)
V1 (   1)
V2
(3) 2.303 RT log V (4) None of these
1
9. When a gas undergoes adiabatic expansion, it gets cooled. This is because
(1) It is an exothermic process (2) It is an endothermic process
(3) Internal energy of the system decreases (4) Ideal gas becomes a real gas
10. Which of the following is correct expression for 1st law of thermodynamics under adiabatic condition?
(1) U = Q + W (2) U = Q – W
(3) Q = –W (4) U = W
ENTHALPY CHANGE, rH OF A REACTION – REACTION ENTHALPY

The enthalpy change accompanying a reaction is called the reaction enthalpy. The enthalpy change of a
chemical reaction, is given by the symbol rH.
rH = (Sum of enthalpies of products) – (Sum of enthalpies of reactants)
S.No. Name of Enthalpy H Definition Example

Changed
1. Enthalpy of Combustion HCº Enthalpy change when (i) C(s) + O2(g)  CO2(g)
1 mole o f substan ce
is completely burned with (ii) CH4(g)+2O2(g)CO2(g)
required amount of oxygen + 2H2O()
2. Enthalpy of Formation Hºf 1

Enthalpy change when 1 (i) H2(g) + O2(g)  H2O()
mole of substance is formed 2
from its element in their (ii) S(s) + O2(g)  SO2(g)
most stable physical state
3. Enthalpy of atomisation Haº Enthalpy change when 1 Na(s)  Na(g)

mole of substance broken
up into its isolated atoms in
the gas phase
4. Enthalpy of neutralization HNº Enthalpy change (fix for

strong acid - strong base
neutralization i.e. –57.1 kJ or CH3COONa(aq) + H2O()
–13.7 kcal) when one mole (ii) H SO (aq) + 2NaOH(aq) 
of water is formed by the 2 4
neutralization of an acid by a Na2SO4(aq) + 2H2O()

base.
5. Enthalpy of fusion Hºf Enthalpy change when 1 H2O(s)  H2O()

mole of substance
u n de r g o es m e l t i n g i n
standard state.
6. Enthalpy of Vapourization HVap

º Enthalpy change when H2O()  H2O(g)
1 mole of liquid at constant
temperature of boiling point
and under pressure
undergoes vapourization.
7. Enthalpy of Sublimation º Enthalpy change when 1 CO2 (s)  CO2 (g)

HSub
mole of solid substance is
directly converted into
gaseous state at a constant
temperature and standard
pressure.
8. Enthalpy of Solution HºSol Enthalpy change when 1 KCl + aq  KCl (aq)

mole of sub stance is
dissolved in specif ied
quantity of solvent.
BOND ENERGY
The amount of energy required to break one mole of a particular type of a bond in the gaseous state is called
bond dissociation energy.
It is generally expressed in terms of kJ/mol. For example, 433 kJ of energy is required to dissociate the
H–H bonds in one mole of H2 molecules, therefore, the bond dissociation energy is 433 kJ mol–1.
Bond energy and bond dissociation energy : The bond dissociation energy depends upon the bond and
also the molecule in which the bond is present. When a molecule contains a number of bond of the same
kind, average value of the dissociation energies of a given bond is taken. The dissociation energy required to
dissociate each bond in a substance is called bond energy. In water, there are two O–H bonds. The bond
dissociation energies of two O–H bonds in water.
H2O(g)  H(g) + OH(g); H = 497.8 kJ

OH(g)  H(g) + O(g); H = 428.5 kJ
The bond energy is the average of these two bond dissociation energies, i.e.
Bond energy of O–H bond = (497.8 + 428.5)/2

= 463.15 kJ mol–1.
Note:
rH = (Hf)P – (Hf)R

rH = (BE)R – (BE)P
rH = (Hc)R – (Hc)P
Ionization enthalpy : However, when 1 g equivalent each of weak acid and strong base or a strong
acid and weak base or weak acid and weak base are allowed to react, the apparent value of heat
of neutralization is lesser than 13.7 kcal, e.g.,
HCl(aq)  NH4OH(aq) 
 NH4Cl(aq)  H2O; H  12.3 kcal ...(i)
Strong Weak
CH3COOH(aq)  NaOH(aq) 
 CH3COONa(aq)  H2O; H  13.4 kcal ...(ii)
Weak Strong
CH3COOH(aq)  NH4OH(aq) 
 CH3COONH4 (aq)  H2O; H  11.9 kcal ...(iii)
The lower values of apparent heat of neutralization are explained on the basis of the fact that a part of heat given
out during neutralization is utilized to bring in complete dissociation of weak component used in reaction.
CH3COOH(aq)  CH3COO–(aq) + H+ (aq); H = q
Thus, by eq. (ii)
CH3COO–(aq) + H+ (aq);
H = q + Na+ (aq) + OH– (aq)  CH3COO– (aq) + Na+ (aq) + H2O; H = –13.4 kcal
 H+ + OH–  H2O; H = –13.4 –q
 –13.4 – q = – 13.7 or q = + 0.3 kcal
Thus, heat of dissociation of acetic acid is 0.3 kcal/mol.
Lattice Enthalpy (Symbol : latticeHs)

The lattice enthalpy of an ionic compound is the enthalpy change which occurs when one mole of an ionic
compound dissociates into ions in the gaseous state.
Max Born and Fritz Haber put forward a method based on Hess’s law for the calculation of lattice enthalpy.
Since it is not possible to determine it directly, an indirect method is used by constructing an enthalpy
diagram called as Born-Haber Cycle. It is briefly described by taking the example of NaCl.
Heat of formation of NaCl is found to be –410 kJ mol–1 i.e.,
1
Na(s) + Cl (g)  NaCl(s); fHs = –410 kJ mol–1
2 2
Suppose that one mole of NaCl(s) is prepared through the following steps
(i) Na(s)  Na(g); subHs = 108.4 kJ mol–1
Sodium undergoes sublimation.
(ii) Na(g)  Na+(g) + e–(g); iHs = 496.0 kJ mol–1
Sodium atom undergoes ionization.
1
(iii) Cl (g)  Cl(g); aHs = 121 kJ mol–1
2 2
Chlorine molecule dissociates to produce Cl atom.
1
The reaction enthalpy will be half of the bond dissociation enthalpy. Hence,  Hs = 121 kJ mol–1
2 bond
(iv) Cl(g) + e–(g)  Cl–(g); egHs = –348.6 kJ mol–1
Chlorine atom gains an electron.
The electron gain enthalpy, egHs, is negative.
(v) The gaseous Na+ and Cl– ions combine to form 1 mole of crystalline sodium chloride.
Na+(g) + Cl–(g)  NaCl(s)
latticeH = U (lattice enthalpy or lattice energy)
Applying Hess’s law, we get
fHs = subHs + iHs + aHs + egHs + latticeHs
So,latticeHs = 411.2 + 108.4 + 121 + 496 – 348.6
= +788 kJ
Na(s) s –1
Na(g) s –1
Na+(g) + e–(g)
subH = +108.4 kJ mol iH = 496 kJ mol
Na+(g) + Cl–(g)
–
1 +e
Cl–(g)
s
Cl (g) Cl(g) latticeH = +788 kJ
2 2 1

s
H = +121 kJ mol
–1 s
egH = –348.6 kJ mol
–1
2 bond
Na+Cl–(s)
Now we use the value of lattice enthalpy to calculate enthalpy of solution from the expression
solHs = latticeHs + hydHs
For one mole of NaCl(s)
Lattice enthalpy = +788 kJ mol–1
and hydHs = –784 kJ mol–1
solHs = +788 kJ mol–1 – 784 kJ mol–1
= +4 kJ mol–1
The dissolution of NaCl(s) is accompanied by very little heat change.
Resonance enthalpy :
  
HRe sonance  Hf (experimental)  Hf (calculated)
HESS’S LAW OF CONSTANT HEAT SUMMATION

The enthalpy change accompanying a given chemical process is always the same, no matter whether it takes
place in one or more ways involving one or several steps Suppose a substance A is changed into D (i) directly
and (ii) indirectly.
(i) Direct change A  D + Q1 kJ
(ii) Indirect change A  B + q1 kJ
B  C + q2 kJ
C  D + q3 kJ
Thus total heat evolved = q1 + q2 + q3 = Q2 kJ (say). Then, according to Hess’s law, Q1 = Q2.
z Calorific values : The energy released due to oxidation of any fuel is measured in terms of calorific values.
It may be defined as the amount of heat given out when one gram of substance is burnt completely in oxygen.
This is expressed in kilocalories or kilo joules per gram of the fuel.
Example 5 : Calculate the enthalpy change where the standard heat of formation for gaseous NH3 is
–11.02 kcal / mol at 298 K. The reaction given is
1 3
N2(g) + H2(g)  NH3(g)
2 2
Solution : rHs = fHsProduct – fHsReactant
1  3 
= [fHs(NH3)] –  Hof (N2 )   Hof (H2 )
2  2 
1  3 
= [–11.02 kcal mol–1] –   (0)    (0)
2  2 
= –11.02 kcal mol–1 – 0
= –11.02 kcal mol–1
The standard enthalpies of formation of element in its reference state is taken as zero, therefore
fHs for N2 and H2 has been taken as zero.
Example 6 : If 150 kJ of energy is needed for muscular work to walk a distance of one km, then how much
of glucose one has to consume to walk a distance of 5 km. Provided only 30% energy is available
for muscular work. The enthalpy of combustion of glucose is 3000 kJ mol–1.
Solution : Energy consumed for walking a distance of 5 km = 150 × 5 kJ = 750 kJ
1 mole of glucose, C6H12O6 (180 g) gives theoretically energy = 3000 kJ
30
Actual energy available = × 3000 = 900 kJ
100
Thus, for 900 kJ of energy, glucose required = 180 g
180
 For 750 kJ of energy glucose required = × 750 = 150 g
900
Example 7 : Calculate amount of heat evolved when

(a) 500 cm3 of 0.5M hydrochloric acid is mixed with 200 cm3 of 0.8M NaOH solution.
(b) 250 cm3 of 0.4M H2SO4 is mixed with 500 cm3 of 0.2 M NaOH solution.
Solution : (a) 500 cm3 of 0.5 M HCl provides
500  0.5
=
1000
= 0.25 mol H+ ions

200 cm3 of 0.8 M NaOH solution provides
200  0.8
=
1000
= 0.16 mol (OH)– ions

So amount of heat produced = 57.1 × 0.16 = 9.136 kJ.
(b) 250 cm3 of 0.4 M H2SO4 provides
(250  0.4)
= ×2
1000
= 0.2 mol H+ ions

500 cm3 of 0.2 M NaOH provides
500  0.2
=
1000
= 0.1 mol OH– ions.

