NUMERICAL ASSIGNMENT– I: THERMODYNAMICS 1

Problems related with First law of thermodynamics : Heat (q), work (w) and ΔE
1. Predict sign of work done in following reactions at constant pressure.
Initial state Final state
(i) 𝐻2 𝑂 (𝑔) → 𝐻2 𝑂(𝑙 )
(ii) 𝐻2 𝑂(𝑠) → 𝐻2 𝑂(𝑔)
(iii) 𝐻2 𝑂(𝑙 ) → 𝐻2 𝑂(𝑠)
(iv) 𝐶𝑎𝐶𝑂3 (𝑠) → 𝐶𝑎𝑂(𝑠) + 𝐶𝑂2 (𝑔)
2. The gas is cooled such that it loses 65 J of heat. The gas contracts as it cools and work done on the system
equal to 20 J is exchanged with the surroundings. What are q, w and ΔE?
3. The enthalpy of combustion of glucose is −2808 𝑘𝐽 𝑚𝑜𝑙 − at 250C. How many grams of glucose do you need to
consume [Assume wt = 62.5 kg].
(a) to climb a flight of stairs rising through 3 M.
(b) to climb a mountain of altitude 3000 M?
Assume that 25% of enthalpy can be converted to useful work.
4. Water expands when it freezes. Determine amount of work, in joules, done when a system consisting of 1.0 L
of liquid water freezes under a constant pressure of 1.0 atm and forms 1.1 L of ice.
5. Lime made commercially by decomposition of limestone, CaCO3. What is the change in internal energy when
1.00 mole of solid CaCO3 (V = 34.2 ml) absorbs 177.9 kJ of heat and decomposes at 250C against a pressure of
1.0 atm to give solid CaO. (Volume = 16.9 ml) and CO2(g) (V = 24.4 L).
6. One mole of solid Zn is placed in excess of dilute H2SO4 at 270C, in a cylinder fitted with a piston, Find the value
of ΔE, q and w for the process if the area of piston is 500 cm2 and it moves out by 50 cm against a pressure of 1
atm during the reaction. The heat given to surrounding is 36.5 kJ.
𝑍𝑛(𝑠) + 2𝐻 + (𝑎𝑞) ⇌ 𝑍𝑛2+ (𝑎𝑞) + 𝐻2 (𝑔)
7. When a system is taken from state A to state B along the path ACB, 80 J of heat flows into the system and the
system does 30 J of work. (a) How much heat flows into the system along path ADB if the work done is 10 J?
(b) When the system is returned from state B to A along the curved path, the work done on the system is 20 J.
Does the system absorb or liberate heat, and how much? (c) If U D – UA = 40 J, find the heat absorbed in the
process AD and DB.
C B

A D
V
Problems related with ΔU and ΔH
8. The enthalpy change for the reaction of 50 ml of ethylene with 50.0 ml of H2 at 1.5 atm pressure is
∆𝐻 = −0.31 𝐾𝐽. What is the ΔU?
9. What is ΔE when 2.0 mole of liquid water vaporises at 1000C? The heat of vaporisation, ΔH vap. Of water at
1000C is 40.66 kJ 𝑚𝑜𝑙− .
10. If 1.0 kcal of heat is added to 1.2 L of O2 in a cylinder of constant pressure of 1 atm, the volume increases to 1.5
L. Calculate ΔE and ΔH of the process.
11. When the following reaction was carried out in a bomb calorimeter, ΔE is found to be – 742.7 kJ/mol of
NH2CN(s) at 298 K.
3
𝑁𝐻2 𝐶𝑁(𝑠) + 2 𝑂2 (𝑔) → 𝑁2 (𝑔) + 𝐶𝑂2 (𝑔) + 𝐻2 𝑂(𝑙)
Calculate ΔH298 for the reaction.
12. When 1 mole of ice melt at 00C and at constant pressure of 1 atm. 1440 calories of heat are absorbed by the
system. The molar volumes of ice and water are 0.0196 and 0.0180 litre respectively. Calculate ΔH and ΔE for
the reaction.
13. 1 mole of ice at 00C and 4.6 mm Hg pressure is converted to water vapour at a constant temperature and
pressure. Find ΔH and ΔE if the latent heat of fusion of ice is 80 Cal/gm and latent heat of vaporisation of liquid
water at 00C is 596 Cal per gram and the volume of ice in comparison to that of water (vapour) is neglected.
14. The molar enthalpy of vaporization of benzene at its boiling point (353 K) is 30.84 kJ 𝑚𝑜𝑙− . What is the molar
internal energy change? For how long would a 12 volt source need to supply a 0.5 A current in order to
vaporise 7.8 g of the sample at its boiling point?

