Set of questions on Thermodynamics

(ChE – 604 // Module II and Module III)

• Barnik Goswami (01) & Deepangshu Chatterjee (02)

1.1. Draw T-x-y and P-x-y diagram of a vapour liquid mixture.
1.2. What is Lewis-Randell Rule? State the assumptions of this rule.
1.3. Derive modified Raoult’s Law from VLE.
[ 6+4+5=15]
• Prantik Das (03) & Sk. Muntazir (04)

2.1. Prove that,

𝜕 ln 𝛾𝑖 𝑉𝑖𝐸 𝜕 ln 𝛾𝑖 𝐻𝐸
| = and | =−
𝜕𝑃 𝑇,𝑥𝑖 𝑅𝑇 𝜕𝑇 𝑃,𝑥𝑖 𝑅𝑇 2

The superscript E denotes the excess property.

2.2. Why the excess properties have no meaning for pure species?

2.3. What is Lewis-Randall Rule? State the assumptions of this rule. Plot fi vs xi curve.

• Amartya Ghosh (10) & Arghyadeep Paul (09)

3.1. “In a binary solution if one component obeys Henry’s Law, the other must obey
L-R rule” – Justify.

3.2. A methanol – water vapor liquid system is at equilibrium at 600C and 60 kPa.
The mole fraction of CH3OH in liquid is 0.5 and in vapor is 0.8. Vapor pressure
of CH3OH and water at 600C are 85 kPa and 20 kPa respectively. Assume vapor
pressure to be an ideal gas mixture.

(i) What is the activity coefficient of water in liquid phase?

(ii) What is the excess Gibbs free energy (GE in J/mol) of liquid mixture?

• Soumen Das (11) & Akhil Kr. Golu (13)

4.1. The fugacity of component 1 in binary liquid mixture of components 1 and 2 at

298 K and 20 bar is given by –
̅̅̅
𝒇𝟏 = 𝟓𝟎𝒙𝟏 − 𝟖𝟎𝒙𝟐𝟏 + 𝟒𝟎𝒙𝟑𝟏

where 𝑓̅1 is in bar and 𝑥1 is the mole fraction of component 1. Determine ---

a) The fugacity f1 for pure component 1

b) The fugacity coefficient Φ1
c) The Henry’s law constant K1
d) The activity coefficient γ1

1|Page
 4.2. Define activity coefficient. How do you distinguish between the activity
coefficient based on Lewis-Randall rule and that based on the ideal dilute
solution?

4.3. Derive the effect of pressure on activity coefficients.

[8+(2+3)+2=15]

• Rajdeep Mullick (28) & Sampan Sengupta (26)

5.1. Express Gibbs-Duhem relation at constant temperature and pressure in terms

of activity coefficient.

5.2. An equilibrium mixture of benzene and toluene is contained in a piston/cylinder

arrangement at a temperature T. What is the maximum pressure below which
this mixture will exist as a vapor phase alone?

At the given temperature, the vapor pressure of benzene and toluene are 1530
and 640 respectively. Assume the Raoult’s law is valid.

5.3. A binary system consists of n-pentane (1) and n- hexane (2) at 300C. Determine
the composition of vapor of the component (1) which is in equilibrium with a
liquid containing 20 mol% n-pentane (1) at 300C.

Given,

At 300C vapor pressures of n-pentane (1) and n-hexane (2) are 4.306 x 10-3 bar
(𝒑𝒗𝟏 ) & 249.5 x 10-3 bar (𝒑𝒗𝟐 ) respectively.

The activity coefficients of (1) & (2) at 𝑥1 = 0.2 at 300C are 𝛾1 = 2.831 ; 𝛾2 =
1.1716
Assume that in low pressure are in local state but liquid phase is not, use the
following equation ---

𝑦1 𝜋𝑎𝑖𝑉 = 𝑎𝑖𝑠𝑎𝑡 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡

𝑉
where π = total pressure and 𝑎𝑖 and 𝑎𝑖𝑠𝑎𝑡 are fugacity coefficient of vapor
and saturated vapor respectively.