So amount of water formed = 0.1 mol
and amount of heat evolved = 57.1 × 0.1 = 5.71 kJ.
Example 8 : Determine the enthalpy change for the given reaction,

CH4(g) + Cl2(g)  CH3Cl(g) + HCl(g)
Bond energies are given as follows :
C – H = 412 kJ mol–1
C – Cl = 338 kJ mol–1
Cl – Cl = 242 kJ mol–1
H – Cl = 431 kJ mol–1
Solution : rHs = [Total energy used in dissociation of bonds] – [Total energy used in formation of bonds]
= [4HC – H + HCl – Cl] – [3HC – H + HC – Cl + HH – Cl]
= [4(412) + 1(242)] – [3(412) + 1(338) + 1(431)]
= [1648 + 242] – [1236 + 338 + 431]
= [1890] – [2005]
= –115 kJ mol–1
Example 9 : When 1 mole of anhydrous CuSO4 is dissolved in excess of water, –66.4 kJ heat is evolved. When
one mole of CuSO4  5H2O is dissolved in water, the heat change is +11.7 kJ. Calculate enthalpy
of hydration of CuSO4 (anhydrous).
Solution : We have to calculate enthalpy of reaction for
CuSO4 + 5H2O  CuSO4 5H2O; H = ?
Given that
CuSO4 (anhyd.) + aq.  CuSO4 (aq.); H1 = –66.4 kJ ...(i)
CuSO4 5H2O + aq.  CuSO4 aq.; H2 = +11.7 kJ ...(ii)
On the basis of two equations
H = H1 – H2
= –66.4 kJ – (+11.7 kJ)
= –78.1 kJ
The enthalpy of hydration of CuSO4 = –78.1 kJ
SPONTANEOUS PROCESSES
The term spontaneity means the feasibility of a process. A process which can take place by itself under the
given set of conditions once it has been initiated if necessary, is said to be a spontaneous process. The
spontaneous processes are called feasible or probable processes. The actual rate of the process may vary
from very slow to extremely fast.
z Spontaneous processes where no initiation is needed
Sugar dissolves in water and forms a solution
Sugar + water  Solution of sugar in water
Water keep on evaporating from ponds, rivers, sea and open vessels
H2O (l)  H2O (g)
z Spontaneous processes where some initiation is required
Once a reaction between hydrogen and oxygen is initiated by passing electric spark through it, then it
occurs itself spontaneously even at room temperature.
Electric
2H2 (g) + O2(g) 
Spark
 2H O (l)
2
In domestic oven, coal (carbon) keeps on burning once initiated

ignition
C (s) + O2(g)   CO2(g)
Energy and Spontaneity :
z It is a well known fact that all physical and chemical processes are accompanied by energy changes. Let us
try to interpret various spontaneous processes on the basis of changes in energy. Think of spontaneous
process such as falling of a cricket ball from our hands to the ground ; flowing of water from higher level to
lower level. We know that the ball or water possesses more potential energy at higher level than at lower
level. This suggests that these spontaneous processes proceed by decrease of energy.
z Moreover, the state of lowest energy corresponds to the state of maximum stability. Therefore, the natural
tendency of all systems in this universe to go from instability to stability supports the fact that any process
which involves a decrease in energy should have an inherent tendency to take place.
Most of the spontaneous chemical reaction are found to be exothermic. For example :
C(s) + O2(g)  CO2 (g) ; H = –394 kJ mol–1
N2(g) + 3H2(g)  2NH3 (g) ; H = –92.4 kJ mol–1
1
H2(g) + O (g)  H2O (l) ; H = –285.7 kJ mol–1
2 2
z Thus, it may be concluded that all those processes which are accompanied by decrease of energy
(exothermic reactions, having negative value of H) occur spontaneously. In other words, the sign of
H may
H may be taken as a criterion for the spontaneity of a process and decrease of enthalpy i.e. –
be regarded as the driving force behind the spontaneous processes.
z But there are many reactions which occurs endothermically and are spontaneous for example evapouration
of H2O. Thus decrease in energy alone cannot define a spontaneous process.
Randomness-Disorder and Entropy

z The thermodynamic property Entropy is the measure of disorderness or randomness.
z Entropy is the state function and is extensive property.
z Increase in disorderness increases entropy, thus solid < liquid < gas.
q rev
z The entropy change, S is given by S  .
T
Where qrev is heat absorbed when the process is reversible and isothermal.
z Entropy change is given in unit of J/K or JK–1 or calK–1.
1
z Heat absorbed at low temperature it becomes more disordered than at higher temperature i.e., S  ,
T
if compared for two systems.
z The use of entropy change for determining direction of spontaneity of a process leads to second law
of thermodynamics.
SECOND LAW OF THERMODYNAMICS
z The second law of thermodynamics introduces the concept of entropy and its relation with spontaneous
processes.
z In an isolated system such as mixing of gases, there is no exchange of energy or matter between the
system and the surroundings. But due to increase in randomness, there is increase in entropy. Thus,
we can say that for a spontaneous process in an isolated system, the change in entropy is positive. i.e.,
S > 0.
z However, if the system is not isolated, we have to take into account the entropy changes of the system
and the surroundings. Then, the total entropy change (Stotal) will be equal to the sum of the change in
entropy of the system (Ssystem) and the change in entropy of the surroundings (Ssurroundings) i.e.,
Stotal = Ssystem + Ssurroundings
z For a spontaneous process, Stotal must be positive, i.e.,
Stotal = Ssystem + Ssurroundings > 0
z But system and surroundings constitute universe for thermodynamic point of view so that for spontaneous
change
Suniverse > 0
Statement of Second Law of Thermodynamics : This states that the entropy of the universe always
increases in the source of every spontaneous (natural) change.
Thus, combining the first and second law of thermodynamics, the combined statement becomes :
The energy of the universe is conserved whereas the entropy of the universe always increases in any natural
process.
Characteristics of Entropy :
The important characteristics of entropy are summed up below :
z Entropy is an extensive property. Its value depends upon the amount of the substance present in the
system.
z Entropy of a system is a state function. It depends upon the state variables (T, P, V, n). Thus, the change
in entropy is given as :
S = Sfinal state – Sinitial state
z In a reversible process, Suniverse = 0 and therefore, Ssystem = –Ssurroundings
dqrev w V
z For a reversible process,S = =  2.303nR log 2
T T V1
dqp(rev )
z At constant pressure, dS rev =
T
dH
dS =
T
H
 S =
T
This is normally for transition process.
Example 10 : The entropy change in the conversion of water to ice at 272 K for the system is –21.85 JK–1mol–1
and that of surrounding is +21.93 JK–1mol–1. State whether the process is spontaneous or not?
Solution : Stotal = Ssys + Ssurr
= –21.85 JK–1mol–1 + (+21.93 JK–1mol–1)
= 0.08 JK–1mol–1
∵ Sprocess > 0 at 272 K, the freezing of ice
H2O(l)  H2O(s) is a spontaneous process at 272 K.
ENTROPY CHANGE DURING PHASE TRANSFORMATIONS
The change of matter from one state (solid, liquid or gas) to another is called phase transition. Such changes
occur at definite temperatures such as melting point (solid to liquid), boiling point (liquid to vapours) etc., and
are accompanied by absorption or evolution of heat.
The entropy change for these may be calculated as :
Entropy changes during phase transformations
 fusH
(i) Entropy of fusion : fus S = (Tm = melting point of solid in K)
Tm
 vapH
(ii) Entropy of vaporisation : vap S = (Tb = boiling point of liquid in K)
Tb
 sub H
(iii) Entropy of sublimation : sub S = (T = temperature in K at which sublimation occurs).
T
Similarly for a given chemical reaction
S = Sproduct – Sreactant
Ex. A2 + B2 2AB
Sreaction = [2 entropies of formation of AB] – [Entropies of formation of A2 and B2]
Driving force as the overall tendency for a process
We have learnt that the spontaneous processes occur because of the two tendencies :
(i) Tendency of a system to acquire a state of minimum energy.
(ii) Tendency of a system to acquire a state of maximum randomness.
The overall tendency for a process to take place by itself is called the driving force.
GIBB'S FREE ENERGY
z Free energy of a system is defined as the maximum amount of energy available to a system during a
process that can be converted into useful work.
z In the words, it is a measure of capacity of a system to do useful work. It is denoted by symbol G and
is given by
G = H – TS
where H is the enthalpy of the system, S is its entropy and T is the absolute temperature.
Now H = U + PV
G = U + PV – TS
z Free energy change. The change in free energy may be expressed as
G = U + (PV) – (TS)
z If the process is carried out at constant temperature and pressure, the terms (PV) and (TS) become
(PV) = PV and
(TS) = TS
G = U + PV – TS
or G  H  TS
z Free energy (G) :

