Chemical

Thermodynamics
FAST TRACK : QUICK REVISION

w System: Specific part of universe in which observations are made.

w Surroundings: Everything which surrounds the system.
w Types of the System:
Open System: Exchange both matter and energy with the surroundings.
For example – Reactant in an open test tube.
Closed System: Exchange energy but not matter with the surroundings.
For example – Reactants in a closed vessel.
Isolated System: Neither exchange energy nor matter with the surroundings.
For example – Reactants in a thermos flask.
w Thermodynamic Processes:
(i) Isothermal Process: ∆T = 0
(ii) Adiabatic process: ∆q = 0
(iii) Isobaric process: ∆P = 0
(iv) Isochoric process: ∆V = 0
(v) Cyclic process: ∆U = 0
(vi) Reversible process: Process which proceeds infinitely slowly by a
series of equilibrium steps.
(vii) Irreversible process: Process which proceeds rapidly and the system
does not have chance to achieve equilibrium.
w Extensive Properties: Properties which depend upon the quantity or size
of matter present in the system. For example – mass, volume, internal
energy, enthalpy, heat capacity, work etc.
Chemical Thermodynamics 88
 w Intensive Properties: Properties which do not depend upon the quantity
or size of matter present in the system. For example – temperature, density,
pressure, surface tension, viscosity, refractive index, boiling point, melting
point etc.
w State Functions: The variables of functions whose value depend only on
the state of a system or they are path independent.
For example – pressure (P), volume (V), temperature (T), enthalpy (H),
free energy (G), internal energy (U), entropy (S), amount (n) etc.
w Internal Energy: It is the sum of all kind of energies possessed by the
system.
w First Law of Thermodynamics: “The energy of an isolated system is
constant.”
Mathematical Form: ∆U = q + w
w Sign Conventions for Heat (q) and Work (w):
(i) W = + ve , if work is done on system
(ii) W = – ve , if work is done by system
(iii) q = + ve , if heat is absorbed by the system
(iv) q = – ve , if heat is evolved by the system
w Work of Expansion/ compression: w = –Pext (Vf – Vi)
w Work done in Isothermal Reversible Expansion of an Ideal Gas:
wrev = –2.303 nRT log Vf / Vi
or wrev = –2.303 nRT log Pi / Pf
w Significance of ∆H & ∆U: ∆H = qp and ∆U = qv
w Relation between ∆H & ∆U: ∆H = ∆U + (np – nr)RT for gaseous reaction
(i) ∆H = ∆U if (np – nr) is zero; e.g. H2 (g) + I2 (g) —→ 2 HI(g)
(ii) ∆H > ∆U if (np – nr) is positive; e.g. PCl5 (g) —→ PCl3 (g) + Cl2 (g)
(iii) ∆H < ∆U if (np – nr) is negative; e.g. N2 (g) + 3H2 (g) —→ 2NH3 (g)
w Heat Capacity (C): Amount of heat required to raise the temperature of a
substance by 1°C or 1 K.
q = C ∆T

Chemical Thermodynamics 89
 w Specific Heat Capacity (Cs): Amount of heat required to raise the
temperature of 1 g of a substance by 1°C or 1 K.
q = Cs × m × ∆T
w Molar Heat Capacity (Cm): Amount of heat required to raise the
temperature of 1 mole of a substance by 1°C or 1 K.
q = Cm × n × ∆T
w Standard State of a Substance: The standard state of a substance at a
specified temperature is its pure form at 1 bar.
w Standard Enthalpy of Formation(∆f Ho): Enthalpy change accompanying
the formation of one mole of a substance from its constituent elements
under standard condition of temperature (normally 298 K) and pressure
(1bar).
• ∆f H0 of an element in standard state is taken as zero.
• Compounds with –ve value of ∆f H0 more stable than their constituents.
• ∆rH0 = ∑ai ∆f H0 (products) – ∑bi ∆f H0 (reactants) ; Where ‘a’ and ‘b’
are coefficients of products and reactants in balanced equation.
w Standard Enthalpy of Combustion(∆cH0): Enthalpy change accom-
panying the complete combustion of one mole of a substance under
standard conditions ( 298 K, 1bar)
w Hess’s Law of Constant Heat Summation: The total enthalpy change
of a reaction remains same whether it takes place in one step or in several
steps.
w Bond Dissociation Enthalpy: Enthalpy change when one mole of a
gaseous covalent bond is broken to form products in gas phase.
For example, Cl2 (g) —→ 2Cl(g); ∆Cl – Cl H0 = 242 kJ mol–1
• For diatomic gaseous molecules; Bond enthalpy = Bond dissociation
Enthalpy = Atomization Enthalpy
• For Polyatomic gaseous molecules; Bond Enthalpy = Average of the
bond dissociation enthalpies of the bonds of the same type.
• ∆r H0 = ∑∆bond H0 (Reactants) – ∑∆bond H0 (Products)
w Spontaneous Reaction: A reaction which can take place either an its own
or under some initiation.