[3+6+6=15]

• Priya Singh (35) & Tousif Jamal (34)

6.1. Calculate the bubble point of a n-pentane (1) / n- heptane (2) solution at P =
600 torr and x1 = 0.4

Given, Antoine’s equation ---

A’ B’ C’
1. 6.87632 1075.78 233.205

2|Page
 2. 6.89386 1264.37 216.640

6.2. Draw the T-x-y and P-x-y diagram of a VLE.

[10+5=15]
• Monami Mitra (25) & Anuj Debnath (42)

7.1. State Duhem’s theorem.

7.2. What are the assumptions required to reduce VLE calculation to Raoult’s law?

7.3. For the system methanol (1) / methyl acetate (2), the following equations
provide a reasonable correlation for the activity coefficients

𝐥𝐧 𝜸𝟏 = 𝑨𝒙𝟐𝟐 & 𝐥𝐧 𝜸𝟐 = 𝑨𝒙𝟐𝟏 , where A = 2.771 – 0.00523T

𝟑𝟔𝟒𝟑.𝟑𝟏
𝐥𝐧 𝑷𝒔𝒂𝒕
𝟏 = 𝟏𝟔. 𝟓𝟗𝟏𝟓𝟖 − 𝑻−𝟑𝟑.𝟒𝟐𝟒

𝟐𝟔𝟔𝟓.𝟓𝟒
𝟐 = 𝟏𝟒. 𝟐𝟓𝟑𝟐𝟔 − 𝑻−𝟓𝟑.𝟒𝟐𝟒 where T is in Kelvin & vapor pressure are in
𝐥𝐧 𝑷𝒔𝒂𝒕
kPa.

(a) P and [yi] for T = 318.15 K and x1 = 0.25

(b) P and [xi] for T= 318.15 K and y1 = 0.60
(c) T and [yi] for P = 101.33 kPa and x1 = 0.85

(Assume modified Raoult’s law)

[2+3+10=15]

• Ayan Kanti Santra (27) & Sreejita Banerjee (19)

8.1. Prove that for a first order phase transition for an ideal gas,

𝑑 ln 𝑃𝑠𝑎𝑡 △𝐻
=−
𝑑(1⁄𝑇 ) 𝑅

8.2. Prove that:

𝐺𝑗𝑅 𝑃 𝑑𝑃
= ln ∅𝑗 = ∫0 (𝑍𝑗 − 1) where 𝐺𝑗𝑅 = Residual Gibbs free energy of
𝑅𝑇 𝑃
the jth species, ∅𝑗 = Fugacity coefficient of jth species, 𝑍𝑗 = Compressibility factor.

8.3. An equimolar liquid mixture of species 1 and 2 is in equilibrium with its vapor
at 400 K. At this temperature, the vapor pressure of the species are 𝑃1𝑠𝑎𝑡 =
180 𝑘𝑃𝑎 and 𝑃2𝑠𝑎𝑡 = 120 𝑘𝑃𝑎. Assuming Raoult’s law is valid, calculate the value
of 𝑦1 and 𝑦2 .

8.4. The van Laar constants A and B for the system nitromethane (1) / carbon
tetrachloride (2) at 450C are 2.230 and 1.959 respectively. Calculate the activity
coefficients of the components in a solution containing 30 mol% nitromethane.

• Moumita Maity (29) & Amrita Debnath (14)

3|Page
 9.1. Prove that change of entropy increases for ideal gas mixing.

9.2. A chamber with a partition contains 0.1 lb mol of N2 & 0.1 lb mol O2 at 700C &
1 atm. The partition is removed & gases are allowed to mix. Calculate the total
change of entropy of the system due to mixing.

9.3. Ethanol (1) / Benzene (2) system forms an azeotrope with 44.8% (mole) of
ethanol with a boiling point of 68.240C at 760 torr. The vapor pressure of
ethanol & benzene at 68.240C are 506 torr & 517 torr. Estimate the van Laar
constant for the system & evaluate the activity coefficients for a solution
containing 10% (mole) ethanol.

[4+4+7=15]

• Sayani Rakshit (41) & Maharghya Biswas (24)

10.1. A methanol-water vapor liquid stream is at equilibrium at 600C & 60 kPa. The
mole fraction of CH3OH in liquid is 0.5 & in vapor is 0.8. vapor pressure of
CH3OH & water at 600C are 85 kPa & 20 kPa relatively. Assume vapor pressure
to be an ideal gas mixture.

(a) What is the activity coefficient of water in liquid phase?