When G is +ve, then the free energy of reactant is less than free energy of product (non spontaneous).
When G is –ve, then free energy of product is less than free energy of reactant (Spontaneous).
When G = 0, free energy of reactant is equal to free energy of product hence reaction exists at
equilibrium.
Spontaneity : When G < 0 the reaction will be spontaneous:
Spontaneity of the reaction
H S G = H – T S Reaction Spontaneity
– + – Spontaneous at all temperature
Spontaneous at low temperatures where H outweighs TS (T S <  H)
– – – or +
Nonspontaneous at high temperatures where TS outweighs H
+ – + Nonspontaneous at all temperatures
Spontaneous at high temperatures where TS outweighs H (T S >  H)
+ + – or +
Nonspontaneous at low temperatures where H outweighs T S
Note :
z Relation between G and G°
G = G° + 2.303RT logQ (Q = concentration coefficient)
z G° and equilibrium constant
at equilibrium G = 0 and Q = K
 Gº = –RTlnK = –2.303RTlogK
z Gro  Gfo (products)  Gfo (reactants)
Example 11 : For the reaction

N2(g) + 3H2  2NH3(g)
H = –95.4 kJ and S = –198.3 JK–1
Calculate the temperature at which Gibbs energy change (G) is equal to zero. Predict the nature
of the reaction at this temperature and above it.
Solution : G = H – TS
G = 0
H – TS = 0
or H = TS
H
T
S
95.4  1000 J

198.3 JK 1
 481 K
At this temperature, the reaction would be in equilibrium and with the increase in temperature
the opposing factor TS would become more and hence, G would become positive and the
reaction would become non-spontaneous. The reaction would be spontaneous at the temperature
below 481 K.
THIRD LAW OF THERMODYNAMICS

At absolute zero the entropy of a perfectly crystalline substance is taken as zero (Nernst). The third law
helps to calculate the absolute entropies of pure substances at different temperatures. The entropy (S)
of the substance at different temperature T may be calculated by the measurement of heat capacity
changes. If S0 be the entropy of the substance at 0 K and S be its entropy at T K, then
T
Cp
S = S – S0 =  T
dT
0
Since S0 is 0 according to third law
T
Cp
S=  T
dT
0
When the entropy of one mole of the substance is expressed in its standard state, it is called
standard entropy of the substance and is denoted as S0.
Sum of the standard  Sum of the standard 

S° =   – entropies of reactants  or
entropies of products   
S° = S° (products) – S° (reactants)
EXERCISE
11. The enthalpy of reaction is maximum in which of the following reaction?
(1) NaOH + HCl  NaCl + H2O
(2) NaOH + HF  NaF + H2O
(3) NaOH + HBr  NaBr + H2O
(4) All have same value
H = a
A P
12. H = b H = d
H = c
Q B
On the basis of Hess’s law of constant heat summation, choose the correct relation:
(1) b = a – d + c (2) c = a – b + d
(3) d = a + b + c (4) a – c = b + d
13. In which of the following H = U?
(1) N2(g) + 3H2(g)  2NH3(g) (2) C(s) + O2(g)  CO2(g)
(3) PCl5(g)  PCl3(g) + Cl2(g) (4) CaCO3(s)  CaO(s) + CO2(g)
14. Heat of combustion of CH4, C2H4 and C2H6 are –890, –1411 and –1560 kJ/mol respectively. Which has the lowest
calorific fuel value in kJ/g?
(1) CH4 (2) C2H4
(3) C2H6 (4) All of these
15. The heat of neutralisation of four acids P, Q, R, S are –13.7, –9.4, –11.2 and –12.4 kcal, respectively when
they are neutralised by a common base. The acidic character obeys the order
(1) P > Q > R > S (2) P > S > R > Q
(3) S > R > Q > P (4) S > Q > R > P
16. When H and TS both are negative, then for spontaneous process which option is true?
(1) H > TS (2) H < TS
(3) H = TS (4) H = U

17. Which of the following relation is false?
(1) G = H – TS (2) S = q + T
(3) H = U + ngRT (4) H = U + PV
18. In a reversible process, the value of Ssys + Ssurr is
(1) > 0 (2) < 0
(3) = 0 (4) All of these
19. A boiled egg shows a/an ______ in entropy
(1) Increase (2) Decrease
(3) No change (4) None of these
20. The G in the process of melting of ice at –15°C is
(1) G < 0 (2) G > 0
(3) G = 0 (4) All of these

t
en
nm nment
ssigAssig
Assignment
Assignment
A
5. Consider the following

SECTION - A
H°sol = u kJ/mol + –
AB(s) A (aq) + B (aq)
NCERT Based MCQs
1. Consider the given reaction
ol
H
/m
kJ
° LE
PCl5(g)  PCl3(g) + Cl2(g)
v
=
=
w
n
kJ
tio
If the enthalpy change (i.e. H) for the given
ra
/m
yd
ol
°h
reaction is –x J at T K then the value of U is
H
+ –
A (g) + B (g)
[NCERT Pg. 167]
The correct relation between u, v & w is
(1) (–x + 8.314 T) J (2) –(x + 8.314 T) J
[NCERT Pg. 180]
(3) (x + 8.314 T) kJ (4) –(x + 8.314 T) kJ
(1) w = v + u (2) u = w + v
2. The heat of combustion of ethene from the given
(3) v = 2(u + w) (4) v = w + u
data is
6. For a reaction to be non-spontaneous
CH2 = CH2(g) + 3O2(g)  2CO2(g) + 2H2O(l)
[NCERT Pg. 185]
Bond Bond energy
(1) TS < H & both H & S are +ve
C=C x kJ/mol
(2) TS = 0
C–H y kJ/mol
(3) TS = H & both H & S are +ve
O=O z kJ/mol
(4) TS > H & both H & S are +ve
C=O a kJ/mol
7. Which of the following are state function?
O–H b kJ/mol [NCERT Pg. 177]
[NCERT Pg. 162]
(1) x – a + b + 4y – 3z
(a) q (b) q + w
(2) x + b – 3z + a + 4y
(c) H – TS (d) w
(3) x + 4y + 3z – 4(a + b)
(1) Only (a) (2) Only (b) & (c)
(4) a + b – (x + 4y + 3z)
(3) Only (d) (4) Only (c)
3. If energy required to dissociate 16 g of gaseous
8. Among the following, which is not a state function?
hydrogen into free atoms is 3488 kJ at 25°C then
the bond energy of H – H bond will be [NCERT Pg. 162]
[NCERT Pg. 177] (1) Volume (2) Temperature
(1) 384 kJ/mol (2) 436 kJ/mol (3) Pressure (4) Heat
(3) 384 J/mol (4) 436 J/mol 9. If an ideal gas expands isothermally from 50 L to
4. The correct relation between molar heat capacities 100 L against 2 atm external pressure, then values
CP and CV is [NCERT Pg. 169] of W, U and Q respectively will be
(1) CP + CV = R [NCERT Pg. 166]
(2) CP – CV = 2R (1) –100 L atm, zero and +100 L atm
(3) CP – CV = R (2) –50 L atm, zero and +50 L atm

(3) +100 L atm, zero and –100 L atm
R
(4) CP  CV  (4) +50 L atm, zero and –50 L atm
2
10. If 1 mol of an ideal gas at constant temperature 2. Consider the following statements :
changes its pressure from 5 atm to 2 atm and
a. q and w are state function
volume from 4 L to 10 L, then enthalpy change will
be [NCERT Pg. 167] b. q + w is a state function.
(1) 20 L-atm (2) 120 L-atm c. G is a state function
(3) Zero (4) 100 L-atm The correct statements is/are
11. If equal moles of following gases are taken at (1) a only
constant temperature and pressure then gas of (2) a & b only
highest entropy is [NCERT Pg. 182]
(3) b & c only
(1) He(g) (2) H2(g)
(4) All of these
(3) CO2(g) (4) PCl5(g)
3. The incorrect statement is
12. Correct expression of enthalpy of combustion is
[NCERT Pg. 176] (1) wrev > wirr in isothermal process
5 (2) U = wadiabatic
(1) C2H6 (g)  O  g  2CO  g  3H2O  
2 2 (3) q = 0 for cyclic process
1 (4) Work and heat appear only at the boundary of
(2) C(s)  O  g  CO  g
(diamond) 2 2 the system
4. Which of the following statement is correct?
1
(3) C(s)  O2  g  CO  g
graphite 2 (1) Entropy of egg decreases on boiling
S(s)  O2 g  SO2  g