90 Chemistry Class XI
 w Entropy(S): It is measure of degree of randomness or disorder of a system.
( q rev )sys DHsys
• DS=
sys =
DT DT
• Unit of Entropy = JK–1 mol–1

w Second Law of Thermodynamics: For all the spontaneous processes

totally entropy change must positive.
∆Stotal = ∆Ssys + ∆Ssurr > 0

w Gibbs Helmholtz Equation for determination of Spontaneity:

∆G = ∆H – T∆S
(i) If ∆G = –ve, the process is spontaneous
(ii) If ∆G = +ve, the process is non-spontaneous
(iii) If ∆G = 0, the process is in equilibrium
w Relation between Gibbs Energy Change and Equilibrium Constant:
∆Go = –2.303 RT logKc
w Third Law of Thermodynamics: The entropy of a perfectly crystalline
solid at absolute zero (0 K) is taken to be zero.

Chemical Thermodynamics 91
92
MIND MAP : CHEMICAL THERMODYNAMICS

Chemistry Class XI
 MULTIPLE CHOICE QUESTIONS (MCQ)

1. Which one of the following thermodynamic quantities is not a state

function?
(a) Gibbs free energy (b) Enthalpy
(c) Entropy (d) Work
2. All of the following have a standard heat of formation value of zero at
25°C and 1.0 atm except:
(a) N2 (g) (b) Fe(s)
(c) Ne (g) (d) H(g)
3. For the following reaction at 25°C, DH° = +115 kJ and DS° = +125 J/K.
Calculate DG° for the reaction at 25℃ :
SBr4(g) ___→ S(g) + 2Br2(l)
(a) +152 kJ (b) –56.7 kJ
(c) +77.8 kJ. (d) +37.1 kJ
4. Calculate DrH0 for the following reaction at 25°C :
Fe3O4(s) + CO(g) ___→ 3FeO(s) + CO2(g)
DHfo (kJ/mol) –1118 –110.5 –272 –393.5
(a) –263 kJ (b) 54 kJ
(c) 19 kJ. (d) –50 kJ
5. A system suffers an increase in internal energy of 80 J and at the same time
has 50 J of work done on it. What is the heat change of the system?
(a) +130 J (b) +30 J
(c) –130 J (d) –30 J
6. The DH0 for the following reaction at 298 K is –36.4 kJ.
1/2 H2 (g) + 1/2 Br2 (l) ___→ HBr(g)
Calculate DU0 at 298 K. The universal gas constant, R, is 8.314 J/mol K.
(a) –35.2 kJ (b) +35.2 kJ
(c) –36.4 kJ (d) –37.6 kJ.
7. For which of the following reactions would the Ho for the reaction be
labeled DHf0 ?
(a) Al(s) + 3/2 H2 (g) + 3/2 O2 (g) ___→ Al(OH)3(s)
(b) PCl3 (g) + 1/2 O2 (g) ___→ POCl3 (g)

