 System : Speci®c part of universe in which observations are made.

 Surroundings : Everything which surrounds the system.

 Types of the System :
(i) Open System : Exchange both matter and energy with the
surroundings. For example : Reactant in an open test tube.
(ii) Closed System : Exchange energy but no matter with the surroundings.
For example : Reactants in a closed vessel.
(iii) Isolated System : Neither exchange energy nor matter with the
surroundings. For example : Reactants in a thermos ¯ask.
 Please note no system is perfectly isolated.
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 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 in®nitely slowly by a
series of equilibrium steps.
(vii) Irreversible process : Process which proceeds rapidly and the system
does not have chance to achieve equilibrium.
 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.

Thermodynamics 59
  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.
 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.
 Internal Energy : It is the sum of all kind of energies possessed by the
system.
 First Law of Thermodynamics : “The energy of an isolated system is
constant.”
Mathematical Form : U = q + 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
 Work of Expansion/compression : w = – Pext (Vf — Vi)
 Work done in Isothermal Reversible Expansion of an Ideal Gas :
wrev = – 2.303 nRT log

Or, wrev = – 2.303 nRT log

 Signi®cance of H and U : H = qp and U = qv

 Relation between H and 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., PC15(g)  PCl3(g) + C12(g)
(iii) H < U if (np – nr) is negative; e.g., N2(g) + 3H2(g)  2NH3(g)
 Heat capacity (C) : Amount of heat required to raise the temperature of
a substance by 1°C to 1 K.
q = CT
 Speci®c heat capacity (Cs) : Amount of heat required to raise the

60 Chemistry Class XI
 temperature of 1g of a substance by 1°C or 1K.
q = Cs × m × T
 Molar Heat Capacity (Cm) : Amount of heat required to raise the
temperature of 1 mole of a substance by 1°C or 1K.
q = Cm × n × T
 Standard State of a Substance : The standard state of a substance at a
speci®ed temperature is its, pure form at 1 bar.
 Standard Enthalpy of Formation (f H°) : 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
(1 bar).
 f H° of an element in standard state is taken as zero.
 Compounds with – ve value of fH°are more stable than their
constituents.
 rH° = iaif H° (products) – ibif H° (reactants) : Where ‘a’ and
‘b’ are coef®cients of products and reactants in balanced equation.
 Standard Enthalpy of Combustion ( cH°) : Enthalpy change
accompanying the complete combustion of one mole of a substance under
standard conditions (298 K, 1 bar)
 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.
 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 H° = 242k/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.
 rH° = bondH° (Reactants) bondH° (Products)
 Spontaneous Reaction : A reaction which can take place either of its own
or under some initiation.

Thermodynamics 61
  Entropy (S) : It is measure of degree of randomness or disorder of a
system.

 Ssys =

 Unit of Entropy = JK–1 mol–1

 Second Law of Thermodynamics : For all the spontaneous processes
totally entropy change must positive.
Stotal = Ssys + Ssurr > 0
 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 nonspontaneous
(iii) If G = 0, the process is in equilibrium
 Relation between Gibbs Energy Change and Equilibrium Constant :
G0 = – 2.303 RT log Kc.
 Third law of thermodynamic : The entropy of a perfectly crystalline
solid at absolute zero (0 K) is taken to be zero.
1-Mark Questions
Thermodynamic Concepts and First Law of Thermodynamics
1. Day temp. Name the thermodynamic system to which following belong:
(i) Human body (ii) Milk in Thermos ¯ask (iii) Tea in steel kettle
2. Identity State functions out of Ihe following : Enthalpy, Entropy, Heat,
Temperature, Work, Free energy.
3. Give two examples of state functions.
4. Write the mathematical statement of ®rst law of thermodynamics.
Work, Enthalpy, Internal Energy and Heat Capacity
5. Predict the internal energy change for an isolated system ? [Ans. Zero]
6. Why AH is more signi®cant 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 :

62 Chemistry Class XI
 C(s) + O2(g)  CO2(g).
Different types of Enthalpy Changes and Hess’s Law
10. De®ne standard enthalpy of formation.
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 H° = 0, at 298 K : – Br2, Cl2, CH4 .
[Hint : Cl2(Br2 is liquid at 298K)]
Spontaneity, Entropy , Second and Third Law of Thermodynamics
14. For the reaction 2Cl(g)  C12(g); what are the sign of H and S ?
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 H2O(l) at25°C or 1 mol H2O(l) at 35°C.
22. At what temperature the entropy of a perfectly crystalline solid is zero?
Gibbs Energy and Spontaneity, Effect of Temperature on Spontaneity
23. For a certain reaction G° = 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 Question
Thermodynamic Concepts and First Law of Thermodynamics
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]

Thermodynamics 63
 2. Neither q nor w is state functions but q + w is a state function. Explain.
Work, Enthalpy, Internal Energy and Heat Capacity
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 (C18 H18) is burnt in excess of oxygen in a
bomb calorimeter. The temperature of the calorimeter rises from 294.05
to 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.
Different types of Enthalpy Changes and Hess’s Law
9. State and explain Hess’s Law of Constant Heat Summation with a suitable
example.
10. Derive the relationship between H and U. Given, N2(g) + 3H2(g) 
2NH3(g); rH° = – 92.4 kJ mol1; What is the standard enthalpy of formation
of NH3 gas ? [Ans. – 46.2 kJ mol–1]
11. Calculate the enthalpy change for the reaction : H2(g) + Br2(g)  2HBr(g).
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 CH 4 same?
Give reason in support of your.
Spontaneity, Entropy, Second and Third Law of Thermodynamics
13. De®ne 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 HiO(I)
is formed under standard conditions; f H°= – 286 kJ mol–1.