(2) Entropy of rubber band decreases on
(4)
r hombic stretching
13. Select the pair of intensive properties (3) Entropy decreases during fusion of ice
[NCERT Pg. 168] (4) All of these
(1) Volume, entropy 5. Enthalpy of formation of NO2, SO2, CO2 and NH3
(2) Refractive index, density are 33.18, –296, –393 and –46 kJ/mol respectively.
The order of their increasing stabilities are
(3) Temperature, enthalpy
(1) NO2 < NH3 < SO2 < CO2
(4) Enthalpy, Gibbs free energy
(2) NH3 < SO2 < CO2 < NO2
14. If calorific fuel value of C2H6 is x kJ/g then the heat
of combustion of C2H6 is [NCERT Pg. 176] (3) NO2 < SO2 < CO2 < NH3
(1) x (2) 30 x (4) SO2 < CO2 < NH3 < NO2
(3) x/30 (4) 30/x 6. Enthalpy of solution of BaCl2 and BaCl2.2H2O are
–x and y kJ/mol respectively. The enthalpy of
15. Work done is always zero for [NCERT Pg. 166]
hydration of BaCl2 to BaCl2.2H2O is
(1) Isobaric process (2) Adiabatic process (1) (x – y) kJ (2) (y – x) kJ
(3) Isochoric process (4) Cyclic process (3) –(x + y) kJ (4) (x + y) kJ
7. Enthalpies of combustion of propane, butane and
SECTION - B pentane are –2220, –2878, –3537 kJ/mol
respectively. Order of calorific value (per gram) of
Objective Type Questions fuel will be
1. Correct option for an endothermic gaseous reaction (1) Propane > Butane > Pentane
A + B  3C will be (2) Butane > Pentane > Propane
(1) H > 0; S < 0 (2) H = 0; S > 0 (3) Propane < Butane < Pentane
(3) H > 0; S > 0 (4) S = 0; S < 0 (4) Pentane > Butane < Propane
8. For the process 13. The respective examples of extensive and intensive
properties are
X Y
(1) Enthalpy, entropy
(2) Entropy, enthalpy
A B
(3) Entropy, temperature
H for (A  X) = 50 kJ
(4) Temperature, entropy
H for (Y  X) = 20 kJ
14. According to first law of thermodynamics
H for (B  Y) = 30 kJ
(1) U = q – w (2) U = q + H
Then H for A  B will be
(3) U = q + w (4) U = q – H
(1) 100 kJ
15. Consider the following reactions
(2) –100 kJ
C (graphite) + O2(g)CO2(g) : H = – x1 cal
(3) Zero kJ
C (diamond) + O2(g) CO2(g) : H = – x2 cal
(4) –50 kJ
What is the heat of transition of graphite into
9. Which of the following methods for calculation of diamond?
heat of reaction is not correct?
(1) x1 + x2 (2) x2 – x1
(1) Hreaction =  Hf(products) –  Hf(reactants) (3) x1 – x2 (4) x1x2
(2) Hreaction =  B.E(reactants) –  B.E(products) 16. A system absorbs 10 kJ of heat and does 4 kJ of
work. The internal energy of the system
(3) Hreaction =  Hcomb(reactants) –  Hcomb(products)
(1) Decreases by 6 kJ
(4) Hreaction =  Hsolution (reactants) +  Hsolution (products) (2) Increases by 6 kJ
10. Enthalpy changes for two reactions are given by (3) Decreases by 14 kJ
the equation
(4) Increases by 14 kJ
3
2Cr(s)  O2 (g)  Cr2O3 (s), H  1130 kJ 17. For the given reactions, A 
 D, H = x. Steps
2 involved are
1
C(s)  O2 (g)  CO(g), H  110 kJ A 
 B H1 = x1
2
The enthalpy change for the reaction B 
 C H2 = ?
Cr2O3 + 3C  2Cr + 3CO will be
C 
 D H3 = x3
(1) –1460 kJ (2) –800 kJ
The value of H2 is
(3) +800 kJ (4) 1020 kJ
(1) H2 = x – (x1 + x3) (2) H2 = x + x1 + x3
11. If temperature of the system is T, then the process
will be spontaneous at all temperature only if (3) H2 = x1 – x3 – x (4) H2 = (x1 + x) – x3
(1) H < 0 and S > 0 18. Energy required to dissociate 4 g of gaseous H2
into free gaseous atoms is 872 kJ at 25°C. The
(2) H > 0 and S > 0 bond energy of H-H bond will be
(3) H < 0 and S < 0 (1) 8.72 kJ (2) 4.36 kJ
(4) H = 0 and S < 0 (3) 436 kJ (4) 43.6 kJ
12. Tea placed in thermoflask is an example of 19. The difference between H and U for the reaction
(1) Open system 2C6H6 (l) +15O2(g)  12 CO2(g) + 6H2O (l) at 25°C
(2) Close system in kJ is
(3) Isolated system (1) –7.43 kJ (2) +3.72 kJ
(4) It can't act as system (3) –3.72 kJ (4) +7.43 kJ
20. An athlete takes 100 gm of glucose of energy 27. The specific heat of a gas is found to be
equivalent to 1560 kJ. How much amount of energy 0.075 calories at constant volume and its formula
is uptaken by 1 gm molecule of glucose? wt is 40. The atomicity of the gas would be
(1) 15.6 kJ (2) 2808 kJ (1) One (2) Two
(3) 1560 kJ (4) 28.08 kJ (3) Three (4) Four
21. The dissociation energy of CH4 (g) is 360 kcal mol–1 28. Under the same condition heats of formation of
and that of C2H6 (g) is 620 kcal mol–1. The C – C water & CO 2 are –285 and –394 kJ mol —1
bond energy is respectively. The heat of combustion of methane is
–890 kJ mol—1. The heat of formation of methane
(1) 260 kcal mol–1 (2) 180 kcal mol–1
(in kJ mol–1) is
(3) 130 kcal mol–1 (4) 80 kcal mol–1
(1) –964 (2) –890
22. The enthalpy of formation of ammonia is
–46.0 kJ mol–1. The enthalpy for the reaction (3) –222 (4) –74
2N2(g) + 6H2(g)  4NH3(g) is 29. Specific heat at constant volume (Cv) of a mono
atomic gas is
(1) –46 kJ (2) 46 kJ
3 5
(3) 184 kJ (4) –184 kJ (1) R (2) R
2 2
23. The volume of a gas expands by 0.25m3 at a
constant pressure of 103N m-2. The work done is 7 4
equal to (3) R (4) R
5 3
(1) 2.5 erg (2) 250 J 30. At 298 K the standard enthalpies of formation of
(3) 250 eV (4) 250 cal H 2 O(l) and H 2 O 2 (l) are –286.0 kJ mol –1 and
–188.0 kJ mol–1. The enthalpy change for reaction
24. Using bond energy data, calculate heat of formation
of isoprene 2H2O2(l)  2H2O(l) + O2(g) will be
5C(s) + 4H2(g) H2C==C—CH ==CH2 (1) – 948 kJ/mol
CH 3 (2) – 196 kJ mol–1
Given : BE for C–H, H–H, C–C, C = C and C(s)  (3) + 196 kJ mol–1
C(g) respectively as 98.8 kcal, 104 kcal, 83 kcal, (4) + 948 kJ mol–1
147 kcal, 171 kcal
31. The standard entropies of N2 (g), H 2 (g) and
(1) – 20.6 kcal
NH3 (g) are 191.5, 130.5, 192.6 JK–1 mol–1. The
(2) 20.6 kcal value of Sº of formation of ammonia is
(3) 40 kcal (1) –98.9 JK–1 mol–1 (2) Zero
(4) 50 kcal (3) +129.4 JK–1 mol–1 (4) –29.4 JK–1 mol–1
25. When 1 g of anhydrous oxalic acid is burnt at 32. For the melting of NaCl heat required is
25°C, the amount of heat liberated is 2.835 kJ. H 7.26 kcalmol–1 and S increases by 6.73 cal mol–1
combustion is K–1. The melting point of the salt is
(1) 255.15 kJ (2) 445.65 kJ (1) 805.75°C (2) 500 K
(3) 295.24 kJ (4) 155.16 kJ (3) 1.77 K (4) 1.77°C
26. The most exothermic neutralisation reaction would 33. The standard free energy change G° is related to
be between K (equilibrium constant) as
(1) NH4OH and HCl (1) G° = –2.303 RT logK
(2) CH3COOH and NaOH (2) G° = 2.303 RT logK
(3) NH4OH and H2SO4 (3) G° = RT logK
(4) NaOH and HCl (4) G° = –RT logK
34. It is impossible for a reaction to take place if 2. In which case change in entropy is negative?
[NEET-2019]
(1) H is +ve and S is +ve
(1) Evaporation of water
(2) H is –ve and S is +ve
(2) Expansion of a gas at constant temperature
(3) H is +ve and S is –ve
(3) Sublimation of solid to gas
(4) H is –ve and S is –ve
(4) 2H(g)  H2(g)
35. The least random state of H2O is
3. The bond dissociation energies of X2, Y2 and XY are
(1) Ice
in the ratio of 1 : 0.5 : 1. H for the formation of XY is
(2) Liquid water –200 kJ mol–1. The bond dissociation energy of X2
(3) Steam will be [NEET-2018]
(4) Randomness is same in all states (1) 200 kJ mol–1 (2) 100 kJ mol–1
36. Entropy of vaporisation of water at 100°C, if molar (3) 400 kJ mol–1 (4) 800 kJ mol–1
heat of vaporisation is 9710 cal mol—1 will be 4. A gas is allowed to expand in a well insulated
(1) 20 cal mol–1 K–1 container against a constant external pressure of 2.5
atm from an initial volume of 2.50 L to a final volume
(2) 26 cal mol–1 K–1 of 4.50 L. The change in internal energy U of the
(3) 24 cal mol–1 K–1 gas in joules will be [NEET-2017]
(4) 28 cal mol–1 K–1 (1) 1136.25 J (2) –500 J
37. The heat of neutralisation of HCl by NaOH is (3) –505 J (4) +505 J
–55.9 kJ/mole. If the heat of neutralization of HCN by 5. For a given reaction, H = 35.5 kJ mol –1 and
NaOH is –12.1 kJ/mole, the energy of dissociation S = 83.6 JK–1 mol–1. The reaction is spontaneous
of HCN is at : (Assume that H and S do not vary with
(1) –43.8 kJ (2) 43.8 kJ temperature) [NEET-2017]
(3) 68 kJ (4) –68 kJ (1) T < 425 K (2) T > 425 K
38. Molar heat capacity of water in equilibrium with ice (3) All temperatures (4) T > 298 K
at constant pressure is 6. For a sample of perfect gas when its pressure is
(1) Zero (2) Infinity changed isothermally from pi to pf, the entropy change
is given by [NEET (Phase-2) 2016]
(3) 40.45 kJ K–1 mole–1 (4) 75.48 J K–1 mole–1
39. Identify intensive quantity from the following p  p 
(1) S  nRln  f  (2) S  nRln  i 
(1) Enthalpy (2) Temperature  pi   pf 
(3) Volume (4) Heat capacity
p  p 
(3) S  nRT ln  f  (4) S  RTln  i 
 pi   pf 
SECTION - C
7. The correct thermodynamic conditions for the
Previous Years Questions spontaneous reaction at all temperatures is
1. Under isothermal condition, a gas at 300 K expands [NEET-2016]
from 0.1 L to 0.25 L against a constant external (1) H < 0 and S < 0 (2) H < 0 and S = 0
pressure of 2 bar. The work done by the gas is
(3) H > 0 and S < 0 (4) H < 0 and S > 0
[NEET-2019]
(Given that 1 L bar = 100 J) 8. The heat of combustion of carbon to CO 2 is
–393.5 kJ/mol. The heat released upon formation of
(1) –30 J 35.2 g of CO2 from carbon and oxygen gas is
(2) 5 kJ [Re-AIPMT-2015]
(3) 25 J (1) –630 kJ (2) –3.15 kJ
(4) 30 J (3) –315 kJ (4) +315 kJ
9. For the reaction, X2O4(l)  2XO2(g) 15. If the enthalpy change for the transition of liquid
U = 2.1 k cal, S = 20 cal K–1 at 300 K water to steam is 30 kJ mol–1 at 27°C, the entropy
change for the process would be
Hence, G is [AIPMT-2014]
[AIPMT (Prelims)-2011]
(1) 2.7 kcal (2) –2.7 kcal
(1) 100 J mol –1 K–1
(3) 9.3 kcal (4) –9.3 kcal
(2) 10 J mol –1 K–1
10. In which of the following reactions, standard reaction
(3) 1.0 J mol –1 K–1
entropy change (S°) is positive and standard Gibb's
energy change (G°) decreases sharply with (4) 0.1 J mol –1 K–1
increasing temperature? [AIPMT (Prelims)-2012] 16. Enthalpy change for the reaction, 4 H(g) 2H2 (g)
1 is –869.6 kJ. The dissociation energy of H – H
(1) Mg(s)+ O (g)MgO(s) bond is [AIPMT (Prelims)-2011]
2 2
1 1 1 (1) + 217.4 kJ
(2) C graphite + O2(g) CO2(g)
2 2 2 (2) – 434.8 kJ
1 (3) – 869.6 kJ
(3) C graphite + O (g)CO(g)
2 2 (4) + 434.8 kJ
1 17. Consider the following process
(4) CO(g)+ O (g)CO2(g)
2 2 H(kJ/mol)
11. Standard enthalpy of vapourisation vapH(0) for
1
water at 100C is 40.66 kJmol –1 .The internal A B + 150
energy of vapourisation of water at 100C (in 2
kJmol–1) is [AIPMT (Prelims)-2012] 3B  2C + D – 125
(1) +43.76 (2) +40.66 E + A  2D + 350
(3) +37.56 (4) –43.76 For; B + D  E + 2C, H will be
12. The enthalpy of fusion of water is 1.435 kcal/mol. [AIPMT (Mains)-2011]