Chemical Thermodynamics 93
 (c) 1/2 N2O (g) + 1/4 O2 (g) ___→ NO (g)
(d) CaO(s) + SO2 (g) ___→ CaSO3(s)
8. Which statement is ture for reaction? 2H2 (g) + O2 (g) ___→ 2H2O (g)
(a) S = +ve (b) H > U
(c) H < U (d) H = U
9. The heat of combustion of yellow phosphorous is –9.91 KJ and the red
phosphorous is –8.78 KJ. The heat of transition of yellow phosphorous to
red phosphorous is :
(a) –9.91 kJ (b) –8.78 kJ
(c) –9.34 kJ (d) –1.13 kJ
10. Entropy of universe is :
(a) Increasing (b) decreasing
(c) Constant (d) None of these
11. Which is state function?
(a) q (b) w
(c) q + w (d) None of these
12. According to second law of thermodynamics
(a) ∆Stotal = +ve (b) ∆Stotal = –ve
(c) ∆Ssystem = +ve (d) ∆Ssystem = –ve
ns: 1.(d), 2.(d), 3.(c),
A 4.(c), 5.(b), 6.(d), 7.(a),
8. (a), 9.(d), 10.(c), 11.(d), 12.(a), 13.(c), 14.(a)

FILL IN THE BLANKS

(i) ……… is a measure of the degree of randomness or disorder of a system.
(ii) A process which can take place either of its own or under some initiation
is known as ………………..
(iii) For evaporation of water the sign of ∆H is….…. and sign of ∆S is…..…
(iv) The entropy of a perfectly crystalline solid is zero at ………..
(v) The heat energy exchanged between the system and surroundings at
constant temperature and pressure is known as……....…
(vi) ………… is the quantity of heat needed to raise the temperature of one
mole of a substance by 1o
(vii) Cp – Cv = ..............…

94 Chemistry Class XI
 (viii) ….......... = ∆H – T∆S.
(ix) According to ………. law of thermodynamics, ∆Stotal = + ve.
(x) If ∆H = +ve and ∆S = +ve, the reaction is spontaneous at ……... temperature
Ans: (i) Entropy (ii) spontaneous (iii) +ve, +ve (iv) –273℃
(v) Enthalpy (vi) molar heat capacity (vii) R (viii) ∆G
(ix) second (x) high

TRUE AND FALSE TYPE QUESTIONS

Write true or false for following statements:
(i) For every chemical reaction at equilibrium ∆G0 is zero.
(ii) Entropy is not a state function because its value depends upon the condition
of temperature and pressure.
(iii) During isothermal expansion of an ideal gas, there is no change in internal
energy.
(iv) q and w are not state function but q+w is a state function.
(v) The enthalpy of neutralization of a strong acid by a strong base is always
constant.
(v) For a spontaneous process ∆Ssystem= +ve.
(vii) The energy of universe is conserved while its entropy is increasing.
(viii) Volume is extensive property while temperature is intensive property.
(ix) At 0°C the entropy of a perfectly crystalline solid is zero.
(x) Hess’ law is a corollary of the first law of thermodynamics.
Ans: (i) False (ii) False (iii) True (iv) True (v) True
(vi) False (vii) True (viii) True (ix) False (x) True

MATCH THE COLUMNS

1. Column I Column II
(i) State function (a) Pressure
(ii) Extensive property (b) Work
(iii) Intensive property (c) q + w
(iv) Path function (d) Heat capacity

Chemical Thermodynamics 95
2.
Column I Column II
(i) ∆H = +ve; ∆S = +ve (a) Spontaneous at all temperatures
(ii) ∆H = –ve; ∆S = +ve (b) Non-spontaneous at all temperatures
(iii) ∆H = +ve; ∆S = –ve (c) Non-spontaneous at high temperature
(iv) ∆H = –ve; ∆S = –ve (d) Spontaneous at high temperature
Ans: 1. (i) → (c), (ii) → (d), (iii) → (a), (iv) → (b).
2. (i) → (d), (ii) → (a), (iii) → (b), (iv) → (c).

