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6
SOME IMPORTANT THERMODYNAMIC TERMS
Thermodynamics
The System and The Surroundings
System in thermodynamics refers to that part of universe in which
observations are made and remaining universe constitute the
surroundings.
Universe = system + surroundings
Types of System
(i) Open System : In this system there is exchange of energy
and matter between system and its surroundings
(ii) Closed System : In this system there is no exchange of matter,
but exchange of energy is possible between system and its
surroundings
(iii) Isolated System : In this system there is no exchange of
matter and energy between system and surroundings.
State of the System and State Variables
The state of a thermodynamic system is described by its
measurable or macroscopic properties. Variables like pressure (P),
volume (V) and temperature (T) are called state variables or state
functions because their values depend only on state of system
and not on how it is reached.
The state of a system is specified by state functions or state
variables.
Macroscopic System and Macroscopic Properties
If a system contains a large no. of chemical species, it is called a
macroscopic system. The properties of macroscopic system like
temperature, pressure, volume, density, melting point, boiling point,
etc are called macroscopic properties.
They are further divided into two types :
(i) Extensive properties
They depend on quantity of matter contained in system
Example : mass, volume, heat capacity etc.
(ii) Intensive properties depend only on nature of substance
and are independent of amount of substance present in
system
Example : temperature, pressure, density, etc.
Thermodynamic Processes
These are said to occur when a system changes from one state to
another.
(i) Isothermal process occurs when temperature remains
constant throughout the process.
(ii) Adiabatic process occurs when no heat can flow from system
to its surroundings and vice-versa.
CHEMISTRY
(iii) Isochoric process occurs when volume of the system is kept
constant.
(iv) Isobaric process occurs when pressure of the system is kept
constant.
(v) Cyclic Process – The process in which a system proceeds
via many intermediate steps and returns to the initial state.
Change in internal energy (dE) = 0, change in enthalpy (dH)=0
Thermodynamic Quantities
Internal energy
The energy stored within a substance is called its internal energy.
It is represented by ‘U’ or ‘E’. It is the sum of different types of
energies associated with atoms and molecules.
The change in internal energy is given by:
DU = U2 – U1.
where,
U2 : final state
U1 : initial state
The internal energy of a system changes when
(i) heat passes in or out of the system.
(ii) work is done on or by the system.
(iii) matter enters or leaves the system.
It is a state function and is an extensive property.
DU is negative if energy is evolved andDU is positive if energy is
absorbed.
Internal energy of one mole of a monoatomic gas at ‘T’ Kelvin is
3
RT . Internal energy of ideal gas is a function of temperature
2
only.
In isothermal processes (T is constant), DU = 0.
Work
There are two types of work in Thermodynamics :
(i) Electrical work = EMF × quantity of electricity
(ii) Pressure – volume work
W = – Pext DV
(DV = V2 – V1 = Vfinal – Vinitial)
Work done on the system is positive while work done by the
system is negative
For free expansion of an ideal gas, Pext = 0, \ W = 0
Heat
It is a mode of energy exchanged between the system and the
surroundings as a result of difference of temperature between
them. It is represented by ‘q’, when heat is given by the system, it
 Thermodynamics 125

is given negative sign. Enthalpy is a state function and an extensive property.

When heat is absorbed by the system, it is given positive sign. 5
Work and heat are not state functions. Enthalpy of monoatomic gas = RT per mole.
2
FIRST LAW OF THERMODYNAMICS Change in enthalpy of the products and reactants at 298 K and 1
atmospheric pressure is called standard molar enthalpy change.
It is the law of conservation of energy.
In a cyclic process, i.e. when the system returns to the original
According to this law, energy can neither be created nor
state after a number of changes, DU or DH = 0.
destroyed although it may be converted from one form to another
Relationship between heat of reaction at constant pressure and
or
at constant volume
The energy of an isolated system is constant. We know qp = DH and qv = DU,
Mathematically, DU = q + W
where, q = energy absorbed by the system DH = DU + PDV = DU + P ( V2 - V1 ) = DU + ( PV2 - PV1 )
W = workdone on the system. Putting PV = n1RT, PV2 = n2RT,
SOME IMPORTANT RESULTS DH = DU + ( n 2 RT - n1RT )
(i) For isothermal irreversible expansion,
q = –W = Pext (V2 – V1) DH = DU + Dn g RT
(ii) For isothermal reversible expansion or compression from or, qp = qv + Dng RT
volume V1 to V2
HEAT CAPACITY
V
q = - W = nRT ln 2 It is the amount of heat required to raise the temperature of a
V1 system through 1°C. It is given by:
(iii) For isothermal expansion of an ideal gas against vacuum i.e. q q
for free expansion, C= =
T2 - T1 DT
DU = 0, W = 0, q = 0
(iv) Since internal energy of an ideal gas is a function of \ q = C × DT
temperature, for all isothermal processes involving ideal gas, Specific Heat Capacity
DU =0, whether the process is reversible or irreversible. It is the amount of heat required to raise the temperature of one gm
(v) For adiabatic change, q = 0, therefore DU = Wad. of substance through 1°C.
(vi) For isochoric process , W = 0 q = m × c × DT where m : mass of sample, c : specific heat
\ DU = qv + 0 i.e., heat given to system at constant volume Molar Heat Capacity
changes internal energy.
It is amount of heat required to raise the temperature of 1 mole of
ENTHALPY, H a substance through 1°C.
The total heat content of a system at constant pressure is known C
as its enthalpy i.e., Cm =
n
From 1st law of thermodynamics,
Types of heat capacities or molar heat capacities
DU = q + W
(i) Heat capacity at constant volume (CV)
As W = – P D V
At constant volume, qv = Cv DT = DU
\ q = DU + P D V
(ii) Heat capacity at constant pressure (C p)
At constant volume, D V = 0, we have
At constant pressure, qp = CpDT = DH
qV = DU
Relation between Cp and Cv
At constant pressure, we have
qp = DU + PDV As DH = DU + D ( PV ) = DU + D ( RT )
or, qp = (U2 – U1) + P (V2 – V1) DH = DU + RDT
qp = (U2 + PV2) – (U1 + PV1) .... (1) \ CP DT = Cv DT + RDT
The quantity (U + PV) is called heat content or enthalpy of the Þ CP = Cv + R
system.
or, CP - Cv = R
\ H = U + PV
Relation between ratio Cp/Cv and atomicity of a gas
Also, H 2 = U 2 + PV2 and H1 = U1 + PV1 (i) For monoatomic gases Cp/CV = 1.66
Putting these values in eq (1), (ii) For Diatomic gases Cp/Cv = 1.40
q p = H 2 - H1 (iii) For Triatomic gases Cp/CV = 1.33
EXOTHERMIC AND ENDOTHERMIC REACTIONS
or, q p = DH
Exothermic reactions are those which are accompanied by evolution
as q p = DU + PDV of heat. DH is negative for exothermic reactions
Endothermic reactions are those in which heat is absorbed. DH is
\ D H = DU + PDV positive for endothermic reactions.
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THERMOCHEMICAL EQUATION (v) Heat of hydration : The amount of heat released on complete
When a balanced chemical equation not only indicates the hydration of one mole of an anhydrous substance is called
quantities of different reactants and products but also indicates heat of hydration.
the amount of heat evolved or absorbed, it is called thermochemical (vi) Lattice enthalpy and its calculation
equation. The lattice enthalpy of an ionic compound is the enthalpy
HEAT OF REACTION OR ENTHALPY OF REACTION change which occurs when one mole of an ionic compound
dissociates into its ions in gaseous state.
OR ENTHALPY CHANGE OF REACTION
Lattice energy is calculated using the Born-Haber Cycle. It is
The amount of heat evolved or absorbed in a chemical reaction explained by taking the examples of NaCl.
when the number of moles of reactants as represented by the
chemical equation have completely reacted, is called heat of (a) Na(s) ¾¾
® Na (g) i.e., sublimation
reaction or enthalpy of reaction or enthalpy change of reaction
(DrH). Dsub H° = 108.4kJ mol-1
Change in total heat of reaction at 25°C and 1 atm pressure is + –
(b) Na(g) ¾¾
® Na (g) + e i.e., ionization of
called standard heat of reaction
Different types of heats/ enthalpies of reaction Di H° = 496kJ mol-1
(i) Enthalpy of combustion :
It is the heat evolved when 1 mole of substance is completely 1
(c) Cl2 ( g ) ¾¾
® Cl ( g ) i.e., dissociation of Cl
burnt or oxidised in oxygen. It is represented as DcH. 2
ex: CH 4 ( g ) + 2O2 ( g ) ¾¾
® CO2 ( g ) + 2H 2O ( g ) 1
D bond H° = 121 kJ mol-1
DcH° is standard enthalpy of combustion i.e. combustion 2
taking place under standard conditions, i.e., 298 K and 1 bar
pressure. (d) Cl ( g ) + e - ¾¾
® Cl - ( g ) i.e. gain of e– by Cl.
(ii) Enthalpy of formation :
It is the heat change i.e. heat evolved or absorbed when 1 D EG H° = -348.6 k J mol-1
mole of the substance is formed from its elements under given
conditions of T and P. It is represented by Df H.
(e) Na + ( g ) + Cl- ( g ) ¾¾
® Na + Cl- ( s )
Standard enthalpy of formation arises when the substance is and
formed in the standard state from its elements, which is also
1
taken in the standard state (i.e. 298 K and 1 bar pressure). It is Na(s) + Cl2 ( g ) ® NaCl (s) Δf H =–411.2 kJ mol -1
represented by Df H° 2
The standard enthalpy change of the reaction is: This is the Born – Haber Cycle .
Applying Hess’s law, we get
Dr H° = å Df H° ( products ) - å D f H° ( reactants )
1
For elementary substances in standard state, D f Ho is taken DfH° = DsubH° + D bond H° + I.E. + E. A. + Dlattice H°
2
as zero.
(iii) Enthalpy of Neutralization D lattice H° = 411.2 +108.4+121+496 – 348.6
The enthalpy of neutralization of an acid by a base is defined = + 788 k J
as the heat change when one gram equivalent of the acid is
Now, Dsol H° = Dlattice H° + Dhyd H°
neutralized by a base, the reaction being carried out in dilute
aqueous solution. = + 788 kJ mol–1 + (– 784 kJ mol–1)
The enthalpy of neutralization of any strong acid with a strong = + 4 kJ mol–1.
base or vice-versa, is always the same, i.e. 57.1kJ. (vii) Enthalpy of Atomization
(iv) Enthalpy of solution When one mole of a given substance dissociates into gaseous
It is defined as the enthalpy change when 1 mole of the atoms, the enthalpy change accompanying the process is
substance is dissolved in a specified amount of the solvent. called enthalpy of atomization. It is represented by DaH°.
For ionic compounds, enthalpy of solution depends upon
e.g., H 2 ( g ) ® 2H(g), D a H o = 435.0 kJ mol -1
lattice enthalpy and hydration enthalpy, i.e.,
(viii) Bond Enthalpy or Bond energy
Dsol H° = Dlattice H° + D hyd H°
It is the amount of energy released when one mole of bonds
For most ionic compounds, Dsol H° is positive and are formed from the isolated atom in gaseous state or the
dissociation process is endothermic. Thus, solubility of most amount of energy required to dissociate one mole of bonds
salts in water increases with increase in T. If lattice enthalpy present between the atoms in gaseous molecules. It is
of a salt is very high, the dissolution of the compound may represented by DbH or DbondH. It is expressed in kcal/mole
not take place at all. For this reason fluorides are less soluble DrH = å B.E. (Reactants) – å B.E. (Products)
than chlorides.
 Thermodynamics 127

Enthalpy Changes During Phase Transitions SECOND LAW OF THERMODYNAMICS

(i) Heat of sublimation : The amount of heat required to change It states that the energy of universe is constant whereas the
one mole of a solid substance into vapour state is called heat entropy of universe is continuously increasing and tends to a
of sublimation. maximum.
I2(s) ® I2(g) DH = +62.07 kJ/mole
GIBBS FREE ENERGY AND SPONTANEITY
(ii) Heat of fusion : The amount of heat required to completely
change one mole of a solid substance into liquid at its melting The available amount of energy to the system during the process
point is called heat of fusion. which can be changed into useful work, is called free energy of
H2O(s) ––––® H2O(l) DH = 6.0 kJ the system.
(iii) Heat of vapourisation : The amount of heat required to Gibbs energy helps in predicting the spontaneity of a process.
completely change one mole of a liquid into vapours at its It is denoted by ‘G’ and is given by
boiling point is called heat of vapourisation. G = H – TS
H2O(l) ––––® H2O(g) DH = +44 k cal The change in Gibb’s energy is given by:
DG = DH – TDS
HESS’S LAW OF CONSTANT HEAT SUMMATION The decrease in the value of Gibbs free energy during a process is
It states that the total amount of heat evolved or absorbed in a equal to the maximum possible useful work that can be obtained
reaction is the same whether the reaction takes place in one step from the system.
or in a number of steps. In other words, the total amount of heat According to Gibbs energy equation :
change in a reaction depends only upon the nature of initial DG = DH – TDS
reactants and nature of final products and is independent of the It combines both the factors of spontaneity, namely, energy factor
path or manner by which this change is brought about. DH and entropy factor TDS
A q2 B Spontaneity in Terms of Free Energy Change
q1 q3 (i) If DG is negative, the process is spontaneous
Reactant R Product, P (ii) If DG = 0, the process does not occur or system is in
equilibrium.
Q
(iii) If DG = positive, process does not occur in forward direction.
Q = q1 + q 2 + q3 It may occur in backward direction.
SPONTANEITY At equilibrium, DrG° = DrH° – T DrS°
= – RT ln K = – 2.303 RT logK
A spontaneous process is an irreversible process and may only
(K ® equilibrium constant)
be reversed by some external agency.
The tendency for a process to occur depends upon two factors: Relation Between DG and emf of Cell
(i) tendency for minimum energy DG = – nFEcell
(ii) tendency for maximum randomness where, Ecell = emf of the cell
The resultant of the above two tendencies which gives the overall n = number of moles of electrons involved
tendency for a process to occur is called driving force of the F = Faraday’s constant i.e., 96500 coulomb
process. If reactants and products are in their standard state,
DG° = – nFE°
ENTROPY
where E° = standard cell potential
It is a measure of randomness or disorder of the system.
Unit of entropy is JK–1mol–1 Effect of Temperature on Spontaneity of Reactions
Greater the randomness, higher is the entropy.
Entropy change during a process is given by: D r H° D r S° Dr G° Description of reaction
DS = S2 – S1 = å Sproduct – å Sreactant - + - Spontaneous at all T
DS is related to q and T for a reversible process as follows:
- - - ( lowT ) spontaneous at low T
q rev
DS = - - + ( high T ) non-spontaneous at high T
T
+ + + ( low T ) spontaneous at low T
In any process :
+ + - ( high T ) spontaneous at high T
D S Total = D Ssystem + D Ssurrounding
+ - + ( at all T ) non-spontaneous at all T
At equilibrium, entropy of the system is maximum and DS = 0
For irreversible process,
THIRD LAW OF THERMODYNAMICS
DSTotal = DSsystem + DSsurrounding > O
At absolute zero temperature, the entropy of a perfectly crystalline
substance is taken as zero. This law was formulated by Nernst in
1906.
CONCEPT MAP
128
CHEMISTRY