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NUMERICAL ASSIGNMENT– I: THERMODYNAMICS 2
Problems related with work done
15. Five moles of an ideal gas at 300 K, expanded isothermally from an initial pressure of 4 atm to a final pressure
of 1 atm against a cont. ext. Pressure of 1 atm. Calculate q, w, ΔU & ΔH. Calculate the corresponding value of
all if the above process is carried out reversibly.
16. Find the work done when one mole of the gas is expanded reversibly and isothermally from 5 atm to 1 atm at
250C.
17. Two mole of ideal diatomic gas (CV,m = 5/2 R) at 300 K and 5 atm expanded irreversibly & adiabatically to a final
pressure of 2 atm against a constnt presure of 1 atm. calculate q, w, ΔH & ΔU.
18. Calculate the work done by system in an irreversibly (single step) adiabatic expansion of 1 mole of a
polyatomic gas (𝛾 = 1.33) from 300K and pressure 10 atm to 1 atm.
19. 1 mole of CO2 gas at 300K is expanded under reversible adiabatic condition such that its volume becomes 27
times. (a) What is the final temperature? (b)What is work done?
−1 −1
Given 𝛾 = 1.33 𝑎𝑛𝑑 𝐶𝑉 = 25.08 𝐽 𝑚𝑜𝑙 𝐾 for CO2.
20. A real gas obeys the equation 𝑃 (𝑉𝑚 − 𝑏) = 𝑅𝑇, where (b = 0.1 L/mol), if 2 moles of gas is slowly compressed
from 1.2 litre to 0.6 litre at 300K then work done in the process is :
21. Three moles of a ideal gas at 200K and 2.0 atm pressure undergo reversible adiabatic compression until the
temperature becomes 250 K for the gas CV is 27.5 𝐽𝐾 −1 𝑚𝑜𝑙 −1 in this temperature range. Calculate q, w, ΔU,
ΔH and final V and final P.
22. 2 mole of an idel gas undergoes isothermal compression along three different paths
(i) Reversible compression from Pi = 2 bar and Vi = 4 L to Pf = 20 bar
(ii) A single stage compression against a constant external pressure of 20 bar, and
(iii) A two stage compression consisting initially of compression against a constant external pressure of 10
bar until Pgas = Pext, followed bycompression against a constant pressure of 20 bar until Pgas = Pext.
Calculate the work (in bar. L) for each of these processes and for which of the irreversibly processes is the
magnitude of the work greater? [Given : R = 0.08 bar. L/mole. L]
Problems related with cyclic process
23. One mole of an ideal monoatomic gas is carried through the reversible cycle of the given figure consisting of
step A, B and C and involving state 1, 2 and 3. Fill in the blank space in the table given below assuming
reversible steps.
V
State P V T 3
44.8 L
1 C B
2 22.4 L 2
1 A
3

273 K 546 K T

Ste p Nam e of proce s s q w w H

A
B
C
24. One mole of an ideal monoatomic gas is put through reversible path as shown in figure. Fill in the blank in the
table given below :

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NUMERICAL ASSIGNMENT– I: THERMODYNAMICS 3
State P V T 1 A
1 atm 2
1 B
C
2 0.5 atm 3
3