ASSERTION AND REASON TYPE QUESTIONS

In the following questions a statement of assertion (A) followed by a statement
of Reason (R) is given. Choose the correct option out of the choices given below
for each question.
(i) A and R both are correct, and R is correct explanation of A.
(ii) A and R both are correct, but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) A and R both are false.
1. Assertion (A): Enthalpy of graphite is lower than that of diamond.
Reason (R): Entropy of graphite is greater than that of diamond.
2. Assertion (A): Enthalpy of formation of H2O(l) is greater than that of
H2O(g).
Reason (R): Enthalpy change is negative for condensation reaction, H2O(g)
H2O(l)
3. Assertion (A): ∆H and ∆U are same for the reaction N (g) + O (g) ___→ 2NO(g)
2 2
Reason (R): All the reactants and products are gases.
4. Assertion (A): if both ∆H0 and ∆S0 are positive than the reaction will be
spontaneous at high temperature
Reason (R): All processes with positive entropy change are spontaneous.
5. Assertion (A): Enthalpy of formation of HCl is equal to bond energy of
HCl.
Reason (R): Enthalpy of formation and bond energy both involve the
formation of one mole of HCl from the elements.
Ans: 1. (ii) 2. (i) 3. (ii) 4. (iii) 5. (i)

96 Chemistry Class XI
 ONE WORD ANSWER TYPE QUESTIONS

1. ‘w’ amount of work is done by the system and ‘q’ amount of heat is supplied
to the system. What type of system would it be?
2. What is the work done in free expansion of an ideal gas?
3. What is the sign of ∆GO for spontaneous reaction?
4. Write the relation between ∆H and ∆U for H2 (g) + I2 (g) → 2HI (g).
5. Write the SI unit of entropy.
6. Name the calorimeter used to measure∆U.
7. What is the standard enthalpy of formation of graphite?
8. What is the sign of DH for H (g) ___→ 2H (g)?
2
9. If Kc = 1, what will be the value of DG?
10. An exothermic reaction is spontaneous at all temperature. What is the sign
of S?
Ans: 1. Closed system 2. W = 0 3. ∆G = –ve 4. ∆H = ∆U 5. J K–1 mol–1
6. Bomb calorimeter 7. Zero 8. ∆H = –ve 9. Zero 10. ∆S = +ve

1-MARK QUESTIONS

1. Day temp Name the thermodynamic system to which following belong:

(i) Human body (ii) Milk in Thermos flask (iii) Tea in steel kettle
2. Identify State functions out of the following: Enthalpy, Entropy, Heat,
Temperature, Work, Free energy
3. Give two examples of state functions.
4. Write the mathematical statement of first law of thermodynamics.
5. Predict the internal energy change for an isolated system? [Ans. Zero]
6. Why ∆H is more significant than ∆U?
7. Write one example each of extensive and intensive properties.
8. Write a chemical equation in which ∆H and ∆U are equal.
9 Write the relationship between ∆H and ∆U for the reaction:
C(s)+ O2(g) ___→ CO2(g)
10. Define standard enthalpy of formation.

Chemical Thermodynamics 97
 11. Why is the standard enthalpy of formation of diamond not zero although it
is an element?
12. The enthalpy of atomization of CH4 is 1665 kJ mol–1. What is the bond
enthalpy of C – H bond? [Ans. 416.25 kJ]
13. Identify the species for which ∆f Hθ = O3, at 298 K; Br2, Cl2, CH4 .
[Hint: Cl2 (Br2 is liquid at 298K)]
14. For the reaction 2Cl(g) ___→ Cl (g) ; what are the sign of ∆H and ∆S ?
2
15. For an isolated system ∆U= 0, what will be ∆S ?
16. Why entropy of steam is more than that of water at its boiling point?
17. Out of Diamond and Graphite which has higher entropy?
18. Write an example of endothermic spontaneous reaction.
19. State second law of thermodynamics.
20. State third law of thermodynamics.
21. Which has more entropy? 1 mol H2 O(l) at 25°C or 1 mol H2O(l) at35°C.
22. At what temperature the entropy of a perfectly crystalline solid is zero?
23. For a certain reaction ∆Gθ = 0,what is the value of Kc?
24. How can a non spontaneous reaction be made spontaneous?
25. For a reaction both ∆H and ∆S are negative. Under what conditions does
the reaction occur.