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 Thermodynamics 129

1. For precipitation reaction of Ag+ ions with NaCl, which of 11. One mole of an ideal gas at 300 K is expanded isothermally
the following statements is correct ? from an initial volume of 1 litre to 10 litres. The DE for this
(a) D H for the reaction is zero process is (R =2 cal. mol–1 K–1)
(a) 163.7 cal (b) zero
(b) D G for the reaction is zero
(c) 1381.1 cal (d) 9 lit. atm
(c) D G for the reaction is negative 12. In a closed insulated container, a liquid is stirred with a
(d) | D G | = | D H | paddle to increase the temperature, which of the following
2. Calorie is equivalent to : is true?
(a) 0.4184 Joule (b) 4.184 Joule (a) DE = W ¹ 0, q = 0 (b) DE = W = q ¹ 0
(c) 41.84 Joule (d) 418.4 Joule
3. In the isochoric process, DH for a system is equal to (c) DE = 0, W = q ¹ 0 (d) W = 0, DE = q ¹ 0
(a) P. DV (b) PV 13. The heat of combustion of methane at 298° K is expressed
(c) E + P. DV (d) DE by
4. If DH is the change in enthalpy and DE is change in internal CH 4(g ) + 2O 2(g) ¾
¾® CO 2(g) + 2H 2 O and DH = 890.2 kJ.
energy accompanying a gaseous reaction, then
Magnitude of DE of reaction at this temperature is
(a) DH is always greater than DE
(a) infinity (b) equal to DH
(b) DH < D E only if the number of moles of the products
is greater than the number of moles of the reactants (c) less than DH (d) greater than DH
14. For the reaction
(c) D H is always less than D E
(d) D H < D E only if the number of moles of products is C3H8 ( g ) + 5O2 ( g ) ® 3CO2 ( g ) + 4H2O(l )
less than the number of moles of the reactants. at constant temperature, DH – DE is
5. Which of the following is correct order ? (a) – RT (b) + RT
(a) 1 erg > 1 Joule > 1 calorie (c) – 3 RT (d) + 3 RT
(b) 1 erg > 1 calorie > 1 joule 15. The work done during the expansion of a gas from a volume
(c) 1 calorie > 1 Joule > 1 erg of 4 dm3 to 6 dm3 against a constant external pressure of
(d) 1 Joule > 1 calorie > 1 erg 3 atm is (1 L atm = 101.32 J)
6. For the reaction (a) – 6 J (b) – 608 J
(c) + 304 J (d) – 304 J
N 2 ( g ) + 3H 2 ( g ) 2NH3(g), DH = ? 16. The molar heat capacity of water at constant pressure is 75
(a) DE + 2RT (b) DE –2RT JK–1 mol–1. When 1kJ of heat is supplied to 100 g of water,
(c) DE – RT (d) None of these which is free to expand, the increase in temperature of water
7. The following is an endothermic reaction : is
(a) decomposition of water (a) 6.6 K (b) 1.2 K
(b) conversion of graphite to diamond (c) 2.4 K (d) 4.8 K
(c) dehydrogenation of ethane to ethylene 17. Assume each reaction is carried out in an open container.
(d) All of these For which reaction will DH = DE ?
8. Which process takes place on chemical bond formation : (a) C(s) + 2H2O (g) ® 2H2 (g) + CO2 (g)
(a) Decrease is energy (b) PCl5 (g) ® PCl3 (g) + Cl2 (g)
(b) Increase in energy (c) 2CO (g) + O2 (g) ® 2CO2 (g)
(c) No change in energy (d) H2 (g) + Br 2 (g) ® 2 HBr (g)
(d) Attractive and repulsive forces are equal 18. Which of the following is combustion reaction?
9. Gibbs free energy, for the reaction at equilibrium, is (a) C + O 2 ® CO2
(a) zero (b) – ve (b) CH 4 + O 2 ® CO 2 + H 2O
(c) + ve (d) either (a) or (c)
10. For which of the following changes, DH¹ DU (c) Mg + O2 ® MgO
(a) N 2 ( g ) + O 2 ( g ) ® 2NO( g ) (d) all of these.
19. An ideal gas expands in volume from 1×10–3 to 1 × 10–2 m3
(b) H 2 ( g ) + Cl2 ( g ) ¾¾
® 2HCl( g ) at 300 K against a constant pressure of 1×105 Nm–2. The
(c) C( s) + O2 ( g ) ¾¾® CO2 ( g ) work done is
(d) (a) 270 kJ (b) – 900 kJ
CaCO3 ( s ) ¾¾ ® CaO( s ) + CO 2 ( g )
(c) – 900 J (d) 900 kJ
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130 CHEMISTRY

20. Consider the reaction : N 2 + 3H 2 ® 2 NH 3 carried out at 30. What is the enthalpy change for,
2H 2O2 (l ) ® 2 H 2O(l ) + O 2 ( g ) if heat of formation of
constant temperature and pressure. If DH and DU are the
H2O2 (l) and H2O (l) are –188 and –286 kJ/mol respectively?
enthalpy and internal energy changes for the reaction, which
(a) –196 kJ/mol (b) + 948 kJ/mol
of the following expressions is true ?
(c) + 196 kJ/mol (d) –948 kJ/mol
(a) DH > DU (b) DH < DU
31. C (dia ) + O 2 ¾
¾® CO 2 ; DH = –395.4 kJ/mole
(c) DH = DU (d) DH = 0 ¾® CO 2 ; DH = –393.5 kJ/mole
C (gr ) + O 2 ¾
21. (DH – DU) for the formation of carbon monoxide (CO) from
its elements at 298 K is (R = 8.314 J K–1 mol–1) ¾® C ( dia ) ; DH = ?
C (gr ) ¾
(a) –2477.57 J mol –1 (b) 2477.57 J mol–1 (a) –3.8 (b) –1.9
(c) –1238.78 J mol –1 (d) 1238.78 J mol–1 (c) +3.8 (d) +1.9
22. Two moles of an ideal gas is expanded isothermally and 32. The D f H ° of O3, CO2, NH3 and HI are 142.2, –393.3, –46.2
reversibly from 1 litre to 10 litre at 300 K. The enthalpy change
and + 25.9 kJ per mol respectively. The order of their
(in kJ) for the process is
increasing stabilities will be
(a) 11.4 kJ (b) – 11.4 kJ
(a) O3, CO2, NH3, HI (b) CO2, NH3, HI, O3
(c) 0 kJ (d) 4.8 kJ
(c) O3, HI, NH3, CO2 (d) NH3, HI, CO2, O3
23. For a reaction Ag 2 O (s ) ¾¾® 2Ag + O , the value of DH =
33. If the bond energies of H - H, Br - Br, and H-Br are 433,
132.6 kJ, DS = 66 JK–1 mol–1
The free energy change for the reaction will be zero at which 192 and 364 kJ mol–1 respectively, the DH° for the reaction
of the temperature : H 2 ( g ) + Br2 ( g ) ® 2HBr( g ) is
(a) 2000 K (b) 2009 K (a) – 261 kJ (b) + 103 kJ
(c) 2023 K (d) 2029 K (c) + 261kJ (d) – 103 kJ
24. For the reaction 34. The absolute enthalpy of neutralisation of the reaction:
MgO (s) + 2HCl (aq) ¾® MgCl2 (aq) + H2O (l) will be:
A( g ) + 2B( g ) ¾¾
® 2C( g ) + 3D( g )
(a) -57.33 kJ mol-1
the change of enthalpy at 27°C is 19 kcal. The value of DE is (b) greater than -57.33 kJ mol- 1
(a) 21.2 kcal (b) 17.8 kcal (c) less than -57.33 kJ mol-1
(c) 18.4 kcal (d) 20.6 kcal (d) 57.33 kJ mol-1
25. For a chemical reaction the enthalpy and entropy change
35. A2(g) + B2(g) 2AB(g); DH = +ve, It :
are –2.5 × 103 cals and 7.4 cals deg–1 respectively. At 25ºC
(a) increases by pressure
the reaction is :
(b) it occurs at 1000 atm pressure
(a) spontaneous (b) non-spontaneous
(c) it occurs at high temperature
(c) reversible (d) irreversible
(d) it occurs at high pressure and temperature
26. A well stoppered thermos flask contains some ice cubes.
36. The enthalpy of hydrogenation of cyclohexene is – 119.5
This is an example of a
kJ mol–1. If resonance energy of benzene is –150.4 kJ mol–1,
(a) closed system
its enthalpy of hydrogenation would be
(b) open system
(a) – 208.1 kg mol–1 (b) – 269.9 kg mol–1
(c) isolated system –1
(c) – 358.5 kg mol (d) – 508.9 kg mol–1
(d) non-thermodynamic system
37. Which of the following equations correctly represents the
27. Given that C + O 2 ® CO 2 : DH º = - x kJ
standard heat of formation (D f H° ) of methane ?
2 CO + O 2 ® 2CO 2 : DH º = - y kJ (a) C (diamond) + 4H( g ) ® CH 4 ( g )
the enthalpy of formation of carbon monoxide will be
(b) C (diamond) + 2H 2 ( g ) ® CH 4 ( g )
2x - y y - 2x
(a) (b) (c) C (graphite) + 2H 2 ( g ) ® CH 4 ( g )
2 2
(c) 2x – y (d) y – 2x (d) C (graphite) + 4H( g ) ® CH 4 ( g )
28. The values of DH for the combustion of ethane and acetylene 38. Enthalpy of solution of NaOH (solid) in water is – 41.6
are –341.1 and –310.0 kcal, respectively. The better fuel is : kJ mol–1. When NaOH is dissolved in water, the temperature
(a) ethane (b) acetylene of water :
(c) both (d) none of these (a) increases (b) decreases
29. The values of heat of formation of SO2 and SO3 are –298.2 (c) does not change (d) fluctuates indefinitely
kJ and –98.2 kJ. The heat of formation of the reaction 39. For a Carnot engine, the source is at 500 K and the sink at
SO 2 + (1 / 2)O 2 ® SO 3 will be 300 K. What is efficiency of this engine :
(a) –200 kJ (b) –356.2 kJ (a) 0.2 (b) 0.4
(c) + 200 kJ (d) – 396.2 kJ (c) 0.6 (d) 0.3
 Thermodynamics 131

