Chemistry : Energetics

ASSIGNMENTS

SECTION - I
SUBJECTIVE QUESTIONS
LEVEL - I

1. Heat of formation of water is – 68 kcal mol–1. What is heat of formation of OH–?

2. Heat of solution of a solute MX is 20 kJ mol–1 and that of MX. H2O is 10 kJ mol–1. What is hydration
energy of MX?
3. For the reaction,
2NO(g) + O2(g) —2NO2(g)
Calculate G at 700 K when enthalpy and entropy changes are –113.0 kJ mol–1 and –145 JK–1 mol–1
respectively.
4. 10 g of argon gas is compressed isothermally and reversibly at a temperature of 27º from 10 L to 5 L.
Calculate Q , W ,  E &  H for this process . Atomic weight of Ar = 40.
5. Calculate the resonance energy of N2O from the following data .
 Hfº of N2O = 82 k J mol 1 . Bond energy of N  N , N = N , O = O & N = O bonds is 946 , 418,
498 & 607 k J mol 1 respectively .
6. A gas expands from 3 dm3 to 5 dm3 against a constant pressure of 3 atm . The work done during
expansion is used to heat 10 mmole of water of temperature 290 k . Calculate final temperature of
water , specific heat of water .
7. The heats of combustion of C2H4 (g) , C2 H6 (g) & H2 (g) are  1409.5 k J ,  1558.3 k J and
 285.6 k J respectively . Calculate the heat of hydrogenation of ethylene .
8. Calculate º H for chloride ion from the following data .

1 1
H2 (g) + Cl2 (g)  HCl (g) º Hf =  92.4 k J
2 2
HCl + n H2O  H+ (aq) + Cl (aq) H298 =  74.8 k J
 Hf (H+) aq = 0.0 k J
9. The standard heat of formation of CH 4 (g) , CO2 (g) and H2 O (g) are  76.2 ,  394.8 and
 241.6 k J mol 1 respectively . Calculate the amount of heat evolved by burning 1 m3 of methane
measured under normal conditions .
10. The heat liberated on complete combustion of 7.8 g benzene is 327 k J . This heat has been measured at
constant volume and at 27 ºC . Calculate the heat of combustion of benzene at constant pressure .
 Chemistry : Energetics

LEVEL - II
1. A gas expands by 0.5 litre against a constant pressure of one atmosphere. Calculate the work done in
calorie.
2. A gas contained in a cylinder fitted with a frictionless piston expands against a constant pressure
1 atmosphere from a volume of 4 litre to a volume of 14 litre. In doing so, it absorbs 800 J thermal
energy from surroundings. Determine E for the process.
3. Calculate the amount of work done by 2 mole of an ideal gas at 298 K in reversible isothermal expansion
from 10 litre to 20 litre.
4. The standard heats of formation at 298 K for CCl4(g). H2O(g), CO2(g) and HCl(g) are – 25.5, – 57.8,
– 94.1 and – 22.1 kcal mol–1 respectively. Calculate Ho298 for the reaction.

CCl4(g) + 2H2O(g)  CO2(g) + 4HCl(g)

5. The bond dissociation energies of gaseous H2, Cl2 and HCl are 104, 58 and 103 kcal mol–1 respectively.
Calculate the enthalpy of formation of HCl(g).
6. Given that
3C(s) + 2Fe2O3(s)  4Fe(s) + 3CO2(g); H° = – 93657 kcal at 25°C
3C(s) + 3O2(g) 3CO2(g) H° = – 94050 kcal at 25°C

What is the value of ΔH of (Fe 2 O3 ) is at 25°C?

7. The amount of heat required to raise the temperature of 1 mole diatomic gas by 1°C at constant
pressure is 60 cal. What is the amount of heat which goes as internal energy of the gas.
8. The heat of combustion of carbon is 394 kJ. What is the heat evolved in combustion of
6.023  1022 atoms of carbon.
9. Find bond enthalpy of S – S bond from the following data :

C2H5 — S — C2H5 ΔH °f = –147.2 kJ mol-1

C2H5 — S – S — C2H5 ΔH °f = –201.9 kJ mol-1

S(g) ΔH °f =222.8 kJ mol-1

10. From the data at 25°C :

Fe2O3(s) + 3C(graphite) 
 2Fe(s) + 3CO(g), ΔH ° =492.6 kJ/mol
FeO(s) + C(graphite) 
 CO2(g), ΔH ° =155.8 kJ/mol