2-MARKS QUESTIONS

1. In a process 701 J of heat is absorbed by a system and 394 J work is done

by the system. What is the change in internal energy for the process?
[Ans. 307 J]
2. Neither q nor w is state functions but q + w is a state function. Explain.
3. Classify the following as extensive or intensive properties :-
Heat capacity, Density, Temperature, Molar heat capacity.
4. Derive the relationship between ∆H and ∆U.
5. Derive the relationship Cp – Cv = R.
6. A 1.25g sample of octane (C8H18) is burnt in excess of oxygen in a bomb
calorimeter. The temperature of the calorimeter rises from 294.05 to

98 Chemistry Class XI
 300.78K.If heat capacity of the calorimeter is 8.93 kJ K–1. Find the heat
transferred to calorimeter. [Ans. 0.075 kJ]
7. Show that for an ideal gas, the molar heat capacity under constant volume
conditions is equal to 3/2 R.
8. Expansion of a gas in vacuum is called free expansion. Calculate the work
done and change in internal energy when 1 mol of an ideal gas expands
isothermally from I L to 5 L into vacuum.
9. State and explain Hess’s Law of Constant Heat Summation with a suitable
example.
10. Derive the relationship between ∆H and ∆U.
Given, N (g) + 3H (g) ___→ 2NH (g); ∆ Hq = –92.4 kJ mol–1;
2 2 3 r
What is the standard enthalpy of formation of NH3 gas?
[Ans. –46.2 kJ mol–1]
11. Calculate the enthalpy change for the reaction:
H (g) + Br (g) ___→ 2 HBr(g).
2 2
Given the bond enthalpies H2, Br2 and HBr are 435 kJ mol–1, 192 kJ mol–1
and 368 kJ mol–1 respectively. [Ans. –109 kJ mol–1]
12. Is the bond dissociation enthalpy of all the four C – H bonds in CH4 same?
Give reason in support of your.
13. Define the term entropy. Write its unit. How does entropy of a system
change on increasing temperature?
14. Dissolution of ammonium chloride in water is endothermic but still it
dissolves in water readily. Why?
15. Calculate the entropy change in the surroundings when 1.00 mol of H2O(l)
is formed under standard conditions; ∆f Hθ = –286 kJ mol–1.
[Ans. 959.7 J K–1 mol–1]
16. The enthalpy of vaporization of a liquid is 30 kJ mol–1 and entropy of
vaporization is 75 J K–1 mol–1. Calculate the boiling point of liquid at
1 atm. [Ans. 400 K]
17. The equilibrium constant for a reaction is 10.What will be the value of
∆Gθ? R = 8.314J K–1 mol–1, T = 300K. [Ans. –5.527 kJ mol–1]
18. Derive the relationship, ∆G = –T∆Stotal for a system.

Chemical Thermodynamics 99
 19. The ∆H and ∆S for 2Ag2 O(s) ___→ 4Ag(s) +O2(g) are given + 61.17kJ
mol–1 and +132 J K–1mol–1 respectively. Above what temperature will the
reaction be spontaneous? [Ans. >463.4 K]

3-MARKS QUESTIONS

1. Differentiate between the following (with examples)

(i) Open and Closed System.
(ii) Adiabatic and Isothermal process.
(iii) State function and path function
2. Calculate the maximum work obtained when 0.75 mole of an ideal gas
expands isothermally and reversibly at 27°C from a volume of 15L to
25L. [Ans. –955.7 J]
3. Calculate the number of kJ necessary to raise the temperature of 60 g of
aluminium from 35 to 55℃ . Molar heat capacity of Al is 24 J mol–1 K–1.
[Ans. 1.067 kJ]
4. The reaction of cyanamide, NH2CN (s), with Dioxygen was carried out
in a bomb calorimeter, and ∆U was found to be –742.7 kJ mol–1 at 298K.
Calculate Enthalpy change for the reaction at 298K,
NH CN (s) +3/2 O (g) ___→ N (g) + CO (g) +H O (l)
2 2 2 2 2
[Ans. –741.5 kJ mol–1]
5. The enthalpy of combustion of methane, graphite and dihydrogen at
298 K are –890.3 kJ mol–1, –393.5 kJ mol–1 and –285.8 kJ mol–1 respectively.
Calculate enthalpy of formation of methane gas. [Ans. –74.8 kJ mol–1]
6. Explain the Born Haber Cycle to determine the lattice enthalpy of NaCl.
7. Enthalpies of formation of CO(g), CO2(g), N2O(g) and N2O4 (g) are –110,
–393, 81 and 9.7 kJ mol-1 respectively. Find the value of ∆rH for the
reaction; N2O4(g) + 3 CO (g) ___→ N2O (g) + 3CO2 (g)
[Ans. –777.7 kJ mol–1]
8. The combustion of 1 mol of benzene takes place at 298K .After
combustionCO2 and H2O are formed and 3267 kJ mol–1 of heat is liberated.
Calculate ∆f H0 (C6H6).
Given: ∆fH0 (CO2) = –286 kJ mol–1, ∆fH0(H2O) = –393 kJ mol–1
[Ans. 48.51 kJ mol–1]