The molar entropy change for the melting of ice at (1) –325 kJ/mol (2) 325 kJ/mol
0C is [AIPMT (Prelims)-2012] (3) 525 kJ/mol (4) –175 kJ/mol
(1) 5.260 cal/(mol K) 18. Standard entropies of X2, Y2 and XY3 are 60, 40
(2) 0.526 cal/(mol K) and 50 JK–1 mol–1 respectively. For the reaction
(3) 10.52 cal/(mol K) 1 3

X2  Y2  XY 3 ; H = –30kJ to be at
2 2
(4) 21.04 cal/(mol K)
equilibrium, the temperature should be
13. Equal volumes of two monoatomic gases, A and B,
at same temperature and pressure are mixed. The
ratio of specific heats (Cp/Cv) of the mixture will be (1) 750 K (2) 1000 K
[AIPMT (Mains)-2012] (3) 1250 K (4) 500 K
(1) 0.83 (2) 1.50 19. A monatomic gas at pressure P1 and volume V1 is
(3) 3.3 (4) 1.67 1

compressed adiabatically to th its original volume.
8
14. Which of the following is correct option for free
expansion of an ideal gas under adiabatic What is the final presssure of the gas ?
condition? [AIPMT (Prelims)-2011] [AIPMT (Mains)-2010]
(1) q = 0, T < 0, w  0 (1) 64 P1
(2) q = 0, T  0, w = 0 (2) P1
(3) q  0, T = 0, w = 0 (3) 16 P1
(4) q = 0, T  0, w = 0 (4) 32 P1
20. Match List-I (Equations) with List-II (Type of 25. From the following bond energies
process) and select the correct option H–H bond energy : 431.37 kJ mol–1
List-I List-II C = C bond energy : 606.10 kJ mol–1
(Equations) (Type of process)
C – C bond energy : 336.49 kJ mol–1
a. Kp > Q (i) Non-spontaneous
C – H bond energy : 410.50 kJ mol–1
b. G< RT ln Q (ii) Equilibrium
Enthalpy for the reaction,
c. Kp = Q (iii) Spontaneous and
H H H H
endothermic
C=C+H–H H–C–C–H
H H H H H
d. T > (iv) Spontaneous
S will be [AIPMT (Prelims)-2009]
[AIPMT (Mains)-2010] (1) –243.6 kJ mol–1 (2) –120.0 kJ mol–1
(1) a(i), b(ii), c(iii), d(iv) (2) a(iii), b(iv), c(ii), d(i) (3) 553.0 kJ mol–1 (4) 1523.6 kJ mol–1
(3) a(iv), b(i), c(ii), d(iii) (4) a(ii), b(i), c(iv), d(iii) 26. Bond dissociaton enthalpy of H2, Cl2 and HCl are
21. Three moles of an ideal gas expanded 434, 242 and 431 kJ mol–1 respectively. Enthalpy
spontaneously into vacuum. The work done will be of formation of HCl is [AIPMT (Prelims)-2008]
(1) 245 kJ mol–1 (2) 93 kJ mol–1
[AIPMT (Mains)-2010]
(3) –245 kJ mol–1 (4) –93 kJ mol–1
(1) Infinite (2) 3 joules
27. For the gas phase reaction,
(3) 9 joules (4) Zero