C(graphite) + O2(g) 
 CO2(g), ΔH ° = –282.98 kJ/mol
Calculate standard heat of formation of FeO(s).
Chemistry : Energetics

LEVEL - III
1. The enthalpy for the following reactions ( Hº) at 25 ºC are given below :
1 1
(i) H2 (g) + O (g)  OH (g) ; 10.06 k Cal
2 2 2
(ii) H2 (g)  2 H (g) ; 104.18 k Cal
(iii) O2 (g)  2 O (g) ; 118.32 k Cal
Calculate the O  H bond energy in the hydroxyl radical .
2. Given the following standard heats of reactions .
(i) heat of formation of water =  68.3 k Cal
(ii) heat of combustion of acetylene =  310.6 k Cal
(iii) heat of combustion of ethylene =  337.2 k Cal
Calculate the heat of reaction for the hydrogenation of acetylene at constant volume and 25º C .
3. An athelete is given 100 g of glucose (C6H12O6) of energy equivalent to 1560 k J . He utilizes 50 percent
of this gained energy in the event . In order to avoid storage of energy in the body calculate the weight
of water he would need to perspire . The enthalpy of evaporation of water is 44 k J/mole .
4. Determine the enthalpy change of the reaction , C3H8 (g) + H2 (g)  C2H6 (g) + CH4 (g) at 25 ºC ,
using the given heat of combustion values under standard condition .
Compound H2 (g) CH4 (g) C2H6 (g) C (graphite)
 Hº (K J/mole)  285.8  890.0  1560.0  393.5
The standard heat of formation of C3H8 (g) is  103.8 k J/mole .
5. Assume that for a domestic hot water supply 150 kg of water per day must be heated from 10°C to
65°C and gaseous fuel propane is used for this purpose. What moles and volume of propane in litres at
STP would have to be used for heating domestic water. H of combustion of propane is – 2050 kJ and
specfic heat of water is 4.18  10–3 kJ / g
6. The heat of combustion of Acetylene is 312 kcals. If the heat of formation of CO2 is 94.38 kcals and
that of water is 68.38 kcals. Calculate the C  C bond energy; assuming that the bond energy of C – H
is 93.6 kcals. Heat of atomisation of C and H are 150 and 51.5 kcals respectively.
7. The heat of solution of anhydrous CuSO4 is – 15.9 kcal and that of CuSO4.5H2O is 2.8 Kcal. Calculate
the heat of hydration of CuSO4.
8. The commercial production of water gas utilizes the reaction under standard conditions:
C + H2O(g)  H2 + CO. The heat required for this endothermic reaction may be supplied by adding
a limited amount of air and burning some carbon to CO2. How many gm of carbon must be burnt to
CO2 to provide enough heat for the water gas conversion of 100g carbon. Neglect all heat losses to
environment. H0f of CO, H2O(g) and CO2 are –110.53, –241.81 and –393.51 kJ/mol respectively..
9. Calculate the heat of neutralization from the following data 200 ml of 1M HCl is mixed with 400 ml of
0.5 M NaOH. The temperature rise in calorimeter was found to be 4.4°C. Water equivalent of
calorimeter is 12 g and specific heat is 1 cal / ml / degree for solution.
10. At 1000K from the data, N2(g) + 3H2(g)  2NH3(g)
H0 = – 123.77 kJ mole–1
Substance N2 H2 NH 3
Cp/R 3.5 3.5 4
Calculate the heat of formation of NH3 at 300K.
 Chemistry : Energetics

SECTION - II
SINGLE CHOICE QUESTIONS
1. For the spontaniety of a reaction which statement is true?
(a) G = +ve; H = +ve (b) H = +ve; S = –ve
(c) G = –ve; S = –ve (d) H = –ve; S = +ve
3
2. S  O 2 
 SO3  2x kcal
2
1
SO 2  O 2   SO3  y kcal
2
Find out the heat of formation of SO2
(a) (y – 2x) (b) (2x + y)
(c) (x + y) (d) 2x/y
3. For the process Dry ice  CO2(g)
(a) H is positive and S is negative (b) Both H and S are negative
(c) Both H and S are positive (d) H is negative whereas S is positive
4. A heat engine absorbs heat Q1 at temperature T1 and heat Q2 at temperature T2. Work done by the
engine is J (Q1 + Q2). This data
(a) violates 1st law of thermodynamics
(b) violates 1st law of thermodynamics if Q1 is – ve
(c) violates 1st law of thermodynamics if Q2 is – ve
(d) does not violate 1st law of thermodynamics
5. For the reaction
C3H8(g) + 5O2(g)  3CO2(g) + 4H2O(l)
at constant temperature, H – E is
(a) + RT (b) – 3 RT
(c) + 3 RT (d) – RT
6. In an irreversible process taking place at constant T and P and in which only pressure-volume work is
being done, the change in Gibbs free energy (dG) and the change in entropy (dS), satisfy the criteria
(a) (dS) V,E  0, (dG)T, P  0 (b) (dS) V,E  0, (dG)T, P  0