(b) What is the excess Gibbs free energy (GE in J/mol) liquid mixture?

10.2. Derive Henry’s law from Lewis-Randall Rule.

[(7+3)+5=15]

• Dipanjan Ghosh (16) & Rajeev Ranjan (17)

11.1. Calculate the bubble point of a n-pentane (1) / n- heptane (2) solution at P =
600 torr and x1 = 0.6

Given, Antoine’s equation ---

A’ B’ C’
1. 6.87632 1075.78 233.205
2. 6.89386 1264.37 216.640

11.2. Derive modified Raoult’s law from VLE.

[10+5=15]

• Sumanta Goswami (39) & Sourav Mondal (30)

12.1. State the Modified Raoult’s law.

12.2. The system acetone (1), acetonitrile (2), nitromethane (3) at 800C and 110 kPa
has theoverall composition, Z1 = 0.45, Z2 = 0.35, Z3 = 0.20. Assuming that

4|Page
 Raoult’s law is appropriate to this system, determine ℒ, 𝜈, {𝑥𝑖 }, {𝑦𝑖 }. The vapor
pressures of the pure species at 800C are

𝑃1𝑠𝑎𝑡 = 195.75 , 𝑃2𝑠𝑎𝑡 = 97.84 , 𝑃3𝑠𝑎𝑡 = 50.32 𝑘𝑃𝑎

12.3. Show that the fugacity coefficient of a real gas in a multicomponent gas
mixture can be expressed as

𝑉 𝑅𝑇
𝑅𝑇 ln 𝜙̂𝑖 = − ∫∞ [(𝜕𝑃⁄𝜕𝑁 ) − ] 𝑑𝑉 − 𝑅𝑇 ln 𝑧
𝑖 𝑇,𝑁 𝑉
𝑗 ,𝑉

[3+6+6=15]

• Arnab Bandyopadhyay (37) & Dolan Bijali (32)

13.1. The need arises in laboratory for 2000 cm3 of an anti-freeze solution
consisting of 30 mol% methanol in water. What volume of pure methanol and
pure water at 250C must be mixed to form the 2000 cm3 of the anti-freeze
also at 250C.

Partial molar volumes for methanol, water in a 30 mol% methanol solution

and their pure species molar volumes both at 250C are ---

Methanol (1) ̅̅̅1 = 38.632 𝑐𝑚3 𝑚𝑜𝑙 −1

𝑣 𝑣1 = 40.727 𝑐𝑚3 𝑚𝑜𝑙 −1
Water (2) 𝑣2 = 17.1765 𝑐𝑚3 𝑚𝑜𝑙 −1
̅̅̅ 𝑣2 = 18.068 𝑐𝑚3 𝑚𝑜𝑙−1

13.2. What is Poynting factor? Derive the equation ---

𝑣 𝑙 (𝑃 − 𝑃𝑖𝑠𝑎𝑡 )⁄
𝑓𝑖 = ∅𝑖𝑠𝑎𝑡 𝑃𝑖𝑠𝑎𝑡 exp{ 𝑖 𝑅𝑇}
13.3. Prove that,

𝜕(𝑛𝐺 𝑅 ⁄𝑅𝑇 )
ln ∅̂𝑖 = |
𝜕𝑛𝑖 𝑇,𝑃,𝑛𝑗 (𝑖≠𝑗)

[5+5+5=15]

• Dipanjan Sarkar (07) & Biswadeep Mondal (08)

14.1. Calculate the bubble point of a n-pentane (1) / n- heptane (2) solution at P =
600 torr and x1 = 0.6

5|Page
 Given, Antoine’s equation ---

A’ B’ C’
1. 6.87632 1075.78 233.205
2. 6.89386 1264.37 216.640

14.2. Draw T-x-y & P-x-y diagram of a vapor-liquid mixture.

[10+5=15]

• Rajath Goswami (45) & Bapan Halder (42)

15.1. Show that in a binary mixture, if one component obeys Henry’s law, the other
must obey L-R rule and vice versa.

15.2. Provide a relation with 𝛾𝑖 𝑎𝑛𝑑 𝑥𝑖 in a methyl ethyl ketone (1) / toluene (2)
solution at 500C binary solution.

[9+6=15]

• Amarendra Sinha (20) & Amit Das (22)

16.1. In a binary solution if one component obeys Henry’s law, the other must obey
L-R rule ---justify.

16.2. The enthalpy of a binary liquid system of species 1 and 2 at fixed temperature
and pressure is represented by the equation ---

𝐻 = 400𝑥1 + 600𝑥2 + 𝑥1 𝑥2 (40𝑥1 + 20𝑥2 ), where H is in J/mol.

