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NOTE: PART 1 CONTAINS QUESTIONS FROM ENTHALPY AND HESS’S LAW
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ENTROPY
1) The Kelvin’s statement of second law of thermodynamics is
1) The entropy of universe increases in a spontaneous process.
2) It is impossible to take heat from a hotter reservoir and completely convert into work by a
cyclic process with out transferring a part of heat to a cooler reservoir.
3) It is impossible for a cyclic process to transfer heat from a body at lower temperature to one at a
higher temperature with out converting some work to heat.
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4) All.
Note: 3rd statement is known as Clausius statement of second law of thermodynamics.
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2) Choose the incorrect statement.
1) Entropy is a measure of the degree of spreading and sharing of thermal energy within a system.
temperature.
2) Absolute entropy value of the system is proportional to temperature. But the change in entropy is inversely
related to temperature.
3) The thermodynamical expression for change in entropy is given by
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qrev q w q w
1) 2) irrev 3) 4) irrev
T T T T
4) The unit of molar entropy is
1) J.mol-1 2) J.K-1.mol-1 3) J.K-1 4) J.K.mol-1
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1) Precipitation of silver chloride from a solution containing silver ions and chloride ions.
2) Dissolving table salt in water.
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3) Decomposition of liquid hydrogen peroxide to produce liquid water and oxygen gas..
4) Melting of ice.
3) The reaction will be spontaneous only if Ssys is greater in magnitude than Ssurr.
4) The reaction will be spontaneous only if Ssurr is greater in magnitude than Ssys.
Note: For a spontaneous process, S universe S sys S surr 0
15) Which of the following processes will result in a decrease in the entropy of the closed system?
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entropy of gas during this process is
1) -38.29 J K-1mol-1 2) +38.29 J K-1 3) -38.29 J K-1 4) +38.29 J K-1mol-1
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Pi
Formula: For isothermal processes, S 2.303 x nR log
Pf
Formula: S
Tb
25) The enthalpy of vaporization of ethanol is 38.7 kJ/mol at its boiling point of 78oC. The change in
entropy of the surroundings when one mole of ethanol is vaporized at 78oC and one atm of pressure
will be
1) +110 J K-1mol-1 2) +220 J K-1mol-1 3) -110 J K-1mol-1 4) 0 J K-1mol-1
26) The significance of the Second Law of Thermodynamics is that for spontaneous processes the:
1) entropy of the universe is increasing.
2) entropy of the surroundings must decrease.
3) entropy of an ideal solid does not change.
4) absolute value for entropy can be calculated.
27) For HI the molar entropy of vaporization is 89.0 J/K mol and the molar enthalpy of vaporization is
21.16 kJ/mol. Therefore, the normal boiling point of HI is:
1) -273oC 2) -35.4oC 3) 23.8 K 4) 42oC
28) A change of state occurs within a system and produces 64.0 kJ of heat. This heat is transferred to the
surroundings at a constant pressure and a constant temperature of 300 K. For this process, S of
the surroundings is :
1) 64.0 J/K 2) -213 J/K 3) -64.0 J/K 4) 213 J/K
29) Which of the following statements is false?
Thermodynamics Part-2: Prepared by V. Aditya vardhan adichemadi(at)gmail.com 4
1) Entropy is a measure of the driving force behind chemical reactions.
2) Entropy is a measure of disorder or randomness.
3) Entropy can be created and destroyed.
4) Entropy is a measure of the number of ways energy can be distributed among the motions of
particles.
Note: Strictly speaking, entropy is a measure of spreading and sharing of thermal energy among the microstates possible in
a system under given conditions.
30) Boiling point of Bromine is 59.20C. The standard molar enthalpy of it is
1) 28 kJ mol-1 2) 38 kJ mol-1 3) -28 kJ mol-1 4) -38 kJ mol-1
Note: According to Trouton’s rule, the standard molar entropy of vaporisation values of a wide range of liquids are almost
same (85 J K-1mol-1)
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vap H -1 -1
vap S 85 J K mol
Tb
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31) The efficiency of engine that is working between a lower temperature 27oC and a higher temperature
327oC is
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1) 0.2 2) 0.35 3) 0.5 4) 1
TH TL
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3) Which of the following is incorrect for a reaction A B?