(c) (dS) V,E  0, (dG)T, P  0 (d) (dS) V,E  0, (dG) T, P  0

7. Given the bond energies of N  N, H —H and N—H bonds are 945, 436 and 391 kJ mole–1 respectively,
the enthalpy of the reaction
N2(g) + 3 H2(g)  2NH3 (g) is
(a) – 93 kJ (b) 102 kJ
(c) 90 kJ (d) 105 kJ
8. Based on the following thermochemical equations
H2O(g) + C(s)  CO(g) + H2(g); H = 131 kJ
CO(g) + 1/2 O2(g)  CO2(g); H = – 282 kJ
H2(g) + 1/2 O2(g)  H2O(g); H = – 242 kJ
C(s) + O2(g)  CO2(g); H = X kJ
Chemistry : Energetics

the value of X will be

(a) – 393 kJ (b) – 655 kJ
(c) + 393 kJ (d) + 655 kJ
9. The heat of combustion of carbon is – 94 kcal at 1 atm pressure, the intrinsic energy of CO2 is
(a) + 94 kcal (b) – 94 kcal
(c) + 47 kcal (d) – 47 kcal
10. –1 –1
Given the following entropy values (in JK mol ) at 298 K and 1 atm : H2(g) : 130.6, Cl2(g) : 223.0 and
HCl(g) : 186.7. The entropy change (in JK mol–1) for the reaction
H2(g) + Cl2(g)  2HCl (g) is
(a) + 540.3 (b) + 727.0
(c) – 166.9 (d) 19.8
11. Calculate the free energy change for the following reaction at 300 K.
1
2CuO(s)   Cu 2O(s)  O 2 (g)
2
Given H = 145.6 kJ mol–1
and S = 116 JK–1 mol–1
(a) 110.8 kJ mol–1 (b) 221.5 kJ mol–1
(c) 55.4 kJ mol –1 (d) 145.6 kJ mol–1
12. What percent T1 is of T2 for a heat engine whose efficiency is 10%?
(a) 80% (b) 90%
(c) 10% (d) 100%
13. One gram sample of NH4NO3 is decomposed in a bomb calorimeter. The temperature of the calorimeter
increases by 6.12 K. The heat capacity of the system is 1.23 kJ/g/deg. What is the molar heat of
decomposition for NH4NO3?
(a) – 7.53 kJ/mol (b) – 398.1 kJ/mol
(c) – 16.1 kJ/mol (d) – 602 kJ/mol
14. 2 mole of an ideal gas at 27°C temperature is expanded reversibly from 2 lit to 20 lit. Find entropy
change (R = 2 cal/mol K)
(a) 92.1 (b) 0
(c) 4 (d) 9.2
15. One mole of an ideal gas is allowed to expand reversibly and adiabatically from a temperature of 27°C.
If the work done during the process is 3 kJ, the final temperature will be equal to (Cv = 20 JK–1)
(a) 150 K (b) 100 K
(c) 26.85 K (d) 295 K
16. The standard state Gibbs free energy change for the isomerization reaction

cis  2  pentene trans  2  pentene

is – 3.67 kJ/mol at 400 K. If more trans-2-pentene is added to the reaction vessel, then
(a) additional trans-2-pentene is formed
(b) more cis-2-pentene is formed
(c) equilibrium is shifted in the forward direction
(d) equilibrium remains unaffected
 Chemistry : Energetics