22.4 L 44.8 L

Ste p Nam e of proce s s q w w H

A
B
C
Cyclic
25. One mole of a perfect monoatomic gas is put through a cycle consisting of
the following three reversible steps: T1 T2
(CA) Isothermal compression from 2 atm and 10 litres to 20 atm and 1 litre. 20
A B
(AB) Isobaric expansion to return the gas to the original volume of 10 litres
P
with T going from T1 to T2.
(BC) Cooling at constant volume to bring the gas to the original pressure
and temperature. 2 C
T1
The steps are shown schematically in the figure shown.
1 V 10
(a) Calculate T1 and T2.
(b) Calculate ΔE, q and w in calories, for each step and for the cycle.
26. The given figure shows a change of state A to state C by two paths ABC
and AC for an ideal gas. Calculate the :
B C
(a) Path along which work done is least. 15

(b) Internal energy at C if the internal energy of gas at A is 10 J and 10

amount of heat supplied to change its state to C through the
P(N/m2)

path AC is 200 J. 5
A

(c) Amount of heat supplied to the gas to go from A to B, if internal

0 2 4
energy change of gas is 10 J. 6
3
V(m )
27. A monoatomic ideal gas of two moles is taken through a reversible cyclic V
𝑉 D
process starting from A as shown in figure. The volume ratios are 𝐵 = 2 and VD
C
𝑉𝐴
𝑉𝐷
𝑉𝐴
= 4. If the temperature TA at A is 270C, calculate :
B
VB
(a) The temperature of the gas at point B.
(b) Heat absorbed or released by the gas in each process. VA A
(c) The total work done by the gas during complete cycle.
0 TA TB T

28. One mole of an ideal gas (not necessarily monoatomic) is subjected to the following sequence of steps.
(a) It is heated at constant volume from 298 K to 373 K.
(b) It is expanded freely into a vacuum to double volume.
(c) It is cooled reversibly at constant pressure to 298 K.
Calculate q, w, ΔU and ΔH for the overall process.
Kirchoff’s Rule : Variation of Enthalpy with Temperature
29. The standard enthalpy for the reaction 𝐻2 (𝑔) + 1 𝑂2 (𝑔) → 𝐻2 𝑂(𝑙 )𝑖𝑠 − 285.76 𝑘𝐽 𝑎𝑡 298 𝐾. Calculate
2
the value of ΔH at 373 K. The molar heat capacities at constant pressure (C P) in the given temperature range of
H2(g), O2(g) and H2O (𝑙) are respectively 38.83, 29.16 and 75.31 𝐽𝐾 −1 𝑚𝑜𝑙−1 2.
30. Methane (Considered to be an ideal gas) initially at 250C and 1 bar pressure is heated at constant pressure
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NUMERICAL ASSIGNMENT– I: THERMODYNAMICS 4
until the volume has doubled. The variation of the molar heat capacity with absolute temperature is given by
𝐶𝑃 = 22.34 + 48.1 × 10−3 𝑇 where CP is in 𝐽𝐾 −1 𝑚𝑜𝑙 −1 . Calculate molar (a) ΔH (b) ΔU.
Second and third law & Entropy change in thermodynamic processes
31. One mole of NaCl (s) on melting absorved 30.5 KJ of heat and its entropy is increased by 28.8 𝐽𝐾 −1 . What is
the melting point of sodium chloride?
32. Oxygen is heated from 300 to 600 at a constant pressure of 1 bar. What is the increases in molar entropy? The
molar heat capacity in 𝐽𝐾 −1 𝑚𝑜𝑙 −1 for the O2 is 𝐶𝑃 = 25.5 + 13.6 × 10−3 𝑇 − 42.5 × 10−7 𝑇 2
33. Calculate ∆𝑆𝑓0 at 298 K of ; (i) NaCl (s), (ii) NH4Cl (s) & (iii) diamond.
The values of S0 of Na, Cl2, NaCl, NH4Cl, N2, H2, diamond & graphite are 51, 223, 72, 95, 192, 131, 2.43 & 5.69
𝐽𝐾 −1 𝑚𝑜𝑙 −1 respectively.
34. A heat engine absorbs 760 kJ heat from a source at 380 K. It rejects (i) 650 kJ, (ii) 560 kJ, (iii) 504 kJ of heat to
sink at 280 K. State which of these represent a reversible, an irreversible and an impossible cycle.
35. The efficiency of a carnot cycle is 1/6. On decreasing the temperature of the sink by 650C, the efficiency
increases to 1/3. Calculate the temperature of source and sink.
36. A carnot cycle has an efficiency of 40%. Its low temperature reservoir is at 70C. What is the temperature of
source?
37. Calculate the entropy of a substance at 600 K using the following date.
(i) Heat capacity of solid from 0 K to normal melting point 200 K
𝐶𝑃,𝑚 (𝑠) = 0.035 𝑇 𝐽𝐾 −1 𝑚𝑜𝑙 −1 .
(ii) Enthalpy of fusion = 7.5 𝑘𝐽 𝑚𝑜𝑙 −1,
(iii) Enthalpy of vaporisation = 30 𝑘𝐽 𝑚𝑜𝑙 −1 .
(iv) Heat capacity of liquid from 200 K to normal boiling point 300 K
𝐶𝑃,𝑚 (𝑙 ) = 60 + 0.016 𝑇 𝐽𝐾 −1 𝑚𝑜𝑙−1 .
(v) Heat capacity of gas from 300 K to 600 K at 1 atm
𝐶𝑃,𝑚 (𝑔) = 50.0 𝐽𝐾 −1 𝑚𝑜𝑙 −1 .
Gibb’s Function
38. Calculate the free energy change at 298 K for the reaction ;
𝐵𝑟2 (𝑙 ) + 𝐶𝑙2 (𝑔) → 2𝐵𝑟𝐶𝑙(𝑔). For the reaction ΔH0 = 29.3 kJ & the entropies of 𝐵𝑟2 (𝑙 ), 𝐶𝑙2 (𝑔) &
BrCl (g) at the 298 K are 152.3, 223.0, 239.7 J 𝑚𝑜𝑙−1 𝐾 −1 respectively.
39. Animals operate under conditions of constant pressure and most of the processes that maintain life are
electrical (in a board sense). How much energy is available for sustaining this type of muscular and nervous
activity from the combustion of 1 mol of glucose molecules under standard conditions at 370C (blood
temperature)? The entropy change is +182.4 𝐽𝐾 −1 for the reaction as stated.
∆𝐻𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛 [𝑔𝑙𝑢𝑐𝑜𝑠𝑒] = −2808 𝐾𝐽
40. The entropies of H2(g) and H(g) are 130.6 and 114.6 J 𝑚𝑜𝑙 −1 𝐾 −1 respectively at 298 K. Using the data given
below calculate the bond energy of H2 (in kJ/mol) :
𝐻2 (𝑔) → 2𝐻 (𝑔); ∆𝐺 0