40. The D f H° for CO2(g) CO(g) and H2O(g) are –393.5, –110.5 51. The latent heat of vaporisation of water at 100° C is 540 cal
g–1. Calculate the entropy increase when one mole of water
and –241.8 kJ/mol respectively, the standard enthalpy change at 100°C is evaporated?
(in kJ) for the reaction CO2(g) + H2(g) ® CO(g) + H2O(g) is : (a) 1.82 cal K–1 mol–1 (b) 540 × 18 cal K–1 mol–1
(a) 524.1 (b) 41.2 –1
(c) 26 cal K mol –1 (d) 367 cal K–1 mol–1
(c) – 262.5 (d) – 41.2 52. The entropy change in the fusion of one mole of a solid
41. If enthalpies of formation of C 2 H 4 ( g ) , CO 2 (g) and melting at 27ºC (Latent heat of fusion, 2930 J mol–1) is :
H 2O(l ) at 25°C and 1atm pressure are 52, – 394 and – 286 (a) 9.77 J K–1 mol–1 (b) 10.73 J K–1 mol–1
kJ/mol respectively, the change in enthalpy is equal to (c) 2930 J K–1 mol–1 (d) 108.5 J K–1 mol–1
(a) – 141.2 kJ/mol (b) – 1412 kJ/mol 53. 2 mole of an ideal gas at 27ºC temperature is expanded
(c) + 14.2 kJ/mol (d) + 1412 kJ/mol reversibly from 2 lit to 20 lit. Find the entropy change
42. How many joules of heat are absorbed when 70.0 grams of (R = 2 cal/mol K)
water is completely vaporised at its boiling point? (a) 92.1 (b) 0
(a) 23,352 (b) 7,000 (c) 4 (d) 9.2
(c) 15,813 (d) 158, 200 54. Considering entropy (S) as a thermodynamic parameter, the
43. Heat of neutralization of strong acid against strong base is criterion for the spontaneity of any process is
constant and is equal to (a) DSsystem + DS surroundin gs > 0
(a) 13.7 kcal (b) 57.3 kJ (b) DSsystem - DSsurroundings > 0
(c) 5.73 × 104 J (d) All of the above (c) DSsystem > 0 only
44. Work done during isothermal expansion of one mole of an
ideal gas from 10 atm. to 1 atm. at 300 K is : (d) DSsurroundin gs > 0 only
(a) 4938.8 joule (b) 4138.8 joule 55. Entropy of vaporisation of water at 100°C, if molar heat of
(c) 5744.1 joule (d) 6257.2 joule vaporisation is 9710 cals mol–1, will be
45. Given the bond energies N º N, H – H and N – H bonds are (a) 28 cal mol–1 K–1 (b) 26 cal mol–1 K–1
(c) 24 cal mol–1 K–1 (d) 20 cal mol–1 K–1
945,436 and 391 kJ mole–1 respectively, the enthalpy of the
56. For conversion C (graphite) ® C (diamond) the DS is
following reaction N 2 ( g ) + 3H 2 ( g ) ® 2NH 3 ( g ) is (a) zero (b) positive
(a) –93 kJ (b) 102 kJ (c) negative (d) cannot be predicted
(c) 90 kJ (d) 105 kJ 57. The following thermochemical reactions are given :
46. The H2O(g) molecule dissociates as
1
(i) H 2O ( g ) ® H ( g ) + OH ( g ) ; DH = 490 kJ M + O 2 ® MO + 351.4kJ
2
(ii) OH ( g ) ® H ( g ) + O ( g ) ; DH = 424 kJ 1
X + O 2 ® XO + 90.8 kJ
The average bond energy (in kJ) for water is 2
(a) 490 (b) 424 It follows that the heat of reaction for the following process
(c) 914 (d) 914/2 M + XO ® MO + X
47. DS° will be highest for the reaction is given by :
1 (a) 442.2kJ (b) 260.7 kJ
(a) Ca( s) + O 2 ( g ) ¾¾ ® CaO( s )
(c) – 442.2 kJ (d) 260.6 kJ
2
(b) CaCO3 ( s ) ¾¾ ® CaO( s ) + CO 2 ( g ) 58. According to second law of thermodynamics heat is partly
(c) C( s) + O 2 ( s) ¾¾ ® CO 2 ( g ) converted into useful work and part of it :
(a) becomes electrical energy
(d) N 2 ( g ) + O 2 ( g ) ¾¾
® 2NO( g ) (b) always wasted
48. The maximum work which a system can perform at constant (c) increases the weight of the body
temperature and pressure equals (d) becomes K.E.
(a) DH – DE (b) (– DG)
(c) q – DE (d) P.DV – DG 59. If C(s) + O2(g) ¾¾
® CO2(g); DH = R and
49. For which of the following process, DS is negative? 1
(a) H2 (g) ¾¾ ® 2 H(g) CO(g) + O2 (g) ¾¾ ® CO 2 (g); DH = S,
(b) 2SO3 (g) ¾¾ 2
® 2SO2(g) + O2 (g)
compressed
then heat of formation of CO is:
(c) N 2 (4l) ¾¾¾¾¾ ® N 2 (2l) (a) R + S (b) R – S
(d) C(diamond) ¾¾ ® C (graphite) (c) R × S (d) S – R
50. Which one of the following is correct ? 60. Which of the following pairs of processes is certain to occur
in a spontaneous chemical reaction?
1
(a) DH = DG – TDS (b) DS = [DG – DH] (a) Exothermic and increasing disorder
T (b) Exothermic and decreasing disorder
1 (c) Endothermic and increasing disorder
(c) DS = [DH – DG] (d) – DG = DH – T D S (d) Endothermic and decreasing disorder
T
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61. The H–H bond energy is 430 kJ mol–1 and Cl–Cl bond (c) Both statements (A) and (B) are true
energy is 240 kJ mol–1. DH for HCl is – 90 kJ/mol. The H–Cl (d) Both statements (A) and (B) are false
bond energy is about : 71. DE of combustion of isobutylene is – X kJ mol–1. The value of
(a) 180 kJ mol–1 (b) 360 kJ mol–1 DH is :
(c) 213 kJ mol–1 (d) 425 kJ mol–1 (a) = DE (b) > DE
62. A chemical reaction will be spontaneous if it is accompanied (c) = 0 (d) < DE
by a decrease of
(a) entropy of the system 1
72. For the reaction CO( g ) + O2 ( g ) ¾¾ ® CO2 ( g ), DH, and
(b) enthalpy of the system 2
(c) internal energy of the system DS are –283 kJ and –87 JK–1, respectively. It was intended to
(d) free energy of the system carry out this reaction at 1000, 1500, 3000 and 3500 K. At
63. For a reaction in which all reactants and products are liquids, which of these temperatures would this reaction be
which one of the following equations is most applicable ? thermodynamically spontaneous?
(a) DH < DE (b) DH = DS (a) 1500 and 3500 K (b) 3000 and 3500 K
(c) DH = DE (d) DH = DG (c) 1500, 1500 and 3000 K (d) 1500, 3000 and 3500 K
64. Highest entropy is in :
(d) Energy due to gravitational pull
(a) hydrogen (b) water
(c) graphite (d) mercury 73. The enthalpy of combustion of C 6 H 6 is – 3250 kJ, when
65. If the value of Cp for nitrogen gas is 7 JK–1mol–1, then the 0.39 gm of C 6 H 6 is burnt in excess of oxygen in an open
value of DH on heating 28 g of nitrogen gas from 0°C to 100°C
vessel, the amount of heat evolved is
at constant pressure will be :
(a) 1200 J (b) 1300 J (a) 8.32 kJ (b) 12.36 kJ
(c) 1400 J (d) 1500 J (c) 16.25 kJ (d) 20.74 kJ
66. The enthalpy and entropy change for the reaction 74. The free energy change for the following reactions are given
Br2(l) + Cl2 (g) ® 2 BrCl (g) below,
are 30kJ mol –1 and 105 JK–1 mol –1 respectively. The 5
temperature at which the reaction will be in equilibrium is C2 H2 (g) + O2 (g) ® 2CO 2 (g) + H 2O(l); DG° = -1234kJ
2
(a) 273 K (b) 450 K
(c) 300 K (d) 285.7 K C(s) + O 2 (g) ® CO 2 (g); DG° = -394kJ
67. Given the value of DH= 177.9 kJ and
1
-1 -1
H 2 (g) + O 2 (g) ® H 2 O(l); DG ° = -237kJ
DS= 160.4 JK mol . For the reaction 2
What is the standard free energy change for the reaction
CaCO 3 ( s ) ¾¾
® CaO( s) + CO 2 ( g ) H2(g) + 2C (s) ¾¾ ® C2H2(g)
at 298 K, the free energy change per mole would be : (a) – 209 kJ (b) –2259 kJ
(a) + 130.1 kJ (b) – 130.1 kJ (c) + 2259 kJ (d) 209 kJ
(c) – 4.90 kJ (d) + 4.90 kJ 75. One mole of an ideal gas is allowed to expand reversibly and
68. For spontaneous cooling of a hot metal rod (system) in air : adiabatically from a temperature of 27°C. If the work done
(a) DS system > 0, DS universe < 0 during the process is 3kJ, then final temperature of the gas is
(b) DS system > 0, DS universe > 0 (Cv = 20 J/K):
(c) DS system < 0, DS universe > 0 (a) 100 K (b) 150 K
(d) DS system < 0, DS universe < 0 (c) 195 K (d) 255 K
69. Following reaction occurrs in an automobile
76. The heat of atomization of PH3(g) is 228 kcal mol–1 and that
2C8 H18 ( g ) + 25O 2 ( g ) ® 16CO 2 ( g ) + 18H 2 O ( g ) . The of P2H4(g) is 335 kcal mol–1. The energy of the P–P bond is
sign of DH, DS and DG would be (a) 102 kcal mol–1 (b) 51 kcal mol–1
(c) 26 kcal mol –1 (d) 204 kcal mol–1
(a) +, –, + (b) –, +, –
(c) –, +, + (d) +, +, – 77. The value DH – DE for the following reaction at 27°C will be
70. Consider the following reactions at 1000°C 2NH3(g) ¾¾ ® N2 + 2H2(g)
1 (a) 8.314 × 273 × (–2) (b) 8.314 × 300 × (–2)
-1
(A) Zn( s) + O2 ( g ) ® ZnO( s); DG° = -360kJmol . (c) 8.314 × 27 × (–2) (d) 8.314 × 300 × (2)
2
78. Given that bond energies of H – H and Cl – Cl are
1 -1 430 kJ mol– 1 and 240 kJ mol–1 respectively and DfH for HCl is
(B) C ( gr ) + O2 ( g ) ® CO( g ); DG° = -460kJmol .
2 – 90 kJ mol– 1, bond enthalpy of HCl is
Choose the correct statement at 1000°C (a) 380 kJ mol–1 (b) 425 kJ mol–1
(a) Zinc can be oxidized by carbon monoxide (c) 245 kJ mol –1 (d) 290 kJ mol–1
(b) Zinc oxide can be reduced by graphite
 Thermodynamics 133

79. Which of the following are not state functions ? 88. The standard enthalpy of formation of NH3 is – 46.0 kJ mol–1.
(I) q + w (II) q If the enthalpy of formation of H2 from its atoms is
(III) w (IV) H - TS – 436 kJ mol–1 and that of N2 is – 712 kJ mol–1, the average
(a) (I) and (IV) (b) (II), (III) and (IV) bond enthalpy of N – H bond in NH3 is
(c) (I), (II) and (III) (d) (II) and (III) (a) – 964 kJ mol–1 (b) + 352 kJ mol–1
(c) + 1056 kJ mol –1 (d) – 1102 kJ mol–1
80. For vaporization of water at 1 atmospheric pressure, the values
of DH and DS are 40.63 kJmol–1 and 108.8 JK–1 mol–1, 89. The value of enthalpy change (DH) for the reaction
respectively. The temperature when Gibbs energy change C2H5 OH(l) + 3O2 ( g ) ® 2CO2 ( g ) + 3H 2O(l)
( DG ) for this transformation will be zero, is: at 27° C is – 1366.5 kJ mol–1. The value of internal energy
(a) 293.4 K (b) 273.4 K change for the above reaction at this temperature will be :
(c) 393.4 K (d) 373.4 K. (a) – 1369.0 kJ (b) – 1364.0 kJ
81. The following two reactions are known : (c) – 1361.5 kJ (d) – 1371.5 kJ
90. The heats of atomization of PH3(g) and P2H4(g) are 954 kJ
® 2Fe(s) + 3CO2(g); DH = –26.8 kJ
Fe2O3(s) + 3CO (g) ¾¾
mol–1 and 1485 kJ mol–1 respectively. The P–P bond energy
FeO(s) + CO(g) ¾¾
® Fe(s) + CO2(g); DH = –16.5 kJ in kJ mol–1 is
The value of D H for the following reaction (a) 213 (b) 426
Fe2O3(s) + CO(g) ¾¾ ® 2FeO(s) + CO2(g) is; (c) 318 (d) 1272
(a) + 6.2 kJ (b) + 10.3 kJ 91. Pick out the wrong statement
(c) – 43.3 kJ (d) – 10.3 kJ (a) The standard free energy of formation of all elements is
82. Three moles of an ideal gas expanded spontaneously into zero
vacuum. The work done will be : (b) A process accompanied by decrease in entropy is
(a) Zero (b) Infinite spontaneous under certain conditions
(c) 3 Joules (d) 9 Joules (c) The entropy of a perfectly crystalline substance at
absolute zero is zero
83. If the enthalpy change for the transition of liquid water to
(d) A process that leads to increase in free energy will be
steam is 30 kJ mol–1 at 27ºC, the entropy change for the
spontaneous
process would be :
92. Which one of the following demonstrates a decrease in
(a) 10 J mol –1 K–1 (b) 1.0 J mol–1 K–1
–1 –1
entropy?
(c) 0.1 J mol K (d) 100 J mol–1 K–1
(a) Dissolving a solid into solution
84. Enthalpy change for the reaction, (b) An expanding universe
4H( g ) ¾¾
® 2H 2 ( g ) is – 869.6 kJ. (c) Burning a log in a fireplace
The dissociation energy of H–H bond is : (d) Raking up leaves into a trash bag
(a) – 434.8 kJ (b) – 869.6 kJ 93. A certain reaction is at equilibrium at 82° C and the
(c) + 434.8 kJ (d) + 217.4 kJ enthalpy change for this reaction is 21.3 kJ. The value of
85. The enthalpy of fusion of water is 1.435 kcal/mol. DS (in JK mol–1) for the reaction is
The molar entropy change for the melting of ice at 0°C is : (a) 55.0 (b) 60.0
(a) 10.52 cal / (mol K) (b) 21.04 cal / (mol K) (c) 68.5 (d) 120.0
(c) 5.260 cal / (mol K) (d) 0.526 cal / (mol K) 94. The bond enthalpy is the highest for
86. Equal volumes of two monoatomic gases, A and B, at same (a) F2 (b) Cl2
temperature and pressure are mixed. The ratio of specific (c) Br2 (d) H2
heats (Cp/Cv) of the mixture will be : 95. At the sublimation temperature, for the process
(a) 0.83 (b) 1.50 ˆˆ† CO2(g)
CO2(s) ‡ˆˆ
(c) 3.3 (d) 1.67 (a) DH, DS and DG are all positive
87. Identify the correct statement regarding a spontaneous (b) DH > 0, DS > 0 and DG < 0
process (c) DH < 0, DS > 0 and DG < 0
(a) Lowering of energy in the process is the only criterion (d) DH > 0, DS > 0 and DG = 0
for spontaneity.
96. The enthalpy of solution of sodium chloride is
(b) For a spontaneous process in an isolated system, the 4 kJ mol–1 and its enthalpy of hydration of ions is –784 kJ
change in entropy is positive. mol–1. Then the lattice enthalpy of NaCl (in kJ mol –1) is
(c) Endothermic processes are never spontaneous. (a) + 788 (b) + 4
(d) Exothermic processes are always spontaneous. (c) + 398 (d) + 780
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97. Calculate the work done (in Joules) when 0.2 mole of an ideal 99. A chemical reaction is spontaneous at 298 K but non-
gas at 300 K expands isothermally and reversibly from an spontaneous at 350 K. Which one of the following is true for
initial volume of 2.5 litres to the final volume of the reaction?
25 litres. DG DH DS
(a) – – +
(a) 996 (b) 1148 (b) + + +
(c) 11.48 (d) 897 (c) – + –
98. Choose the reaction with negative DS value. (d) – – –
(a) 2NaHCO3(s) ® Na2CO3(s) + CO2(g) + H2O(g) 100. A reaction cannot take place spontaneously at any
temperature when
(b) Cl2(g) ® 2Cl(g) (a) both DH and DS are positive
(c) 2SO2(g) + O2(g) ® 2SO3(g) (b) both DH and DS are negative
(d) 2KClO3(s) ® 2KCl(s) + 3O2(g) (c) DH is negative and DS is positive
(d) DH is positive and DS is negative