17. For the alltropic change represented by the equation C (graphite)  C (diamond), the enthalpy change
H = 1.9 kJ. If 6 g of diamond and 6g of graphite are spearately burnt to yield CO2, the heat liberated
in first case is
(a) less than in the second case by 1.9 kJ (b) more than in the second case by 11.4 kJ
(c) more than in the second case by 0.95 kJ (d) less than in the second case by 11.4 kJ
18. A solution of 200 ml of 1 M KOH is added to 200 ml of 1 M HCl and the mixture is well shaken. The rise
in temperature T1 is noted. The experiment is repeated by using 100 ml of each solution and increase in
temperature T2 is again noted. Which of the following is correct?
(a) T1 = T2 (b) T2 is twice as large as T1
(c) T1 is twice as large as T2 (d) T1 is four times as large T2
19. Cp for a reaction is given by
2.0 + 0.2 T cal/deg
Its enthalpy of reaction at 10 K is – 14.2 kcal. Its enthalpy of reaction at 100 K in kcal will be
(a) – 13.21 (b) – 15.37
(c) 16.02 (d) 07.08
20. When one mole of an ideal gas is compressed to half of its initial volume and simultaneously heated to
twice its initial temperature, the change in entropy (S) is :
(a) Cp in 2 (b) Cp in 2
(c) R ln 2 (d) (Cv – R) ln 2
Chemistry : Energetics

SECTION - III
MULTIPLE CHOICE QUESTIONS
1. In which of the reaction H > U
(a) H2 + I2  2HI (b) PCl5  PCl3 + Cl2
(c) 2H2O2  2H2O + O2 (d) C + O2  CO2
2. The correct expressions for an adiabatic process

 1 1
T2  V1  P T  r
(a)   (b) 2   1 
T1  V2  P1  T2 

(c) P1V1  P2 V2 (d) P1V1 1  P2 V2 1

3 If a and b are arbitary extensive variables then

(a) (a + b) is an extensive variable (b) (a + b) is an intensive variable

da
(c) a/b is an intensive variable (d) is an intensive variable
db
4. One mole of an ideal monoatomic gas at 27°C expands adiabatically against a constant external pressure
of 1 atm from a volume of 10 dm3 to a volume of 20 dm3.
(a) W = – 1013 J
(b) U = – 1013 J
(c) H = – 1688 J
(d) The final temperature achieved is = 291.8 K
5. Which of the following statements is/are correct
(a) Absolute value of enthalpy cannot be determined
(b) Absolute value of internal energy cannot be determined
(c) Absolute value of entropy can be determined
(d) Internal energy, enthalpy and entropy are intensive properties
6. The enthalpy change for the process
C (graphite)  C(g) is called
(a) heat of vaporisation (b) heat of sublimation
(c) heat of allotropic change (d) heat of atomisation
7. Which of the following relations are correct?
(a) G = H + TS (b) E = H + PV
(c) E = q + w (d) qv = qp – ngRT
 Chemistry : Energetics

8. The second law of thermodynamics states that

(a) All spontaneous processes are thermodynamically irreversible
(b) Entropy of the universe is continuously increasing
(c) Energy can neiher be created nor destroyed
(d) Energy of the universe remains constant
9. The criteria for spontaneity of a process is/are
(a) (dG)T,P < 0 (b) (dE)S, V < 0
(c) (dH)S,P < 0 (d) (dS)E, V < 0
10. Which of the following conditions will apply to the conversion of ice into water?
H S G
(a) – – – at low T
(b) – – + at low T
(c) + + + at low T
(d) + + – at high T
Chemistry : Energetics

MISCELLANEOUS QUESTIONS
SECTION - IV
COMPREHENSION TYPE QUESTIONS

Write-up I
Work done by a system in irreversible isothermal process is zero. Work done by the system in
V2
isothermal reversible process is wrev. = 2.303 nRT log . Also in case of adiabatic reversible
V1

nR
process work done by the system is given by : wrev. = [T – T1]. During expansion disorder
 1 2
q rev.
increases and the increase in disorder is expressed in terms of change in entropy S = . The
T
H
entropy changes also occur during transformation of one state to other and expressed as S = .
T
Both entropy and enthalpy changes obtained for a process were taken as a measure of spontaniety
of process but finally it was recommended that decrease in free energy is responsible for spontaneity
and G = H – TS.

1. Which statements are correct :

(1) The expansion work for a gas into vacuum is equal to zero.
(2) 1 mole of a gas occupying 3 litre volume on expanding to 15 litre at constant pressure of 1 atm
does expanstion work 1.215 kJ.
(3) The maximum work done during expansion of 16g O2 at 300 K from 5 dm3 to 25 dm3 is 2.01 kJ.
(4) The S for Solid Liquid is almost negligible in comparison to S for Liquid G.as
V2
(5) S  2.303 nR log . (at constant T)
V1
(a) 2, 3, 4, 5 (b) 1, 2, 3, 4, 5
(c) 1, 2 (d) 4, 5
Svap.
2. The heat of vaporisation and heat of fusion of H2O are 540 cal/g and 80 cal/g. The ratio of for
Sfusion
water is :
(a) 6.75 (b) 9.23
(c) 4.94 (d) 0.2
3. A chemical change will definitely be spontaneous if :
(a) H = –ve, S = –ve and low temperature
(b) H = +ve, S = –ve and high temperature
(c) H = –ve, S = +ve and any temperature
(d) H = +ve, S = +ve and TS < H
 Chemistry : Energetics