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 NUMERICAL ASSIGNMENT– I: THERMODYNAMICS 5
ANSWER KEY
1. (i) w, (ii) – w, (iii) – w, (iv) – w 2. 𝑞 = −65 𝐽 ; 𝑤 = 20 𝐽 ; ∆𝐸 = −45 𝐽
3. (a) 0.47 gm, (b) 0.47 kg 4. −10 𝐽
5. 𝑞 = 177.9 𝑘𝐽, 𝑤 = −2.5 𝑘𝐽; ∆𝐸 = 175.4 𝑘𝐽 6. ∆𝐸 = −39.03 𝑘𝐽/𝑚𝑜𝑙𝑒; 𝑞 = −36.5 𝑘𝐽; 𝑤 = −2.53 𝑘𝐽
7. (a) + 60 J (b) – 70 J (c) 50 J, + 10 J 8. −0.3024 𝑘𝐽
9. ∆𝐸 = 75.11 𝑘𝐽 10. ∆𝐸 = 0.993 𝑘 𝑐𝑎𝑙, ∆𝐻 = 1 𝑘 𝑐𝑎𝑙
11. −741.5 𝑘𝐽 12. ∆𝐻 ≅ ∆𝐸 = 1440 𝑐𝑎𝑙𝑜𝑟𝑖𝑒𝑠
13. ∆𝐻 = 12168 𝑐𝑎𝑙𝑜𝑟𝑖𝑒𝑠; ∆𝐸 = 11623 𝑐𝑎𝑙𝑜𝑟𝑖𝑒𝑠 14. ∆𝐸 = 27.91 𝑘𝐽 𝑚𝑜𝑙 −1 , 𝑡 = 514 𝑠𝑒𝑐.
15. 𝑤𝑖𝑟𝑟 = −9353.25, 𝑤𝑟𝑒𝑣 = −17288.47 𝐽, ∆𝑈 = ∆𝐻 = 0 16. 𝑤 = −3.988 𝑘𝐽
17. ∆𝑈 = 𝑤 = −1247.1; ∆𝐻 = −1745.94 𝐽 18. −1.683 𝑘𝐽
19. 𝑇2 = 100 𝐾; 𝑤 = −5.016 𝑘𝐽 20. 4. 59 kJ
3
21. 𝑞 = 0; 𝑤 = ∆𝑈 = 4.12 𝑘𝐽; ∆𝐻 = 5.37 𝑘𝐽; 𝑉𝑓 = 11.8 𝑑𝑚 ; 𝑃 = 5.21 𝑎𝑡𝑚
22. (i) 18.424 bar.L; (ii) 72 bar.L; (iii) 40 bar.L
Magnitude of work is maximum in single stage compression
23.
Table – 1
State P V T
1 1 atm 22.4 273
2 2 atm 22.4 546
3 1 atm 44.8 546