1. In which of the following equations, the enthalpy change 6. For the reactions,
will represent DH ºf of N2H4(l) with sign reversed? C + O2 ® CO2 ; DH = –393 J
2Zn + O2 ® 2ZnO ; DH = –412 J
(a) N 2 ( g ) + 2 H 2( g ) ® N 2 H 4 ( g ) (a) carbon can oxidise Zn
(b) 2N (g ) + 4H (g ) ® N 2 H 4(l ) (b) oxidation of carbon is not feasible
(c) oxidation of Zn is not feasible
(c) N 2 H 4(l ) ® 2N (g ) + 4H (g ) (d) Zn can reduce carbon dioxide.
7. The internal energy change when a system goes from state A
(d) N 2 H 4( l) ® N 2(g ) + 2H 2(g)
to B is 40 kJ/mole. If the system goes from A to B by a reversible
2. Equal volumes of molar hydrochloric acid and sulphuric acid path and returns to state A by an irreversible path what would
are neutralized by dil. NaOH solution and x kcal and y kcal of be the net change in internal energy ?
heat are liberated respectively. Which of the following is true? (a) > 40 kJ (b) < 40 kJ (c) Zero (d) 40 kJ
1 8. In an irreversible process taking place at constant T and P and in
(a) x = y (b) x = y which only pressure-volume work is being done, the change in
2
(c) x = 2y (d) None of these Gibbs free energy (dG) and change in entropy (dS), satisfy the
3. Hydrogen has an ionisation energy of 1311 kJ mol–1 and for criteria
chlorine it is 1256 kJ mol–1. Hydrogen forms H+ (aq) ions but (a) (dS)V, E > 0, (dG)T, P < 0 (b) (dS)V, E = 0, (dG)T, P = 0
chlorine does not form Cl+ (aq) ions because (c) (dS)V, E = 0, (dG)T, P > 0 (d) (dS)V, E < 0, (dG)T, P < 0
(a) H+ has lower hydration enthalpy
9. If the bond dissociation energies of XY, X 2 and Y2 (all
(b) Cl+ has lower hydration enthalpy
(c) Cl has high electron affinity diatomic molecules) are in the ratio of 1 : 1 : 0.5 and D f H for
(d) Cl has high electronegativity the formation of XY is – 200 kJ mole–1 . The bond dissociation
4. The factor of DG values is important in metallurgy. The DG energy of X 2 will be
values for the following reactions at 800ºC are given as :
-1
S2 ( s ) + 2O 2 ( g ) ¾¾
® 2SO 2 ( g ) ; DG = – 544 kJ (a) 400 kJ mol (b) 300 kJ mol -1
-1 -1
® 2ZnS( s ) ; DG = – 293 kJ
2Zn( s ) + S2 ( s ) ¾¾ (c) 200 kJ mol (d) 800 kJ mol
® 2ZnO( s ) ; DG = – 480 kJ
2Zn( s ) + O 2 ( g ) ¾¾ 10. The standard enthalpy of formation (DfHº) at 298 K for
Then DG for the reaction : methane, CH4 (g) is –74.8 kJ mol–1. The additional information
required to determin e th e average energy for
2ZnS( s ) + 3O 2 ( g ) ¾ ¾
® 2ZnO( s ) + 2SO 2 ( g ) C – H bond formation would be
will be : (a) the first four ionization energies of carbon and electron
(a) –357 kJ (b) –731 kJ (c) –773 kJ (d) –229 kJ gain enthalpy of hydrogen
5. For the reaction A ® B; DH = + 24 kJ/mol and B ® C;
(b) the dissociation energy of hydrogen molecule, H2
DH = – 18 kJ/mol, the decreasing order of enthalpy of A, B
and C follows the order (c) the dissociation energy of H2 and enthalpy of sublimation
(a) A, B, C (b) B, C, A of carbon
(c) C, B, A (d) C, A, B (d) latent heat of vapourization of methane
 Thermodynamics 135

11. The enthalpy changes for the following processes are listed 19. If DH and DE are the change in enthalpy and change in
below : internal energy respectively for a gaseous reaction, then
Cl2(g) ® 2Cl(g), 242.3 kJ mol–1 (a) DH > DE, always
I2(g) ® 2I(g), 151.0 kJ mol–1 (b) DH < DE, onlyif nproduct > nreactants
ICl(g) ® I(g) + Cl(g), 211.3 kJ mol–1
(c) DH < DE ,always
I2(s) ® I2(g), 62.76 kJ mol–1
Given that the standard states for iodine and chlorine are I2(s) (d) DH < DE, only if nproduct < nreactants
and Cl2(g), the standard enthalpy of formation for ICl(g) is : 20. Consider the following reactions:
(a) +16.8 kJ mol–1 (b) +244.8 kJ mol–1 (i) H +(aq) + OH–(aq) ¾¾ ® H2O(l),
(c) –14.6 kJ mol –1 (d) –16.8 kJ mol–1 DH = – X1 kJ mol–1
12. The heat of neutralisation of strong base and strong acid is 1
57.0 kJ. The heat released when 0.5 mole of HNO3 is added to (ii) H2(g) + O (g) ¾¾ ® H2O(l),
2 2
0.20 mole of NaOH solution is : DH = – X2 kJ mol–1
(a) 34.9 kJ (b) 57.0 kJ (c) 11.4 kJ (d) 28.5 kJ (iii) CO2(g) + H2(g) ¾¾ ® CO(g) + H2O,
13. Energy required to dissociate 4g of gaseous hydrogen into DH = – X3 kJ mol–1
free gaseous atoms is 208 kcal at 25°C. The bond energy of
5
H–H will be : (iv) C 2 H 2 ( g ) + O2 ( g ) ¾¾
® 2CO2(g) + H2O(l),
(a) 104 kcal (b) 52 kcal (c) 10.4 kcal (d) 1040 kcal 2
14. Given that heat of neutralisation of strong acid and strong DH = + 4X4 kJ mol –1

base is – 57.1 kJ. The heat produced when 0.25 mole of HCl is Enthalpy of formation of H2O (l) is
neutralised with 0.25 mole of NaOH in aqueous solution is : (a) + X3 kJ mol– 1 (b) – X4 kJ mol– 1
(a) 14.275 kJ (b) 57.1 kJ (c) 22.5 kJ (d) 28.6 kJ (c) + X1 kJ mol – 1 (d) – X2 kJ mol– 1
15. The heat of neutralisation of HCl by NaOH is 21. For the gas phase reaction,
–55.9 kJ/mole.The energy of dissociation of HCN is : ˆˆ† PCl3(g) + Cl2(g)
PCl5(g) ‡ˆˆ
(HCN + OH - ® CN - + H 2 O; DH = -12.1 kJ)
(a) 43.8 kJ (b) – 43.8 kJ (c) – 68 kJ (d) 68 kJ which of the following conditions are correct ?
16. Calculate enthalpy change for the change 8S( g ) ¾¾ (a) DH = 0 and DS < 0 (b) DH > 0 and DS > 0
® S8 ( g ),
(c) DH < 0 and DS < 0 (d) DH > 0 and DS < 0
given that
22. Bond dissociation enthalpy of H2, Cl2 and HCl are 434 , 242 and
® 2H( g ) + 2S( g ), DH = 239.0 k cal mol-1 ;
H 2S2 ( g ) ¾¾ 431 kJ mol–1 respectively. Enthalpy of formation of HCl is :
H 2S( g ) ¾¾® 2H( g ) + S( g ), DH = 175.0 k cal mol-1 (a) 93 kJ mol–1 (b) – 245 kJmol–1
(a) + 512.0 k cal (b) – 512.0 k cal (c) – 93 kJmol–1 (d) 245 kJmol–1
(c) 508.0 k cal (d) – 508.0 k cal 23. The values of DH and DS for the reaction,
17. If x1, x2 and x3 are enthalpies of H–H, O=O and O–H bonds C(graphite) + CO2 (g) ® 2CO(g) are 170 kJ and 170 JK–1,
repectively, and x4 is the enthalpy of vaporisation of water, respectively. This reaction will be spontaneous at
estimate the standard enthalpy of combustion of hydrogen: (a) 910 K (b) 1110 K (c) 510 K (d) 710 K
24. From the following bond energies:
x x H – H bond energy: 431.37 kJ mol–1
(a) x1 + 2 - 2 x3 + x4 (b) x1 + 2 - 2 x3 - x 4
2 2 C = C bond energy: 606.10 kJ mol–1
x2 x C – C bond energy: 336.49 kJ mol–1
(c) x1 + - x3 + x 4 (d) 2 x3 - x1 - 2 - x4 C – H bond energy: 410.50 kJ mol–1
2 2 Enthalpy for the reaction,
18. If for a given substance melting point is TB and freezing
point is TA, then correct variation shown by, graph between H H H H
entropy change and temperature is | | | |
C = C + H - H ¾¾ ® H - C- C - H
TB | | | |
DS TB DS
H H H H
TA will be:
(a) TA (b) (a) – 243.6 kJ mol–1 (b) –120.0 kJ mol–1
T T (c) 553.0 kJ mol–1 (d) 1523.6 kJ mol–1
25. Standard entropies of X2 , Y2 and XY3 are 60, 40 and
TB
TB TA 50 JK–1mol–1 respectively. For the reaction
DS TA DS 1 3
X 2 + Y2 ƒ XY3 , DH = – 30 kJ
(c) (d) 2 2
to be at equilibrium, the temperature should be:
T T (a) 750 K (b) 1000 K (c) 1250 K (d) 500 K
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26. Match List -I (Equations) with List-II (Type of processes) 32. Oxidising power of chlorine in aqueous solution can be
and select the correct option. determined by the parameters indicated below:
List I List II 1 Q
Equations Type of processes 1 D H
2 diss D eg HQ
Cl2 ( g ) ¾¾¾¾¾ ® Cl( g ) ¾¾¾¾ ® Cl– ( g )
(1) Kp > Q (i) Non spontaneous 2
(2) DG ° < RT lnQ (ii) Equilibrium D HQ
(3) Kp = Q (iii) Spontaneous and
Hyd
¾¾¾¾ ® Cl – (aq)
–1
endothermic (using the data, D diss H Cl = 240 kJ mol ,
2
DH
(4) T > (iv) Spontaneous –1
D eg H Cl = –349 kJ mol , D hyd H Cl – = –381 kJ mol ),
–1
DS
Options: will be
(1) (2) (3) (4) (a) + 152 kJ mol–1 (b) – 610 kJ mol–1
(a) (ii) (i) (iv) (iii) (c) – 850 kJ mol –1 (d) + 120 kJ mol–1
(b) (i) (ii) (iii) (iv) 33. On the basis of the following thermochemical data :
(c) (iii) (iv) (ii) (i) +
[Δ f H°(H (aq) = 0)]
(d) (iv) (i) (ii) (iii)
27. Consider the following processes : H 2O(l ) ® H + ( aq ) + OH – ( aq ); DH = 57.32kJ
DH (kJ/mol)
1
1/2 A® B +150 H2 (g )+ O2 (g ) ¾¾ ® H2O(l); ΔH= –286.20kJ
3B ® 2C + D –125 2
The value of enthalpy of formation of OH– ion at 25° C is:
E + A ® 2D +350
(a) –228.88 kJ (b) +228.88 kJ
For B + D ® E + 2C, DH will be :
(a) 525 kJ/mol (b) – 175 kJ/mol (c) –343.52 kJ (d) –22.88 kJ
(c) – 325 kJ/mol (d) 325 kJ/mol 34. For a particular reversible reaction at temperature T, DH and
28. In which of the following reactions, standard entropy change DS were found to be both +ve. If Te is the temperature at
(DS°) is positive and standard Gibb’s energy change (DG°) equilibrium, the reaction would be spontaneous when
decreases sharply with increase in temperature ?
(a) Te > T (b) T > Te
1
(a) C (graphite) + O2(g) ® CO(g) (c) Te is 5 times T (d) T = Te
2
1 35. Consider the reaction
(b) CO(g) + O2(g) ® CO2(g)
2 4NO2 ( g ) + O 2 ( g ) ® 2N 2O5 ( g ),
1 DrH = – 111 kJ.
(c) Mg(s) + O2(g) ® MgO(s)
2
If N2O5(s) is formed instead of N2O5(g) in the above reaction,
1 1 1 the DrH value will be :
(d) C (graphite) + O2(g) ® CO2(g)
2 2 2 (given, DH of sublimation for N2O5 is –54 kJ mol–1)
29. Standard enthalpy of vapourisation Dvap H° for water at (a) + 54 kJ (b) + 219 kJ
100°C is 40.66 kJ mol–1. The internal energy of vaporisation
of water at 100°C (in kJ mol–1) is : (c) – 219 J (d) – 165 kJ
(a) + 37.56 (b) – 43.76 ˆˆ† B is
36. The value of log10 K for a reaction A ‡ˆˆ
(c) + 43.76 (d) + 40.66
(Assume water vapour to behave like an ideal gas). (Given : D r H °298K = -54.07 kJ mol- 1 ,
30. In conversion of lime-stone to lime,
CaCO3 ( s ) ® CaO( s ) + CO 2 ( g ) the values of DH° and DS° D r S°298K = 10 JK–1 mol–1 and R = 8.314 JK–1 mol–1;
are + 179.1 kJ mol-1 and 160.2 J/K respectively at 298 K and 2.303 × 8.314 × 298 = 5705)
1 bar. Assuming that DH° and DS° do not change with (a) 5 (b) 10
temperature, temperature above which conversion of (c) 95 (d) 100
limestone to lime will be spontaneous is
(a) 1118 K (b) 1008 K 37. For the process H2O(l) (1 bar, 373 K) ® H2O(g) (1 bar, 373
(c) 1200 K (d) 845 K. K), the correct set of thermodynamic parameters is
31. Assuming that water vapour is an ideal gas, the internal (a) DG = 0, DS = +ve (b) DG = 0, DS = –ve
energy change (DU) when 1 mol of water is vapourised at (c) DG = +ve, DS = 0 (d) DG = –ve, DS = +ve
1 bar pressure and 100°C, (given : molar enthalpy of 38. The species which by definition has ZERO standard molar
vapourisation of water at 1 bar and 373 K = 41 kJ mol –1 and enthalpy of formation at 298 K is
R = 8.3 J mol–1 K–1) will be
(a) 41.00 kJ mol–1 (b) 4.100 kJ mol–1 (a) Br2 (g) (b) Cl2 (g)
(c) 3.7904 kJ mol –1
(d) 37.904 kJ mol–1 (c) H2O (g) (d) CH4 (g)
 Thermodynamics 137