100 Chemistry Class XI

 9. Calculate the standard enthalpy of formation of CH3OH(l) from the
following data:
CH OH (l) + 3/2 O (g) ___→ CO (g) + 2H O (l); ∆ Hθ = –726 kJ mol–1
3 2 2 2 c
C (g) + O2 (g) ___→ CO2 (g); ∆f Hθ = –393 kJ mol–1
H2(g) + 1/2 O2 (g) ___→ H2O (l); ∆f HO – 286 kJ mol–1
[Ans. –239 kJ mol–1]
10. For oxidation of iron, 4 Fe(s) + 3 O2(g) →2 Fe2O3(s) entropy change is
–549.4 J K–1 mol–1 at 298 K. In spite of negative entropy change of this
reaction, why is the reaction spontaneous? (∆rHθ for this reaction is –1648
kJ mol–1) [Ans. ∆Stotal = +4980.6 J K–1 mol–1]
11. Give reasons:
(i) Evaporation of water is and endothermic process but it is spontaneous.
(ii) A real crystal has more entropy than an ideal crystal.
(iii) Entropy of universe is increasing.
12. For the reaction at 298 K, 2A + B ___→ C ; ∆H = 400 kJ mol–1, ∆S = 0.2
kJ K–1 mol–1. At what temperature will the reaction become spontaneous
considering ∆H and ∆S to be constant over the temperature range.
[Ans. T > 2000 K]
13. Reaction X → Y; ∆H = +ve is spontaneous at temperature ‘T’. Determine
(i) Sign of ∆S for this reaction.
(ii) Sign of ∆G for Y___→ X
(iii) Sign of ∆G at a temperature < T

5-MARKS QUESTIONS

1. (a) What is reversible process in Thermodynamics?

(b) Name the thermodynamic processes for which : (i) q = 0 (ii) ∆U = 0
(iii) ∆V = 0 (iv) ∆P = 0
(c) Water decomposes by absorbing 286.2 kJ of electrical energy per
mole. When H2 and O2 combine to form one mole of H2O, 286.2 kJ
of heat is produced. Which thermodynamic law is proved? Write its
statement.
2. (a) Although heat is a path function but heat absorbed by the system under
certain specific conditions is independent of path. What are those
conditions? Explain. [Hint: qv = ∆U and qp = ∆H]

Chemical Thermodynamics 101

 (b) It has been found that 221.4 J is needed to heat 30g of ethanol from
15℃ to 18℃. Calculate (a) specific heat capacity, and (b) molar heat
capacity of ethanol. [Ans. (a) 2.46 Jg–1 ℃–1, (b) 113.2 J mol–1 ℃–1]
3. (a) Differentiate the terms Bond dissociation enthalpy & Bond Enthalpy.
(b) Calculate enthalpy change for the process CCl (g) ___→ C(g) + 4Cl(g)
4
and calculate Bond enthalpy of C – Cl bond in CCl4.
Given: ∆vap Hθ = 30.5 kJ mol–1; ∆f Hθ(CCl4) = –135.5 kJ mol–1;
∆aHθ(C) = 715 kJ mol–1 and ∆aHθ(Cl2) = 242 kJ mol–1
[Ans. 1304 kJ mol–1, 326 kJ mol–1]
4. Predict the sign of ∆S for the following changes:
(i) Freezing of water.
(ii) C(graphite) ___→ C(diamond)
(iii) H2(g) at 298 k and 1 bar ___→ H2(g) at 298 k and 10 bar
(iv) H (g) + I (g) ___→ 2HI(g)
2 2
(v) 2NaHCO3(s) ___→ Na2CO3(s) + CO2(g) + H2O(g)
5. (i) Define Gibbs Energy. Give its mathematical expression. What is
Gibb‘s energy criteria of Spontaneity.
(ii) For the reaction:
2A(g) + B (g) → 2D(g), ∆Uθ = –10.5 kJ and ∆Sθ = –44.1 J K–1.
Calculate ∆rG° for the reaction, and predict whether the reaction will
occur spontaneously.
[Ans. ∆rGθ = +0.16 kJ, Non-spontaneous]