Write-up II
Dependence of Spontaneity on Temperature : For a process to be spontaneous, at constant
temperature and pressure, there must be decrease in free energy of the system in the direction of the
process, i.e., GP.T  0 . GP.T  0 implies the equilibrium condition and GP.T  0 corresponds
to non-spontaneity. Gibbs-Helmholtz equation relates the free energy change to the enthalpy and
entropy changes of the process as :
GP.T  H  T S
The magnitude of H does not change much with the change in temperature but the entropy factor
T S changes appreciably. Thus, spontaneity of a process depends very much on temperature.
For endothermic process, both H and S are positive. The energy factor of equation, opposes the
spontaneity whereas entropy factor favours it. At low temperature the favourable factor T S will
be small and may be less than G , H will have positive value indicating the nonspontaneity of the
process. On raising temperature, the factor T S increases appreciably and when it exceeds H , G
would become negative and the process would be spontaneous.
For an exothermic process, both H and S would be negative. In this case the first factor of
equation 1 favour the spontaneity whereas the second factor opposes it. At high temperature, when
T S  H , G will have positive value, showing thereby the non-spontaneity of the process.
However, on decreasing temperature, the factor T S decreases rapidly and when T S  H , G
becomes negative and the process occurs spontaneously. Thus, an exothermic process may be
spontaneous at low temperature and non-spontaneous at high temperature.

4. For the reaction at 25C , X 2O4( l )  2 XO2

–1
H = 2.1 Kcal and S = 20 cal K . The reaction would be
(a) spontaneous (b) non-spontaneous
(c) at equilibrium (d) unpredictable
5. For the reactionat 298 K, 2A + B  C
–1
H = 100 kcal and S = 0.050 kcal K . If H and S are assumed to be constant over the
temperature range, at what temperature will the reaction become spontaneous?
(a) 1000 K (b) 1500 K
(c) 2000 K (d) 2500 K
6. The enthalpy change for a certain reaction at 300 K is –15.0 Kcal mol–1. The entropy change under
these conditions is –7.2 cal K –1 mol –1 . The free energy change for the reaction and its
spontaneous/nonspontaneous character will be
(a) –12.84 kcal mol–1, spontaneous
(b) 12.84 kcal mol–1, non spontaneous
(c) –17.16 kcal mol–1,spontaneous
(d) None of these
Chemistry : Energetics

MULTIPLE MATCHING TYPE QUESTIONS

Match the following

7. Column – I Column – II
(a) E = 0 H = 0 (p) CH2=CH2(g) + H2(g)  CH3 CH3(g)
(b) H = – ve (q) For a reversible process
(c) Suniv = 0 (r) Non ideal solutions with negative deviation
(d) GMix = – ve (s) For an ideal gas undergoing expansion
isothermally

8. Column – I Column – II
(a) Temperature of a system always decreases (p) CH2 = CH-CH=CH2

 E 
(b)   0 (q) Internal energy increases
 V T
(c) Temperature of the system increases (r) Ideal gas
(d) H Hydrogeneation (experimenta)
(s) Adiabatic expansion
< H Hydrogenation (calculated)

ASSERTION-REASON TYPE QUESTIONS

The question given below consist of an ASSERTION and the REASON. Use the following key for the
appropriate answers
(a) If both Assertion and Reason are correct and Reason is the correct explanation for Assertion
(b) If both Assertion and Reason are correct and Reason is not the correct explanation for
Assertion
(c) If Assertion is correct but Reason is not correct.
(d) If Assertion is incorrect but Reason is correct.
9. Assertion : Mass, volume and pressure are extensive properties.
Reason : Extensive properties depend upon the amount of the substance.
10.Assertion : Heat of neutralisation of HF is more than that of HCl by NaOH.
Reason : HF is stronger acid than HCl
11. Assertion : When a real gas is allowed to expand adiabatically though a fine hole from a region of high
pressure to the region of low pressure, the temperature of the gas falls.
Reason : Work is done at the cost of internal energy of the gas.
 Chemistry : Energetics

12.Assertion : Internal energy change in a cyclic process is zero.