39. Using the data provided, calculate the multiple bond energy 45. The enthalpies of the following reactions are shown below.
(kJ mol–1) of a C º C bond in C2H2. That energy is (take the [AFMC 2011]
bond energy of a C – H bond as 350 kJ mol–1) 1 1
H (g) + O2(g) ® OH(g) ; DH = 42.09 kJ mol–1
2C(s) + H2(g) ¾¾ ® HC º CH(g); DH = 225 kJ mol–1 2 2 2
H2(g) ® 2H(g) ; DH = 435.89 kJ mol–1
2C(s) ¾¾ ® 2C(g) ; DH = 1410 kJ mol–1
O2(g) ® 2O(g) ; DH = 495.05 kJ mol–1
H2(g) ¾¾ ® 2H(g) ; DH = 330 kJ mol–1
Calculate the O –– H bond energy for the hydroxyl radical.
(a) 1165 (b) 837 (a) 223.18 kJ mol–1 (b) 423.38 kJ mol–1
(c) 865 (d) 815 (c) 513.28 kJ mol –1 (d) 113.38 kJ mol–1
40. A piston filled with 0.04 mol of an ideal gas expands DIRECTIONS for Qs. 46 to 50 : These are Assertion-Reason
reversibly from 50.0 mL to 375 mL at a constant temperature type questions. Each of these question contains two statements:
of 37.0ºC. As it does so, it absorbs 208 J of heat. The values Statement-1 (Assertion) and Statement-2 (Reason). Answer these
of q and w for the process will be: questions from the following four options.
(R = 8.314 J/mol K) (ln 7.5 = 2.01) (a) Statement-1 is True, Statement-2 is True, Statement-2 is a
(a) q = + 208 J, w = – 208 J (b) q = – 208 J, w = – 208 J correct explanation for Statement-1
(c) q = – 208 J, w = + 208 J (d) q = + 208 J, w = + 208 J (b) Statement-1 is True, Statement-2 is True Statement-2 is
41. Four grams of graphite is burnt in a bomb calorimeter of heat NOT a correct explanation for Statement-1
capacity 30 kJ K–1 in excess of oxygen at 1 atmospheric
(c) Statement - 1 is True, Statement-2 is False
pressure.The temperature rises from 300 to 304 K. What is
the enthalpy of combustion of graphite (in kJ mol–1)? (d) Statement -1 is False, Statement-2 is True
(a) 360 (b) 1440 [Kerala PMT 2011] 46. Statement 1 : Many endothermic reactions that are not
(c) –360 (d) –1440 spontaneous at room temperature become spontaneous at
42. The enthalpy change for reaction high temperature.
Statement 2 : Entropy of the system increases with increase
1 3
X 2 ( g ) + Y2 ( g ) ® XY3 ( g ) is – 50 kJ mol–1. If the in temperature. [AIIMS 2013]
2 2 47. Statement 1 : For an isothermal reversible process Q = –W
bond enthalpies of X–X and X–Y are respectively 380 and i.e. work done by the system equals the heat absorbed by
150 kJ mol–1 the bond enthalpy of Y–Y in kJ mol–1 is the system.
(a) 35 (b) 210 [Kerala PMT 2013] Statement 2 : Enthalpy change (DH) is zero for isothermal
(c) 280 (d) 140 process. [AIIMS 2013]
43. Consider the following spontaneous reaction 48. Statement 1 : The mass and volume of a substance are the
2C8 H18 ( g ) + 25 O 2 ( g ) ® 16CO 2 ( g ) + 18H 2O ( g ) extensive properties and are proportional to each other.
The sign of DH, DS, DG would be respectively Statement 2 : The ratio of mass of a sample to its volume is
(a) +, –, + (b) –, + , – [Kerala PMT 2013] an intensive property.
(c) +, +, – (d) –, –, – 49. Statement 1 : Internal energy is an extensive property.
44. One mole of solid iron was vaporized in an oven at its boiling Statement 2 : Internal energy depends upon the amount of
point of 3433 K and enthalpy of vaporization of iron the system.
is 344.3 kJ mol–1 . The value of entropy vaporization 50. Statement 1 : Absolute value of internal energy of a
(in J mol–1) of iron is [Kerala PMT 2013] substance cannot be determined.
(a) 100 (b) 10
Statement 2 : It is impossible to determine exact values of
(c) – 100 (d) 110
constitutent energies of the substances.

Exemplar Questions (b) There is an exchange of energy as well as matter

1. Thermodynamics is not concerned about
(a) energy changes involved in a chemical reaction
(b) the extent to which a chemical reaction proceeds
(c) the rate at which a reaction proceeds
(d) the feasibility of a chemical reaction
2. Which of the following statement is correct?
(a) The presence of reacting species in a covered beaker
is an example of open system.
between the system and the surroundings in a closed
system.
(c) The presence of reactants in a closed vessel made up
of copper is an example of a closed system.
(d) The presence of reactants in a thermos flask or any
other closed insulated vessel is an example of a closed
system.
 EBD_7753
138 CHEMISTRY

3. The state of a gas can be described by quoting the (a) DS (system) decreases but DS (surroundings) remains
relationship between the same
(a) pressure, volume, temperature (b) DS (system) increases but DS (surroundings) decreases
(b) temperature, amount, pressure (c) DS (system) decreases but DS (surroundings) increases
(c) amount, volume, temperature (d) DS (system) decreases but DS (surroundings) also
(d) pressure, volume, temperature, amount decreases
4. The volume of gas is reduced to half from its original volume. 10. On the basis of theromochemical equations (1), (2) and (3),
The specific heat will be find out which of the algebraic relationships given in options
(a) reduce to half (b) be doubled (a) to (d) is correct
(c) remain constant (d) increase four times 1. C (graphite) + O2 (g) ® CO2 (g); DrH = x kJ mol–1
5. During complete combustion of one mole of butane,
1
2658 kJ of heat is released. The thermochemical reaction for 2. C (graphite) + O (g) ® CO (g); DrH = y kJ mol–1
above change is 2 2

(a) 2C4 H10 ( g ) + 13O 2 ( g ) ® 8CO 2 ( g ) + 10H 2O ( l ) ; 3. CO (g) +

1
O (g) ® CO2 (g); DrH = z kJ mol–1
2 2
D c H = -2658.0 kJ mol -1 (a) z = x + y (b) x = y – z
(c) x = y + z (d) y = 2z – x
13
(b) C4 H10 ( g ) + O 2 ( g ) ® 4CO2 ( g ) + 5H 2 O ( l ) ; 11. Consider the reactions given below. On the basis of these
2 reactions find out which of the algebraic relationship given
D c H = -1329.0 kJ mol -1 in options (a) to (d) is correct?
1. C (g) + 4 H (g) ® CH4 (g); DrH = x kJ mol–1
13 2. C (graphite) + 2H2 (g) ® CH4 (g); DrH = y kJ mol–1
(c) C4 H10 ( g ) + O 2 ( g ) ® 4CO2 ( g ) + 5H 2 O ( l ) ;
2 (a) x = y (b) x = 2y
(c) x > y (d) x < y
D c H = -2658.0 kJ mol -1 12. The enthalpies of elements in their standard states are taken
as zero. The enthalpy of formation of a compound
13
(d) C4 H10 ( g ) + O 2 ( g ) ® 4CO2 ( g ) + 5H 2 O ( l ) ; (a) is always negative
2 (b) is always positive
D c H = +2658.0 kJ mol -1 (c) may be positive or negative
(d) is never negative
6. DfU° of formation of CH4 (g) at certain temperature is
13. Enthalpy of sublimation of a substance is equal to
–393 kJ mol–1. The value of DfH° is
(a) enthalpy of fusion + enthalpy of vaporisation
(a) zero (b) < DfU°
(b) enthalpy of fusion
(c) > DfU° (d) equal to DfU°
(c) enthalpy of vaporisation
7. In an adiabatic process, no transfer of heat takes place
(d) twice the enthalpy of vaporisation
between system and surroundings. Choose the correct
14. Which of the following is not correct?
option for free expansion of an ideal gas under adiabatic
(a) DG is zero for a reversible reaction.
condition from the following.
(b) DG is positive for a spontaneous reaction.
(a) q = 0, DT ¹ 0, W = 0 (b) q ¹ 0, DT = 0, W = 0
(c) DG is negative for a spontaneous reaction.
(c) q = 0, DT = 0, W = 0 (d) q = 0, DT < 0, W ¹ 0
(d) DG is positive for a non-spontaneous reaction.
8. The pressure-volume work for an ideal gas can be calculated
Vf
NEET/AIPMT (2013-2017) Questions
by using the expression W = - ò pex dV. The work can also 15. When 5 litres of a gas mixture of methane and propane is
Vi
perfectly combusted at 0°C and 1 atmosphere, 16 litre
of oxygen at the same temperature and pressure is
be calculated from the pV-plot by using the area under the consumed. The amount of heat released from
curve within the specified limits. When an ideal gas is this combustion in kJ (DHcomb (CH4) = 890 kJ mol –1,
compressed (a) reversibly or (b) irreversibly from volume Vi DHcomb (C3H8) = 2220 kJ mol–1) is
to Vf . Choose the correct option. [NEET Kar. 2013]
(a) W (reversible) = W (irreversible) (a) 32 (b) 38
(b) W (reversible) < W (irreversible) (c) 317 (d) 477
(c) W (reversible) > W (irreversible) 16. Three thermochemical equations are given below:
(d) W (reversible) = W (irreversible) + pex.DV (i) C(graphite) + O2(g) ® CO2(g); DrH° = x kJ mol–1
9. The entropy change can be calculated by using the 1
(ii) C(graphite) + O (g) ® CO(g); DrH° = y kJ mol–1
q 2 2
expression DS = rev . When water freezes in a glass beaker,,
T 1
choose the correct statement amongst the following. (iii) CO(g) + O (g) ® CO2(g); DrH° = z kJ mol–1
2 2
 Thermodynamics 139

Based on the above equations, find out which of the 19. The correct thermodynamic conditions for the spontaneous
relationship given below is correct? [NEET Kar. 2013] reaction at all temperatures is [2016]
(a) x=y–z (b) z = x + y (a) DH < 0 and DS = 0 (b) DH > 0 and DS < 0
(c) x=y+z (d) y = 2z – x (c) DH < 0 and DS > 0 (d) DH < 0 and DS < 0
17. For the reaction : [2014] 20. For a given reaction, DH = 35.5 kJ mol-1 and DS = 83.6 JK-1
X2O4(l) ® 2XO2(g) mol-1. The reaction is spontaneous at : (Assume that DH and
DS do not vary with tempearature) [2017]
DU = 2.1 k cal, DS = 20 cal K–1 at 300 K
(a) T > 425 K (b) All temperatures
Hence DG is:-
(c) T > 298 K (d) T < 425 K
(a) 2.7 k cal (b) – 2.7 k cal
21. A gas is allowed to expand in a well insulated container
(c) 9.3 k cal (d) – 9.3 k cal
against a constant external pressure of 2.5atm from an initial
18. The heat of combustion of car bon to CO 2 is volume of 2.50 L to a final volume of 4.50L. The change in
–393.5 kJ/mol. The heat released upon formation of 35.2 g of internal energy DU of the gas in joules will be:- [2017]
CO2 from carbon and oxygen gas is [2015 RS] (a) – 500J (b) – 505J
(a) –315 kJ (b) +315kJ (c) + 505J (d) 1136.25J
(c) –630 kJ (d) –3.15 kJ
 EBD_7753
140 CHEMISTRY