PCl 5(g)
PCl 3(g) + Cl 2(g), which of the
22. For vaporization of water at 1 atmospheric following conditions is correct ?
pressure, the values of H and S are 40.63 kJ
mol –1 and 108.8 JK –1 mol –1 respectively. The [AIPMT (Prelims)-2008]
temperature when Gibbs energy change (G) for (1) H > 0 and S < 0 (2) H = 0 and S < 0
this transformation will be zero, is (3) H > 0 and S > 0 (4) H < 0 and S < 0
[AIPMT (Mains)-2010] 28. Which of the following are not state functions?
(1) 273.4 K (2) 393.4 K (I) q + w (II) q
(3) 373.4 K (4) 293.4 K (III) w (IV) H–TS
23. The following two reactions are known : [AIPMT (Prelims)-2008]
Fe2O3(s) + 3CO(g)  2Fe(s) + 3CO2(g) ; (1) (II) and (III) (2) (I) and (IV)
H = –26.8 kJ (3) (II), (III) and (IV) (4) (I), (II) and (III)
29. Consider the following reactions :
FeO(s) + CO(g)  Fe(s) + CO2(g);H = –16.5 kJ
(i) H+(aq) + OH– (aq) = H2O(l); H = –X1 kJ mol–1
The value of H for the following reaction
1
Fe2O3(s) + CO(g)  2FeO(s) + CO2(g) is (ii) H2(g) + O (g) = H2O(l); H = –X2 kJ mol–1
2 2
[AIPMT (Mains)-2010]
(iii) CO2(g) + H2(g) = CO(g) + H2O(l);
(1) +10.3 kJ (2) –43.3 kJ H = –X3 kJ mol–1
(3) –10.3 kJ (4) +6.2 kJ
5
(iv) C2H2(g) + O (g) = 2CO(g) + H2O(l);
24. The values of H and S for the reaction, 2 2
C(graphite) + CO2(g)  2CO(g) H = +X4 kJ mol–1
are 170 kJ and 170 JK–1 respectively. This reaction Enthalpy of formation of H2O(l) is
will be spontaneous at [AIPMT (Prelims)-2009] [AIPMT (Prelims)-2007]
(1) 910 K (2) 1110 K (1) +X1 kJ mol–1 (2) +X2 kJ mol–1
(3) 510 K (4) 710 K (3) +X3 kJ mol–1 (4) +X4 kJ mol–1
30. Given that bond energies of H–H and Cl – Cl are 35. A reaction occurs spontaneously if
430 kJ/mol and 240 kJ/mol respectively and fH of [AIPMT (Prelims)-2005]
HCl is –90 kJ/mol. Bond enthalpy of HCl is
(1) TS < H and both H and S are +ve
(2) TS > H and both H and S are +ve
(1) 245 kJ mol–1
(3) TS = H and both H and S are +ve
(2) 2909 kJ mol–1
(4) TS > H and H is +ve and S is –ve
(3) 380 kJ mol–1
36. Which of the following pairs of a chemical reaction
(4) 425 kJ mol–1 is certain to result in a spontaneous reaction ?
31. Identify the correct statement for change of Gibbs [AIPMT (Prelims)-2005]
energy for a system (G system ) at constant
(1) Exothermic and decreasing disorder
temperature and pressure
(2) Endothermic and increasing disorder
(3) Exothermic and increasing disorder
(1) If Gsystem > 0, the process is spontaneous
(4) Endothermic and decreasing disorder
(2) If G system = 0, the system has attained
equilibrium 37. The absolute enthalpy of neutralisation of the reaction
(3) If Gsystem = 0, the system is still moving in MgO(s) + 2HCl(aq)  MgCl2(aq) + H2O(l)
a particular direction will be [AIPMT (Prelims)-2005]
(4) If G system < 0, the process is not (1) Less than – 57.33 kJ mol–1
spontaneous
(2) –57.33 kJ mol–1
32. Assume each reaction is carried out in an open
container. For which reaction will H = E? (3) Greater than –57.33 kJ mol–1
(4) 57.33 kJ mol–1
(1) H2(g) + Br2(g)  2HBr(g) Questions asked Prior to Medical Ent. Exams. 2005
(2) C(s) + 2H2O(g)  2H2(g) + CO2(g) 38. Which reaction, with the following values of H,
S, at 400 K is spontaneous and endothermic?
(3) PCl5(g) PCl3(g) + Cl2(g)
(1) H = –48 kJ; S = + 135 J/K
(4) 2CO(g) + O2(g) 2CO2(g)
(2) H = –48 kJ; S = – 135 J/K
33. The enthalpy and entropy change for the reaction
(3) H = +48 kJ; S = + 135 J/K
Br2(l) + Cl2(g)  2BrCl(g)
(4) H = +48 kJ; S = – 135 J/K
are 30 kJ mol–1 and 105 JK–1 mol–1 respectively.
The temperature at which the reaction will be in 39. Three thermochemical equations are given below:
equilibrium is [AIPMT (Prelims)-2006] (i) C(graphite) + O2(g)  CO2(g); rH° = x kJ mol–1
(1) 285.7 K (2) 273 K
1
(ii) C(graphite) + O (g)  CO(g); rH° = y kJ mol–1
(3) 450 K (4) 300 K 2 2
34. The enthalpy of combustion of H2, cyclohexene
(C6H10) and cyclohexane (C6H12) are – 241, –3800 1
(iii) CO (g) + O (g)  CO2(g); rH° = z kJ mol–1
and –3920 kJ per mol respectively. Heat of 2 2
hydrogenation of cyclohexene is
Based on the above equations, find out which of
[AIPMT (Prelims)-2006] the relationship given below is correct:
(1) – 121 kJ per mol (1) x = y – z
(2) + 121 kJ per mol (2) z = x + y
(3) + 242 kJ per mol (3) x = y + z
(4) – 242 kJ per mol (4) y = 2z – x
40. Following reaction occurring in an automobile 46. One mole of an ideal gas at 300 K is expanded
2C8H18(g) + 25O2(g)  16CO2(g) + 18H2O (g). The isothermally from an initial volume of 1 litre to 10 litres.
sign of H, S and G would be The E for this process is (R = 2 cal. Mol–1K–1)
(1) –, +, + (2) +, +, – (1) 1381.1 cal (2) Zero
(3) +, –, + (4) –, +, – (3) 163.7 cal (4) 9 L atm
41. When 5 litres of a gas mixture of methane and 47. In the reaction : S + 3/2 O2  SO3 + 2x kcal and
propane is perfectly combusted at 0°C and SO 2 + 1/2 O 2  SO 3 + y kcal, the heat of
1 atmosphere, 16 litre of oxygen at the same formation of SO2 is
temperature and pressure is consumed. The
(1) (2x + y) (2) (x – y)
amount of heat released from this combustion in kJ
(H comb (CH 4) = 890 kJ mol –1, H comb (C 3H8) (3) (x + y) (4) (y – 2x)
= 2220 kJ mol–1) is 48. At 27°C latent heat of fusion of a compound is
(1) 32 (2) 38 2930 J/mol. Entropy change is
(3) 317 (4) 477 (1) 9.77 J/mol·K (2) 10.77 J/mol·K
42. If enthalpies of formation for C2H4(g), CO2(g) and (3) 9.07 J/mol·K (4) 0.977 J/mol·K
H2O(l) at 25°C and 1 atm pressure are 52, –394
49. For the reaction
and –286 kJ/mol respectively, then enthalpy of
combustion of C2H4(g) will be C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(l), which
one is true?
(1) + 14.2 kJ/mol
(1) H = E – RT (2) H = E + RT
(2) + 1412 kJ/mol
(3) H = E + 2RT (4) H = E – 2RT
(3) – 141.2 kJ/mol
(4) – 1412 kJ/mol 50. Change in enthalpy for reaction, 2H2O2 (l )  2H2O (l )
+O2 (g) if heat of formation of H2O2(l ) and H2O(l ) are
43. For a reaction to occur spontaneously –188 and –286 kJ/mol respectively, is
(1) H must be negative
(1) –196 kJ/mol
(2) S must be negative
(2) +196 kJ/mol
(3) (H – TS) must be negative
(3) +948 kJ/mol
(4) (H + TS) must be negative
(4) –948 kJ/mol
44. Given that C + O2  CO2, H° = –x kJ
51. When 1 mol of gas is heated at constant volume
2CO + O2  2CO2, H° = –y kJ temperature is raised from 298 to 308 K. Heat
What is heat of formation of CO? supplied to the gas is 500 J. Then which
statement is correct?
y  2x
(1) (2) 2x – y (1) q = U = –500 J, w = 0
2
(2) q = U = 500 J, w = 0
2x  y
(3) y – 2x (4) (3) q = w = 500 J, U = 0
2
45. Identify the correct statement regarding entropy (4) U = 0, q = w = –500 J
(1) At absolute zero of temperature, the entropy of 1

all crystalline substances is taken to be zero 52. Enthalpy of CH4 + O  CH3OH is negative. If
2 2
(2) At absolute zero of temperature, the entropy enthalpy of combustion of CH4 and CH3OH are x
of a perfectly crystalline substance is +ve and y respectively. Then which relation is correct?
(3) At absolute zero of temperature, entropy of a (1) x > y
perfectly crystalline substance is taken to be
(2) x < y
zero
(3) x = y
(4) At 0°C, the entropy of a perfectly crystalline
substance is taken to be zero (4) x  y
53. Unit of entropy is 61. Considering entropy (S) as a thermodynamic
parameter, the criterion for the spontaneity of any
(1) JK–1 mol–1 (2) J mol–1
process is
(3) J–1 K–1 mol–1 (4) JK mol–1
(1) Ssystem + Ssurroundings > 0
54. In a closed insulated container a liquid is stirred
(2) Ssystem – Ssurroundings > 0
with a paddle to increase the temperature which of
the following is true? (3) Ssystem > 0 only
(1) E = W  0, q = 0 (2) E = W = q  0 (4) Ssurroundings > 0 only
(3) E = 0, W = q  0 (4) W = 0, E = q  0 62. The work done during the expansion of a gas from
a volume of 4 dm3 to 6 dm3 against a constant
55. 2 mole of ideal gas at 27°C temperature is
external pressure of 3 atm is (1 L atm = 101.32 J)
expanded reversibly from 2 lit. to 20 lit. Find
entropy change (R = 2 cal/mol K) (1) –6 J (2) –608 J
(1) 92.1 (2) 0 (3) +304 J (4) –304 J
(3) 4 (4) 9.2 63. The enthalpy of hydrogenation of cyclohexene is
–119.5 kJ mol–1. If resonance energy of benzene is
56. Heat of combustion for C(s), H2(g) and CH4(g) are
–150.4 kJ mol–1, its enthalpy of hydrogenation
–94, –68 and –213 kcal/mol, then H for
would be
C(s) + 2H2(g)  CH4(g) is
(1) –358.5 kJ mol–1 (2) –508.9 kJ mol–1
(1) –17 kcal (2) –111 kcal
(3) –208.1 kJ mol–1 (4) –269.9 kJ mol–1
(3) –170 kcal (4) –85 kcal
64. 2Zn + O2  2ZnO; G° = –616 J
57. For the reaction
2Zn + S2  2ZnS; G° = –293 J
C3H8(g) + 5O2(g)  3CO2(g) + 4H2O(l)
S2 + 2O2  2SO2; G° = –408 J
at constant temperature, H – E is
G° for the following reaction
(1) + RT (2) – 3RT
2ZnS + 3O2  2ZnO + 2SO2 is
(3) + 3RT (4) – RT
(1) –1462 J (2) –1317 J
58. What is the entropy change (in JK–1 mol–1) when
one mole of ice is converted into water at 0°C? (3) –501 J (4) –731 J
(The enthalpy change for the conversion of ice to
liquid water is 6.0 kJ mol–1 at 0°C) SECTION - D
(1) 20.13 (2) 2.013 NEET Booster Questions
(3) 2.198 (4) 21.98 1. U = 0 always when in a process