Step Name of process q w ΔE ΔH

A Isochoric 3/2R(273) 0 3/2 R(273) 5/2 R(273)
B Isothermal 546 R ℓn2 – 546 R ℓn2 0 0
C Isobaric – 5/2 R(273) R(273) – 3/2 R(273) – 5/2 R(273)

24.
Table – 1
State P V T
1 1 atm 22.4 273
2 1 44.8 546
3 0.5 44.8 546

Step Name of process q w ΔE ΔH

A Isobaric 5/2R(273) – R (273) 3/2 R(273) 5/2 R(273)
B Isochoric – 3/2 R(273) 0 – 3/2 R(273) – 5/2 R(273)
C Isothermal – 273 R ℓn2 273 R ℓn2 0 0
Cyclic R(273) – 273 R ℓn2 – R(273) + 273 R ℓn2 0 0
25. (a) 𝑇1 = 243.60 𝐾; 𝑇2 = 2436.0 𝐾, (𝑏)∆𝐸 = 0; 𝑞 = −𝑤 = +3262.88 𝑐𝑎𝑙
26. (a) AC, (b) 170 J, (c) 10 J
27. (𝑎)600 𝐾, (𝑏)𝑞𝐴𝐵 = 3000 𝑐𝑎𝑙; 𝑞𝐵𝐶 = 1663 𝑐𝑎𝑙; 𝑞𝐶𝐷 = −1800 𝑐𝑎𝑙; 𝑞𝐷𝐴 = −1663 𝑐𝑎𝑙; 𝑇𝑜𝑡𝑎𝑙 = 1200 𝑐𝑎𝑙 (𝑐)𝑤 =
−1200 𝑐𝑎𝑙
28. ∆𝑈 & ∆𝐻 = 0; 𝑤 = 623.55; 𝑞 = −623.55 𝐽 𝑚𝑜𝑙 −1 29. ∆𝐻373 (𝐻2 𝑂(𝑙)) = −284.11 𝑘𝐽
30. (𝑎)13.064 𝑘𝐽 𝑚𝑜𝑙 −1 , (𝑏)10.587 𝑘𝐽 𝑚𝑜𝑙 −1 31. 𝑇 = 1059 𝐾
32. 21.18 𝐽𝐾 −1 𝑚𝑜𝑙−1
33. (𝑖 ) − 90.5 (𝑖𝑖 ) − 374.5 (𝑖𝑖𝑖 ) − 3.26 (𝑎𝑙𝑙 𝑖𝑛 𝐽 𝑚𝑜𝑙 −1 𝐾 −1 ) 34. (i) irreversible, (ii) reversible, (iii) impossible
35. 1170C, 520C 36. 193.660C
37. 205.08 𝐽𝐾 −1 𝑚𝑜𝑙−1 38. −1721.8 𝐽
39. −2864.5 𝐾𝐽 40. 436 𝑘𝐽/𝑚𝑜𝑙

S. Bagchi Classes (School of Chemistry) | Salt Lake- CD-293 | Gariahat | 9830705367