Hints & Solutions

EXERCISE - 1 = D H – (1 – 3)RTT
= D H + 2RT = 890 + 2RT T
1. (c) Ag + (aq) + NaCl(aq) ¾¾
® AgCl(s) + Na + (aq)
D
Hence E > H D
The precipitation reaction is spontaneous and hence Option (d) is correct.
DG P,T < 0 . 14. (c) DH = DE + nRT
2. (b) 1 calorie = 4.184 joule Dn = 3 – (1 + 5) = 3 – 6 = –3
3. (d) DH = DE + P DV DH - DE = (-3RT )
For isochoric process, DV = 0 15. (b) W = – pDV = -3(6 - 4) = -6 litre atmosphere
\ DH = DE = -6 ´101.32 = -608 J
4. (d) As DH = DE + DngRT
16. (c) Given Cp = 75 JK–1 mol–1.
if np < nr; D ng = np – n r = – ve
100
Hence D H < D E n= mole , Q = 1000 J DT = ?
18
5. (c) 107 erg = 1 Joule, 1 cal = 4.183 J
Hence calorie is the largest amount of energy.
Q = nCpDT Þ DT = 1000 ´ 18 = 2.4 K
6. (b) D ng = 2 – 4 = – 2, D H = D E – 2RT.T. 100 ´ 75
7. (d) Heat energy is absorbed during endothermic reaction. In 17. (d) We know that DH = DE + DngRT
all the given reactions, heat is absorbed during reaction. In the reaction, H2(g) + Br2(g) ® 2HBr(g)
\ All of them are endothermic reactions. Dn = np – nr = 2 – 2 = 0
8. (b) When a chemical bond is formed between the two free So, DH = DE for this reaction
atoms in a gaseous state to form a molecular product in a 18. (d) Combustion is heating of substance in excess of oxygen
gaseous state, some heat is always evolved which is so as to form carbon bioxide and water. Sometimes water
known as bond energy. Hence, there is increase in energy. is not formed during combustion.
9. (a) The Gibb’s free energy is zero at equilibrium because the
rate of backward reaction is equal to the rate of forward 19. (c) W = -PDV = -105 (1 ´ 10 -2 - 1 ´ 10-3 ) = -900J
reaction. 20. (b) DH = DU + DnRT for N 2 + 3H 2 ¾
¾® 2 NH 3
Hence, option (a) is correct. Dng = 2 – 4 = – 2
10. (d) DH = DU + Dn(g) RT ; Dn(g) = 1 in (d); Dn(g) = 0 in \ D H = D U - 2 RT or D U = D H+ 2R T \ D U > D H
other cases. 1
21. (d) C( s) + O 2 ( g ) ¾¾® CO (g)
11. (b) For an isothermal process DE = 0 2
12. (a) Internal energy is dependent upon temperature and 1 1
according to first law of thermodynamics total energy of [ Dn = 1 - = ]
2 2
an isolated system remains same, i.e., in a system of
constant mass, energy can neither be created nor 1 -1
DH – DU = DnRT = ´ 8.314 ´ 298 = 1238.78 J mol
destroyed by any physical or chemical change but can 2
be transformed from one form to another 22. (c) DH = nCp DT solution; since DT = 0 so, DH = 0
DE = q + W 23. (a) DG = DH - T DS
For closed insulated container, q = 0, so, DE = + W, as 0 = 132.6 × 1000 – T × 66
work is done by the system 132.6 ´ 1000
T= = 2000K
13. (d) CH 4 (g) + 2O 2 (g) ¾¾® CO 2 (g) + 2H 2 O 66
(1) (2) (1) 24. (b) A( g ) + 2B( g ) ¾¾
® 2C( g ) + 3D( g )
D H = 890 kJ (given) Dn = 5 - 3 = 2
By Ist law of thermodynamics
DH = DE + nRT or DE = DH - nRT
D H = D E + D nRT T = 19 – 2 × 2 × 10–3 × 300 = 17.8 kcal
Where,
D H = change in enthalpy of reaction 25. (a) DH = -2.5 ´ 103 Cals ; DS = 7.4Cals deg -1
D E = change in internal energy of reaction Now, DG = DH - TDS
D n = change in number of gaseous moles. -
= -2.5 ´ 10 3 - 298 ´ 7.4 = -4705.2 = - ve
= ( nP - n R )
As, DG is negative so, reaction is spontaneous.
According to question,
26. (c) In isolated system neither exchange of matter nor
Þ D E = D H – D nRT T exchange of energy is possible with surroundings.
 Thermodynamics 141

27. (b) Given C + O2 ® CO 2 , DH º = -x kJ ....(i)

2CO2 ® 2CO + O2 DH º = + y kJ … (ii) 36. (a) + H2 ¾
¾® ; DH = – 119.5 kJ
or CO2 ® CO + 1/ 2O2 , DH º = + y / 2 kJ ...(iii)
By adding no. (i) and (iii) eq. + 3 H2 ¾ ; DH = 3(– 119.5)
¾®
1
C + O2 + CO 2 ¾¾
® CO 2 + CO + O 2 = – 348.5 kJ
2
The resonance energy provides extra stability to the
1 y - 2x benzene molecule so it h as to be overcome for
C + O2 ¾¾ ® CO , DH º = y / 2 - x = kJ
2 2 hydrogenation to take place. So DH = – 358.5 – (–150.4)
28. (b) M.W. of ethane (C2H6) = 30 gm. = –208.1 kJ
M.W. of acetylene (C2H2) = 26 gm. 37. (c) Standard heat of formation of a substance is amount of
Heat evolved per gm of ethane heat evolved or absorbed when one mole of substance is
341 formed from its elements in their standard states. Since
= = 11.36 cal/gm. standard state of carbon and hydrogen are graphite and
30
Heat evolved per gm of acetylene gaseous H2 respectively. Hence standard heat of
formation of methane is given by
310
= = 11.92 cal/gm C( graphite) + 2H 2 ( g ) ® CH 4 ( g )
26
So, acetylene is better fuel. 38. (a) Dissolution of NaOH in water is an exothermic reaction
as indicated by negative value of enthalpy leading to
1 increase in temperature.
29. (c) SO 2 + O2 ¾
¾® SO 3
2 T1 - T2 200
39. (b) Efficiency of engine = = = 0.4
DH = DH of (SO ) - DH fo (SO ) T1 500
3 2
= –98.2 + 298.2 = 200 kJ/mole é ù é ù
40. (b) DH = S ê DH f° products ú -S ê DH f° reactants ú
30. (a) 2H 2 O 2 (l ) ¾¾
® 2H 2O(l ) + O 2 ( g ) DH = ? ë û ë û

DH = [2´DH f of H 2O(l ) + (DHf of O2 ) DH° = [DH f° (CO)(g) + DH f° (H 2O)(g)] –

-(2´DHf of H 2O2 (l ))]
[DH f° (CO 2 )(g) + DH f° (H 2 )(g)]
= [(2 ´ -286) + (0) - (2 ´ -188)]
= [– 110.5 + ( – 241.8)]– [– 393.5 + 0] = 41.2
= [-572 + 376] = -196 kJ / mole 41. (b) C 2 H 4 + 3O 2 ® 2CO 2 + 2H 2O.
31. (d) C(dia ) + O 2 ¾
¾® CO 2 .....(i) DH = -395.4 kJ/mole Change in enthalpy,
DH = DH products - DH reactants
C(gr ) + O 2 ¾
¾® CO 2 .....(2) DH = -393.5 kJ/mole
= 2 ´ (-394) + 2 ´ (-286) - (52 + 0) = – 1412 kJ/ mol.
(ii) – (i), C( gr ) - C(dia ) ¾
¾® O
42. (d) Q = mL
C(gr ) + ¾
¾® C(dia ) where L = latent heat of vapourisation of water
= 2260 kJ/kg
DH = -393.5 + 395.4 kJ/mole = + 1.9 kJ/mole. = 2260 × 103 J/kg
1 Q = 70 × 10–3 × 2260 × 103 = 158155 Joule
32. (c) Energy absorbed µ 43. (d) 13.7 kcal = 57 kJ = 5.7 × 104 J.
stability of compound
Energy released µ stability of compound p1
Thus, the order of stability is 44. (c) Work done by a gas = 2.303RT log
p2
142.2 > 25.9 > – 46.2 > – 393.2
i.e.. O3 > HI > NH3 > CO2 10
= 2.303 ´ 8.314 ´ 300 ´ log
33. (d) H 2 ( g ) + Br2 ( g ) ® 2HBr( g ) 1
DHº = (BE)reactant – (BE) product = 2.303 ´ 8.314 ´ 300 = 5744.1Joule
= (433 + 192) - (2 ´ 364) = 625 – 728 = – 103 kJ
H
34. (c) As MgO is a weak base hence some energy got
consumed to break MgO (s). Hence enthalpy is less than 45. (a) N º N + 3H – H 2N – H
–57.33 kJ mol–1. 945 + 3 × 436
H
ˆˆ† 2AB
35. (c) A 2 + B2 ‡ˆˆ absorbed energy 2 × (3× 391) = 2346
There is no change in volume so pressure will have no
Energy released
effect on it. As the reaction is endothermic ( DH is
positive), high temperature favours the forward reaction. DH = 2253 – 2346 = – 93 kJ
 EBD_7753
142 CHEMISTRY

46. (d) eq. (i) + eq. (ii) find the required result and divide by 2. DH v 9710
47. (b) Eq. (b) shows largest phase change i.e., gas ¾¾ ® solid Using DS = = cal mol–1 K –1
48. (b) Maximum work done by a system at constant pressure T 373
and constant temperature is –DG. If can be derived as = 26.032 cal mol –1 K–1
follows : 56. (c) Conversion of graphite into diamond is an endothermic
From first law of thermodynamics, reaction. But DS would be negative for the conversion
q = DE + wexp. + wnon exp. of graphite into diamond. Diamond has more compact
At constant pressure, wexp = PDV structure so the volume is smaller. However, the atoms in
q = DE + PDV + wnon-exp. graphite are able to move with in their lattice so the entropy
q = DH + wnon exp. ....... (1) is higher.
For the reversible change at const temp., 57. (d) Given reactions are

q rev 1
DS = or qrev = TDS M + O2 ® MO + 351.4 kJ ...(i)
T 2
so from equ. (1), TDS = DH + wnon exp. 1
X + O 2 ® XO + 90.8 kJ ...(ii)
Þ DH – TDS = –wnon exp. ...... (2) 2
For a change taking place under constant pressure and Subtracting equation (ii) from (i), we get
constant temperature, M + XO ® MO + X + (351.4 – 90.8) k J
DH – TDS = DG or DH = (351.4 – 90.8) k J
so from equ (2) = 260.6 k J
DG = –wnon exp. 58. (b) Follow II law of thermodynamics.
(it means wnon exp. or wuseful)
or wmax = –DG 59. (b) Let, C(s) + O2 (g) ¾¾
® CO2(g);
49. (c) When gas is compressed its entropy decreases so, DS is DH = R .......... (i)
negative. 1
50. (c) According to Gibb's – Helmholtz equation and CO(g) + O 2 (g) ¾¾ ® CO2(g);
2
DG = DH – TDS DH = S .......... (ii)
Þ TDS = DH – DG Subtracting equ. (i) from equ (ii), we get
1 1
Þ DS = [DH – DG] C(s) + O2(g) – CO(g) – O 2 (g) ¾¾
®
T 2
51. (c) Latent heat of vaporisation of water CO2(g) – CO2(g); DH = R – S
= 540 cal g–1
\ latent heat of vaporisation for 1 mol of water = 540 × 1
or C(s) + O 2 (g) ¾¾® CO (g); DH = R – S
18 cal = 9720 cal 2
Thus DHvap. = 9720 cal mol–1 Hence, heat of formation of CO = R – S
and T = 100°C = 373 K 60. (a) Measure of disorder of a system is nothing but entropy.
For a spontaneous reaction, DG < 0. As per Gibbs
DH vap 9720 Helmholtz equation,
and DS = = cal mol–1 K–1
T 373 DG = DH – TDS
» 26.6 cal mol–1 K–1 Thus DG is –ve only
When DH = –ve (exothermic)
Latent heat of fusion DH and DS = +ve (increasing disorder)
52. (a) DS = =
Melting point T 61. (d) For the reaction,
H2 + Cl2 ¾ ¾® 2HCl
2930 DH for HCl = – 90 kJ
= J K–1 mol–1 = 9.77 J K–1 mol–1
300 for 2 HCl = – 180 kJ
53. (d) For isothermal reversible expansion DH = S(bond enersies of reactants)
– S(bond energies of product)
V2
w = q = nRT´2.303 log Þ –180 kJ = (B.E.H–H + B.ECl–Cl) – 2BEH–Cl
V1 Þ – 180 kJ = (430 kJ + 240 kJ) – 2 B.E.HCl
20 Þ 2 B.E.HCl = 670 kJ + 180 kJ = 850 kJ
= 2 RT ´ 2.303 log
2 850
Þ B.EH-Cl = kJ = 425 kJ
= 2 × 2 × T × 2.303 × 1 = 9.2 T 2
So, the H – Cl bond energy is 425 kJ mol–1
q 9.2T
Entropy change, DS =
= = 9.2 cal. 62. (d) D G is negative for a spontaneous process.
T T
63. (c) As all reactants and products are liquid D n (g ) = 0
54. (a) For a spontaneous process, DS total is always positive
DH = DE - DnRT
55. (b) Given DHv = 9710 cals mol–1
T = 100°C = 373 K DH = DE (Q Dn = 0)
 Thermodynamics 143