HOTS QUESTIONS

1. Does entropy increase or decrease when egg is boiled?

Ans.:On boiling egg, entropy decreases as due to denaturation, the helical
structure of protein become more complicated and random coiled structure.
2. 10 g of argon is compressed isothermally and reversibly at a temperature
of 27°C from 10 L to 5 l. Calculate q, w, ∆U and ,∆H.
Solution: q = –2.303 nRT log V2 / V1 = –2.303 × 10/40 mol × 2 Cal K–1
mol–1 × 300 K × log 5/10 = –103.635 Cal

102 Chemistry Class XI

 For isothermal compression ∆U = 0
W = ∆U – q = 0 – (–103.635) = +103.635 Cal
Also when temperature is constant,
PV = constant, ∆H = ∆U + ∆(PV) = 0 + 0 = 0
3. 1 mole of an ideal gas expand isothermally and reversibly from a pressure
of 10 atm to 1 atm at 300 K. Calculate the height to which an object of 50
kg can be lifted by this expansion.
Solution: w(exp.) = –2.303 nRT
log Pi / Pf = –2.303 ×1 mol × 8.314 J K–1mol–1 × 300 K × log 10/1
= 5.74 ×103 J
Now, mgh = 5.74 × 103 J or 50 kg × 9.81 m s–2 × h = 5.744 ×103 J
∴ h = 11.7 m

Chemical Thermodynamics 103

 UNIT TEST
Time Allowed: 1 hr Maximum Marks : 20
General Instructions:
(i) All questions are compulsory.
(ii) Maximum marks carried by each question are indicated against it.

1. For the reaction 2Cl(g) → Cl2 (g); what are the sign of ∆H and ∆S? [1]
2. Write an example of endothermic spontaneous reaction. [1]
3. ‘w’ amount of work is done by the system and ‘q’ amount of heat [1]
is supplied to the system. What type of system would it be?
4. In a process 701 J of heat is absorbed by a system and 394 J work [2]
is done by the system. What is the change in internal energy for
the process?
5. State and explain Hess’s Law of Constant Heat Summation with [2]
a suitable example.
6. Calculate the number of kJ necessary to raise the temperature of [3]
60 g of aluminium from 35 to 55°C . Molar heat capacity of
Al is 24 J mol–1 K–1.
7. Calculate the standard enthalpy of formation of CH3OH (l) from
the following data:
CH3OH(l) + 3/2 O2 (g) → CO2 (g) + 2H2O (l);
∆c Hθ = –726 kJ mol–1
C (g) + O2 (g) → CO2 (g); ∆f Hθ= –393 kJ mol–1
H2(g) + ½ O2 (g) → H2O (l); ∆f Hθ = –286 kJ mol–1
8. (a) For oxidation of iron, 4 Fe(s) + 3 O2(g) → 2 Fe2O3(s) entropy change
is –549.4 J K–1 mol–1 at 298 K. In spite of negative entropy change of
this reaction, why is the reaction spontaneous? (∆r H° for this reaction is
–1648 kJ mol–1) [2]
(b) For the reaction: 2A (g) + B (g) → 2D (g), ∆Uo = –10.5 kJ and
∆So = –44.1 J K–1. Calculate ∆rGo for the reaction, and predict whether
the reaction will occur spontaneously. [3]
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104 Chemistry Class XI