Reason : Internal energy is a state function.
13.Assertion : An exothermic process, non-spontaneous at high temperature, may become spontaneous at
low temperature.
Reason : With decrease in temperature, randomness (entropy) decreases.
14.Assertion : The enthalpy of formation of H2O (l) is greater than that of H2O(g).
Reason : Enthalpy change is negative for condensation reaction: H2O(g)  H2O(l)
15.Assertion : Enthalpy of graphite is lower than that of diamond.
Reason : Entropy of graphite is greater than that of diamond.
Chemistry : Energetics

SECTION - V

A. Only one option is correct (Objective Questions)

1. The value of log10K for a reaction A B is
o
(Given :  r H 298K   54.07 kJ mol 1 ,  r So298K  10 JK 1mol 1 and R = 8.314 JK –1 mol –1 ;
2.303  8.314  298 = 5705)
(a) 5 (b) 10
(c) 95 (d) 100
2. For the process H2O(l) (1 bar, 273 K)  H2O(g) (1 bar, 373 K), the correct set of thermodynamic
parameters is
(a) G = 0, S = +ve (b) G = 0, S = –ve
(c) G = +Ve, S = 0 (d) G = –ve, S = +ve
3. When one mole of monoatomic ideal gas at TK undergoes adiabatic change under a constant external
pressure of 1 atm changes volume from 1L to 2L The final temperature in kelvin would be:

T 2
(a) (b) T 
22 / 3 3  0.0821

2
(c) T (d) T 
3  0.0821
4. 2 mole of an ideal gas expanded isothermally an reversibly from 1L to 10L at 300 K. What is the
enthalpy chagne?
(a) 4.98 kJ (b) 11.47 kJ
(c) – 11.47 kJ (d) 0 kJ

5. Hvap = 30 kJ/mol and Svap = 75 J mol–1K–1. Find temperature of vapour, at one atmosphere
(a) 400 K (b) 350 K
(c) 298 K (d) 250 K
6. Spontaneous adsorption of a gas on solid surface is an exothermic process because :
(a) H increases for system (b) S increases for gas
(c) S decreases for gas (d) G increases for gas
7. Which of the reaction defines H°f ?

1 1
(a) C(diamond) + O2(g)  CO2(g) (b) H 2 (g)  F2 (g) 
 HF(g)
2 2

1
(c) N2 (s) + 3H2(g)  2NH3(g) (d) CO(g)  O2 (g) 
 CO 2 (g)
2
 Chemistry : Energetics

8. One mole of a non-ideal gas undergoes a change of state (2.0 atm, 3.0 L, 95K)  (4.0 atm,
5.0 L, 245 K) with a change in internal energy, U = 30.0 L-atm. The change in enthalpy (H) of the
process in L-atm is :
(a) 40.0
(b) 42.3
(c) 44.0
(d) not defined, because pressure is not constant
9. In thermodyanmics, a process is called reversible when :
(a) surrounding and system change into each other
(b) there is no bondary between system and surroundings
(c) the surroundings are always in equilibrium with the system
(d) the system changes into the surroundings spontaneously
10. The H°f for CO2(g), CO(g) and H2O(g) are – 393.5, – 110.5 and – 241.8 kJ mol–1 respectively. The
standard enthalpy change (in kJ mol–1) for the reaction CO2(g) + H2(g)  CO(g) + H2O(g) is:

(a) 524.1 (b) + 41.2

(c) – 262.5 (d) 41.2

B. More than one options are correct (Objective Questions)

1. Identify the intensive quantities from the following :
(a) enthalpy (b) temperature
(c) volume (d) refractive index
2. The following is (are) endothermic reaction (s) :
(a) combustion of methane (b) decomposition of water
(c) dehydrogeneration of ethane to ethylene (d) conversion of graphite to diamond
3. Which one of the following staement is false?
(a) Work is a state function
(b) Temperature is a state function
(c) Change in the state is completely defined when the initial and final states are specified
(d) Work appears at the boundary of the system
4. Find the molar heat capacity of an ideal monoaticmi gas for a process for which p/v is constant and is
equal to 1.
(a) 3/2R (b) 4/2R
(c) 5/2R (d) 0
5. The reaction A to B is not feasible directly but it takes place through series of steps C D
S (A  C) = 50 eu; S (C D) = 30 eu; S (B D) = 20 eu;
The entropy change for A  B would be
(a) 100 eu (b) 60 eu A B
(c) – 60 eu (d) – 100 eu
Chemistry : Energetics