64. (a) Entropy is a measure of randomness of the system which 3000

is highest in gases. So, entropy of hydrogen is highest Change in temperature = K = 150 K
among the given options. 20
65. (c) As we know that, Initial temperature = 300 K
DH = nCpDT (where n is no. of moles) Since the gas expands so the temperature decreases and
thus, final temperature is
28 150 K (300 – 150 = 150)
= ´ 7 ´ (373K - 273K)
14 76. (b) Bond dissociation energy of PH3(g)
= 2 × 7 × 100 J = 1400 J = 228 kcal mol–1
66. (d) We know that, DG = DH – TDS 228
When the reaction is in equilibrium, DG = 0 P – H bond energy = = 76 kcal mol -1
3
DH H H
0 = DH - T DS Þ T =
DS P—P
30 ´ 1000 H H
T= = 285.7 K Bond energy of 4 (P – H) + (P –P)
105
67. (a) DG = DH – TDS = 355 kcal mol–1
or 4 × 76 + (P – P) = 355 kcal mol–1
= 177.9 – (298 × 160.4/1000) = 177.9 – 47.79 = + 130.1kJ
68. (c) For spontaneous cooling of hot metal rod in air DSsystem P–P bond energy = 51 kcal mol–1
decreases (as metal rod cools down ) and DSair increases 77. (d) Dn = DE + PDV
(as surrounding air becomes hot). So, DSsystem < 0 and Now PV = nRT
DSuniverse > 0. where n = no of gaseous moles.
69. (b) For combustion reaction, DH is negative, From this we derive
Dn = (16 + 18) – ( 25 + 2 ) = +7, so DS is + ve, reaction is DH = DE + Dn g RT
spontaneous, hence DG is –ve. Dng = n2 – n 1
70. (b) where n1 = no of moles of gaseous reactant
71. (d) Isobutylene on combustion gives CO2 and H2O as shown n2 - no of moles of gaseous moles product
below : For the reaction,
CH3 2NH3(g) ¾¾
® N2(g) + 3H2 (g)
|
Dn g = 4 - 2 = 2.
CH3 - C = CH 2 (g) + 6O2 (g) ¾¾®
isobutylene Hence,
D H - D E = D n g R T = 2 × 8.314 × (273 + 27)
4CO2 (g) + 4H 2O(l)
Here Dng = 4 – 7 = – 3 < 0 = 2 × 8.314 × 300
Using IInd law of thermodynamics, 1 1
78. (b) H 2 + Cl 2 ¾¾ ® HCl
DH = DE + DngRT 2 2
DH = (DE) + (–ve term)
Þ DH < DE
D f H HCl = å B.E. of reactants
72. (c) Q DG = DH - T × DS - å B.E. of products
For a spontaneous reaction DG should be negative
DH = – 238 kJ, DS = – 87 JK –1 1 1
-90 = ´ 430 + ´ 240 - B.E. of HCl
Hence, reaction will be spontaneous when DH > T × DS . 2 2
Therefore, at 1000, 1500 and 3000 K the reaction would be \ B.E. of HCl = 215 + 120 + 90
spontaneous. = 425 kJ mol–1
15 79. (d) We know that heat (q) and work (w) are not state functions
73. (c) C6 H 6 + O2 ¾¾ ® 6CO2 + 3H 2O but (q + w) is a state function. H – TS (i.e. G) is also a state
2
function. Thus II and III are not state functions so the
1 mole º 3250 KJ correct answer is option (d).
0.39 0.39
80. (d) H 2O ( l) ‡ˆˆˆ
mole º 3250 ´ = 16.25 kJ 1atm
ˆˆˆˆ†
ˆ H2O(g)
78 78
74. (d) By 2× (ii) – (i) + (iii) DH = 40630 J mol –1
H2(g) + 2C(s) ® C2H2(g), DG° = 209 kJ DS = 108.8 JK–1 mol –1
75. (b) Since the gas expands adiabatically (i.e., no change in DG = DH - T DS When DG = 0, DH - T DS = 0
enthalpy) so the heat is totally converted into work.
For the gas CV = 20 J/K. Thus, 20 J of heat is required for DH 40630 J mol-1
1° change in temperature of the gas. T = DS = 108.8 Jk -1 mol-1 = 373.4 K.
Heat change involved during the process (i.e., work done)
= 3 kJ = 3000 J \ Correct choice : (d)
 EBD_7753
144 CHEMISTRY

81. (a) Fe2O3(s) + 3CO(g) ¾¾ ® 2Fe(s) + 3CO2(g) ; 954

DH = –26.8 KJ ...(i) = = 318 kJ mol -1
3
FeO(s) + CO(g) ¾¾ ® Fe(s) + CO2(g) ;
In P2H4(g), energy of 1 P – P bond + 4 P – H bonds
DH = –16.5 KJ ...(ii)
eq. (i) – 2 × eq. (ii), we get = 1485 kJ mol–1
Q Energy of 1 P – H bond = 318 kJ mol–1
Fe2O3(s) + CO(g) ¾¾ ® 2FeO(s)+ CO2(g)
\ Energy of 4 P – H bond = 318 × 4
D H = –26.8 + 33.0 = + 6.2 kJ = 1272 kJ mol–1
82. (a) Ideal gas during spontaneous expansion into vacuum Thus, the P – P bond energy = 1485 – 1272
does not do any external work.
= 213 kJ mol–1
83. (d) Given DH = 30 kJ mol–1 T = 273 + 27 = 300 K
91. (d) A process is spontaneous only when there is decrease in
DH T 3 ´ 10 4 the value of free energy, i.e., DG is –ve.
DST = = J mol–1
T 300 92. (d) Raking up leaves into a thrash bag results in decrease
= 100 J mol–1 K–1 in randomness i.e. decrease in entropy.
84. (c) Given 93. (b) According to Gibb's equation,
4H( g ) ¾¾ ® 2H 2 ( g ); DH = -869.6 kJ DG = DH – TDS
or 2H 2 ( g ) ¾¾ ® 4H( g ); DH = 869.6 kJ Since reaction is at equilibrium
\ DG = 0, \ DH = TDS
869.6 DH = 21.3 kJ = 21300 J.
H 2 ( g ) ¾¾
® 2H( g ); DH = = 434.8 kJ
2 T = 82ºC = (82 + 273) K = 355 K.
On substituting these values,
DH 1.435 ´ 103
85. (c) DS = = = 5.260 cal / molK DH 21300 –1
T 273 DS = = = 60.0JK –1 mol .
T 355
5 94. (d) Lesser the bond length higher is the bond energy.
R
CP 2 5 H—H bond energy is the highest.
86. (d) = = = 1.67
CV 3 R 3 Bond energy
2 Bond Bond length
(kJ) mol -1
87. (b) Spontaneity of reaction depends on tendency to acquire H—H 0.74 435.1
minimum energy state and maximum randomness. For a F—F 1.42 154.8
spontaneous process in an isolated system the change Cl—Cl 1.99 242.7
in entropy is positive. Br—Br 2.28 192.5
I—I 2.26 149.0
88. (b) N 2 + 3H 2 ¾¾ ® 2NH 3 DH = 2 ´ -46.0 kJ mol–1
95. (d) Since the process is at equilibrium DG = 0 for DG = 0,
Let x be the bond enthalpy of N – H bond then
they should be DH > 0, DS > 0.
[Note : Enthalpy of formation or bond formation enthalpy
96. (a) DHsol = DHlattice + DHhydration
is given which is negative but the given reaction involves
bond breaking hence values should be taken as positive.] DHlattice = DHsol – DHhydration
DH = S Bond energies of reactants – S Bond energies 4 – (– 784) = DHlattice Þ DHlattice = + 788
of products 97. (b) Work done in reversible isothermal expansion
2 × – 46 = 712 + 3 × (436) – 6x V2
W = –2.303nRT log
– 92 = 2020 – 6x V1
6x = 2020 + 92 25
6x = 2112 = –2.303 × 0.2 × 8.314 × 300 log
2.5
x = + 352 kJ/mol = –2.303 × 0.2 × 8.314 × 300 = – 1148
89. (b) C2H5 OH(l) + 3O 2 ( g ) ® 2CO 2 ( g ) + 3H 2O(l) 98. (c) DS has negative value if number of gaseous moles
decreases during a reaction, Dng = –ve
Dng = 2 - 3 = -1 For the reaction
DU = DH - Dng RT 2SO2 + O2 ® 2SO3
Dng = 2 – 3 = –1
8.314 99. (d) DG = DH – TDS
= -1366.5 - ( -1) ´ ´ 300
103 For a reaction to be spontaneous,
DH = –ve, DS = +ve
8.314
= -1366.5 + (1) ´ ´ 300 at all temperatures.
103 but at high temperature, DG = D { H-T{DS
= – 1366.5 + 0.8314 × 3 = – 1364 .006 kJ - ve + ve
90. (a) In PH3(g), energy required to break 3 P–H bonds Thus the second term will have high positive value
= 954 kJ mol–1 and reaction will be non-spontaneous.
\ Energy required to break 1 P – H bond 100. (d) Gibb’s-Helmholtz equation is
DG = DH – TDS
 Thermodynamics 145

For a reaction to be non-spontaneous at all C( s ) + 2H 2 ( g ) ¾ ¾

® CH 4 ( g )
temperatures, DH should be +ve and DS should be –ve Hence, dissociation energy of hydrogen and enthalpy
\ DG = +ve – T × (–ve); the value of DG is always of sublimation of carbon is required.
positive for such a reaction and hence it will be non- 11. (a) I 2 ( s ) + Cl2 ( g ) ¾¾ ® 2ICl( g )
spontaneous at all temperatures. DrH = [DH(I2(s) ®I2(g)) + DHI–I + DHCl–Cl] – [DHI – Cl]
EXERCISE - 2 = 151.0 + 242.3 + 62.76 –2 × 211.3 = 33.46
1. (d) 33.46
2. (b) 1 M H2SO4 = 2g eq. of H2SO4. Df H°(ICl) = = 16.73 kJ / mol
2
1
Hence y = 2x or x = y.. 12. (c) Given NaOH + HNO3 ® NaNO3 + H 2O
2 1 mol 1 mol DH = 57.0 kJ
3. (b) Hydration energy of Cl+ is very less than H+ hence it 0.2 mol 0.5 mol DH = ?
doesn’t form Cl+ (aq) ion. Given heat of neutralisation of strong acid by strong base
4. (b) For the reaction = 57.0 kJ
2 ZnS ® 2 Zn + S2 ; DG1º = 293 kJ ..........(1) Q 0.2 mole NaOH is limiting reagent.
2 Zn + O2 ®2 ZnO ; DG2º = –480 kJ ..........(2) \ Heat of neutralization = 0.2 × 57 = 11.4 kJ
S2 + 2 O2 ®2 SO2 ; DG3º = –544 kJ .........(3) 13. (a) No. of moles of hydrogen
DGº for the reaction
2 ZnS + 3 O2 ®2 ZnO + 2 SO2 Mass 4
= = = 2 moles
can be obtained by adding eqn. (1), (2) and (3) Molecular mass 2
Þ DGº = 293 – 480 – 544 = – 731 kJ Given 2H 2 ( g ) ® 4H( g ), DH = 208 kcal
5. (b) A ¾¾ 4g
® B, DH = + 24 kJ / mol
Þ HB – HA = + 24 ...(i) \ H ( g ) ® 2H( g ) DH = 104 kcal
2
B ¾¾ ® C, DH = – 18 kJ/mol 1 mol
Þ HC – HB = – 18 \ Bond energy of H–H bond is 104 kcal mol–1
or HB – HC = + 18 14. (a) Conc. of HCl = 0.25 mole
From Eqs. (i) and (ii), we have Conc. of NaOH = 0.25 mole
HC – HA = 6 ...(ii) Heat of neutralization of strong acid by strong base
\ HB > HC > HA = – 57.1 kJ
6. (d) CO 2 ¾¾
® C + O 2 , DH = 393J ...(i) HCl + NaOH ¾ ¾® NaCl + H2O – 57.1kJ
1 mole of HCl neutralise 1 mole of NaOH, heat evolved
2Zn + O 2 ¾¾ ® 2ZnO, DH = -412J ...(ii) = 57.1 kJ
By adding eq. (i) and (ii) we get \ 0.25 mole of HCl neutralise 0.25 mole of NaOH
\ Heat evolved = 57.1 × 0.25 = 14.275 kJ
2Zn + CO 2 ¾¾
® 2ZnO + C, DH = -19J
reversible path 15. (a) NaOH + HCl ¾¾ ® NaCl + H2O, DH = – 55.9 kJ
7. (c) Actually, heat of neutralisation of a strong acid by a strong
base means heat of formation of water.
A B Thus,
H + + OH - ® H 2O; DH = -55.9 kJ
irreversible path
or H 2 O ® H + + OH - ; DH = 55.9 kJ ..(i)
For a cyclic process the net change in the internal energy
is zero because the change in internal energy does not Given, HCN + OH - ® CN - + H 2 O; DH = -12.1kJ
depend on the path. …(ii)
8. (a) For spontaneous reaction, dS > 0 and dG should be Adding equations (i) and (ii), we get
negative i.e., < 0.
HCN ® H + + CN - ; DH = 55.9 - 12.1 kJ = 43.8 kJ
9. (d) X 2 + Y2 ¾ ¾® 2 XY , DH = 2(–200) kJmol–1
16. (b) DHS-S + 2DH H -S = 239 2DH H -S = 175
Let x be the bond dissociation energy of X2. Then
DH = -400 = Sx-x +S y-y - 2Sx-y Hence, DHS-S = 239 - 175 = 64 kcal mol -1

= x + 0.5x – 2x = -0.5x
Then, DH for 8S(g ) ® S8(g ) is 8 × (–64) = –512k cal
17. (b)
400 18. (a) For a pure substance TA and TB represent the same
or x = = 800 kJ mol -1
0.5 temperature. Hence A is a correct choice.
10. (c) The standard enthalpy of formation of CH4 is given by
the equation :
 EBD_7753
146 CHEMISTRY