59. For which one of the following equations is Hreact (1) T  0 (2) T = 0
(3) V = 0
equal to H for the product?
(4) W = 0
f
2. The value of H and U will be same for
(1) N2(g) + O3(g)  N2O3(g)
(1) N2(g) + 3H2(g)  2NH3(g)
(2) CH4(g) + 2Cl2(g)  CH2Cl2(l) + 2HCl(g)
(2) H2(g) + I2(g)  2HI(g)
(3) Xe(g) + 2F2(g)  XeF4(g)
(3) CaCO3(s)  CaO(s) + CO2(g)
(4) 2CO(g) + O2(g)  2CO2(g)
1
60. Standard enthalpy and standard entropy changes (4) SO2 (g) + O2 (g)  SO3 (g)
for the oxidation of ammonia at 298 K are 2
–382.64 kJ mol–1 and –145.6 J mol–1, respectively. 3. Expansion of ideal gas takes place from 1 L to
Standard Gibb’s energy change for the same 10 L in vacuum isothermally at 300 K. Which of
reaction at 298 K is the following is correct?
(1) –221.1 kJ mol–1 (2) –339.3 kJ mol–1 (1) H = 0 (2) q = 0
(3) –439.3 kJ mol–1 (4) –523.2 kJ mol–1 (3) w = 0 (4) All of these
4. If HC–H = 300 kJ/mol, Hatm of C(s) = 500 kJ and 12. In which of the following both species have zero
HH–H = 200 kJ/mol then the fH(CH4) will be standard enthalpy of formation?
(1) –500 kJ (2) –300 kJ (1) H2(g), H (aq) (2) D2(g), D2O(l)
(3) –200 kJ (4) –100 kJ (3) P(s) (white), I2(g) (4) O2(g), O3(g)
5. The difference between the value of Cp of H2 and 13. For the combustion of C 3 H 8 (g) at constant
Cv of He will be temperature H – U is
(1) R (2) 2 R (1) – RT (2) + RT

(3) – 3RT (4) + 3RT
(3) 3 R (4) 4 R
14. Incorrect among the following is
6. Which of the following can be correct?
(1) H  U = nRT 1
(1) C(s)  O2 (g)  CO(g) Hro  Hof CO
2
(2) CP – CV = R
(2) C(s)  O2 (g)  CO2 (g) Hro  Hof CO2  Hco C(s)
 dH   dU 
(3)  dT    dT   R
 P  V 1
(3) CO(g)  O2 (g)  CO2 (g) Hro  Hof CO2  Hoc CO(g)
2
(4) All of these
(4) Both (1) & (2)
7. Zeroth law of thermodynamics states that
15. 100 ml of 3 mol H2SO4 reacts with 100 ml of 3
(1) Heat is path function mol NaOH. Enthalpy of neutralisation of reaction will
(2) Energy is conserved be
(3) Heat transfer takes place till thermal equilibrium (1) – 57.1 kJ/mol (2) –2 × 57.1 kJ
is achieved (3) – 0.3 × 57.1 kJ (4) – 3 × 57.1 kJ
(4) Entropy is conserved 16. One mole of a perfect gas expands isothermally to
8. In which of the following maximum amount of heat ten times its original volume. The change in
is released if one mole of each reactant is taken? entropy at 298 K will be
(1) H2SO4 + NaOH (2) HCl + NaOH (1) 0.1 × 298 × R (2) 2.303 × 298 × R
(3) HF + NaOH (4) CH3COOH + KOH (3) 2.303 R (4) 0.1 R
9. Consider the following statements 17. Strongest bond among the following is
(a) q is state function in isochoric process
(1) O—H (2) C—H
(b) w is state function in isobaric process
(3) C—C (4) N N
(c) Work done by the system will be zero in
18. Correct for an endothermic gaseous reaction
adiabatic free expansion
A + B  3C will be
Correct among the following is/are
(1) (a) only (2) (b) only (1) H > 0; S < 0 (2) H = 0; S > 0
(3) (b) & (c) (4) (a), (b) & (c) (3) H > 0; S > 0 (4) S = 0; S < 0
10. When an ideal gas undergoing expansion in 19. Heat of formation of benzene; assuming no
vacuum shows resonance. Given that
(1) U = 0 (2) w = 0 BE (C–C) = 83 k cal
(3) q = 0 (4) All of these BE (C=C) = 140 k cal
11. Which of the following correctly represents the BE (C–H) = 99 kcal
standard enthalpy of formation of CCl4? Heat of atomisation of C = 170.9 kcal
(1) C(graphite) + 2Cl2(l)  CCl4(g) Heat of atomisation of H = 104.2 kcal
(2) C(graphite) + 4Cl(g)  CCl4(g) will be
(3) C(diamond) + 2Cl2(g)  CCl4(g) (1) 39 kcal (2) 75 kcal
(4) C(graphite) + 2Cl2(g)  CCl4(g) (3) 1263 kcal (4) 421 kcal
20. At 0°C, ice and water are in equilibrium and (1) Wisothermal > Wadiabatic
H fusion of ice = 6 kJ/mol. Correct among the
(2) Ratio of slope of adiabatic to isothermal will be r
following is/are
(1) G = S = 0 (3) T1 = T2 = T3
(2) Ssurr = – 21.98 JK–1 (4) Uisothermal > Uadiabatic
(3) G = 0 26. When an ideal gas is compressed adiabatically
(4) Both (2) & (3) and reversibly, the final temperature is
21. Volume of gas is doubled from its original volume. (1) Higher than the initial temperature
The specific heat will be (2) Lower than the initial temperature
(1) Reduced to half (2) Doubled (3) The same as the initial temperature
(3) Remain same (4) Increased four times (4) Dependent on the rate of compression
22. 5.6 dm3 of gas at STP requires 52.25 J of heat to 27. A closed flask contains a substance in all its three
raise its temperature by 10ºC at constant volume.
states, solids, liquids and vapour at its triple point.
Gas can be
In this situation the average KE of the water
(1) He (2) H2 molecule will be
(3) NO2 (4) CO2 (1) Maximum in vapour state
23. Two moles of an ideal gas undergoes following
(2) Maximum in solid state
process as
(3) Greater in the liquid than in vapour state
A (T1)
1.0 B (4) Same in all the three states
P  (atm)
T1 = T2 28. In thermodynamics a process is called reversible