Determine expression for ̅𝐻̅̅1̅ and ̅𝐻̅̅2̅ as a function of 𝑥1 , numerical values for
the pure species enthalpies are 𝐻1 and 𝐻2 and numerical values for partial
enthalpies at infinite dilution are 𝐻 ̅2𝛼 .
̅1𝛼 and 𝐻

[8+7=15]

• Debrup Chakraborty (46) & Abesh Chatterjee (47)

17.1. (a) What is retrograde condensation?

(b) What is maxcondenbar or cricondenbar & maxcondentherm or

cricondentherm?

(c) At which condition retrograde condensation of 1st kind and 2nd kind occur?

17.2. A binary system consists of n-pentane (1) & n-hexane (2) at 300C. Determine
the composition of vapor of component (1) which is in equilibrium with a liquid
containing 20 mol% n-pentane (1) at 300C.

Given,

6|Page
 At 300C vapor pressures of n-pentane (1) and n-hexane (2) are 53.3329 x 10-3
bar (𝒑𝒗𝟏 ) & 249.5 x 10-3 bar (𝒑𝒗𝟐 ) respectively.

The activity coefficients of (1) & (2) at 𝑥1 = 0.2 at 300C are 𝛾1 = 2.831 ; 𝛾2 =
1.1716
Assume that in low pressure are in local state but liquid phase is not, use the
following equation ---

𝑦1 𝜋𝑎𝑖𝑉 = 𝑎𝑖𝑠𝑎𝑡 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡

where π = total pressure and 𝑎𝑖𝑉 and 𝑎𝑖𝑠𝑎𝑡 are fugacity coefficient of vapor
and saturated vapor respectively.

[(2+3+1)+9=15]

• Rahul Roy (18) & Rima Parui (21)

18.1. From a set of experimental VLE data of P-x1-y1 for methyl ethyl ketone (1) /
toluene (2) system at 500C. Calculate the liquid phase properties:

(a) 𝑓̂1𝑙 , 𝑓̂2𝑙 , 𝛾1 , 𝛾2

𝐺𝐸 𝐺𝐸
(b) ,
𝑅𝑇 𝑅𝑇𝑥1 𝑥2

Saturation Pressure for (2) and (1) are 12.30 kPa & 36.09 kPa respectively.

P (kPa) X1 Y1
12.3 (𝑃2𝑠𝑎𝑡 ) 0 0
05.51 0.0895 0.2716
18.61 0.1981 0.4565
21.63 0.3195 0.5934
24.01 0.4232 0.6815
25.92 0.5119 0.7440
27.96 0.6096 0.8050
30.12 0.7135 0.8639
31.75 0.7934 0.9048
34.14 0.9102 0.9590
36.09 (𝑃1𝑠𝑎𝑡 ) 1 1

[8+7 = 15]

• Sohrab Khan (15) & Avishek Kundu (38)

19.1. Define simple and non-simple solutions.
19.2. Graphically depict the variation of 𝜈1 and 𝜈2 vs mole fraction for Two Suffix
Margules’ Model.

7|Page
 19.3. The van Laar activity coefficient model for a binary mixture is given by the form
---
𝑨∗ 𝑩∗
𝐥𝐧 𝜸𝟏 = 𝟐 ; 𝐥𝐧 𝜸𝟐 = 𝟐
𝑨∗ 𝒙 𝑩∗ 𝒙
(𝟏+ ∗ 𝟏 ) (𝟏+ ∗ 𝟐 )
𝑩 𝒙𝟐 𝑨 𝒙𝟏

Given, 𝜸𝟏 =1.40, 𝜸𝟐 =1.25, 𝒙𝟏 =0.25, 𝒙𝟐 = 0.75, determine the constants A* and

B*.
[4+4+7=15]