19. (d) If n p < nr then Dn( g ) = n p - nr = ‘–’ve 27. (b) Given DH

1
Since DH = DE + DnRT A ¾¾ ®B + 150 ...(1)
2
\ DH = DE – some quantity [Q Dn is - tive] 3B ¾¾ ® 2C + D –125 ...(2)
or DH < DE E + A ¾¾ ® 2D +350 ...(3)
20. (d) This reaction shows the formation of H2O, and the – X2 To calculate DH operate
represents the enthalpy of formation of H2O because as 2 × eq. (1) + eq. (2) – eq. (3)
the definition suggests that the enthalpy of formation is DH = 300 – 125 – 350 = – 175
the heat evolved or absorbed when one mole of substance 28. (a) Since, in the first reaction value of Dn is positive.
is formed from its constituent elements. 1 1
21. (b) For the reaction Dn = 1 - = hence entropy will increase i.e.,
2 2
PCl5 ( g ) ƒ PCl3 ( g) + Cl2 ( g) Ds = +ve.
The reaction given is an example of decomposition
reaction and we know that decomposition reactions are C (gr.) + 1 O2(g) ® CO(g); DS° = + ve
endothermic in nature, i.e., DH > 0. 2
Since, DG° = DH° – TDS hence the value of DG decreases
Further
on increasing temperature.
Dn = (1+1) – 1= +1
Hence more number of gaseous molecules are present in 29. (d) H 2O (l) H 2O (g) DH = 40.66 KJmol–1
products which shows more randomness i.e., DS > 0 T = 373 K
(DS is positive) DE = DH – DnRT
22. (c) The reaction for formation of HCl can be written as = 40.66×103 Jmol–1–1× 8.314JK–1mol–1× 373 K
H2 + Cl2 ® 2HCI D E = 37558 J / mol
H – H + Cl – Cl ® 2 (H – Cl) D E = 37.56 kJ mol–1
Substituting the given values, we get enthalpy of 30. (a) DG° = DH° – TDS°
formation of For a spontaneous reaction DG° < 0
2HCl = ( 676 – 862) = –186 kJ. DH °
or DH° – TDS° < 0 Þ T >
-186 DS°
\ Enthalpy of formation of HCl = kJ = –93 kJ.
2 3
Þ T > 179.1 ´ 10 > 1117.9K » 1118K
23. (b) DG = DH – T D S 160.2
At equilibrium, DG = 0 31. (d) Given DH = 41 kJ mol–1 = 41000 J mol–1
Þ 0 = (170 × 103 J) – T (170 JK– 1) T = 100°C = 273 + 100 = 373 K
Þ T = 1000 K n=1
For spontaneity, DG is – ve, which is possible only if DU = DH – DnRT = 41000 – (1 × 8.314 × 373)
T > 1000 K. = 37898.88 J mol–1 ; 37.9 kJmol–1
24. (b) Enthalpy of reaction 32. (b)
= B.E(Reactant)– B.E(Product) 33. (a) Given, for reaction
® H + (aq.) + OH – ( aq.);
(i)H2O (l) ¾¾
= éë B.E (C= C) + 4 B.E.(C–H) + B.E.(H - H) ùû
DH r = 57.32 kJ
- éë B.E.(C - C) + 6 B.E.(C - H) ùû 1
(ii) H 2 ( g ) + O 2 ( g ) ¾¾ ® H 2 O(l );
= [606.1 + (4 × 410.5) + 431.37)] – [336.49 + (6 × 410.5)] 2
= –120.0 kJ mol–1 DH r = –286.20 kJ
1 3 For reaction (i)
25. (a) ΔS for the reaction X 2 + Y2 ƒ XY3
2 2
DH r = DH°f (H + .aq)+DH°f (OH – .aq)–
ΔS = 50 – (30 + 60) = – 40 J
DH°f (H2 O, l)
For equilibrium DG = 0 = DH – T DS
DH -30000 57.32 = 0 + DH°f (OH – , aq) – DH°f (H 2 O, l) …(iii)
T= = = 750 K
DS -40 For reaction (ii)
26. (d) DH r = DH°f (H 2 O, l) –
(1) Kp > 0 (iv) Spontaneous 1
(2) D G < R T ln Q (i) Non spontaneous DH°f (H 2 , g) – DH°f (O 2 , g )
2
(3) Kp = 0 (ii) Equilibrium
–286.20 = DH°f (H 2 O, l)
DH
(4) T> (iii) Spontaneous On replacing this value in eq. (iii) we have
DS
and endothermic 57.32 = DH°f (OH – , aq) – (–286.20)
 Thermodynamics 147

42. (d) The bond enthalpy of reaction =

DH°f (OH - , aq) = –286.20 + 57.32 = –228.88 kJ [Sum of bond enthalpies of reactants] –
34. (b) At equilibrium DG = 0 [Sum of bond enthalpies of products]
Hence, DG = DH – TeDS = 0 é1 3 ù 3
–50 = ê ´ 380 + ´ Y - Y ú - 3 ´ 150 = (Y - Y) - 260
DH ë2 2 û 2
\ DH = TeDS or Te < 210 ´ 2
DS Y-Y= = 140
3
For a spontaneous reaction 43. (b) 2C8 H18(g) + 25O 2(g) ¾¾® 16CO 2(g) + 18H 2O (g)
DG must be negative which is possible only if DH – TDS < 0
The given reaction is a combustion reaction. Hence
\ DH < TDS
this will be an exothermic reaction.
DH i.e. DH = –ve
or T > ; Te ; T
DS Further Dn = + ve i.e. DS = +ve
DG = DH – TDS = –DH – TDS = –ve
35. (d) 4NO 2 (g) + O 2 (g) ® 2N 2 O5 (g), D r H = – 111 kJ
D H 344.3 ´ 103
44. (c) DS = = = 100 J mol- 1
– 54 kJ T 3443
DH' 45. (b) We have to calculate the enthalpy of the reaction
2N 2 O5 (s) OH (g) ® O(g) + H(g)
From the given reactions, this can be obtained as follows.
– 111 – 54 = D H'
é1 1 ù
D H' = – 165 kJ – ê H 2 (g) + O2 (g) ® OH(g) ú ; DH = – 42.09 kJ mol–1
ë2 2 û
36. ˆˆ† B
(b) A ‡ˆˆ 1 1
DG° = D H° – TDS° + [H2(g) ® 2H(g)] ; DH = × 435.89 kJ mol–1
2 2
DG° = – 2.303 RTlog10 K 1 1
– 2.303 RT log10 K = DH° – TDS° + [O2(g) ® 2O(g)]; DH = × 495.05 kJ mol–1
2.303 RT log10 K = TDS° – DH° 2 2
Add
T DS ° - DH ° 298×10 +54.07×1000
log10 K = = OH(g) ® H(g) + O(g) ; DH = 423.38 kJ mol-1
2.303RT 2.303×8.314×298 46. (b) The factor TDS increases with increase in temperature.
= 9.998 » 10 47. (b) In an isothermal process change in internal energy (DE)
37. (a) Since, liquid is passing into gaseous phase so is zero (as it is a function of temperature).
entropy will increase and at 373 K during the phase \ According to first law of thermodynamics
transformation it remains at equilibrium. So, DG = 0. Q Q + W = DE. Hence Q = –W (if DE = 0)
38. (b) The species in its elemental form has zero standard If a system undergoes a change in which internal energy
molar enthalpy of formation at 298 K. At 298K, Cl2 is of the system remains constant (i.e. DE = 0) then
gas while Br2 is liquid. –W = Q. This means that work done by the system
39. (d) (i) 2C(s) + H2(g) ¾¾
® H – C º C – H(g) equals the heat absorbed by the system.
DH = 225 kJ mol–1 48. (b) The mass and volume depend upon the quantity of
matter so these are extensive properties while ratio of
(ii) 2C(s) ¾¾
® 2C(g) DH = 1410 kJ mol–1 mass to its volume does not depend upon the quantity
1410 of matter so this ratio is an extensive property.
C( s) ¾¾
® C( g )DH = = 705kJmol -1 49. (a) The properties whose magnitude depends upon the
2
quantity of matter present in the system are called
extensive properties eg, internal energy.
(iii) H2(g) ¾¾® 2H(g) DH = 330 kJ mol–1
50. (a) It is fact that absolute values of internal energy of
From equation (i) : substances cannot be determined. It is also true that it
is not possible to determine exact values of constitutent
225 = éë 2 ´ DHC(s) ¾¾
® C( g )
+ 1 ´ BE H – H ù
û energies of a substance.
- [2 ´ BE C – H + 1 ´ BECº C ] EXERCISE - 3
225 = [1410 + 1 × 330] – [2 × 350 + 1 × BEC º C]
225 = [1410 + 330] – [700 + BEC º C] Exemplar Questions
225 = 1740 – 700 – BEC º C 1. (c) Thermodynamics deals with the energy change,
BEC º C = 815 kJ mol–1 feasibility and extent of a reaction, but not with the
40. (a) Process is isothermal reversible expansion, hence rate and mechanism of a process.
DU = 0, therefore q = – W. 2. (c) For a closed vessel made of copper, there will be no
Since q = + 208 J, W = – 208 J exchange of matter between the system and the
M 12 surroundings but energy exchange can occur through
41. (c) DE = C × Dt × = 30 × 4 × = 360
m 4 its walls.
DE = – 360 kJ mol–1
 EBD_7753
148 CHEMISTRY

3. (d) The state of a gas can be described by quoting the 10. (c)
relationship between pressure, volume, temperature and (a) C (graphite) + O2 (g) ® CO2 (g); DrH = x kJ mol–1 …
amount. The ideal gas equation is (i)
PV = nRT
1
4. (c) Specific heat is an intensive property which depends (b) C (graphite) + O 2 (g) ® CO (g); D r H = y kJ mol –1
only on the nature of the gas. Hence, if the volume of 2
gas is reduced to half from its original volume the … (ii)
specific heat will remain constant. On subtracting eqn (i) & (ii) we get
5. (c) The complete combustion of one mole of butane is 1
represented by CO ( g ) + O 2 ( g ) ® CO 2 ( g ) ; Dr H = z kJ mol -1
2
13
C 4 H10 ( g ) + O 2 ( g ) ® 4CO2 ( g ) + 5H 2 O ( l ) Hence, x – y = z or x = y + z
2 11. (c) x > y because same bonds are formed in reaction (1)
Dc H should be negative and have a value of 2658 kJ and (2) but no bonds are broken in reaction (1) whereas
mol–1. in reaction (2) bonds in the reactant molecules are
6. (b) DfH° = DfU° + DngRT broken. As energy is absorbed when bonds are broken,
For the reaction, DfH° energy released in reaction (1) is greater than that in
C(s) + 2H2(g) ® CH4(g) reaction (2).
DfH° = 1 – 2 = –1 12. (c) Enthalpy of formation can be positive or negative.
\ DfH° = DU – 1 × RT For example :
\ DfH° < DfU° C+ O2 ® CO2 is exothermic whereas, C+ 2S ® CS2 is
7. (c) For free expansion, W = 0 ; and endothermic.
For Adiabatic process, q = 0 13. (a) Enthalpy of sublimation of a substance is equal to
According to first law of thermodynamics, enthalpy of fusion + enthalpy of vaporisation.
DU = q + W = 0 Sublimation is, direct conversion of solid to vapour.
Since there is no change in DU hence, temperature Writing in two steps, we have solid ® liquid ® vapour
change will be zero i.e., DT = 0 solid ® liquid requires enthalpy of fusion
8. (b) Area under the curve is always greater in irreversible liquid ® vapour requires enthalpy of vaporisation
compression than that in reversible compression which
14. (b) DG gives a criterion for spontaneity at constant
can be seen from given figure.
pressure and temperature.
(i) If DG is negative (< 0), the process is spontaneous.
(ii) If DG is positive (> 0), the process is non-
spontaneous.
P
(iii) If DG is zero then reaction is at equilibrium.

NEET/AIPMT (2013-2017) Questions

Vf Volume (V) Vi 15. (c) CH 4 + 2O 2 ¾® CO2 + 2H2O

x 2x
Irreversible compression
C3 H8 + 5O 2 ¾® 3CO2 + 4H2O
(5- x ) 5(5- x )
2x + 5(5– x) = 16
P Þ x = 3L
\ Heat released
3 2
= ´ 890 + ´ 2220 = 317
22.4 22.4
Vf Volume (V) Vi 16. (c) Applying Hess’s law, equation (i) can be obtained by
Reversible compression adding equations (ii) and (iii).
9. (c) During the process of freezing, energy is released which \ x =y+ z
is absorbed by the surroundings. 17. (b) Given DU = 2.1 k cal., DS = 20 cal. K– 1
- q rev T = 300 K
\ DSsys =
T Q DH = DU + DngRT
q rev Putting the values given in the equation
DSsurr = i.e., on freezing, entropy of the system
T
decreases and of surrounding increases.
 Thermodynamics 149

which is possible only if

2
DH = 2.1 + 2 ´ ´ 300 DH < 0 and DS > 0
1000 \ spontaneous at all temperatures.
= 2.1 + 1.2 = 3.3 k cal. 20. (a) Given DH 35.5 kJ mol–1
Now, DG = DH – TDS DS = 83.6 JK–1 mol–1
20 Q DG = DH – TDS
= 3.3 - 300 ´ = - 2.7 k cal For a reaction to be spontaneous, DG = –ve
1000
18. (a) C + O2 ® CO2 + 393.5 kJ/mol i.e., DH < TDS
12g 44g DH 35.5 ´ 103 Jmol -1
\ T> =
44g is formed from 12g of carbon DS 83.6 JK -1
So, th e given reaction will be spontan eous at
12 ´ 35.2
35.2g is formed from g of C T > 425 K
44 21. (b) The system is in isolated state.
= 9.6 g of C = 9.6/12 = 0.8 mole Q For an adiabatic process, q = 0
1 mole release heat 393.5 kJ DU = q + w
0.8 mole release heat = 393.5 × 0.8 \ DU = w
= 314.8 kJ » 315 kg = –pDV
19. (c) DG = DH – T · DS = –2.5 atm × (4.5 – 2.5) L
For a spontaneous reaction DG = –ve (always) = –2.5 × 2 L-atm
= –5 × 101.3 J
= –506.5 J » –505J