SUBJECTIVE QUESTIONS
1. Compute the heat of formation of liquid methyl alcohol in kilo joules per mole using the following data .
Heat of vaporization of liquid methyl alcohol = 38 k J/mol .
Heat of formation of gaseous atoms from the elements in their standard states are
H = 218 k J mol 1 . C = 715 k J mol 1 and O = 249 k J mol 1 .
Average bond energyes are : C  H = 415 k J mol 1; C  O = 356 k J mol 1
O  H = 463 k J mol 1 .
2. From the following data calculate the enthalpy change for the combustion of cyclopropane at 298 K.
The enthalpy of formation of CO2 (g) , H2O (l) & propene (g) are ,
 393.5 ,  285.8 & 20.42 k J mol 1 respectively . The enthalpy of isomerisation of cyclopropane to
propene is  33.0 k J mol 1 .
3. Estimate the average S  F bond energy in SF6 . The standard heat of formation values of SF6 (g) , S
(g) & F (g) are  1100 , 275 , 80 k J mol 1 respectively .
4. A sample of argon gas at 1 atm pressure and 27 ºC expands reversible and adiabatically from 1.25 dm3
to 2.50 dm3 . Calculate the enthalpy change in this process . Cvm for argon is 12.48 J k 1 mol 1 .

5. Diborane is a potential rocket fuel which undergoes combustion according to the reaction
B2H6 (g) + 3 O2 (g)   B2O3 (g) + 3 H2O (g) .
2 B (s) + (3/2) O2 (g)  B2O3 (s) ;  H =  1273 k J mol 1
H2 (g) + (1/2) O2 (g)  H2O (l) ;  H =  286 k J mol 1
H2O (l)  H2O (g) ;  H = 44 k J mol 1
2 B (s) + 3 H2 (g)  B2H6 ;  H = 36 k J mol 1
6. Show that the reaction , CO (g) + (1/2) O2 (g)  CO2 (g) at 300 K, is spontaneous and
exothermic . When the standard entropy chage is - 0.094 k J mol 1 , the standard Gibbs feee energies of
formation for CO2 & CO are  394.4 &  137.2 k J mol 1 respectively .
7. When 1-pentyne (A) is treated with 4N alcholic KOH at 175°C, it is converted slowly into an
equilibrium mixture of 1.3% 1-pentyne (A), 95.2% 2-pentyne (B) and 3.5% of, 1, 2-pentadiene
(C). The equilibbrium was maintained at 175°C. Calculate G° for the following equilibria.

B A, G10  ?
B C, G 02  ?

From the calculated value of G10 and G 02 indicate the order of stability of (A), (B) and (C).
Write a reasonable reaction mechanism showing all intermediates leading to (A), (B) and (C)

8. Two moles of a perfect gas undergo the following processes :

(a) a reversible isobaric expansion from (1.0 atm. 20.0 ) to (1.0 atm, 40.0L)
(b) a reversible isochoric change of state from (1.0 atm, 40.0L) to (0.5 atm, 40.0L)
(c) a reversible isothermal compression from (0.5 atm. 40.0L) to (.10 atm, 20.0L)
 Chemistry : Energetics

(i) Sketch with labels each of the processes on the same P-V diagram.
(ii) Calculate the total work (w) and the total heat change (Q) involved in the above processes.
(iii) What will be the values of U, H and S for the overall process?

3R 3R 5R
9. Cv value of He is always but C v value of H2 of at low temperature and at moderate
2 2 2
5R
temperature and more than at higher temperature. Explain in two or three lines.
2
10. 100 mL of a liquid contained in an insulated container at a pressure of 1 bar. The pressure is
steeply increased to 100 bar. The vaolume of the liquid is decreased by 1 mL at this constant
pressure. Find the H and U.
Chemistry : Energetics

ANSWERS
EXERCISE - 1
 nRT 
1. (a) W = – Pext (V2 – V1) = – Pext  P  0  = – nRT = – 1 × 8.314 × 298 J
 ext 
(b) zero (V = constant, V = 0)
V2 V2
 RT   a   V b  1 1 
2. W=   PdV =   V  b    V 2   dV = 2.303 RT log  2 a  
V1 V1  V1  b   V2 V1 
4. – 42.8 kcal

EXERCISE - 2
1 0.33
T2  V1  1 1 273
1. T1 =  V2  = 
8
=
2
, T2 =
2
= 136.5 K;

W = Cv (T2 – T1) = – 3R (T2 – T1) = 3 × 2 × 136.6 cal

2. (ii) 150 J
(iii) 10 J
3. (ii) V = 113.13 × 10–3 m3; P = 0.44 × 105 N/m2
(iii) 12450 J