when
0.5 C (T2) (1) System and surrounding change into each
other
20 L 40 L (2) There is no boundary between system and
V(L) surrounding
Correct among the following is/are (3) The surroundings are always in equilibrium with
(1) U = S = 0 (2) WBC = 0 the system
(3) Wcycle  0 (4) All of these (4) The system changes into the surroundings
spontaneously
24. Exothermic reaction among the following is
29. 16 kg oxygen gas expands at STP (1 atm)
(1) Combustion of N2 to form NO
isobarically to occupy double of its original volume.
(2) Decomposition of water The work done during the process is nearly
(3) Conversion of diamond to graphite (1) 260 kcal (2) 180 kcal
(4) Dehydrogenation of ethane to ethene
(3) 130 kcal (4) 271 kcal
25. Expansion of an ideal gas under isothermal and 30. One mole of a non ideal gas undergoes a change
adiabatic condition is given below. Incorrect of state (2.0 atm, 3.0 L, 95 K)  (4.0 atm,
 CP  5.0 L, 245 K) with a change in internal energy
statements is r  C 
 V U = 30.0 L atm. The change in enthalpy of the
process in L atm is
(P1, V1 , T1) (1) 40.0 (2) 42.3
(3) 44.0 (4) 56.0
P Isothermal
31. Which of the following can be zero for isothermal
P2,V2, T2 reversible expansion?
Adiabatic
P3,V3, T3 (1) E (2) H
v (3) T (4) All of these
32. In an isulated container water is stirred with a rod The A and B systems respectively are
to increase the temperature. Which of the following
(1) Open system, Closed system
is true?
(2) Isolated system, Closed system
(1) U = W  0, q = 0 (2) U = W = q  0
(3) U = 0, W = q  0 (4) W = 0, U = q  0 (3) Adiabatic system, Isolated system
33. Two atoms of hydrogen combine to form a (4) Closed system, Isolated system
molecule of hydrogen gas the energy of the H2 38. Set of intensive properties is shown by
molecule is
(1) Mole fraction, standard electrode potential, heat
(1) Greater than that of separate atoms capacity
(2) Equal to that of separate atoms (2) Viscosity, refractive index, specific heat
(3) Lowers than that of separate atoms (3) Density, Gibbs free energy, internal energy
(4) Sometimes lower and sometimes higher (4) Number of moles, molarity, electrode potential
34. Vapour density of a gas is 8. Its molecular mass 39. For the expansion occurring from initial to final
will be stage in finite time, which is incorrect?
(1) 8 (1) Equilibrium exist in initial and final stage
(2) 16 (2) Work obtained is maximum
(3) 32 (3) Driving force is much greater than the opposing
(4) 64 force
35. If x mole of ideal gas at 27°C expands isothermally (4) Both (1) & (2)
and reversibly from a volume of y to 10y, then the
40. For one mole of an ideal gas
work done is
(Cp and Cv are molar heat capacities at constant
(1) w = x R 300 ln y
presure and constant volume respectively)
y
(2) w = – 300 x R ln 10 y R
(1) Cp – Cv = R (2) Cp – Cv =
2
(3) w = – 300 x R ln 10
(3) Cp – Cv = –2R (4) Cp – Cv = 0
1 41. The molar heat capacity of water at constant
(4) w = 100 x R ln y
pressure P is 75 J K–1 mol–1. When 1.0 kJ of heat
is supplied to 1000 g of water, which is free to
36. A system X undergoes following changes
expand, the increase in temperature of water is
X  W  Z  X (1) 1.2 K (2) 2.4 K
(P1V1T1 ) (P2 V2T1 ) (P3 V2T2 ) (P1V1T1 )
(3) 4.8 K (4) 0.24 K
The overall process may be called as
42. Which statement is correct?
(1) Reversible process
 dH   dE 
(2) Cyclic process (1)    
 dT P  dT  V
(3) Cyclic reversible process
(4) Isochoric process
 dH   dE 
(2)     R
37. Different types of systems are given below  dT P  dT  V
Surrounding Surrounding
Work Matter  dE 
(3)   for ideal gas is zero
Heat Energy  dV  T
System System
(4) All of these
A B
43. S° will be highest for the reaction 50. For a gaseous reaction
1 A(g) + 3B(g)  3C(g) + 3D(g)
(1) Ca(s)  O2 (g)  CaO(s)
2 E is 17 kcal at 27°C. Assuming R = 2 cal K–1
(2) CaCO3(s)  CaO(s) + CO2(g) mol–1 the value of H for the above reaction will be
(3) C(s) + O2(g)  CO2(g) (1) 15.8 kcal
(4) N2(g) + O2(g)  2NO(g) (2) 16.4 kcal
44. In an irreversible process, the value of (3) 18.2 kcal
Ssystem + Ssurr is
(4) 20.0 kcal
(1) +ve (2) –ve
51. A mixture of 2 mole of CO and 1 mol of O2 is
(3) Zero (4) All of these ignited. Correct relationship is
45. The enthalpy and entropy change for a chemical (1) H = U
reaction are –2.5 × 10 3 cal and 7.4 cal K –1
respectively. Predict the nature of reaction at (2) H > U
298 K is (3) H < U
(1) Spontaneous (2) Reversible (4) The relationship depends upon the capacity of
(3) Irreversible (4) Non-spontaneous vessel
46. The temperature at which the given reaction is at 52. Bond dissociation energy of XY, X2 and Y2 (all
equilibrium diatomic molecules) are in the ratio of 1 : 1 : 0.5
and H f of XY is –200 kJ mol –1 . The bond
1 dissociation energy of X2 will be
Ag2O(s)  2Ag(s) + O (g)
2 2
(1) 800 kJ mol–1
H = 30.5 kJ mol–1 and S 0.066 kJ mol–1 K–1 (2) 200 kJ mol–1
(1) 462.12 K (2) 362.12 K
(3) 300 kJ mol–1
(3) 262.12 K (4) 562.12 K
(4) 400 kJ mol–1
47. The temperature of 15 ml of a strong acid
53. Enthalpy of formation of NH 3 is – X kJ and
increases by 2°C when 15 ml of a strong base is
HH–H, HN–H are respectively Y kJ mol–1 andZ kJ
added to it. If 5 ml of each are mixed, temperature
mol–1. The value of HN  N is
should increase by
(1) 0.6°C (2) 0.3°C X
(1) Y – 6Z +
(3) 2°C (4) 6°C 3
48. The standard heat of formation of NO2(g) and (2) – 3Y + 6Z – 2X

N2O4(g) are 8.0 and 4.0 kcal mol–1 respectively.
(3) 3Y + 6Z + X
The heat of dimerisation of NO2 in kcal is
(4) Y + 6X + Z
(1) –12 kcal (2) 12 kcal
(3) 4 kcal (4) 16 kcal 54. The heat of neutralisation for strong acid and strong
base forming 2 moles of water is
1 1 (1) – 2 × 57.1 kJ
49. If X O(s)  X(s) + O2(g); H = 90 kJ.
2 2 4
(2) – 57.1 kJ
Then heat change during reaction of metal X with
one mole of O2 to form oxide to maximum extent 57.1
(3)  kJ
is 2
(1) 360 kJ (2) –360 kJ (4) Strong acid and strong base will not undergo
(3) –180 kJ (4) +180 kJ neutralisation
55. The value of H° in kJ for the reaction will be 58. A schematic representation of enthalpy changes for
CS2(l) + 4NOCl(g)  CCl4(l) + 2SO2 (g) + 2N2(g) 1
the reaction, C( graphite ) 
O (g)  CO (g) is given
if 2 2
below. The missing value is
Hf (CS2 )   x Hf (NOCl)   y Cgraphite + O2(g)
??
Hf (CCl4 )   z Hf (SO2 )   r CO(g) + ½O(g)
– 393.5 kJ
(1) x + 4y – z – 2r – 283.0 kJ
CO2(g)
(2) r + z + 4y – x
(1) + 10.5 kJ
(3) 2r + z + 4y + x
(2) – 11.05 kJ
(4) x + 4y + z – 2r
56. The heat liberated on complete combustion of (3) – 110.5 kJ
1 mole of CH4 gas to CO2(g) and H2O(l) is 890 kJ. (4) – 10.5 J
Calculate the heat evolved by 2.4 L of CH4 on
59. Which of the following equations represent
complete combustion.
standard heat of formation of CH4?
(1) 95.3 kJ
(1) C(diamond) + 2H2(g)  CH4(g)
(2) 8900 kJ
(2) C(graphite) + 2H2(g)  CH4(g)
(3) 890 kJ
(3) C(diamond) + 4H(g)  CH4(g)
(4) 8.9 kJ
(4) C(graphite) + 4H(g)  CH4(g)
57. The work done in an open vessel at 300 K, when
112 g iron reacts with dil HCl to give FeCl2, is 60. Calorific value of ethane, in kJ/g if for the reaction
nearly 2C2H6 + 7O2  4CO2 + 6H2O; H = –745.6 kcal
(1) 1.1 kcal (1) –12.4
(2) 0.6 kcal (2) –52.2
(3) 0.3 kcal (3) –24.8
(4) 0.2 kcal (4) –104.1


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Chapter 6

REVERSIBLE AND IRREVERSIBLE PROCESS

S.No. Reversible process Irreversible process

1. It takes place in infinite number of infinitesimally It takes place in a single step.

S.No. Reversible process Irreversible process

INTERNAL ENERGY (U)

FIRST LAW OF THERMODYNAMICS

W = +ve, work done on the system

W = –ve, work done by the system

q = +ve, heat is absorbed by the system

and wrev =  pex dV  0

For a reaction : H  U  ngRT

Note : H is a state function and is an extensive property.

z Relation between Cp and Cv for an ideal gas

1. Which of the following is an example of open system?

(1) Human body (2) The earth

(3) Pond (4) All of these

2. Which of the following is not a state function?

3. Which of the following is intensive property?

(1) Temperature (2) Heat

(3) Mass (4) Volume

4. Closed system can exchange (with surroundings)

(1) Heat (2) Matter

(3) Heat and matter (4) Neither heat nor matter

5. System and surroundings together constitute

(1) The earth (2) The solar system

(3) Galaxy (4) Universe

6. E and H both are zero in

(1) Isobaric process (2) Adiabatic process

(3) Isochoric process (4) Cyclic process

(1) 600 cal (2) 300 cal

(3) 150 cal (4) 100 cal

8. Work done in reversible isothermal expansion is given by

9. When a gas undergoes adiabatic expansion, it gets cooled. This is because

(1) It is an exothermic process (2) It is an endothermic process

ENTHALPY CHANGE, rH OF A REACTION – REACTION ENTHALPY

rH = (Sum of enthalpies of products) – (Sum of enthalpies of reactants)

S.No. Name of Enthalpy H Definition Example

2. Enthalpy of Formation Hºf 1

3. Enthalpy of atomisation Haº Enthalpy change when 1 Na(s)  Na(g)

4. Enthalpy of neutralization HNº Enthalpy change (fix for

neutralization of an acid by a Na2SO4(aq) + 2H2O()

5. Enthalpy of fusion Hºf Enthalpy change when 1 H2O(s)  H2O()

6. Enthalpy of Vapourization HVap

7. Enthalpy of Sublimation º Enthalpy change when 1 CO2 (s)  CO2 (g)

8. Enthalpy of Solution HºSol Enthalpy change when 1 KCl + aq  KCl (aq)

H2O(g)  H(g) + OH(g); H = 497.8 kJ

Bond energy of O–H bond = (497.8 + 428.5)/2

rH = (Hf)P – (Hf)R

rH = (Hc)R – (Hc)P

Lattice Enthalpy (Symbol : latticeHs)

HESS’S LAW OF CONSTANT HEAT SUMMATION

Example 7 : Calculate amount of heat evolved when

= 0.25 mol H+ ions

= 0.16 mol (OH)– ions

= 0.2 mol H+ ions

= 0.1 mol OH– ions.

Example 8 : Determine the enthalpy change for the given reaction,

In domestic oven, coal (carbon) keeps on burning once initiated