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1) The reaction can spontaneously proceed to the right when G 0 .
2) The reaction can spontaneously proceed to the right when G 0
2) Although Gibbs free energy has the units of energy, it cannot be conserved - which is one of the most important
attributes of energy.
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6) The reaction H 2 ( g ) O2 ( g ) H 2O (l ) is used in fuel cells to produce an electric current.
2
Given the thermodynamic data:
Molar entropies in J mol-1 K-1 for O2(g) =205; for H2(g)=130.6; for H2O(l) =70
and f H o of H2O(l) = –285.9 kJ mol–1.
What is the amount of electrical work the same reaction can perform in the fuel cell when carried out
reversibly at 298 K.
1) -237.2 kJ mol-1 2) +285.9 kJ mol-1 3) +237.2 kJ mol-1 1) +2.859 kJ mol-1
Note: The amount of electrical work done by this reaction is equal to the Gibbs free energy change(-237.2kJ mol-1 ). As it is
negative, the reaction is spontaneous. This is the maximum useful work.
During this process some amount of heat is liberated and is given by
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T S f H G = –285.9 kJ mol-1 - (-237.2 kJ mol-1 ) = 48.7 kJ mol-1
This is the amount of heat liberated during the compression work done on the system as1.5 moles of gas during the reaction
are disappeared. This is equal to PV work and is not useful.
7) For a particular chemical reaction, Ho is positive and So is negative. Which of the following
statements about the spontaneity of the reaction under standard conditions is TRUE?
1) The reaction will be spontaneous only if the magnitude of Ho is large enough to overcome the
Thermodynamics Part-2: Prepared by V. Aditya vardhan adichemadi(at)gmail.com 6
unfavorable entropy change.
2) The reaction will be spontaneous only if the magnitude of So is large enough to overcome the
unfavorable enthalpy change.
3) The reaction will be spontaneous regardless of the magnitudes of Ho and So.
4) The reaction cannot be spontaneous at all temperatures.
8) Which of the following is TRUE for an operating voltaic cell? (Where Ecell = emf of the cell)
1) G > 0 ; Ecell = 0 2) G < 0 ; Ecell < 0
3) G < 0 ; Ecell > 0 4) G = 0 ; Ecell = 0
9) An exothermic reaction which is spontaneous at all temperatures is
1) C(graphite) + O2(g)
CO2(g) ; H° = –393 kJ
2) 3H2 (g) + N2(g) 2NH3(g) ; H°= –46.2 kJ
3) N2O4(g) 2NO2(g) ; H° = + 55.3 kJ
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4) All
10) For a particular chemical reaction, both Ho and So are negative. Which of the following state-
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ments about the spontaneity of the reaction under standard conditions is true?
1) The reaction will be spontaneous at any temperature.
11) Which of the following reactions is unfavorable at low temperatures but becomes favorable as the
temperature increases?
1) 2 CO(g) + O2(g) CO2(g); Ho = -566 kJ; So = -173 J/K
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Note: For reactions with identical signs of H and S there is a unique temperature at which when G = 0 and T S H .
This is the temperature at which G changes its sign. This is also the temperature at which the system reaches equilibrium.
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19) A change in which of the following will also change the value of G for a chemical reaction?
1) partial pressures of either gaseous reactants or products
22. Chemical thermodynamics predicts that materials made of wood, metal, paper, plastic, leather and
rubber react with oxygen in the atmosphere and decompose at 25oC and 1 atm pressure. Which of
the following is responsible for the fact that these reactions are very slow under these conditions?
1) low entropy 2) high enthalpy 3) high activation energy 4) low activation energy
23) Which of the following statements is true?
1) Endothermic reactions are never spontaneous, at any temperature.
2) Exothermic reactions are always spontaneous, at any temperature.
3) Exothermic reactions in which the entropy change for the system is negative are spontaneous at
any temperature.
4) None of the above statements is true.
24) A mixture of hydrogen and chlorine gas remains unreacted until exposed to UV light.Then the follow-
ing reaction occurs very rapidly:
H2(g) + Cl2(g) 2 HCl(g) ; G= -45.54kJ, H= -44.12kJ, S = -4.76 J/K
Select the statements below which best explains this behaviour.
1) The reactants are thermodynamically less stable than the products.