EXERCISE - 3
1. H°398 K = – 11.6 kcal, E°298 K = – 10.404 kcal, E°398 K = – 10.804 kal
2. 3.657 kg 3. – 2058 kJ

EXERCISE - 4
1. – 0.42 kJ 2. – 75.14 kJ
3. – 161.3 kcal

EXERCISE - 5
1. – 41.82 kJ mol–1 3. 88 kJ mol–1
4. – 101. 19 kcal

EXERCISE - 6
1. – 103. 15 kJ 2. – 11451.4 kJ

EXERCISE - 7
1. (a) – ve (b) + ve
(c) + ve (d) – ve
 Chemistry : Energetics

2. (a) shuffled deck in which the cards are arranged randomly

(b) a disordered crystals
(c) 1 mole N2 gas at STP
(d) 1 mole N2 at 273 K and 0.25 atm
3. Spontaneous : (b), (c), (e); Nonspontaneous : (a), (d); S = + ve in (c)
S = – ve in others
4. (a) C2H6 (g) (b) CO2(g)
(c) I2(g) (d) CH3OH(g)

EXERCISE - 8
1. T = 373.4 K, G will be negative; hence, the raction will be spontaneous.
2. Kc = 1.958 × 10–4
3. Gº = –10.632 kJ

SECTION - I
(Subjective Questions)
LEVEL - I

1. – 54.3 k cal mol–1 2. 10 kJ mol–1

3. G = – 11.5 kJ mol–1
4. Q = 103. 6 cal; w = 103.6 cal; E = 0; H = 0
5. – 88 kJ 6. 290.81 k
7. – 136.8 kJ 8. – 167.2 kJ
9. 35794.64 kJ 10. – 3273.732 kJ mol–1
LEVEL - II

1. – 12.10 cal 2. – 213.7 J

3. – 3434.9 J 4. – 41.4 kcal
5. – 22 kcal/mol 6. – 196.5 kcal
7. 42.6 cal 8. 39.4 kJ
9. 277.5 kJ 10. – 393.5 kJ/mol
LEVEL - III

1. 121.31 kcal 2. – 41.104 kcal

3. 319.1 g 4. – 55.7 kJ/mol
5. 377.17 litres 6. 160.94 kcal
7. – 18.7 kcal 8. 33.36 g
9. – 13.464 kcal 10. – 44.42 kJ/mol
Chemistry : Energetics

SECTION - II
(Single Choice Questions)

1. (d) 2. (a)
3. (c) 4. (d)
5. (b) 6. (a)
7. (a) 8. (a)
9. (b) 10. (d)
11. (a) 12. (b)
13. (d) 14. (d)
15. (a) 16. (b)
17. (c) 18. (a)
19. (a) 20. (d)

SECTION - III
(Multiple Choice Questions)

1. (b, c) 2. (a, c)
3. (a, c, d) 4. (a, b, c, d)
5. (a, b, c) 6. (b, c)
7. (c, d) 8. (a, b)
9. (a, b, c) 10. (c, d)

SECTION - IV
(Comprehension Type Questions)

1. (b) 2. (c)
3. (c) 4. (a)
5. (c) 6. (a)

(Multiple Matching Type Questions)

7. (a) (s) (b) (p, r)

(c) (q) (d) (r)
8. (a) (s) (b) (r)
(c) (q) (d) (p)
 Chemistry : Energetics

(Assertion Reason Type Questions)

9. (d) 10. (c)

11. (a) 12. (a)
13. (b) 14. (a)
15. (b)

SECTION - V

A. Only one option is correct (Objective Questions)

1. (b) 2. (a)
3. (d) 4. (d)
5. (a) 6. (c)
7. (b) 8. (b)
9. (c) 10. (b)

B. More than one option are correct (Objective Questions)

1. (b, d) 2. (b, c, d)
3. (a, b) 4. (b)
5. (b)

SUBJECTIVE
1.  266 k J mol 1 2. – 309.17 kJ mol–1
3. 309.6 k J mol 1 4.  114.51 Joules
5.  2035 k J mol 1 6.  285.4 k J mol 1

7. G1o = +15.992 kJ mol–1, G o2 = +12.312 kJ mol–1, B > C > A

8. Total work = 1.409 × 10 3 J, U = 0, S = 0 and H = 0
9. In hints and solution package
10. U = 100 bar mL, H = 9900 bar mL