MCQs:
1. The real solution behaviour approaches to that of ideal solution at two extreme
condition levels at [for a two component] ---
(a) 𝑥𝑖 → 1 (b) 𝑥𝑖 → 1 (c) 𝑥𝑖 → 0.75 (d) 𝑥𝑖 → 1
𝑥𝑖 → 0 𝑥𝑖 → 0.5 𝑥𝑖 → 0.25 𝑥𝑖 → 0.75

2. What is the vapor pressure of 40% gas in a system with partial pressure 20 mmHg?
(a) 5 mmHg, (b)10 mmHg, (c)20 mmHg, (d)50 mmHg

3. Azeotropic solution ---

(a) Obey Henry’s law
(b) Obey Raoult’s law
(c) Don’t obey Raoult’s law
(d) Obey Dalton’s law

4. Consider the following:

1) Air
2) Gaseous combustion products
3) Stream

Which of these are pure substances, assuming there is no phase change?

(a) 1 & 2 (b) 1 & 3 (c) 2 & 3 (d) all of these

5. When is Wilson’s equation superior to Margules & van Laar equation?

(a) Non-ideal & immiscible mixtures
(b) Ideal & miscible mixture
(c) Non-ideal & miscible mixtures
(d) Ideal & miscible mixtures

6. In azeotropic mixture showing positive deviation from Raoult’s law, the volume of
mixture is
(a) Slightly more than the total volume of components
(b) Slightly less than the total volume of the components
(c) Equal to the total volume of the components
(d) None of these

8|Page
7. A gas mixture of three components is brought in contact with a dispersion of an
inorganic phase in water. The degree of freedom of the system are:
(a) 4 (b) 3 (c) 5 (d) 6

8. The standard Gibbs free energy change and enthalpy change at 250C for liquid phase
reaction, 𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 + 𝑪𝟐 𝑯𝟓 𝑶𝑯 → 𝑪𝑯𝟑 𝑪𝑶𝑶𝑪𝟐 𝑯𝟓 + 𝑯𝟐 𝑶 are given as ∆𝐺298 0
=
−4650 𝐽/𝑚𝑜𝑙 and ∆𝐻298 = −3640 𝐽/𝑚𝑜𝑙. If the solution is ideal and enthalpy change is
0

assumed to be constant the equilibrium constant at 950C is

(a) 0.65 (b) 4.14 (c) 6.54 (d) 8.65

9. At 600C, vapor pressure of methanol and water are 84.562 kPa and 19.953 kPa
respectively. An aqueous solution of methanol at 600C exerts a pressure of 39.223 kPa;
the liquid phase and vapor phase mole fractions of methanol are 0.1686 and 0.5714
respectively. Activity coefficient of methanol is
(a) 1.572 (b) 1.9398 (c) 3.389 (d) 4.238

10. When dilute aqueous solution of two salts are mixed, the process is associated with
(a) Decrease in temperature
(b) Increase in temperature
(c) No change in temperature
(d) Change in temperature which is a function of composition

11. What is the temperature dependence of van Laar constant?

𝐴′
(a) 𝐴𝑖𝑗 = 𝑖𝑗⁄𝑇
𝐴′ 𝑅
(b) 𝐴𝑖𝑗 = 𝑖𝑗 ⁄𝑇
𝐴′
(c) 𝐴𝑖𝑗 = 𝑖𝑗⁄𝑇𝑅
(d) 𝐴𝑖𝑗 = 𝐴′𝑖𝑗 × 𝑅𝑇

12. For a pure substance, what are the degrees of freedom for saturated vapor and
superheated vapor respectively?
(a) 1 & 1 (b) 1 & 2 (c) 2 & 1 (d) 2 & 2

13. What is the change in fugacity when a saturated liquid on heating is converted to
saturated vapor?
(a) 0 (b) 1 (c) ∞ (d) cannot be predicted

14. For a coexisting liquid and vapor phase equilibrium, the phase rule gives us
information on
(a) Degrees of freedom only
(b) Distribution of mass between the two phases
(c) Both (a) and (b)

9|Page
 (d) None of these

15. In an ideal plate of distillation tower a binary mixture of benzene and toluene liquid
and vapor are in equilibrium. Which of the following conditions do not apply for the
phase equilibrium?
(a) TL = TV (b) pL = pV (c) SL = SV (d) 𝜇𝑖𝐿 = 𝜇𝑖𝑉

10 | P a g e