2) The reaction is thermodynamically spontaneous, but the reactants are kinetically stable.
3) The ultraviolet light raises the temperature of the system and makes the reaction spontaneous.
4) The negative value for S slows down the reaction.
Thermodynamics Part-2: Prepared by V. Aditya vardhan adichemadi(at)gmail.com 8
25) If a reaction is spontaneous at 27oC and has a standard enthalpy change equal to +150 kJ/mol,
which of the following must be true about the standard entropy of reaction?
1) Standard entropy change < 0 J/mol K
2) Standard entropy change = 27 J/mol K
3) Standard entropy change > 500 J/mol K
4) Standard entropy change = 150 J/mol K
26) The normal freezing point of water is 0oC. Predict the signs of H, S and G when H2O is
supercooled and freezes at -10oC and one atmosphere.
1) H < 0, S < 0, G < 0
2) H < 0, S > 0, G = 0
3) H > 0, S = 0, G > 0
4) H > 0, S > 0, G = 0
27) S > 0 for a certain chemical reaction carried out at constant temperature and pressure . Which of
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the following will be true about spontaneity of the reaction?
1) The reaction is spontaneous if it is endothermic and the temperature is sufficiently high.
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2) The reaction is spontaneous, if it is exothermic, at any temperature.
3) The reaction is not spontaneous if it is exothermic and the temperature is sufficiently low.
This process is endothermic. Which of the following statements is most likely true regarding the
spontaneity of this process at 70oC?
1) The process will be spontaneous because Ssys is negative.
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1) So 2) Go 3) Go 4) So
30) An ideal solution is formed spontaneously by mixing equal volumes of benzene and touene. For this
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process Hsoln is almost zero. Which of the following will be responsible for the spontaneity of this
process?
1) positive Ssoln 2) negative Ssoln 3) positive Vsoln 4) positive Gsoln
31). Consider the gas-phase reaction of hydrogen, H2, and chlorine, Cl2, to produce hydrogen chloride,
H2(g) + Cl2(g) 2HCl(g)
and the following thermodynamic data :
substance fGo, kJ/mol
H2(g) 0
Cl2(g) 0
HCl(g) -95.30
The value of Ho (in kJ) for this reaction at 25oC if the standard state entropy change is equal to
20.0 J/K.
1) 184.6 kJ 2) 101.26 kJ 3) 196.56 kJ 4) 51.3 kJ
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Note: H of the given reaction is to be calculated and not f H .
32) At elevated temperatures, hydrogen iodide, HI, decomposes to produce hydrogen, H2, and iodine,
I2, as shown in the equation below:
2 HI (g) H2 (g) + I2 (g)
Using the thermodynamic data below, calculate the standard free energy change (in kJ) for this
Thermodynamics Part-2: Prepared by V. Aditya vardhan adichemadi(at)gmail.com 9
reaction.
Compound fHo, kJ mol-1 So, J mol-1 K-1
HI(g) 25.9 206.3
H2(g) 0 131.0
I2(g) 62.4 260.6
1) 62.4 kJ 2) 16.9 kJ 3) 32.8 kJ 4) 8.45 kJ
33) Consider the following gas-phase reaction and average bond enthalpies,
2NOCl(g) 2NO(g) + Cl2(g)
bond average bond enthalpy, kJ mol-1
N-Cl 201
N=O 716
Cl-Cl 243
Which of the following statements about the spontaneity of this reaction is true at 25oC?
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1) The reaction will be spontaneous only if the magnitude of H is large enough to overcome the
unfavorable entropy change.
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2) The reaction will be spontaneous only if the magnitude of S is large enough to overcome the
unfavorable enthalpy change.
G for NH3 when NH3 supercools and then freezes at -80oC and one atmosphere.
1) H < 0, S < 0, G = 0 2) H < 0, S > 0, G < 0
3) H < 0, S < 0, G < 0 4) H > 0, S > 0, G = 0
36) Consider the following gas-phase reaction
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42) The equilibrium constant for a chemical reaction will be equal to one when
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1) Ho < 0 and So = 0 2) Ho = 0 and So = 0
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3) Ho < 0 and So > 0 4) Ho > 0 and So < 0
43) The standard free energy change for the following reaction if the complex ion formation equilibrium