64 Chemistry Class XI
 [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]
Gibbs Energy and Spontaneity, Effect of Temperature on Spontaneity
17. The equilibrium constant for a reaction is 10. What will be the value of
G° ? R = 8.314J K–1 mol–1, T = 300 K. [Ans. – 5.527 kJ mol–1]
18. Derive the relationship, G = – TStotal for a system.
19. The H and S for 2Ag2O(s) 4Ag(s) + O(g) are given + 61.17 kJ mol–1
and + 132 K–1 mol–1 respectively. Above what temperature will the reaction
be spontaneous ? [Ans. > 463.4 K]
3 Mark Questions
Thermodynamic Concepts and First Law of Thermodynamics
1. Differentiate between the following (with examples) :
(i) Open and Closed System.
(ii) Adiabatic and Isothermal process
(iii) State function and path function
Work, Enthalpy,Intemal Energy and Heat Capacity
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 15 L to 25
L. [Ans. – 955.7 J]
3. Calculate the number of kJ necessary to raise the temperature of 60 g of
aluminium from 35 to 55°C . Molar heat capacity of Al is 24 J mol–1J
mol–1K–1. [Ans. 1.067kJ]
4. The reaction of cyanamide, NH 2CN(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, NH2CN (s) + O2
(g)  N2 (g) + CO2(g) +H2O (I) [Ans. – 741.5 kJ mol–1]
Different types of Enthalpy Changes and Hess’s Law
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–l respectively.

Thermodynamics 65
 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) + 3CO(g)  N2O(g) + 3CO2(g)
[Ans. – 777.7 kJ mol–1]
8. The combustion of 1 mol of benzene takes place at 298K .After combustion
CO2 and H2O are formed and 3267 kJ mol–1 of heat is liberated. Calculate
f H°(C6H6).
Given : f H°(CO2) = – 286 kJ mol–1, f H°(H2O) = – 393 kJ mol–1
[Ans. 48.51 kJ mol–1]
9. Calculate the standard enthalpy of formation of CH 3OH (1) from the
following data :

CH3OH (1) + O2(g) CO2(g) + 2H2O (1); cH° = – 726 kJ mol–1

C(g) + O2(g)  CO2(g); f H° = – 393 kJ mol–1
H2(g) + ½O2(g)  H2O(1); f H° = – 286 kJ mol–1
[Ans. – 239 kJ mol–1]
Spontaneity, Entropy, Second and Third Law of Thermodynamics
10. For oxidation of iron, 4 Fe(s) + 3O 2(g)  2Fe2O3 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 ? (rH° for this reason 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.
Gibbs Energy and Spontaneity, Effect of Temperature on Spontaneity
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]

66 Chemistry Class XI
 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-Mark Questions
Thermodynamic Concepts and First Law of Thermodynamics
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.
Work, Enthalpy, Internal Energy and Heat Capacity .
2. (a) Although heat is a path function but heat absorbed by the system
under certain speci®c conditions is independent of path. What are those
conditions ? Explain. [Hint : qv = U and qp = H]
(b) It has been found that 221.4 J is needed to heat 30g of ethanol from
15°C to 18°C. Calculate (a) speci®c heat capacity, and (b) molar heat
capacity of ethanol. [Ans. (a) 2.46 Jg–1°C–1, (b) 113.2 J mol–1C–1]
Different types of Enthalpy Changes and Hess’s Law
3. (a) Differentiate the terms Bond dissociation enthalpy and Bond Enthalpy.
(b) Calculate enthalpy change for the process CCl4(g)  C(g) + 4Cl(g)
and calculate Bond enthalpy of C-C1 bond in CCl4.Given : vap H°(CCl4)
= 30.5 kJ mol–1; f H°(CCl4) = – 135.5 kJ mol–1; aH°(C) = 715 kJ mol–1
and aH°(Cl2) = 242 kJ mol–1. [Ans. 1304 kJ mol–1, 326 kJ mol–1]
Spontaneity, Entropy, Second and Third Law
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

Thermodynamics 67
 (iv) H2(g) + I2(g)  2HI(g)
(v) 2NaHCO3(s)  Na2CO3(s) + CO2(g) + H2O(g)
Gibbs Energy and Spontaneity, Effect of Temperature of Sponaneity
5. (i) De®ne Gibbs energy. Give its mathematical expression. What is Gibb’s
energy criteria of spontaneity.
(ii) For the reaction : 2A(g) + B(g)  2D(g), U° = – 10.5 kJ and S°
= – 44.1 J K–1. Calculate rG° for the reaction, and predict whether will
occur spontaneously. [Ans. rG° = + 0.16 kJ, Non spontaneous]

68 Chemistry Class XI